JP2004231973A - Oxy-molybdenum phthalocyanine having new crystal transformation and its producing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crystal transformation of new oxy-molybdenum phthalocyanine useful for an organic photoconducting material, and to provide a producing method of the oxy-molybdenum phthalocyanine. <P>SOLUTION: The oxy-molybdenum phthalocyanine having the new crystal transformation shows a diffraction peak at a Bragg angle (2θ±0.2°) to a CuKα characteristic X ray. The new oxy-molybdenum phthalocyanine is used as a photoconducting material included in a photosensitive layer of an electrophotographic photoreceptor. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a method for producing oxymolybdenum phthalocyanine having a novel crystal modification useful as a photoconductive material and an organic photoconductive material for an electrophotographic photosensitive member using the same.

  Electrophotographic photoreceptors have been widely applied to copiers, printers, and the like to which electrophotographic technology is applied. Conventionally, as this electrophotographic photosensitive member, an inorganic photosensitive member represented by amorphous selenium or the like has been used. However, this inorganic photoreceptor uses harmful selenium or cadmium sulfide to the human body, and has a problem that the disposal cost is increased. In addition, there is a problem that the production cost is generally increased due to the production by the vapor deposition method, and application to a small and low-priced machine is disadvantageous.

  In recent years, with the development of semiconductor laser technology, an organic photoconductive material having a sensitivity around 800 nm, which is the transmission wavelength range of a semiconductor laser, has attracted attention. Many organic photoconductive materials containing such an organic photoconductive substance as an active ingredient have been proposed, and examples thereof include a negatively charged organic photoreceptor containing these as a charge generating material. This type of organic photoreceptor includes a photosensitive layer containing a charge generating material and a charge transporting material as constituents on a conductive substrate, and has a single-layer structure and a two-layer structure with separated functions.

  However, these organic photoreceptors have insufficient electrical properties such as chargeability, dark decay and residual potential in a use situation where charging and exposure are repeated.

  Therefore, as a charge generation material used for a charge generation layer of a function-separated type photoreceptor, an organic photoconductive substance having high sensitivity and high durability has been desired.

  Phthalocyanine has various electrical characteristics depending on the metal-free phthalocyanine, the central metal species of the metal phthalocyanine, and the like, and the electrical characteristics vary depending on the manufacturing method, the processing method, or the difference in the stacking state of the phthalocyanine having the same structure. It is known that there is a large change.

  In particular, since the stacking state of an organic compound is determined by the crystal transformation of the compound, the crystal transformation changes the electronic state, in particular, the perturbation of the Π-electron system, and is a factor that effectively changes the characteristics of an electronic material such as an organic photosensitive material. For this reason, application of metal phthalocyanines such as titanyl and vanadyl to electrophotographic photoreceptors has been proposed, and some of them have been put to practical use. However, the photosensitivity and durability when used as a charge generating material for an organic photoreceptor are still insufficient, and there is room for improvement, and the development of a novel phthalocyanine crystal modification suitable for such an application has been strongly developed. Is desired.

  The present invention is to solve the conventional problems, the purpose is, even when used in an organic photoconductive material such as an organic photoreceptor, stable, good electrical properties (for example, An object of the present invention is to provide an oxymolybdenum phthalocyanine having a novel crystal modification and a method for producing the same, which has good chargeability, low dark decay, and low residual potential.)

  The present invention provides an oxymolybdenum phthalocyanine having a crystal modification exhibiting a diffraction peak at any of the following (i) to (iv) Bragg angle (2θ ± 0.2 °) in an X-ray diffraction spectrum by CuKα radiation. Thereby, the above object can be achieved.

(i) 7.7 °, 9.0 °, 14.6 °, 14.9 °, 16.7 °, 20.2 °, 22.9 °, 26.5 ° and 28.8 °;
(ii) 7.1 °, 17.7 °, 24.0 °, 27.3 ° and 29.1 °;
(iii) 9.5 °, 13.5 °, 14.9 °, 17.9 °, 24.0 ° and 27.2 °; and
(iv) 18.6 ° and 28.8 °.

  The oxymolybdenum phthalocyanine having a novel crystal modification of the present invention is prepared by subjecting oxymolybdenum phthalocyanine synthesized by a conventional method to a specific treatment such as an “acid pasting method” and an “acid slurry method”. .

