JP4661241B2 - Fluorine-substituted indium phthalocyanine, and electrophotographic photosensitive member, electrophotographic photosensitive member cartridge, and image forming apparatus using the same - Google Patents

Description

  The present invention relates to a fluorine-substituted indium phthalocyanine, and an electrophotographic photosensitive member, an electrophotographic photosensitive member cartridge, and an image forming apparatus using the same. In particular, an electrophotographic photosensitive member used in laser printers, copying machines, faxes, etc., can be obtained which is very effective for LED light and semiconductor laser light and has excellent durability. The present invention relates to a charge generating material, and an electrophotographic photosensitive member, an electrophotographic photosensitive member cartridge, and an image forming apparatus using the same.

In recent years, the electrophotographic technique is widely applied not only to the field of copying machines but also to various printers and printing machines because it is excellent in immediacy and provides high-quality images.
As a photoreceptor that is the core of electrophotographic technology, conventionally, a photoreceptor using an inorganic photoconductive material such as selenium, an arsenic-selenium alloy, and zinc oxide has been used, but recently, it is pollution-free. Photoconductors using organic photoconductive materials, which have advantages such as easy film formation / manufacturing and high freedom of material selection / combination, are the mainstream.

  The sensitivity of an electrophotographic photoreceptor using an organic photoconductive material varies depending on the type of charge generating material used. As a charge generation material having sensitivity to long wavelength light, a phthalocyanine compound has attracted attention. In particular, researches on metal-containing phthalocyanines or metal-free phthalocyanines such as chloroaluminum phthalocyanine, chloroindium phthalocyanine, vanadyloxyphthalocyanine, hydroxygallium phthalocyanine, chlorogallium phthalocyanine, magnesium phthalocyanine, and oxytitanium phthalocyanine have been actively conducted.

  In particular, various studies have been conducted on indium phthalocyanine, and various crystal types have been reported (see, for example, Patent Documents 1 to 5), and show high photosensitivity as a charge generation material for electrophotographic photoreceptors. Is clear.

  By the way, devices such as copiers, printers, and fax machines using electrophotographic technology (hereinafter referred to as “electrophotographic devices”) are rapidly increasing in speed and resolution. High responsiveness in the high speed range has been demanded. On the other hand, reduction of running cost is desired with the increase in the penetration rate of these electrophotographic devices.

  The running cost of an electrophotographic device mainly includes the cost of a photoconductor cartridge or a toner cartridge that is a replacement part. The higher the durability of the photoconductor, the longer the life of the photoconductor cartridge and the lower its running cost.

  One of the factors that determine the life of the photoreceptor is repeated stability. If the repetitive stability is inferior, the residual potential increases after light exposure on the photoconductor during short repetitive use, image blurring occurs, and finally the desired image cannot be obtained.

  In addition, if the chargeability of the photoreceptor is inferior, the degree of reduction in chargeability due to repeated use is high, chargeability is reduced due to repeated use, and a desired surface potential cannot be obtained. It can no longer be obtained.

  Although the above-mentioned electrophotographic photosensitive member using indium phthalocyanine as a charge generation material exhibits high photosensitivity, it has a problem that it is poor in repetitive stability due to poor chargeability and high residual potential. The current situation is that the demand cannot be satisfied in terms of high durability which is strongly demanded in recent years.

JP 59-44054 A JP 59-155851 A JP-A-5-70709 Japanese Patent Laid-Open No. 5-70710 JP 7-13375 A

  As described above, an electrophotographic photoreceptor using indium phthalocyanine as a charge generation material has a high residual potential and poor chargeability. Further, the durability against repeated use is low, and it is not satisfactory in terms of high durability, which is one of the performances required for electrophotographic photoreceptors in recent years.

  The present invention has been made in view of the above-described problems, and an object of the present invention is to provide indium phthalocyanine, which is an excellent electrophotographic photoreceptor material, capable of obtaining an electrophotographic photoreceptor having a low residual potential and excellent chargeability. And providing an electrophotographic photosensitive member, an electrophotographic photosensitive member cartridge, and an image forming apparatus using the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors use an indium phthalocyanine in which a specific position of the phthalocyanine skeleton is substituted with a specific number of fluorine atoms. The inventors have found that a photographic photoreceptor can be obtained and have completed the present invention.

（一般式［１］中、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴は、フッ素原子を表わす。ｋ、ｌ、ｍ、ｎは各々独立して、０又は１を表わす。但し、ｋ、ｌ、ｍ、ｎのうち少なくとも一つは必ず１である。Ｙは、インジウムと結合し得る１価の結合基を表わす。） That is, the gist of the present invention resides in fluorine-substituted indium phthalocyanine, which is represented by the following general formula [1].

(In the general formula [1], X ¹ , X ² , X ³ and X ⁴ each represents a fluorine atom. K, l, m and n each independently represents 0 or 1, provided that k, l , M and n must be at least 1. Y represents a monovalent linking group capable of binding to indium.)

  Another gist of the present invention is an electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, wherein the photosensitive layer contains the above-described fluorine-substituted indium phthalocyanine. Exists on the photoreceptor.

  Another aspect of the present invention is the above-described electrophotographic photosensitive member, a charging unit that charges the electrophotographic photosensitive member, an exposure unit that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image, and The electrophotographic photosensitive member cartridge includes at least one developing unit that develops the electrostatic latent image formed on the electrophotographic photosensitive member.

  Another gist of the present invention is the above-described electrophotographic photosensitive member, a charging unit that charges the electrophotographic photosensitive member, and an exposure unit that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image. And an image forming apparatus comprising: a developing unit that develops the electrostatic latent image formed on the electrophotographic photosensitive member.

  When the fluorine-substituted indium phthalocyanine of the present invention is used as an electrophotographic photoreceptor material, an electrophotographic photoreceptor excellent in chargeability, little dark decay, low residual potential, that is, excellent in various characteristics can be obtained. Can do.

  Hereinafter, typical embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit of the present invention. .

[1. (Fluorine-substituted indium phthalocyanine)
<Structure of fluorine-substituted indium phthalocyanine>
The fluorine-substituted indium phthalocyanine of the present invention is represented by the following general formula [1].

In the general formula [1], X ¹ , X ² , X ³ and X ⁴ represent a fluorine atom. The fluorine atom is particularly excellent in terms of the versatility of the reagent, the stability of the substituent to heat during production, and the effect on the produced phthalocyanine crystals.

  k, l, m, and n each independently represents 0, 1, or 2. However, at least one of k, l, m, and n is always 1. In particular, if the number of fluorine atoms is too small, desired chargeability and residual potential cannot be obtained. Therefore, 2 ≦ k + l + m + n is preferably satisfied, and 3 ≦ k + l + m + n is more preferable. On the other hand, even if the number of fluorine atoms is too large, the desired chargeability and residual potential cannot be obtained. Therefore, it is preferable to satisfy the formula of k + 1 + m + n ≦ 6, and phthalonitrile, phthalic anhydride, , 3-diiminoisoindoline and the like tend to have a higher unit price as the number of substituents increases. Therefore, it is more preferable to satisfy k + 1 + m + n ≦ 5 in view of production cost. From the viewpoint of the photoconductivity of the obtained fluorine-substituted indium phthalocyanine, it is particularly preferable that k + l + m + n = 4 is satisfied, and considering the versatility of the production raw material, it is most preferable that k = l = m = n = 1.

  Y represents a monovalent linking group capable of binding to indium. Specific examples include a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, a thioalkyl group, a thioaryl group, and the like. Among these, a halogen atom, a hydroxyl group, and a lower alkoxy group having about 1 to 4 carbon atoms are preferable from the viewpoint of ease of production, and a halogen atom is more preferable from the material stability of fluorine-substituted indium phthalocyanine. Among the halogen atoms, a chlorine atom and a bromine atom are preferable in consideration of the versatility of the reagent. In particular, considering the influence on the crystals of the fluorine-substituted indium phthalocyanine to be produced, atoms having a small volume are preferred, and chlorine atoms are most preferred.

Examples of the position at which X ¹ , X ² , X ³ , and X ⁴ are bonded to the corresponding six-membered ring include the four positions represented by (a) to (d) in the following formula [2] (note that Formula [2] represents the structure of the six-membered ring moiety of Formula [1].) However, the bonding position is not particularly limited, and may be bonded to any position of (a) to (d). However, two fluorine atoms are not bonded to one position.

