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US3708292A - Pi-form metal phthalocyanine - Google Patents

Pi-form metal phthalocyanine Download PDF

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US3708292A
US3708292A US00145678A US3708292DA US3708292A US 3708292 A US3708292 A US 3708292A US 00145678 A US00145678 A US 00145678A US 3708292D A US3708292D A US 3708292DA US 3708292 A US3708292 A US 3708292A
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phthalocyanine
metal
phthalocyanines
temperature
ray
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US00145678A
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P Brach
H Six
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Xerox Corp
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Xerox Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/073—Preparation from isoindolenines, e.g. pyrrolenines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0025—Crystal modifications; Special X-ray patterns
    • C09B67/0026—Crystal modifications; Special X-ray patterns of phthalocyanine pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G17/00—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process
    • G03G17/04—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process using photoelectrophoresis
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0696—Phthalocyanines

Definitions

  • This invention relates, in general, to phthalocyanine materials and, more specifically, to novel forms of metalphthalocyanines as well as to methods for the preparation and use of said forms.
  • Phthalocyanine which also is known as tetrabenzotetraazaporphin and tetrabenzoporphyrazine, may be said to be the condensation product of four isoindole groups.
  • Metal-free phthalocyanine has the following general structure:
  • various metal derivatives of phthalocyanine are known in which the two hydrogen atoms in the center of the molecule are replaced by metals from any group of the Periodic Table. Further, it is well known that from one to sixteen of the peripheral hydrogen atoms in the four benzene rings of the phthalocyanine molecule may be replaced by halogen atoms and by numerous organic and inorganic groups. The following discussion is directed primarily to nuclear-substituted metal-phthalocyanines.
  • Metal-phthalocyanines are known to exist in at least two well known polymorphic forms, namely, the alpha and beta. These forms may be easily distinguished by comparison of their X-ray diffraction patterns and/or infrared spectra.
  • the existence of additional polymorphs of metal-containing phthalocyanines have been disclosed, e.g., R-form disclosed in US. Pat. 3,051,721, delta form described in U.S. Pat. 3,160,635 and another delta form described in US. Pat. 3,150,150.
  • metal-free phthalocyanine an especially sensitive form of metal-free phthalocyanine, known as X metal-free phthalocyanine, could be prepared by extended dry milling or grinding of the alpha or beta form metal-free phthalocyanine.
  • the known methods of preparing metal-phthalocyanines include the reaction of phthalonitrile with a metal or metal salt in quinoline or a mixture of quinoline and trichlorobenzene; the reaction of phthalic anhydride, phthalic acid, or phthalimide, urea metal salts, and a catalyst; the reaction of o-cyanobenzamide with a metal; and the reaction of phthalocyanine or replaceable metalphthalocyanine with a metal forming a more stable phthalocyanine.
  • the metal-phthalocyanines prepared by the above methods are generally in the alpha or beta polymorphic forms.
  • metal-phthalocyanines While known metal-phthalocyanines are widely used in the preparation of inks and paints, there are several disadvantages associated with employing these materials in such a mode. For example, one drawback of employing many of the known metal-phthalocyanines in pigments is that they lack brilliance. Another serious disadvantage of using known metal-phthalocyanine polymorphs in pigments and paints is that they often recrystallize in the presence of heat and strong solvents. Electrophotographic plates comprising metal-phthalocyanines in a binder are disclosed in copending application Ser. No. 518,450, filed Jan. 3, 1966.
  • the rrmetal-form has utility as a paint component, ink component, and as a photoconductive material in electrophotography when dispersed in a binder and coated on a substrate.
  • Inks and paints prepared with the vr-metal polymorph demonstrate surprising brilliance whi-le electrophotographic plates comprising the vr-metal form exhibits photosensitivities suitable for use in electrophotographic processes.
  • 1r-metal phthalocyanines are equivalent in photosensitivity to B-metal phthalocyanines, the X-form exhibiting greater photosensitivity then either of the aforementioned.
  • Thermal stability of ar-metal phthalocyanine are found to be good, e.g., 1r-CUPC melts at approximately 610 C. without undergoing decomposition or transformation to another polymorphic form while the a and X-polymorphs are found to convert to 3 at temperatures above 270 C.
  • B-CuPc is found to melt at 610 C. without undergoing any change analogous to the stable 1r-CuPc.