  Oxymolybdenum phthalocyanine is generally prepared by heating and melting phthalonitrile and a molybdenum compound (e.g., ammonium molybdate, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride), or an organic solvent (e.g., quinoline, 1-chloronaphthalene). , Methylnaphthalene, dichlorobenzene, etc., a reaction-inactive high boiling solvent) in the presence of a phthalonitrile method in which heat reaction is carried out, and phthalic anhydride and urea and metal chlorides are heated and melted, or in the presence of an organic solvent. It is manufactured by the Weyler method or the like in which a heat reaction is performed.

  The oxymolybdenum phthalocyanine that can be used in the method of the present invention is not limited to those obtained by these methods, but in the present invention, it is preferable to use oxymolybdenum phthalocyanine synthesized by the phthalonitrile method.

  For example, oxymolybdenum phthalocyanine is obtained by (a) reacting phthalonitrile with molybdenum halide or molybdenum oxyhalide in a high boiling point organic solvent to obtain crude oxymolybdenum phthalocyanine; (b) obtaining crude oxymolybdenum phthalocyanine Is dispersed in a dilute mineral acid aqueous solution to hydrolyze impurities; (c) a step of washing the filtered cake with DMF; and (d) a step of substituting DMF with alcohol. You.

  The crystal modification of the oxymolybdenum phthalocyanine of the present invention, which shows the diffraction peak of (i), comprises: (a) a step of dissolving the oxymolybdenum phthalocyanine in concentrated sulfuric acid; (C) collecting the precipitated oxymolybdenum phthalocyanine; (d) washing the collected cake until the washing water becomes neutral; and (e) wet milling with an organic solvent. Preferably, it is produced by a method comprising:

  In one embodiment of this production method, first, oxymolybdenum phthalocyanine is obtained by a known method as described above. Next, the obtained oxymolybdenum phthalocyanine is subjected to a so-called acid pasting method. "Acid pasting method" is a method of refining and refining organic pigments by dissolving organic pigments in concentrated sulfuric acid, etc., throwing them into ice water and reprecipitating them, then dispersing the precipitates under stirring. Say.

  The concentrated sulfuric acid used in the acid pasting has a concentration of 80 to 100%, preferably 95 to 100%. This is because if the concentration of concentrated sulfuric acid is less than 80%, it becomes difficult to reduce the size of phthalocyanine. The amount of concentrated sulfuric acid is not particularly limited as long as a good paste suitable for purification and refining is obtained, but is generally 1 to 100 times the amount of oxymolybdenum phthalocyanine (weight ratio), preferably 5 to 50 times. Used in range.

  By performing acid pasting, oxymolybdenum phthalocyanine can be converted into an amorphous state, and at the same time, can be purified and refined. The obtained amorphous-like oxymolybdenum phthalocyanine fine particles serve as a precursor for growing into a crystal modification suitable for an organic photoconductive material such as a photoreceptor.

  Thereafter, the wet cake of oxymolybdenum phthalocyanine collected by a method such as filtration is washed with ion-exchanged water. Washing is performed until the washing liquid becomes neutral. The wet cake (water content: 50 to 90%) after water washing is then wet-milled using an organic solvent.

  In the present invention, “milling” means an operation of crushing, and is generally performed using a crushing device such as a ball mill, a sand mill, a paint shaker, an attritor, and an automatic mortar. If necessary, grinding media such as glass beads, steel beads and alumina beads can be used. "Wet milling" refers to milling performed in the presence of a liquid medium. "Dry milling" refers to milling performed in the absence of a liquid medium.

  The organic solvent used in the wet milling in the present invention is not particularly limited as long as it does not dissolve the pigment, and according to a desired crystal modification, for example, monohydric lower alcohols such as methanol, ethanol, propanol and isopropanol Solvents, chain or cyclic ether solvents such as THF, diethyl ether and dioxane, and hydrocarbon solvents such as benzene, toluene, xylene and tetralin can be used as appropriate. Further, an organic solvent / water mixed solvent obtained by mixing an organic solvent and water up to 50% may be used.

  In the present method for obtaining oxymolybdenum phthalocyanine showing the diffraction peak of (i), organic solvents particularly preferably used in wet milling include alcohols having up to 3 carbon atoms such as methanol, ethanol, propanol and isopropanol. Ethers having up to 6 carbon atoms, such as THF, may be mentioned. It is not preferable to use another organic solvent such as an alcohol having 4 or more carbon atoms, because the growth of the target crystal modification becomes insufficient.