For example, when k = 1 = m = n = 1, X ¹ , X ² , X ³ , X ⁴ is a six-membered ring (a) or ( It is possible to manufacture and separate the structure coupled to the position b) and the structure coupled to the position (c) or (d) to some extent. Specifically, among the isomers of fluorophthalonitrile, which is one of the raw materials, when only 4-fluorophthalonitrile is used, X ¹ , X ² , X ³ , and X ⁴ are all (a) or (b). fluorine-substituted phthalocyanine of the structure bonded to the position of, also, 3-fluorophthalonitrile alone with bound to the position of the ^{X 1, X 2, X 3} , X 4 all (c) or (d) A fluorine-substituted indium phthalocyanine having a structure will be obtained. Of course, it is also possible to obtain fluorine-substituted indium phthalocyanine in which the bonding positions of (a), (b), (c), and (d) are mixed by appropriately using these isomers of fluorophthalonitrile. However, considering the production cost, it is preferable to use 4-fluorophthalonitrile as a raw material. Therefore, as the structure of the fluorine-substituted indium phthalocyanine, all of X ¹ , X ² , X ³ , and X ⁴ are (a) or A structure bonded to the position (b) is preferred.

Further, with respect to fluorine-substituted indium phthalocyanine in which all of X ¹ , X ² , X ³ , and X ⁴ are bonded to the position (a) or (b), the bonding positions of X ¹ , X ² , X ³ , and X ⁴ are also determined. Depending on the combination, there are six types of structural isomers (the structural isomers are represented by the symbols (I) to (VI) for convenience). Table 1 below shows combinations of bonding positions of X ¹ , X ² , X ³ and X ^{4 in} each of the structural isomers (I) to (VI). A plurality of combinations are conceivable for the structural isomers (III) to (VI). Table 1 shows one of them as a representative example.

  The fluorine-substituted indium phthalocyanine of the present invention is not limited to any one of the above-mentioned structural isomers (I) to (VI), and may be any one kind or a mixture of two or more kinds. It is obtained as a mixture of all six structural isomers (I) to (VI). In this case, the composition of each structural isomer (I) to (VI) is not particularly limited.

<Crystallinity of fluorine-substituted indium phthalocyanine>
The fluorine-substituted indium phthalocyanine of the present invention may have crystallinity or may be amorphous (amorphous). However, in consideration of the use as a photoconductive material, the following specific crystal types or It preferably has a fixed nature.

That is, in the X-ray diffraction spectrum, the Bragg angle (2θ ± 0.2 °) is i) having strong peaks at least 7.0 °, 16.6 °, 25.4 ° and 27.0 ° (hereinafter, Appropriately referred to as "crystal (I)"),
ii) those having strong peaks at least at 6.9 °, 13.0 °, 16.2 °, 25.7 °, and 28.0 ° (hereinafter referred to as “crystal (II)” where appropriate); and
iii) No clear peak within the range of 3 ° to 40 ° (hereinafter referred to as “amorphous material” as appropriate)
Is mentioned as a preferred embodiment.

<Shape of fluorine-substituted indium phthalocyanine>
The shape of the fluorine-substituted indium phthalocyanine of the present invention is not particularly limited, but is usually a particle shape. The particle size of the particles is not particularly limited, but is usually 0.01 μm or more, preferably 0.03 μm or more, and usually 0.5 μm or less, preferably 0.8 μm or less from the viewpoint of sufficiently exhibiting the characteristics as a photoconductive material. It is suitable that the range is 3 μm or less, more preferably 0.15 μm or less.

<Method for producing fluorine-substituted indium phthalocyanine>
The fluorine-substituted indium phthalocyanine of the present invention can be produced using a known method for producing phthalocyanine. Examples thereof include phthalonitrile method in which fluorine-substituted phthalonitrile and a metal salt such as metal halide are heated and melted or heated in the presence of an organic solvent, and indoline compounds such as fluorine-substituted 1,3-diiminoisoindoline. A method of heating and melting a metal salt such as a metal halide or heating in the presence of an organic solvent, a winder heating a fluorine-substituted phthalic anhydride with a metal salt such as urea or a metal halide or heating or heating in the presence of an organic solvent. And a method of reacting fluorine-substituted cyanobenzamide with a metal salt, a method of reacting fluorine-substituted dilithium phthalocyanine with a metal salt, and the like.

  The synthesis of the fluorine-substituted indium phthalocyanine of the present invention is preferably performed in the presence of an organic solvent. When synthesizing under solvent-free conditions, for example, when synthesizing fluorine-substituted chloroindium phthalocyanine (that is, a compound in which Y is a chlorine atom in the general formula (1)), chlorination occurs in the phthalocyanine ring, Fluorine-substituted chloroindium phthalocyanine having a desired structure may not be obtained. Moreover, if an organic solvent is not used, impurities present during the reaction, unreacted raw materials, by-products generated by the reaction, etc. are taken into the phthalocyanine solid, which may adversely affect the photoconductive properties of the resulting fluorine-substituted indium phthalocyanine. There is.

  As the organic solvent used for the synthesis, a solvent which is inert to the reaction and has a high boiling point is preferable. Specific examples include halogenated aromatic solvents such as α-chloronaphthalene, β-chloronaphthalene, o-dichlorobenzene and dichlorotoluene; alkylation such as α-methylnaphthalene, β-methylnaphthalene and tetrahydronaphthalene (tetralin). Aromatic solvents; Diarylicated aliphatic solvents such as diphenylmethane and diphenylethane; Alkoxylated aromatic solvents such as methoxynaphthalene; Polyhydric alcohol solvents such as ethylene glycol; Ethers such as diphenyl ether, diethylene glycol dimethyl ether and butyl cellosolve Examples thereof include heterocyclic aromatic solvents such as quinoline; aprotic polar solvents such as sulfolane, dimethyl sulfoxide, N-methylformamide, and 1,3-dimethyl-2-imidazolinone. These solvents may be used alone or in combination of two or more as a mixed solvent.

  When using the phthalonitrile method, the fluorine-substituted indium phthalocyanine of the present invention is produced by stirring the fluorine-substituted phthalonitrile and the indium halide compound with stirring or heating at 25 to 300 ° C. in the above organic solvent. be able to. Moreover, you may react by adding catalysts, such as a quaternary ammonium salt, urea, 1, 8- diazabicyclo [5.4.0] -7-undecene (DBU), as needed.

  The fluorine-substituted indium phthalocyanine obtained by the above-described production method (hereinafter referred to as “fluorine-substituted indium phthalocyanine crude product” or simply “crude product”) has a large particle size as it is, and the preferred particle size range described above. It may not be inside. Therefore, in order to make the obtained fluorine-substituted indium phthalocyanine crude product into particles of a desired size, a step of refining it is necessary. As the miniaturization method, an arbitrary method is selected from a processing method using mechanical force such as a grinding method and a chemical processing method such as an acid paste method and an acid slurry method. Can do. It is also possible to combine two or more of the methods described above. Among them, the acid slurry method and the acid paste method require a large amount of acid, and must be neutralized using a large amount of base in the treatment of the waste acid after production, which costs a lot of waste processing, In addition, there is a very large problem that a large amount of waste is generated, and usually the charging performance of the electrical characteristics due to impurities derived from the anion of the acid used is reduced, so that the grinding method or the like A treatment method using mechanical force is preferably used.

  When grinding is performed using mechanical force, the apparatus used for grinding is not particularly limited. Examples include automatic mortar, planetary mill, ball mill, CF mill, roller mill, sand mill, kneader, and attritor. Is mentioned. When the grinding media is used, the type thereof is not particularly limited, and specific examples include glass beads, steel beads, alumina beads and the like. At the time of grinding, in addition to the grinding media, a grinding aid that can be easily removed after grinding can be used in combination. Examples of grinding aids include sodium chloride and sodium nitrate.