  • the novel system for the preparation of wr-metal-form phthalocyanine comprises mixing, at a suitable reaction temperature, phthalonitrile, a metal salt and ammonia in an alkylalkanolamine solvent or 1,3-diimino-isoindoline and a metal salt in a non-ammonia saturated alkyla-lkanolamine solvent, and heating the mixture to about reflux temperature.
  • Typical solvents are alkylalkanolamines, such as,
  • any suitable solvent may be used in this system, it is preferred that solvents containing a primary alcohol group be employed in order to obtain a higher yield of the final desired product. While any suitable solvent containing a primary alcohol group may be used in this invention, significantly high yields of 1r-metal-form phthalocyanine are obtained with the use of Z-dimethylamino-ethanol and, accordingly, this particular solvent is most preferred- Although the synthesis of the present invention may be carried out at any suitable temperature, the range of about 120 C. to about 280 C. has been found convenient. While any appropriate temperature may be employed, it is preferred that a temperature generally in the range of about 135 C. to about 150 C. be used in order to obtain higher yields of the desired final product.
  • the total reaction time of the instant invention is about 10 to about 70 minutes depending on the particular solvent and the temperature employed. It the reaction proceeds much past about 90 minutes reaction time, beta metal-phthalocyanine formation begins to take place and mixtures of 1r-form and beta-form phthalocyanines are obtained.
  • a preferred reaction time is about 30 to about 55 minutes with Z-dimethylaminoetheinol in order to obtain a high yield of pure 1r-form metal phthalocyanine.
  • Any suitable mixing process may be used to slurry the phthalonitrile in the solvent mix. A complete conversion from phthalonitrile is attained where the mixture is stirred during the conversion and ammonia gas is bubbled through said mixture. The addition of ammonia gas is not necessary where 1,3-diimino-isoindoline is used.
  • the mixing may be carried out by milling with glass or steel balls or merely by stirring with a magnetic bar or simple rotating agitator. While the phthalonitrile or 1,3-diiminoisoindoline may be dissolved in the solvent at any suitable temperature, it is preferable to dissolve these materials when said solvent is heated to about 120 C.
  • phthalonitrile or 1,3-diimino-isoindoline is added to the hot solvent, ammonia is added in the case of phthalonitrile and then a metal salt is added to the mixture and the temperature immediately rises to reflux due to a rapid exothermic reaction. The mixture is then maintained at reflux temperature for about 5 to about minutes depending upon the solvent used, filtered hot, washed, and dried.
  • the rr-form metal phthalocyanine of the present invention may be' used to prepare electrophotographic plates and be used in electrophotographic processes as described in co-pending application Ser. No. 518,450 with excellent results.
  • the migration imaging process of co-pending application Ser. No. 483,675, filed Aug. 30, 1965, now US. Pat. No. 3,656,990 may be used to cause an imagewise migration of a fracturable or microscopically discontinuous thin photoconductive layer into an underlying plastic layer in image configuration, generally corresponding to the electrostatic latent image pattern.
  • Another mode of utilizing the electrostatic latent images formed on the imaging members hereof is to transfer the charge pattern to another layer by bringing the two layers into very close proximity and utilizing breakdown techniques as described, for example, in Carlson Pat. 2,982,647 and Walkup Pats. 2,828,814 and 2,937,943.
  • the layer to which the charge image is transferred may be a surface deformable material which may be caused to deform in image configuration as disclosed in Gunther et a1. Pat. 3,196,011.
  • the electrostatic latent image may also be directly read out utilizing devices such as electrometers which detect potential differences which may be translated into giving the graphic information that was represented by the original electrostatic latent image.
  • Insulating receiving sheets may be brought into contact with the electrostatic latent image bearing plates hereof and the receiving sheet developed with toner utilizing techniques which permit a plurality of such copies to be made from one master electrostatic latent image.
  • the crystal forms of metal-phthalocyanine produced in each of the following examples are analyzed by conventional X-ray and infrared analyses methods.
  • the X- ray and infrared curves produced by the materials prepared in each of the following examples are compared to curves for known alpha, beta, and X-form metalphthalocyanines employing X-ray radiation CuK;
  • Example I About 200 ml. of Z-dimethylaminoethanol is placed in a 4-neck, 500 ml. round bottom flask equipped with a mechanical stirrer, reflux condenser, thermometer, and gas inlet tube. About 65 g. of phthalonitrile is added and the mixture is heated with stirring to about 90 C. A steady stream of ammonia gas is then passed through the resulting solution while heating is continued to raise the temperature to about 120 C., at which point about 11 g. of anhydrous cuprous cyanide is added and the reaction temperature immediately rises to reflux or about 135 C. Ammonia introduction and stirring is continued for about 50 minutes while the temperature is maintained at about 135 C.