  The wet milling is performed at room temperature for 1 to 10 hours, preferably 2 to 6 hours. If this step is performed for less than 1 hour, the growth of the desired crystal transformation will be insufficient, and if performed for more than 10 hours, generally no significant effect will be obtained.

  By this wet milling, the growth of the crystal modification of the present invention is promoted, and oxymolybdenum phthalocyanine having excellent electrical properties can be obtained.

  The oxymolybdenum phthalocyanine of the present invention showing the diffraction peak of (i) is obtained by collecting a solid content from the slurry obtained after milling and drying at room temperature under reduced pressure.

  The crystal modification of the oxymolybdenum phthalocyanine of the present invention showing the diffraction peak of (ii) comprises: (a) a step of dissolving oxymolybdenum phthalocyanine in concentrated sulfuric acid; and (b) charging the resulting concentrated sulfuric acid solution into an alcohol solvent under cooling (C) collecting the precipitated oxymolybdenum phthalocyanine; (d) washing the collected cake until the wash water becomes neutral; and (e) removing the alcohol-based solvent. And a wet milling step.

  This method is performed in the same manner as in the case of oxymolybdenum phthalocyanine showing the diffraction peak of (i) except that the so-called “acid slurry method” is used instead of the “acid pasting method”. `` Acid slurry method '' is to dissolve the organic pigment in concentrated sulfuric acid, etc., add it to a (cold) organic solvent, reprecipitate it, and then disperse the precipitate under stirring to refine and refine the organic pigment. The way to do it.

  By performing the acid slurry method, crude oxymolybdenum phthalocyanine can be converted into low-crystalline phthalocyanine, and at the same time, purification and refinement can be performed. The obtained fine particles of oxymolybdenum phthalocyanine having low crystallinity become a precursor for growing into a crystal modification suitable for an organic photoconductive material such as a photoreceptor.

  The concentrated sulfuric acid used in the acid slurry method has a concentration of 80 to 100%, preferably 95 to 100% as in the case of the acid paste method, and the amount of the concentrated sulfuric acid is 1 to 10% of oxymolybdenum phthalocyanine. The amount is 100 times (weight ratio), preferably 5 to 50 times.

  The organic solvent used in the acid slurry method is preferably the above-mentioned alcoholic solvent having up to 3 carbon atoms. This is because the slurry can be easily formed and the filterability is good.

  Fine particles of oxymolybdenum phthalocyanine having low crystallinity obtained by the acid slurry method are collected, washed with an alcohol solvent, and dried under reduced pressure to obtain oxymolybdenum phthalocyanine having a low crystalline modification. It is subsequently dried and further subjected to wet milling.

  Organic solvents that can be particularly preferably used in the wet milling of the present method include alcohols having up to 3 carbon atoms. It is not preferable to use an alcohol having 4 or more carbon atoms because the growth of the target crystal modification becomes insufficient.

  By this milling operation, oxymolybdenum phthalocyanine having excellent electrical properties can be obtained by promoting the growth of the crystal modification of the present invention. The solid content is collected from the slurry obtained after the milling, and dried at room temperature under reduced pressure to obtain the oxymolybdenum phthalocyanine of the present invention showing the diffraction peak of (ii).

  The crystal modification of the oxymolybdenum phthalocyanine of the present invention showing the diffraction peak of (iii) is the same as that of the oxymolybdenum phthalocyanine showing the diffraction peak of (ii) except that the wet milling is performed using a hydrocarbon / water mixed solvent. It is preferable to manufacture it.

  As a solvent that can be particularly preferably used in the wet milling in the present method, a mixed solvent of an aromatic hydrocarbon having up to 10 carbon atoms such as toluene and xylene and water is exemplified. The mixing ratio between the aromatic hydrocarbon and water is desirably about 80:20 to 99: 1 (volume ratio). If the ratio of water is too large, the desired crystal transformation cannot be obtained, and the use of only aromatic hydrocarbons is not preferable because the state of the slurry deteriorates.

  By this milling operation, oxymolybdenum phthalocyanine having excellent electrical properties can be obtained by promoting the growth of the crystal modification of the present invention. The solid content is collected from the slurry obtained after milling and dried at room temperature under reduced pressure to obtain the oxymolybdenum phthalocyanine of the present invention showing the diffraction peak of (iii).