  Grinding may be carried out dry or in the presence of a solvent. When wet grinding is performed, the solvent to be used is not particularly limited. For example, saturated aliphatic solvents such as pentane, hexane, octane, and nonane; aromatic solvents such as toluene, xylene, and anisole; chlorobenzene, dichlorobenzene, Halogenated aromatic solvents such as chloronaphthalene; Alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, and benzyl alcohol; Aliphatic polyhydric alcohols such as glycerin and polyethylene glycol; Chains such as acetone, cyclohexanone, and methyl ethyl ketone Or cyclic ketone solvents; ester solvents such as methyl formate, ethyl acetate, n-butyl acetate; halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1,2-dichloroethane; diethyl ether, dimethoxyethane, tetrahydro Chain or cyclic ether solvents such as lofrane, 1,4-dioxane, methyl cellosolve, ethyl cellosolve; aprotic such as dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, hexamethylphosphate triamide Polar solvents; nitrogen-containing compounds such as n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine, triethylenediamine, triethylamine; mineral oil such as ligroin, water, and the like. Among them, in consideration of operability during wet grinding, saturated aliphatic solvents, aromatic solvents, alcohol solvents, chain or cyclic ketone solvents, ester solvents, chain or cyclic ether solvents, aprotic The polar solvent and water are preferred. Any one of these solvents may be used alone, or two or more thereof may be used in combination as a mixed solvent. From the viewpoint of productivity, the amount of the solvent used is usually 0.01 parts by weight or more, preferably 0.1 parts by weight or more, and usually 200 parts by weight with respect to 1 part by weight of the fluorine-substituted indium phthalocyanine crude product to be ground. The range is not more than parts by weight, preferably not more than 100 parts by weight. The treatment temperature can be not less than the freezing point of the solvent (or the mixed solvent) and not more than the boiling point, but is usually in the range of not less than 10 ° C. and not more than 200 ° C. from the viewpoint of safety. As an apparatus for performing wet grinding, a kneader or the like can be used in addition to the grinding apparatus exemplified above.

  After the dry or wet grinding treatment, if a grinding media is used, the fine particles of the desired fluorine-substituted indium phthalocyanine can be obtained by separating and removing the grinding media.

  The fine particles of fluorine-substituted indium phthalocyanine obtained by dry grinding / chemical treatment are amorphous having no crystallinity. This is equivalent to iii) the X-ray diffraction spectrum in which the Bragg angle (2θ ± 0.2 °) does not have a clear peak in the range of 3 ° to 40 ° among the three preferred embodiments described above. (Hereinafter referred to as “fluorine-substituted indium phthalocyanine amorphous material” or simply “amorphous material”).

  On the other hand, i) having strong peaks at least 7.0 °, 16.6 °, 25.4 °, and 27.0 °, or ii) at least 6.9 °, 13.0 °, 16.2 ° In order to obtain those having strong peaks at 25.7 ° and 28.0 °, the following treatment is further performed to convert the amorphous material after dry grinding or chemical treatment into the desired crystal form. (This process is hereinafter referred to as “crystal type conversion process” as appropriate).

  The crystal form conversion treatment is performed by contacting with a solvent. As the contact method with the solvent, the particles may be made into a slurry state in the solvent, or any known contact method such as exposure to solvent vapor may be used. Examples of the solvent used include saturated aliphatic solvents such as pentane, hexane, octane, and nonane; aromatic solvents such as toluene, xylene, and anisole; halogenated aromatic solvents such as chlorobenzene, dichlorobenzene, and chloronaphthalene; Alcohol solvents such as methanol, ethanol, isopropanol, n-butanol and benzyl alcohol; aliphatic polyhydric alcohols such as glycerin and polyethylene glycol; chain or cyclic ketone solvents such as acetone, cyclohexanone and methyl ethyl ketone; methyl formate; Ester solvents such as ethyl acetate and n-butyl acetate; halogenated hydrocarbon solvents such as methylene chloride, chloroform and 1,2-dichloroethane; diethyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, 1 Linear or cyclic ether solvents such as 3-dioxolane, methylcellosolve, ethylcellosolve; aprotic polar solvents such as dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide Nitrogen-containing compounds such as n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine, triethylenediamine and triethylamine; mineral oil such as ligroin; water and the like. Among these, in consideration of operability, saturated aliphatic solvents, aromatic solvents, alcohol solvents, chain or cyclic ketone solvents, ester solvents, chain or cyclic ether solvents, aprotic polar solvents, water Is preferred. Any one of these solvents may be used alone, or two or more thereof may be used in combination as a mixed solvent. The treatment temperature can be not less than the freezing point of the solvent (or the mixed solvent) and not more than the boiling point, but is usually in the range of not less than 10 ° C. and not more than 200 ° C. from the viewpoint of safety. From the viewpoint of productivity, the amount of the solvent used is usually 0.1 parts by weight or more, preferably 1 part by weight or more, and usually 500 parts by weight or less, preferably 1 part by weight of amorphous fluorine-substituted indium phthalocyanine. Is in the range of 250 parts by weight or less.

In addition, when the fluorine-substituted indium phthalocyanine amorphous material is brought into contact with a solvent, an operation such as stirring may be added as necessary to enhance the contact property. Moreover, you may use well-known stirring media, such as a wet glass bead, an alumina bead, and a steel bead, at the time of stirring.
Further, when performing the wet grinding process, the wet grinding process and the crystal form conversion process are simultaneously performed by selecting the same solvent for the wet grinding process and the solvent for the crystal form conversion process. It becomes possible.

By the above crystal type conversion treatment, the amorphous substance of fluorine-substituted indium phthalocyanine can be converted into the above-mentioned crystal (I) or crystal (II).
In addition, when the wet grinding treatment and / or the crystal form conversion treatment are performed, the target amorphous substance or crystal of fluorine-substituted indium phthalocyanine is obtained in the state of the above-mentioned solvent and / or a wet cake dispersed in the solvent. Will be. From this wet cake, the solvent and / or the solvent is removed using a known method such as room temperature drying, reduced pressure drying, hot air drying, freeze drying, and the like, and the desired fluorine-substituted indium phthalocyanine amorphous or crystal is dried. Is obtained.

<Others>
The fluorine-substituted indium phthalocyanine of the present invention can be used as various image display devices, optical information recording media, and photoconductive materials, and is particularly preferably used as a photosensitive material of an electrophotographic photosensitive member. By incorporating the fluorine-substituted indium phthalocyanine of the present invention in the photosensitive layer of an electrophotographic photosensitive member, an electrophotographic photosensitive member having a low residual potential and excellent chargeability can be obtained. In addition, according to the electrophotographic photoreceptor using the fluorine-substituted indium phthalocyanine of the present invention, a good image with a small fog value can be obtained. Furthermore, this electrophotographic photoreceptor has high durability against repeated use.

[2. Electrophotographic photoreceptor
The structure of the electrophotographic photosensitive member of the present invention is not particularly limited as long as the photosensitive layer containing the above-described fluorine-substituted indium phthalocyanine of the present invention is provided on a conductive support (substrate).

<Conductive support>
There is no particular limitation on the conductive support, but for example, metal materials such as aluminum, aluminum alloy, stainless steel, copper, and nickel, and conductive powder such as metal, carbon, and tin oxide are added to impart conductivity. A resin material, a resin, glass, paper, or the like on which a conductive material such as aluminum, nickel, or ITO (indium tin oxide) is deposited or applied on the surface is mainly used. These may be used alone or in combination of two or more in any combination and ratio. As a form of the conductive support, a drum form, a sheet form, a belt form or the like is used. Further, a conductive material having an appropriate resistance value may be used on a conductive support made of a metal material in order to control conductivity and surface properties and to cover defects.

  Moreover, when using metal materials, such as an aluminum alloy, as an electroconductive support body, you may use, after giving an anodic oxide film. When an anodized film is applied, it is desirable to perform a sealing treatment by a known method.

  The surface of the support may be smooth, or may be roughened by using a special cutting method or performing a polishing treatment. Further, it may be roughened by mixing particles having an appropriate particle diameter with the material constituting the support. In order to reduce the cost, it is possible to use the drawing tube as it is without performing the cutting process.

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

  Examples of metal oxide particles used for the undercoat layer include metal oxide particles containing one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, calcium titanate, titanium Examples thereof include metal oxide particles containing a plurality of metal elements such as strontium acid and barium titanate. One kind of these particles may be used alone, or a plurality of kinds of particles may be mixed and used. Among these metal oxide particles, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable. The surface of the titanium oxide particles may be treated with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide, or silicon oxide, or an organic substance such as stearic acid, polyol, or silicon. As the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. Moreover, the thing of a several crystal state may be contained.

  In addition, various particle sizes of the metal oxide particles can be used. Among these, from the viewpoint of characteristics and liquid stability, the average primary particle size is usually 1 nm or more, preferably 10 nm or more, and usually 100 nm or less. Preferably it is 50 nm or less.

  The undercoat layer is preferably formed in a form in which metal oxide particles are dispersed in a binder resin. As binder resin used for the undercoat layer, epoxy resin, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, Polyimide resin, vinylidene chloride resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, polyurethane resin, polyacrylic acid resin, polyacrylamide resin, polyvinyl pyrrolidone resin, polyvinyl pyridine resin, water-soluble polyester resin, nitro Cellulose ester resins such as cellulose, cellulose ether resins, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, zirconium chelation Things, organic zirconium compounds such as zirconium alkoxide compounds, titanyl chelate compounds, organic titanyl compounds such as titanyl alkoxide compound, a known binder resin such as a silane coupling agent and the like. These may be used alone or in combination of two or more in any combination and ratio. Moreover, you may use with the hardening | curing form with the hardening | curing agent. Among these, alcohol-soluble copolymerized polyamides, modified polyamides, and the like are preferable because they exhibit good dispersibility and coatability.

  The ratio of the inorganic particles to the binder resin used in the undercoat layer can be arbitrarily selected, but is usually in the range of 10% by weight or more and 500% by weight or less from the viewpoint of dispersion stability and coating properties. Is preferably used.

The thickness of the undercoat layer can be selected arbitrarily, but is usually preferably in the range of 0.1 μm or more and 20 μm or less from the viewpoint of improving the photoreceptor characteristics and applicability.
A known antioxidant or the like may be mixed in the undercoat layer. For the purpose of preventing image defects, pigment particles, resin particles and the like may be contained and used.

<Photosensitive layer>
As a type of the photosensitive layer, a charge generation material and a charge transport material are present in the same layer and are dispersed in a binder resin, a charge generation layer in which a charge generation material is dispersed in a binder resin, and a charge. A function separation type (laminated type) composed of two layers of a charge transport layer in which a transport material is dispersed in a binder resin can be mentioned, but any type may be used. The fluorine-substituted indium phthalocyanine of the present invention is contained as at least one kind of charge generating substance.

  In addition, as the laminated photosensitive layer, a charge generation layer and a charge transport layer are laminated in this order from the conductive support side, and a charge transport layer and a charge generation layer are laminated in this order. There are reverse laminated type photosensitive layers, and any of them can be adopted, but a forward laminated type photosensitive layer capable of exhibiting the most balanced photoconductivity is preferable.

(Charge generation layer)
In the case of a multilayer type photoreceptor (function separation type photoreceptor), the charge generation layer is formed by binding a charge generation material with a binder resin.

  As the charge generation material, the fluorine-substituted indium phthalocyanine of the present invention is used. Any one of the fluorine-substituted indium phthalocyanines of the present invention may be used alone, or two or more of them may be used in a mixed state or mixed crystal state in any combination. Further, one or more of the fluorine-substituted indium phthalocyanines of the present invention may be used in a mixed state or mixed crystal state in combination with one or more other known charge generating materials.

  Examples of the charge generating material used in combination with the fluorine-substituted indium phthalocyanine of the present invention include selenium and its alloys, cadmium sulfide, other inorganic photoconductive materials, and organic photoconductive materials such as organic pigments, Organic photoconductive materials are preferred, and organic pigments are particularly preferred. Specific examples of organic pigments include phthalocyanine pigments, azo pigments, dithioketopyrrolopyrrole pigments, squalene (squarylium pigments), quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthanthrone pigments, and benzimidazole pigments. It is done.

  Among the organic pigments exemplified above, a phthalocyanine pigment or an azo pigment is particularly preferable as the charge generation material used in combination with the fluorine-substituted indium phthalocyanine of the present invention. The phthalocyanine pigment provides a highly sensitive photoreceptor for a relatively long wavelength laser beam having a wavelength of 600 to 900 nm, and the azo pigment is a white light and a relatively short wavelength laser having a wavelength of 300 to 500 nm. Each is excellent in that it has sufficient sensitivity to light.

  When two or more fluorine-substituted indium phthalocyanines of the present invention are used in combination, or when one or two or more fluorine-substituted indium phthalocyanines of the present invention are used in combination with one or more other charge generating materials, The mixing method is not particularly limited, and each component may be used by mixing from a powder state or a dispersion state, or in a mixed state in the production and processing steps of phthalocyanine compounds such as pigmentation and crystallization. It may be the one that gave rise to. As such a treatment method, acid paste treatment, grinding treatment, solvent treatment and the like are known. In order to produce a mixed crystal state, as described in JP-A-10-48859, after mixing two kinds of crystals, they are mechanically ground and made amorphous, and then a specific crystal state is obtained by solvent treatment. The method of converting into is mentioned.

  The binder resin used for the charge generation layer is not particularly limited, but examples include polyvinyl butyral resin, polyvinyl formal resin, polyvinyl acetal type such as partially acetalized polyvinyl butyral resin in which a part of butyral is modified with formal, acetal, or the like. Resin, Polyarylate resin, Polycarbonate resin, Polyester resin, Modified ether type polyester resin, Phenoxy resin, Polyvinyl chloride resin, Polyvinylidene chloride resin, Polyvinyl acetate resin, Polystyrene resin, Acrylic resin, Methacrylic resin, Polyacrylamide resin, Polyamide Resin, polyvinyl pyridine resin, cellulosic resin, polyurethane resin, epoxy resin, silicone resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, casein, vinyl chloride Vinyl chloride-vinyl acetate copolymer such as vinyl acetate copolymer, hydroxy-modified vinyl chloride-vinyl acetate copolymer, carboxyl-modified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer Insulating resin such as polymer, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, styrene-alkyd resin, silicon-alkyd resin, phenol-formaldehyde resin, poly-N-vinylcarbazole, polyvinylanthracene, polyvinylperylene Organic photoconductive polymers such as Any one of these binder resins may be used alone, or two or more thereof may be mixed and used in any combination.

  Specifically, the charge generation layer is prepared by dispersing the fluorine-substituted indium phthalocyanine of the present invention and other charge generation materials used in some cases in a solution obtained by dissolving the above-described binder resin in an organic solvent. Is applied on a conductive support (or an undercoat layer when an undercoat layer is provided).

  The solvent used for preparing the coating solution is not particularly limited as long as it dissolves the binder resin. For example, saturated aliphatic solvents such as pentane, hexane, octane, and nonane, and aromatics such as toluene, xylene, and anisole. Group solvents, halogenated aromatic solvents such as chlorobenzene, dichlorobenzene, chloronaphthalene, amide solvents such as dimethylformamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n-butanol, benzyl alcohol, etc. Alcohol solvents, aliphatic polyhydric alcohols such as glycerin and polyethylene glycol, chain or cyclic ketone solvents such as acetone, cyclohexanone, methyl ethyl ketone, ester solvents such as methyl formate, ethyl acetate, n-butyl acetate, methylene chloride , Chloro Halogenated hydrocarbon solvents such as rum, 1,2-dichloroethane, chain ether or cyclic ether solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, acetonitrile, dimethyl Aprotic polar solvents such as sulfoxide, sulfolane, hexamethylphosphoric triamide, n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine, triethylenediamine, triethylamine and other nitrogen-containing compounds, ligroin and other mineral oils, water, etc. Can be mentioned. Any one of these may be used alone, or two or more of these may be used in combination. In addition, when providing the above-mentioned undercoat layer, what does not melt | dissolve this undercoat layer is preferable.

  In the charge generation layer, the blending ratio (weight) of the binder resin and the charge generation material is usually 10 parts by weight or more, preferably 30 parts by weight or more, and usually 1000 parts by weight with respect to 100 parts by weight of the binder resin. Part or less, preferably 500 parts by weight or less, and the film thickness is usually 0.05 μm or more, preferably 0.1 μm or more, and usually 10 μm or less, preferably 5 μm or less. If the ratio of the charge generation material is too high, the stability of the coating solution may be reduced due to aggregation of the charge generation material, while if the ratio of the charge generation material is too low, the sensitivity as a photoreceptor may be decreased. There is.

  As a method for dispersing the charge generation material, a known dispersion method such as a ball mill dispersion method, an attritor dispersion method, or a sand mill dispersion method can be used. At this time, it is effective to refine the particles to a particle size in the range of 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less.

(Charge transport layer)
The charge transport layer of the multilayer photoconductor contains a charge transport material and usually contains a binder resin and other components used as necessary. Specifically, such a charge transport layer is prepared by, for example, preparing a coating solution by dissolving or dispersing a charge transport material or the like and a binder resin in a solvent. In addition, in the case of a reverse lamination type photosensitive layer, it can be obtained by coating and drying on a conductive support (or on the undercoat layer when an undercoat layer is provided).