  The crystal modification of the oxymolybdenum phthalocyanine of the present invention showing the diffraction peak of (iv) includes (a) a step of dry-milling oxymolybdenum phthalocyanine; and (b) a step of wet-milling using a hydrocarbon / water mixed solvent. It is preferred to produce by the included method.

  In this method, first, oxymolybdenum phthalocyanine is obtained by a conventional method, and dry milling is performed without using a solvent.

  Dry milling is performed at room temperature for 1 to 10 hours, preferably 5 to 6 hours. If the milling step is performed for less than 1 hour, the formation of the crystal transformation becomes insufficient, and if the milling step is performed for more than 10 hours, no significant effect is generally obtained. By this milling operation, oxymolybdenum phthalocyanine is converted into an amorphous state.

  Next, wet milling of the amorphous oxymolybdenum phthalocyanine is performed using an organic solvent. Organic solvents particularly preferably used in the present method include a mixed solvent of water with an aromatic hydrocarbon having up to 10 carbon atoms such as toluene and xylene. The mixing ratio between the aromatic hydrocarbon and water is desirably about 80:20 to 99: 1 (volume ratio). If the ratio of water is too large, the desired crystal transformation cannot be obtained, and the use of only aromatic hydrocarbons is not preferable because the state of the slurry deteriorates.

  The wet milling is performed at room temperature for 10 hours or more, preferably for 20 to 50 hours. If the milling step is performed for less than 10 hours, the formation of the crystal transformation becomes insufficient, and if the milling step is performed for more than 50 hours, no significant effect is generally obtained. By this milling operation, oxymolybdenum phthalocyanine having excellent electrical properties can be obtained by promoting the growth of the crystal modification of the present invention.

  The oxymolybdenum phthalocyanine of the present invention showing the diffraction peak of (iv) is obtained by collecting a solid content from the slurry obtained after milling and drying at room temperature under reduced pressure.

  The oxymolybdenum phthalocyanine having a novel crystal modification of the present invention is useful as a photoconductive material such as an electrophotographic photosensitive member widely applied to a copying machine or the like to which electrophotographic technology is applied. The photoconductive material containing oxymolybdenum phthalocyanine of the present invention as an active ingredient, when applied to a charge generation layer of an electrophotographic photoreceptor, provides a photoreceptor having good chargeability, high sensitivity and high durability.

  Next, application examples of the photoconductive material of the present invention will be described.

  The electrophotographic organic photoreceptor comprising at least one kind of organic photoconductive material such as oxymolybdenum phthalocyanine and a resin may be a laminated type in which a photosensitive layer is separated into a charge generation layer and a charge transport layer. And a single-layer type. However, in order to effectively exhibit the electrical properties of the crystal transformation of oxymolybdenum phthalocyanine, the generated charges are less likely to be captured, and each layer is efficiently transported to the photoreceptor surface without impairing the function of each layer. It is preferably applied to a two-layer structure function-separated type photoconductor.

  Such a function-separated type photoreceptor is formed, for example, by laminating a charge generation layer and a charge transport layer in a thin film shape on a conductive support. As the base material of the conductive support, a metal such as aluminum or nickel, a metal vapor-deposited film, or the like can be used.

  For application to an organic photoconductor for electrophotography, first, a charge generation layer containing the oxymolybdenum phthalocyanine of the present invention as a charge generation material is formed in a thin film on a conductive support. At this time, the charge generation layer can form a thin film by depositing oxymolybdenum phthalocyanine on the conductive support, but generally, the charge generation material is dispersed in a solution obtained by dissolving a binder resin in a solvent. It is formed by preparing a coating solution and applying it on a support.

  As a method for dispersing oxymolybdenum phthalocyanine, a usual dispersion method using a ball mill, a sand mill, a paint shaker, or the like can be employed.

  The means for coating the charge generation layer is not particularly limited, and for example, a bar coater, a dip coater, a spin coater, a roller coater, a calendar coater, or the like can be used as appropriate. Drying can be carried out at a temperature of 30 to 200 ° C. for 5 minutes to 2 hours, still or under blowing.