  The charge transport material is not particularly limited, and any material can be used. Examples of known charge transport materials include aromatic nitro compounds such as 2,4,7-trinitrofluorenone, cyano compounds such as tetracyanoquinodimethane, electron withdrawing materials such as quinone compounds such as diphenoquinone, and carbazole derivatives. , Indole derivatives, imidazole derivatives, oxazole derivatives, pyrazole derivatives, thiadiazole derivatives, benzofuran derivatives and other heterocyclic compounds, aniline derivatives, hydrazone derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives and multiple types of these compounds Or an electron donating substance such as a polymer having a group composed of these compounds in the main chain or side chain. Among these, carbazole derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives, and those in which a plurality of these compounds are bonded are preferable. Any one of these charge transport materials may be used alone, or two or more thereof may be used in any combination.

  Specific examples of the structure of a suitable charge transport material are shown below. However, these specific examples are described for the purpose of illustration, and any charge transport material may be used as long as it is not contrary to the gist of the present invention.

  The binder resin is used for securing the film strength. Examples of the binder resin for the charge transport layer include butadiene resin, styrene resin, vinyl acetate resin, vinyl chloride resin, acrylic ester resin, methacrylic ester resin, vinyl alcohol resin, ethyl vinyl ether and other vinyl compound polymers and copolymer Coalesced, polyvinyl butyral resin, polyvinyl formal resin, partially modified polyvinyl acetal, polycarbonate resin, polyester resin, polyarylate resin, polyamide resin, polyurethane resin, cellulose ester resin, phenoxy resin, silicon resin, silicon-alkyd resin, poly-N- A vinyl carbazole resin etc. are mentioned. Of these, polycarbonate resins and polyarylate resins are preferred. These binder resins can also be used after being crosslinked by heat, light or the like using an appropriate curing agent. Any one of these binder resins may be used alone, or two or more thereof may be used in any combination.

  The ratio of the binder resin and the charge transport material is such that the charge transport material is used in a ratio of 20 parts by weight or more with respect to 100 parts by weight of the binder resin. Among these, 30 parts by weight or more is preferable from the viewpoint of residual potential reduction, and 40 parts by weight or more is more preferable from the viewpoint of stability and charge mobility when repeatedly used. On the other hand, from the viewpoint of thermal stability of the photosensitive layer, the charge transport material is usually used at a ratio of 150 parts by weight or less. Among these, 110 parts by weight or less is preferable from the viewpoint of compatibility between the charge transport material and the binder resin, 80 parts by weight or less is more preferable from the viewpoint of printing durability, and 70 parts by weight or less is most preferable from the viewpoint of scratch resistance.

  The thickness of the charge transport layer is not particularly limited, but is usually 5 μm or more, preferably 10 μm or more, and usually 50 μm or less, preferably 45 μm or less, from the viewpoint of long life, image stability, and high resolution. Is in the range of 30 μm or less.

(Photosensitive layer of single layer type photoreceptor)
In addition to the charge generation material and the charge transport material, the photosensitive layer of the single-layer photoconductor is formed using a binder resin in order to ensure film strength, as with the charge transport layer of the multilayer photoconductor. Specifically, a charge generation material, a charge transport material, and various binder resins are dissolved or dispersed in a solvent to prepare a coating solution, and on a conductive support (or an undercoat layer when an undercoat layer is provided). It can be obtained by coating and drying.

  The types of the charge transport material and the binder resin and the use ratios thereof are the same as those described for the charge transport layer of the multilayer photoreceptor. A charge generating material is further dispersed in a charge transport medium comprising these charge transport materials and a binder resin.

  As the charge generation material, the same materials as those described for the charge generation layer of the multilayer photoreceptor can be used. However, in the case of a photosensitive layer of a single-layer type photoreceptor, it is necessary to sufficiently reduce the particle size of the charge generating material. Specifically, the range is usually 1 μm or less, preferably 0.5 μm or less.

  If the amount of the charge generating material dispersed in the single-layer type photosensitive layer is too small, sufficient sensitivity cannot be obtained, but if it is too large, there are adverse effects such as a decrease in chargeability and a decrease in sensitivity. It is usually used in the range of 0.5% by weight or more, preferably 1% by weight or more, and usually 50% by weight or less, preferably 20% by weight or less based on the whole layer type photosensitive layer.

In addition, the usage ratio of the binder resin and the charge generating material in the single-layer type photosensitive layer is such that the charge generating material is usually 0.1 parts by weight or more, preferably 1 part by weight or more, based on 100 parts by weight of the binder resin. It is 30 parts by weight or less, preferably 10 parts by weight or less.
The film thickness of the single-layer type photosensitive layer is usually 5 μm or more, preferably 10 μm or more, and usually 100 μm or less, preferably 50 μm or less.

(Other)
For the purpose of improving film forming properties, flexibility, coating properties, contamination resistance, gas resistance, light resistance, etc., in both the photosensitive layer and the layers constituting the photosensitive layer, both of the multilayer type photosensitive member and the single layer type photosensitive member. Additives such as well-known antioxidants, plasticizers, ultraviolet absorbers, electron-withdrawing compounds, leveling agents, and visible light shielding agents may be included.
Further, in both the laminated type photoreceptor and the single layer type photoreceptor, the photosensitive layer formed by the above procedure may be the uppermost layer, that is, the surface layer, but another layer may be provided on the photosensitive layer and used as the surface layer. Good.

For example, a protective layer may be provided for the purpose of preventing the photosensitive layer from being worn out or preventing or reducing the deterioration of the photosensitive layer due to discharge products generated from a charger or the like.
The protective layer is formed by containing a conductive material in an appropriate binder resin, or has a charge transporting ability such as a triphenylamine skeleton described in JP-A Nos. 9-190004 and 10-252377. A copolymer using a compound can be used.

  Examples of the conductive material used for the protective layer include aromatic amino compounds such as TPD (N, N′-diphenyl-N, N′-bis- (m-tolyl) benzidine), antimony oxide, indium oxide, tin oxide, and oxide. Metal oxides such as titanium, tin oxide-antimony oxide, aluminum oxide, and zinc oxide can be used, but are not limited thereto.

  As the binder resin used for the protective layer, known resins such as polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyvinyl ketone resin, polystyrene resin, polyacrylamide resin, and siloxane resin can be used. Also, a copolymer of the above resin and a skeleton having a charge transporting ability such as a triphenylamine skeleton as described in JP-A-9-190004 and JP-A-10-252377 can be used.

The electrical resistance of the protective layer is usually in the range of 10 ⁹ Ω · cm to 10 ¹⁴ Ω · cm. If the electric resistance is higher than the above range, the residual potential is increased, resulting in an image with much fog. On the other hand, if the electric resistance is lower than the above range, the image is blurred and the resolution is reduced. Further, the protective layer must be configured so as not to substantially prevent transmission of light irradiated during image exposure.

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

<Method for forming each layer>
Each layer constituting these photoreceptors is formed by immersing, coating, spraying, nozzle coating, bar coating, roll coating, blade coating, etc., on a support, a coating solution obtained by dissolving or dispersing a substance to be contained in a solvent. In this method, the coating and drying steps are sequentially repeated for each layer.

  There are no particular restrictions on the solvent or dispersion medium used in the preparation of the coating solution, but specific examples include alcohols such as methanol, ethanol, propanol and 2-methoxyethanol, tetrahydrofuran, 1,4-dioxane, dimethoxyethane and the like. Ethers, esters such as methyl formate and ethyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene and xylene, dichloromethane, chloroform, 1,2-dichloroethane, 1,1, Chlorinated hydrocarbons such as 2-trichloroethane, 1,1,1-trichloroethane, tetrachloroethane, 1,2-dichloropropane, trichloroethylene, n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine , Nitrogen-containing compounds such as triethylenediamine, acetonitrile, N- methylpyrrolidone, N, N- dimethylformamide, aprotic polar solvents such as dimethyl sulfoxide and the like. These may be used alone or in combination, and two or more may be used in any combination and type.

  The amount of the solvent or dispersion medium used is not particularly limited, but considering the purpose of each layer and the properties of the selected solvent / dispersion medium, it is appropriate so that the physical properties such as solid content concentration and viscosity of the coating liquid are within a desired range. It is preferable to adjust.

  For example, in the case of a charge transport layer layer of a single layer type photoreceptor and a function separation type photoreceptor, the solid content concentration of the coating solution is usually 5% by weight or more, usually 5% by weight or more, preferably 10% by weight or more, Moreover, it is usually 40% by weight or less, preferably 35% by weight or less. Further, the viscosity of the coating solution is usually in the range of 10 cps or more, preferably 50 cps or more, and usually 500 cps or less, preferably 400 cps or less.

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

  Examples of the coating method include a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, an air knife coating method, and a curtain coating method. Other known coating methods can also be used.