  The solvent for the coating liquid is not particularly limited as long as it disperses the oxymolybdenum phthalocyanine uniformly without dissolving and dissolves the binder resin used as needed. For example, alcohol solvents such as methanol, ethanol, isopropanol and butanol; aromatic solvents such as toluene, xylene and tetralin; halogen solvents such as dichloromethane, chloroform, trichloroethylene and carbon tetrachloride; ethyl acetate and acetic acid Ester solvents such as propyl; ether solvents such as ethylene glycol monoethyl ether, dioxane and tetrahydrofuran; dimethylformamide, dimethyl sulfoxide and the like.

  The binder resin can be selected from a wide range of insulating resins. Preferred resins include condensation resins such as polycarbonate, polyacrylate, polyester, and polyamide; polystyrene, styrene-acryl copolymer, polyacrylate, polymethacrylate, polyvinyl butyral, polyvinyl alcohol, polyacrylnitrile, and polyacryl-butadiene copolymer. Addition polymers such as coalesced polyvinyl chloride, vinyl chloride-vinyl acetate copolymer; organic photoconductive resins such as poly-N-vinylcarbazole and polyvinylanthracene; polysulfone, polyethersulfone, silicone resin, epoxy resin, urethane Resins. These can be used by appropriately mixing.

  The amount of the binder resin used is 0.1 to 3 weight ratio to the charge generation material, and if it is more than 3 weight ratio, the charge generation material concentration in the charge generation layer becomes small, and the sensitivity becomes poor. The thickness of the charge generation layer is 0.05 to 5.0 μm. If the thickness is larger than 5.0 μm, it is not preferable because the probability of capturing charges increases and the sensitivity is reduced.

  Next, a charge transport layer containing a charge transport material is formed as a thin film on the charge generation layer. As a method of forming the thin film, the same coating method as that of the charge generation layer is used, and the charge transport material is dissolved in a solvent together with a binder resin as necessary, and is uniformly applied on the charge generation layer, and then dried. You can do it.

  Examples of the charge transport material include known aromatic tertiary monoamino compounds, oxadiazole derivatives, pyrazoline derivatives, hydrazone derivatives, triazine derivatives, and quinazoline derivatives.

  As the binder resin and the solvent for forming the charge transport layer, the same resins as those used for the charge generation layer can be used.

  The amount of the binder resin used is 0.1 to 5 weight ratio with respect to the charge transport material. If the amount is more than 5 weight ratio, the charge transport material concentration in the charge transport layer becomes small, and the sensitivity becomes poor. The thickness of the charge generation layer is 5 to 50 μm, and if it is larger than 50 μm, it takes more time to transport the charge, and the probability of capture of the charge is increased and the sensitivity is reduced. Is not preferred.

  The oxymolybdenum phthalocyanine of the present invention has a novel crystal modification and is useful as a photoconductive material for an electrophotographic photosensitive member such as a copying machine using a semiconductor laser. Further, an organic photoreceptor for electrophotography manufactured using the above-mentioned crystal modification of oxymolybdenum phthalocyanine as a charge generating material has high sensitivity and high chargeability.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In addition, the X-ray diffraction spectrum by the CuKα ray of the present invention was measured using an automatic X-ray diffraction system “MXP3” manufactured by Max Science under the measurement conditions shown in Table 6.

Example 1
Synthesis of oxymolybdenum phthalocyanine (1)
32.0 g of phthalonitrile and 11.3 g of ammonium molybdate tetrahydrate were reacted in 90 ml of 1-chloronaphthalene at 230 ° C. for 5 hours. After the completion of the reaction, the mixture was filtered while hot, sprinkled and washed with a small amount of DMF (dimethylformamide), and the cake was dispersed again in 125 ml of DMF, stirred at 140 ° C. for 2 hours, and filtered while hot. After DMF in the cake was replaced with methanol, the cake was dispersed in 500 ml of ion-exchanged water at 70 ° C. for 90 minutes. After collection, methanol replacement was performed, and the above-mentioned dispersion in DMF was repeated twice. Finally, the DMF in the cake was replaced with methanol and dried overnight under reduced pressure to obtain 21.3 g of a blue-violet solid.

  FIG. 1 shows the IR spectrum of this compound, and Table 1 shows the results of elemental analysis.