  The coating solution is preferably dried by touching at room temperature, followed by heating or drying in a temperature range of usually 30 ° C. or more and 200 ° C. or less for 1 minute to 2 hours, while still or blowing. The heating temperature may be constant or the heating may be performed while changing the temperature during drying.

[3. Image forming apparatus]
Next, an embodiment of an image forming apparatus using the electrophotographic photosensitive member of the present invention (an image forming apparatus of the present invention) will be described with reference to FIG. However, the embodiment is not limited to the following description, and can be arbitrarily modified without departing from the gist of the present invention.

  As shown in FIG. 1, the image forming apparatus includes an electrophotographic photosensitive member 1, a charging device 2, an exposure device 3, and a developing device 4, and further, a transfer device 5, a cleaning device 6 and a fixing device as necessary. A device 7 is provided.

  The electrophotographic photoreceptor 1 is not particularly limited as long as it is the above-described electrophotographic photoreceptor of the present invention, but in FIG. 1, as an example, a drum in which the above-described photosensitive layer is formed on the surface of a cylindrical conductive support. The photoconductor is shown. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5, and a cleaning device 6 are disposed along the outer peripheral surface of the electrophotographic photosensitive member 1.

  The charging device 2 charges the electrophotographic photosensitive member 1 and uniformly charges the surface of the electrophotographic photosensitive member 1 to a predetermined potential. Examples of the charging device include a corona charging device such as a corotron and a scorotron, a direct charging device (contact type charging device) that charges a direct charging member to which a voltage is applied by contacting the photosensitive member surface, and a contact type charging device such as a charging brush. Often used. Examples of direct charging means include contact chargers such as charging rollers and charging brushes. In FIG. 1, a roller-type charging device (charging roller) is shown as an example of the charging device 2. As the direct charging means, either charging with air discharge or injection charging without air discharge is possible. Moreover, as a voltage applied at the time of charging, it is possible to use only a direct current voltage or to superimpose alternating current on direct current.

  The type of the exposure apparatus 3 is not particularly limited as long as it can expose the electrophotographic photoreceptor 1 to form an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor 1. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, LEDs, and the like. Further, exposure may be performed by a photoreceptor internal exposure method. The light used for the exposure is arbitrary. For example, the exposure may be performed using monochromatic light having a wavelength of 780 nm, monochromatic light having a wavelength of 600 nm to 700 nm, slightly short wavelength, or monochromatic light having a wavelength of 380 nm to 500 nm. .

  The type of the developing device 4 is not particularly limited, and an arbitrary device such as a dry development method such as cascade development, one-component insulating toner development, one-component conductive toner development, or two-component magnetic brush development, or a wet development method is used. be able to. In FIG. 1, the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and has a configuration in which toner T is stored inside the developing tank 41. . Further, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary. The replenishing device is configured to be able to replenish toner T from a container such as a bottle or a cartridge.

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

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

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

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

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

  The type of the toner T is arbitrary, and chemical toners such as suspension granulation, suspension polymerization, and emulsion polymerization aggregation can be used in addition to powdered toner. In the case of chemical toners, those having a small particle size of about 4 to 8 μ are preferable, and the toner particles have various shapes ranging from a nearly spherical shape to a potato shape outside the spherical shape. Can be used. In particular, the polymerized toner is excellent in charging uniformity and transferability, and is suitably used for high image quality.

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

  There is no restriction | limiting in particular about the cleaning apparatus 6, Arbitrary cleaning apparatuses, such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, can be used. The cleaning device 6 is for scraping off residual toner adhering to the photoreceptor 1 with a cleaning member and collecting the residual toner.

  The fixing device 7 includes an upper fixing member (fixing roller) 71 and a lower fixing member (fixing roller) 72, and a heating device 73 is provided inside the fixing member 71 or 72. FIG. 1 shows an example in which a heating device 73 is provided inside the upper fixing member 71. Each of the upper and lower fixing members 71 and 72 includes a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicon rubber, a fixing roll in which Teflon (registered trademark) resin is coated, and a fixing sheet. A member can be used. Further, each of the fixing members 71 and 72 may be configured to supply a release agent such as silicone oil in order to improve releasability, or may be configured to forcibly apply pressure to each other by a spring or the like.

When the toner transferred onto the recording paper P passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner is heated to a molten state and cooled after passing through the recording paper. Toner is fixed on P.
The type of the fixing device is not particularly limited, and a fixing device of any type such as heat roller fixing, flash fixing, oven fixing, pressure fixing, etc. can be provided including those used here.

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

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

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

When the charged toner T carried on the developing roller 44 comes into contact with the surface of the photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the photoreceptor 1. This toner image is transferred onto the recording paper P by the transfer device 5. Thereafter, the toner remaining on the photosensitive surface of the photoreceptor 1 without being transferred is removed by the cleaning device 6.
After the transfer of the toner image onto the recording paper P, the final image is obtained by passing the fixing device 7 and thermally fixing the toner image onto the recording paper P.

  In addition to the above-described configuration, the image forming apparatus may have a configuration capable of performing, for example, a static elimination process. The neutralization step is a step of neutralizing the electrophotographic photosensitive member by exposing the electrophotographic photosensitive member, and a fluorescent lamp, an LED, or the like is used as the neutralizing device. In addition, the light used in the static elimination process is often light having an exposure energy that is at least three times that of the exposure light.

  The image forming apparatus may be further modified. For example, the image forming apparatus may be configured to perform a pre-exposure process, an auxiliary charging process, or the like, or may be configured to perform offset printing. A full-color tandem system configuration using toner may be used.

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

  Hereinafter, the present invention will be described in more detail with reference to production examples, examples and comparative examples. In addition, the following examples are shown in order to explain the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof.

Synthesis example (synthesis of fluorine-substituted chloroindium phthalocyanine):
After adding 22.6 parts by weight of 4-fluorophthalonitrile and 8 parts by weight of indium trichloride to 70 parts by weight of α-chloronaphthalene and reacting at 200 ° C. for 11 hours, the product was filtered while hot, and N-methylpyrrolidone was used. , Washed with methanol, water and toluene. Next, 14.2 parts by weight of a crude product of fluorine-substituted chloroindium phthalocyanine was obtained by drying the wet cake. The obtained fluorine-substituted chloroindium phthalocyanine from the raw materials used is considered to be a mixture of all six structural isomers (I) to (VI) shown in Table 1 above. FIG. 2 shows a powder X-ray diffraction pattern of the obtained fluorine-substituted chloroindium phthalocyanine crude product.

Powder X-ray diffraction was performed under the following conditions.
-Powder X-ray diffractometer: PANalytical PW1700
・ X-ray tube: Cu
・ Tube voltage: 40kV
・ Tube current 30mA
・ Scanning axis: θ / 2θ
Measurement range (2θ): 3.0 ° to 40.0 °
・ Measurement mode: Continuous
・ Reading width: 0.05 °
・ Scanning speed: 3.0 ° / min
・ DS: 1 °
・ SS: 1 °
・ RS: 0.20mm

  Moreover, the mass spectrum of the obtained fluorine-substituted chloroindium phthalocyanine crystal was measured. The result is shown in FIG.

The mass spectrum measurement was performed under the following conditions.
Measuring method: MALDI-TOF-MS measuring apparatus: Voyager Elite-DE manufactured by Applied Biosystems
Measurement condition Detection ion: Negative measurement mode: Reflector mode Pressurized voltage: 20 kV
Matrix: None

-Production Example 1:
3 parts by weight of the fluorine-substituted chloroindium phthalocyanine crude product obtained in the synthesis example and 170 parts by weight of glass beads (GB200M manufactured by Potters Ballotini Co., Ltd., particle size φ0.6 to φ0.85 mm) are made of polyethylene. The bottle was filled so that the volume occupied by the space became half or more, and shaken for 20 hours with a dye dispersion tester (paint shaker) to make it amorphous. After the treatment, the mixture of phthalocyanine and glass beads and 300 parts by weight of water are stirred at room temperature for 1.5 hours to separate the glass beads and the solid, and then the solid is separated by filtration and dried to replace the fluorine. An amorphous product of chloroindium phthalocyanine (amorphous type) was obtained. FIG. 4 shows a powder X-ray diffraction pattern of the resulting amorphous fluorine-substituted chloroindium phthalocyanine.