  Also, from the results of the FD-MS spectrum, strong molecular ion peaks were found at 624 and 626 due to the natural presence of molybdenum isotopes, and it was confirmed that there was only a molecular ion peak of oxymolybdenum phthalocyanine. FIG. 2 shows an enlarged part of the FD-MS spectrum at m / z = 550 to 700. From the above, it was confirmed that this compound was oxymolybdenum phthalocyanine. FIG. 3 shows an X-ray diffraction spectrum of this product by CuKα radiation.

  The FD-MS spectrum was measured using a JEOL SX-102A model at an acceleration voltage of 8 kV, a cathode voltage of -1 kV, and an ion source at room temperature.

Example 2
Synthesis of oxymolybdenum phthalocyanine (2)
25.6 g of phthalonitrile and 10.0 g of molybdenum trichloride were reacted with 150 ml of 1-chloronaphthalene for 5 hours. After completion of the reaction, the product was collected while hot, and the cake was sprinkled and washed with DMF, dispersed again in 120 ml of DMF, stirred and refluxed for 5 hours, filtered again while hot, and replaced with DMF with methanol. After drying under reduced pressure overnight, 15.5 g of a blue solid was obtained.

  The results of IR and FD-MS analysis of the obtained compound were the same as those in Example 1. Table 2 shows the results of elemental analysis of this compound.

  From the above, it was confirmed that the present compound was oxymolybdenum phthalocyanine, and FIG. 4 shows a diffraction X-ray spectrum of the product by CuKα radiation. That is, the obtained oxymolybdenum phthalocyanine has a Bragg angle (2θ ± 0.2 °) of 7.5 ° for CuKα characteristic X-rays, 10.5 °, 12.7 °, 13.4 °, 17.0 °, 18.2 °, 22.2 °, 22.5 °, 23.0 °, Diffraction peaks are shown at 24.4 ゜, 25.0 ゜, 25.5 ゜ and 28.8 ゜.

Example 3
Synthesis of oxymolybdenum phthalocyanine (3)
25.6 g of phthalonitrile and 11.9 g of molybdenum tetrachloride were reacted in 100 ml of quinoline at 200 ° C. for 6 hours. The product was collected while hot, and the cake was sprinkled and washed with 50 ml of DMF, replaced with methanol, and dried overnight under reduced pressure. After drying, 2.0 g of a blue solid was obtained.

  The results of IR and FD-MS analysis of the obtained compound were the same as those in Example 1. Table 3 shows the results of elemental analysis of this compound.

  From the above, it was confirmed that this compound was oxymolybdenum phthalocyanine. In addition, the diffraction X-ray spectrum of this product by CuKα radiation was the same as in Example 2.

Example 4
Synthesis of oxymolybdenum phthalocyanine (4)
25.6 g of phthalonitrile and 13.7 g of molybdenum pentachloride were reacted in 150 ml of quinoline at 235 ° C. for 10 hours. The product was collected while hot, sprinkled and washed with DMF, and the obtained cake was dispersed in 3000 ml of 5% hydrochloric acid at 80 ° C. for 1 hour. The collected cake was washed until the filtrate showed neutrality. The obtained cake was again stirred and refluxed in 180 ml of DMF. After filtration while hot, the mixture was replaced with methanol and dried under reduced pressure overnight to obtain 7.7 g of a blue solid.

  The results of IR and FD-MS analysis of the obtained compound were the same as those in Example 1. Table 4 shows the results of elemental analysis of this compound.

  From the above, it was confirmed that this compound was oxymolybdenum phthalocyanine. In addition, the diffraction X-ray spectrum of this product by CuKα radiation was the same as in Example 2.

Example 5
50 g of the oxymolybdenum phthalocyanine obtained in Example 1 was dissolved in 1500 ml of 98% concentrated sulfuric acid at 5 ° C. or lower and stirred for 1 hour. This sulfuric acid solution was put into 1500 ml of ice water to precipitate a solid, and then stirred for 2 hours. The solid content was collected and washed until the filtrate showed neutrality, to obtain a wet cake (including a redispersion treatment step). FIG. 5 shows an X-ray diffraction spectrum of the intermediate oxymolybdenum phthalocyanine obtained by drying, using CuKα radiation.

  9.1 g of the above wet cake after washing with water, 50 g of 3 mmφ glass beads and 18 ml of THF were charged into a 100 ml wide-mouth bottle, and were wet-milled at 750 cpm for 1 to 5 hours using a paint shaker. After separating the glass beads through a filter cloth, the solid content was collected with a membrane filter, and dried to obtain 1.2 g of a blue-green powder.

  When the X-ray diffraction spectrum by CuKα ray was measured, diffraction peaks were found at Bragg angles (2θ ± 0.2 °) of 7.7 °, 9.0 °, 14.6 °, 14.9 °, 16.7 °, 20.2 °, 22.9 °, 26.5 ° and 28.8 °. showed that. FIG. 6 shows the results.

Example 6
After treating 3.0 g of the oxymolybdenum phthalocyanine obtained in Example 1 in the same manner as in Example 5, 60 ml of this sulfuric acid solution was slowly poured into 450 ml of methanol at 10 ° C. or lower to precipitate a solid. The precipitated solid was collected by a membrane filter, sprinkled and washed with 100 ml of methanol, and then dried overnight under reduced pressure. FIG. 7 shows an X-ray diffraction spectrum of the obtained intermediate oxymolybdenum phthalocyanine by CuKα radiation.

  Next, 1.0 g of the intermediate oxymolybdenum phthalocyanine, 50 g of 3 mmφ glass beads and 14 ml of methanol were charged into a 100-ml wide-mouthed bottle, and milling was performed by a wet method at 750 cpm for 1 to 4 hours using a paint shaker. After separating the glass beads through a filter cloth, the solid content was collected by a membrane filter and dried to obtain 0.81 g of a blue powder.

  The X-ray diffraction spectrum measured by CuKα ray showed diffraction peaks at Bragg angles (2θ ± 0.2 °) of 7.1 °, 17.7 °, 24.0 °, 27.3 ° and 29.1 °. FIG. 8 shows the results.

Example 7
2.0 g of the intermediate oxymolybdenum phthalocyanine obtained in Example 6, 100 g of 3 mmφ glass beads and 33 ml of a mixed solvent of toluene: water = 90: 10 (volume ratio) were charged into a 100 ml wide-mouth bottle, and milling was carried out in the same manner as in Example 6. Applied for 3-6 hours. After the same treatment, 1.8 g of a blue-green powder was obtained. The X-ray diffraction spectrum measured by CuKα ray showed diffraction peaks at Bragg angles (2θ ± 0.2 °) of 9.5 °, 13.5 °, 14.9 °, 17.9 °, 24.0 ° and 27.2 °. FIG. 9 shows the results.

Example 8
1.0 g of the oxymolybdenum phthalocyanine obtained in Example 1 and 50 g of 3 mmφ glass beads were charged into a 100 ml wide-mouth bottle, and dry milling was performed for 6 hours using a paint shaker. FIG. 10 shows an X-ray diffraction spectrum of the obtained intermediate oxymolybdenum phthalocyanine by CuKα radiation.

  Next, 20 ml of a 90:10 mixed solvent of toluene: water was added to the jar containing the intermediate oxymolybdenum phthalocyanine, and wet milling was continued for 30 hours or more. By performing the same treatment as in Example 6, 0.7 g of blue powder was obtained.

  When the X-ray diffraction spectrum by CuKα ray was measured, diffraction peaks were shown at Bragg angles (2θ ± 0.2 °) of 18.6 and 28.8 °. The results are shown in FIG.

Example 9
In this embodiment, an example in which the oxymolybdenum phthalocyanine of the present invention is applied to a laminated electrophotographic photosensitive member will be described.

  6 g of the oxymolybdenum phthalocyanine having a crystal modification shown in FIG. A 0.3 μm charge generation film was formed on a plate as a polycarbonate base using a bar coater and air-dried. Next, a charge transporting film having a thickness of 20 μm was formed thereon by dissolving 1.5 g of N, N-diethylamino-p-benzaldehyde phenylnaphthylhydrazone as a charge transporting agent and 1.5 g of a polycarbonate resin in 15 ml of 1,2-dichloroethane. The formed laminated electrophotographic photosensitive member was manufactured.

Example 10
In the same manner as in Example 9, a laminated electrophotographic photosensitive member was produced using 2.0 g of oxymolybdenum phthalocyanine having the crystal modification shown in FIG. 8 and obtained in Example 6 of the present invention.

Example 11
In the same manner as in Example 9, a laminated electrophotographic photoreceptor was produced using 2.0 g of oxymolybdenum phthalocyanine having the crystal modification shown in FIG. 9 and obtained in Example 7 of the present invention.