Production example 2:
1.5 parts by weight of the crude fluorine-substituted chloroindium phthalocyanine obtained in the synthesis example and 85 parts by weight of glass beads (GB200M manufactured by Potters Ballotini Co., Ltd., particle diameter φ0.6 to φ0.85 mm) The bottle was filled so that the volume occupied by the space became half or more, and was shaken with a dye dispersion tester (paint shaker) for 20 hours to make it amorphous. After the treatment, the mixture of the phthalocyanine and glass beads and 100 parts by weight of toluene were mixed and stirred at room temperature for 1.5 hours. Thereafter, the phthalocyanine and glass beads were separated, and the phthalocyanine was further stirred for 1 hour in toluene, filtered and dried to obtain a fluorine-substituted chloroindium phthalocyanine crystal. The powder X-ray diffraction pattern of the obtained fluorine-substituted chloroindium phthalocyanine crystal is shown in FIG. This corresponds to the above-mentioned crystal (II).

-Production Example 3:
A fluorine-substituted chloroindium phthalocyanine crystal was obtained by performing the same operation as in Production Example 2 except that N-methylpyrrolidone was used in place of the toluene used in Production Example 2. FIG. 6 shows a powder X-ray diffraction pattern of the obtained fluorine-substituted chloroindium phthalocyanine crystal. This corresponds to the above-mentioned crystal (II).

Production example 4:
5 parts by weight of the fluorine-substituted chloroindium phthalocyanine crystal obtained in the synthesis example and 170 parts by weight of glass beads (GB200M manufactured by Potters Ballotini Co., Ltd., particle size φ0.6 to φ0.85 mm) are used in a polyethylene bottle. It was filled so that the volume occupied by the space became half or more, and was shaken with a dye dispersion tester (paint shaker) for 20 hours to make it amorphous. After the treatment, the mixture of the phthalocyanine and glass beads and 1000 ml of methanol were stirred at room temperature for 30 minutes, the glass beads and the solid were separated, and the solid was further separated by filtration. The obtained solid was sequentially washed with a mixed solvent of NMP / water = 9: 1, water and methanol and dried to obtain fluorine-substituted chloroindium phthalocyanine crystals. FIG. 7 shows a powder X-ray diffraction pattern of the resulting fluorine-substituted chloroindium phthalocyanine crystal. This corresponds to the above-mentioned crystal (I).

・ Comparative synthesis example:
After adding 50 parts by weight of phthalonitrile and 23.7 parts by weight of indium trichloride to 250 parts of α-chloronaphthalene and reacting at 205 ° C. for 14 hours, the product is filtered while hot, N-methylpyrrolidone, methanol, water , Washed sequentially with toluene. Next, the wet cake was dried to obtain 27 parts by weight of chloroindium phthalocyanine crystals. The powder X-ray diffraction pattern of the resulting chloroindium phthalocyanine crystal is shown in FIG.

Comparative production example 1:
3 parts by weight of the chloroindium phthalocyanine crystal obtained in the comparative synthesis example and 34 parts by weight of glass beads (GB200M manufactured by Potters Ballotini Co., Ltd., particle size φ0.6 to φ0.85 mm) were placed in a polyethylene bottle. It was filled so that the volume occupied by the space became half or more, and shaken with a dye dispersion tester (paint shaker) for 20 hours to make it amorphous. After the treatment, the mixture of phthalocyanine and glass beads and 100 parts by weight of water were mixed, stirred at room temperature for 1.5 hours, filtered and dried to obtain chloroindium phthalocyanine crystals. A powder X-ray diffraction pattern of the obtained chloroindium phthalocyanine crystal is shown in FIG.

Comparative production example 2:
In a polyethylene bottle, 1.5 parts by weight of the chloroindium phthalocyanine crystal obtained in the comparative synthesis example and 11 parts by weight of glass beads having a particle diameter of φ0.4 to φ0.6 mm are halved in space. Then, the mixture was shaken with a dye dispersion tester (paint shaker) for 20 hours to make it amorphous. After the treatment, the mixture of phthalocyanine and glass beads and 50 parts by weight of toluene were mixed and stirred at room temperature for 2 hours. Thereafter, the glass beads and the solid were separated, and the solid was further stirred for 1 hour in toluene, filtered and dried to obtain chloroindium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained chloroindium phthalocyanine crystal is shown in FIG.

Comparative production example 3:
A chloroindium phthalocyanine crystal was obtained by performing the same operation as in Comparative Production Example 2 except that the toluene used in Comparative Production Example 2 was changed to methyl ethyl ketone. The powder X-ray diffraction pattern of the obtained chloroindium phthalocyanine crystal is shown in FIG.

Example 1:
The undercoat layer dispersion was produced as follows. That is, a rutile type titanium oxide having an average primary particle size of 40 nm (“TTO55N” manufactured by Ishihara Sangyo Co., Ltd.) and 3% by weight of methyldimethoxysilane (“TSL8117” manufactured by Toshiba Silicone Co., Ltd.) with respect to the titanium oxide were flowed at high speed. In a mixed solvent of methanol / 1-propanol in a mixed solvent of methanol / 1-propanol, which was introduced into a mixing kneader (“SMG300” manufactured by Kawata Co., Ltd.) and mixed at a high rotational speed of 34.5 m / sec. Then, a dispersion slurry of hydrophobized titanium oxide was obtained by dispersing with a ball mill. The dispersion slurry, a mixed solvent of methanol / 1-propanol / toluene, and ε-caprolactam [compound represented by the following formula (A)] / bis (4-amino-3-methylcyclohexyl) methane [the following formula (B Compound represented by the following formula (C)] / decamethylene dicarboxylic acid [compound represented by the following formula (D)] / octadecamethylene dicarboxylic acid [in the following formula (E) The compositional molar ratio of the compound represented] is 75% / 9.5% / 3% / 9.5% / 3% of the copolymerized polyamide pellets with heating and stirring and mixing to dissolve the polyamide pellets. After that, by carrying out ultrasonic dispersion treatment, the weight ratio of methanol / 1-propanol / toluene is 7/1/2, and hydrophobically treated titanium oxide. The copolymerized polyamide in a weight ratio of 3/1, and a solid concentration of 18.0% of the undercoat layer dispersion.

  Using a conductive support in which an aluminum vapor deposition film (thickness 70 nm) is formed on the surface of a biaxially stretched polyethylene terephthalate resin film (thickness 75 μm), the coating solution for the undercoat layer described above is formed on the vapor deposition layer of the support. Using a bar coater, the film thickness after drying was applied and dried to form an undercoat layer.

  Next, 30 parts by weight of 4-methyl-4-methoxy-pentanone-2 and 270 parts by weight of 1,2-dimethoxyethane were added to 4 parts by weight of the fluorine-substituted chloroindium phthalocyanine obtained in Production Example 1, and a sand grind mill was added. And then pulverized for 2 hours to make a fine particle, and then 1 part by weight of polyvinyl butyral (“Decambutyral # 6000C” manufactured by Denki Kagaku Kogyo Co., Ltd.) as a binder resin and phenoxy resin (“PKHH” manufactured by Union Carbide) ) 1 part by weight was added, and the coating solution for the charge generation layer was prepared by further grinding with a sand grind mill for 1 hour. This coating solution was applied onto the undercoat layer on the conductive support by a bar coater so that the film thickness after drying was 0.4 μm and dried to form a charge generation layer.

  Furthermore, 50 parts by weight of the compound represented by the following formula (2) synthesized according to the method described in [Example 1] of JP-A-2002-80432 as a charge transport material, and the following formula as a binder resin: 51 mol% of a repeating unit containing 2,2-bis (4-hydroxy-3-methylphenyl) propane shown in (3) as an aromatic diol component, and 1,1-bis (4-hydroxyphenyl) -1-phenyl 100 parts by weight of a polycarbonate resin having a terminal structure derived from pt-butylphenol, consisting of 49 mol% of a repeating unit containing ethane as an aromatic diol component, 0.03 parts by weight of silicone oil as a leveling agent, tetrahydrofuran / toluene (Weight ratio 8/2) A coating solution for charge transport layer was prepared by dissolving in 640 parts by weight of a mixed solvent, and this coating solution The electrophotographic photosensitive member having a laminated photosensitive layer was produced by applying a film transporting layer on the charge generation layer with a film applicator so that the film thickness after drying was 25 μm, and drying to form a charge transport layer. .

  About the obtained electrophotographic photoreceptor, the following electrophotographic characteristics were measured by a static method using a photoreceptor evaluation apparatus (Cynthia 55, manufactured by Gientech Co., Ltd.). The results are shown in Table 2.

First, discharge is performed with a scorotron charger in a dark place so that the surface potential of the photosensitive member becomes about −700 V, and the photosensitive member is charged by passing through the photosensitive member at a constant speed (125 mm / sec), and the charged voltage is measured. The initial charging voltage (V ₀ ) was determined. Thereafter, the potential drop (DD) was measured when left for 2.5 seconds. Further, the surface of the photoconductor was charged to about −700 V, and the voltage required at that time (voltage applied to the charger) was defined as the grit voltage (V _g ). Next, 780 nm monochromatic light having an intensity of 1.0 μW / cm ² was irradiated, and a residual potential (V _r ) 10 seconds after the irradiation was obtained.

Example 2:
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the fluorine-substituted chloroindium phthalocyanine produced in Production Example 2 was used in place of the fluorine-substituted chloroindium phthalocyanine used in Example 1, and an electrophotography was produced. Characteristics were evaluated. The results are shown in Table 2.

Example 3:
An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the fluorine-substituted chloroindium phthalocyanine produced in Production Example 3 was used instead of the fluorine-substituted chloroindium phthalocyanine used in Example 1, and an electrophotographic photoconductor was produced. Characteristics were evaluated. The results are shown in Table 2.

Example 4:
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the fluorine-substituted chloroindium phthalocyanine produced in Production Example 4 was used instead of the fluorine-substituted chloroindium phthalocyanine used in Example 1, and an electrophotographic product was produced. Characteristics were evaluated. The results are shown in Table 2.

Comparative example 1:
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the chloroindium phthalocyanine produced in Comparative Production Example 2 was used instead of the fluorine-substituted chloroindium phthalocyanine used in Example 1, and electrophotographic characteristics were obtained. Evaluated. The results are shown in Table 2.

Comparative example 2:
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the chloroindium phthalocyanine produced in Comparative Production Example 3 was used instead of the fluorine-substituted chloroindium phthalocyanine used in Example 1, and electrophotographic characteristics were obtained. Evaluated. The results are shown in Table 2.

From the results of Table 2, the electrophotographic photoreceptors of Examples 1 to 4 using the fluorine-substituted indium phthalocyanine of the present invention are more grit than the electrophotographic photoreceptors of Comparative Examples 1 and 2 using conventional indium phthalocyanine. The ratio (V ₀ / V _g ) of the initial charging voltage (V ₀ ) to the voltage (V _g ) is large. This is because the photoconductor of the example requires a lower voltage to be applied to the charger in order to charge the surface potential to the same potential as the photoconductor of the comparative example, that is, the chargeability is good. It represents that. It can also be seen that the photoreceptors of the examples have less dark decay (DD) and lower residual potential (V _r ) than the photoreceptors of the comparative examples. Therefore, it is clear that the fluorine-substituted indium phthalocyanine of the present invention is superior as a material for an electrophotographic photosensitive member as compared with conventional indium phthalocyanine.

Example 5:
The coating solution for charge generation layer obtained in Example 1 was dip-coated on an aluminum cylinder having a diameter of 3 cm, a length of 250 mm, and a wall thickness of 0.75 mm, which had been anodized on the surface and subjected to sealing treatment. The charge generation layer was provided so that the film thickness after drying was 0.2 g / m ² (about 0.2 μm). Then, the charge transport layer coating solution obtained in Example 1 is dip-coated on the charge generation layer, and the charge transport layer is provided so that the film thickness after drying is 18 μm. A photographic photoreceptor (photoreceptor drum) was prepared.

Example 6:
In Example 5, a photosensitive drum was produced by performing the same operation as in Example 5 except that the charge generation layer coating solution was changed to that obtained in Example 2.

Example 7:
A photoconductor drum was produced in the same manner as in Example 5 except that the charge generation layer coating solution in Example 5 was changed to that obtained in Example 3.

Example 8:
In Example 5, a photosensitive drum was produced by performing the same operation as in Example 5 except that the charge generation layer coating solution was changed to that obtained in Example 4.

Comparative Example 3:
In Example 5, a photosensitive drum was produced by performing the same operation as in Example 5 except that the charge generation layer coating solution was changed to that obtained in Comparative Example 1.

Comparative example 4:
In Example 5, a photosensitive drum was produced by performing the same operation as in Example 5 except that the charge generation layer coating solution was changed to that obtained in Comparative Example 2.

  The photosensitive drums obtained in Examples 5 to 8 and Comparative Examples 3 and 4 were mounted on a drum cartridge of a commercially available monochrome laser printer (LP2400 manufactured by Seiko Epson Corporation) and printed under conditions of a temperature of 35 ° C. and a humidity of 80%. The image was evaluated. Table 3 shows the fog value.

The fog value is adjusted using a colorimetric color difference meter (Nippon Denshoku Industries Co., Ltd. ND-1001DP type) so that the whiteness of the standard white board is 94.4, and printed using this colorimetric color difference meter. The whiteness of the previous paper (A4 size) is measured, and printing is performed on the same paper by inputting a signal that turns the entire surface white into the laser printer. The whiteness was measured and obtained by calculation based on the following formula (1).
Fog value = Whiteness before printing-Whiteness after printing (1)

  From the results of Table 3, the electrophotographic photoreceptors of Examples 5 to 8 using the fluorine-substituted indium phthalocyanine of the present invention are fogged as compared with the electrophotographic photoreceptors of Comparative Examples 3 and 4 using the conventional indium phthalocyanine. It can be seen that the value is low and a good image can be obtained.

  As described above, the fluorine-substituted indium phthalocyanine of the present invention, when used as an electrophotographic photosensitive material, has excellent chargeability, little dark decay, low residual potential, that is, excellent electrophotographic characteristics. A photoreceptor can be obtained. Therefore, it can be suitably used for various electrophotographic devices such as copying machines, printers, and fax machines using electrophotographic technology.

1 is a schematic diagram illustrating a configuration of a main part of an embodiment of an image forming apparatus of the present invention. It is a powder X-ray-diffraction figure of the fluorine substituted indium phthalocyanine of the synthesis example. It is a mass spectrum of the fluorine substituted indium phthalocyanine of the synthesis example. 2 is a powder X-ray diffraction pattern of fluorine-substituted indium phthalocyanine of Production Example 1. FIG. 4 is a powder X-ray diffraction pattern of fluorine-substituted indium phthalocyanine of Production Example 2. FIG. 4 is a powder X-ray diffraction pattern of fluorine-substituted indium phthalocyanine of Production Example 3. FIG. 6 is a powder X-ray diffraction pattern of fluorine-substituted indium phthalocyanine of Production Example 4. FIG. It is a powder X-ray diffraction pattern of indium phthalocyanine of the comparative synthesis example. 2 is a powder X-ray diffraction pattern of indium phthalocyanine of Comparative Production Example 1. FIG. 4 is a powder X-ray diffraction pattern of indium phthalocyanine of Comparative Production Example 2. FIG. 6 is a powder X-ray diffraction pattern of indium phthalocyanine of Comparative Production Example 3. FIG.

Explanation of symbols

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

Claims (7)

A fluorine-substituted indium phthalocyanine represented by the following general formula [1].

(In the general formula [1], X ¹ , X ² , X ³ and X ⁴ each represents a fluorine atom. K, l, m and n each independently represents 0 or 1, provided that k, l , M and n must be at least 1. Y represents a monovalent linking group capable of binding to indium.) The X-ray diffraction spectrum has strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 7.0 °, 16.6 °, 25.4 °, and 27.0 °, respectively. The fluorine-substituted indium phthalocyanine according to 1. The X-ray diffraction spectrum has strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 6.9 °, 13.0 °, 16.2 °, 25.7 °, 28.0 °. The fluorine-substituted indium phthalocyanine according to claim 1. In an X-ray diffraction spectrum, the Bragg angle (2θ ± 0.2 °) is an amorphous material having no clear peak within a range of 3 ° or more and 40 ° or less. The fluorine-substituted indium phthalocyanine according to claim 1. An electrophotographic photoreceptor having at least a photosensitive layer on a conductive support,
An electrophotographic photoreceptor, wherein the photosensitive layer contains the fluorine-substituted indium phthalocyanine according to any one of claims 1 to 4. The electrophotographic photosensitive member according to claim 5,
A charging unit for charging the electrophotographic photosensitive member, an exposure unit for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, and developing the electrostatic latent image formed on the electrophotographic photosensitive member An electrophotographic photosensitive member cartridge comprising at least one of the developing units. The electrophotographic photosensitive member according to claim 5,
A charging unit for charging the electrophotographic photosensitive member;
Exposing the charged electrophotographic photoreceptor to form an electrostatic latent image; and
An image forming apparatus comprising: a developing unit that develops an electrostatic latent image formed on the electrophotographic photosensitive member.

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