Example 12
In the same manner as in Example 9, a laminated electrophotographic photosensitive member was produced using 2.0 g of oxymolybdenum phthalocyanine having the crystal modification shown in FIG. 11 obtained in Example 8 of the present invention.

Example 13
In the same manner as in Example 9, a laminated electrophotographic photoreceptor was produced using 2.0 g of oxymolybdenum phthalocyanine having the crystal modification shown in FIG. 4 obtained in Example 4 of the present invention.

  The photoreceptor thus prepared was evaluated for photosensitivity using a paper analyzer [EPA-8100 manufactured by Kawaguchi Electric Co., Ltd.]. A negative charge of about -1200 V corona was applied, and after dark decay, 2 [lux] was applied. Table 5 shows the results obtained by performing exposure and calculating the half-life exposure amount.

3 is an IR spectrum of the oxymolybdenum phthalocyanine obtained in Example 1. 3 is an FD-MS spectrum (enlarged portion) of the oxymolybdenum phthalocyanine obtained in Example 1. 3 is an X-ray diffraction spectrum of the oxymolybdenum phthalocyanine compound obtained in Example 1 by CuKα radiation. 4 is an X-ray diffraction spectrum of the oxymolybdenum phthalocyanine compound obtained in Example 2 by CuKα radiation. 9 is an X-ray diffraction spectrum of the intermediate oxymolybdenum phthalocyanine compound obtained in Example 5 by CuKα radiation. 9 is an X-ray diffraction spectrum of the oxymolybdenum phthalocyanine compound obtained in Example 5 by CuKα radiation. 9 is an X-ray diffraction spectrum of the intermediate oxymolybdenum phthalocyanine compound obtained in Example 6 by CuKα radiation. 9 is an X-ray diffraction spectrum of the oxymolybdenum phthalocyanine compound obtained in Example 6 by CuKα radiation. 9 is an X-ray diffraction spectrum of the oxymolybdenum phthalocyanine compound obtained in Example 7 by CuKα radiation. 9 is an X-ray diffraction spectrum of the intermediate oxymolybdenum phthalocyanine compound obtained in Example 8 by CuKα radiation. 9 is an X-ray diffraction spectrum of the oxymolybdenum phthalocyanine compound obtained in Example 8 by CuKα radiation.

Claims (5)

In the X-ray diffraction spectrum by CuKα ray, it has crystal modifications showing diffraction peaks at 7.1 °, 17.7 °, 24.0 °, 27.3 ° and 29.1 ° in Bragg angles (2θ ± 0.2 °). In the method for producing oxymolybdenum phthalocyanine,
(a) dissolving oxymolybdenum phthalocyanine in concentrated sulfuric acid;
(b) a step of introducing the resulting concentrated sulfuric acid solution into an alcoholic solvent under cooling to precipitate oxymolybdenum phthalocyanine;
(c) collecting the precipitated oxymolybdenum phthalocyanine;
(d) washing the collected cake with water until the washing water is neutral; and
(e) wet milling using an alcohol solvent;
A method that includes: The method according to claim 1, wherein the alcohol-based solvent is an alcohol having up to 3 carbon atoms. In the X-ray diffraction spectrum by CuKα ray, diffraction peaks were observed at 9.5 °, 13.5 °, 14.9 °, 17.9 °, 24.0 ° and 27.2 ° in Bragg angles (2θ ± 0.2 °). In the method for producing oxymolybdenum phthalocyanine having the crystal modification shown,
(a) dissolving oxymolybdenum phthalocyanine in concentrated sulfuric acid;
(b) a step of introducing the resulting concentrated sulfuric acid solution into an alcoholic solvent under cooling to precipitate oxymolybdenum phthalocyanine;
(c) collecting the precipitated oxymolybdenum phthalocyanine;
(d) washing the collected cake with water until the washing water is neutral; and
(e) wet milling using a hydrocarbon / water mixed solvent;
A method that includes: The method according to claim 3, wherein the alcohol-based solvent is an alcohol having up to 3 carbon atoms, and the hydrocarbon is an aromatic hydrocarbon having up to 10 carbon atoms. An organic photoconductive material for an electrophotographic photoreceptor, comprising oxymolybdenum phthalocyanine obtained by the method according to claim 1 as an active ingredient.

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