  • FIGS. 2-5 and Table I clearly shows shifting of the 0-H out of plane bending mode from 722.5 in a-form copper phthalocyanine to 727.5 in X- form phthalocyanine, to 728 in vr-form copper phthalocyanine and 730.5 in B-form phthalocyanine. Shifting of this absorption band which is the most intense band in the spectra suggests very significant changes in intermolecular overlapping of pi orbitals and hence is evidence of different crystal structures. The small difference noted between X and vr-fOlIIlS, 727.5 to 728 cm.
  • each of the four polymorphic forms of copper phthalocyanine can be identified by either their X- ray diffraction patterns or by their infrared spectra and unequivocal confirmation can be obtained by simultaneously applying both techniques.
  • Example II About 175 ml. of 2-dimethylamineothanol is placed in a 500 ml. flask, equipped as in Example I. About 65 g. of phthalonitrile is added and the mixture is heated with stirring to about C. A steady stream of anhydrous ammonia gas is passed through the resulting solution and said solution is heated slowly to about C., at which point approximately 16.2 g. of anhydrous cobaltous chloride is added and the reaction temperature immediately rises to reflux or about C. Ammonia introduction and stirring is continued for about 10 minutes while the temperature is maintained at about 135 C. A purple precipitate is removed from the hot reaction mixture by filtration and thoroughly washed with ethanol and acetone.
  • the resulting purple needle-like crystals are oven dried at about 75 C. for about 1 /2 hours.
  • the brilliant purple material yield of about 85% is then subjected to conventional X-ray and infrared analyses.
  • X-ray and IR data which are shown in FIGS. 6d and 7 respectively, are compared to known X-ray and IR data for the alpha cobalt, beta cobalt, and X-form cobalt polymorphs, respectively. (See FIGS. 6a, 6b, 6c, 8, 9, and 10 respectively.)
  • X-ray diffraction patterns for cobalt phthalocyanine polymorphs are very similar to those shown above for the copper phthalocyanine forms. Namely, lines are observed at 6.8 and 7.4 for a-form cobalt phthalocyanine, 7.2 and 9.4 for fi-form cobalt phthalocyanine, 7.8 and 9.5 for X-form cobalt phthalocyanine and 5.0, 8.7 and 10.0 for 1r-form cobalt phthalocyanine. All lines are reported as Bragg angles (20).
  • Example IH The experiment of Example I is repeated, except that about 250 ml. of 3-dimethylamino-l-propanol is employed in place of the Z-dimethylaminoethanol, about 100 g. rather than 80 g. of phthalonitrile are used, and heating is maintained for about 30 minutes rather than about 50 minutes prior to filtering.
  • the product obtained in a yield of about 30% when subjected to analyses is proven to be 1r-Cl1PC.
  • Example IV As a control for the conversion process of Example III the experiment is repeated, allowing the mixture to be heated for 90 minutes rather than 30 minutes prior to filtering. X-ray and infrared analyses show the product to be a mixture of ar-form and beta copper phthalocyanines.
  • Example V The conversion process of Example I is attempted, allowing the mixture to be heated for hours rather than 50 minutes prior to filtering. X-ray and infrared analyses show complete conversion to beta copper phthalocyanine.
  • Example VI The experiment of Example I is repeated using l-dimethylamino 2 propanol having a boiling point about 126 C. in place of Z-dimethylaminoethanol having a boiling point about 135 C.
  • the percentage yield of the final product which is found by X-ray and infrared analyses to be rr-fOIIIl copper phthalocyanine, is significantly less than the percentage yield in Example I or about 0.1% yield as opposed to about 80%.
  • Example VII About 250 ml. of Z-dimethylaminoethanol is placed in a 500 m1. flask and heated to about 120 C. at which temperature about 60 g. of 1,3-diiminoisoindoline is added. At this point, about 16.5 g. of anhydrous cobaltous chloride is added and the reaction temperature immediately rises to reflux or about 135 C. Stirring and heating is maintained at about 135 C. for about 20 minutes. The mixture is then filtered hot, washed with ethanol, acetone, and methanol, and air-dried. The resulting product is subjected to conventional X-ray and infrared analyses. The product obtained in a yield of about 25% when subjected to analyses is proven to be 1r-fOI'm cobalt phthalocyanine.
  • Example VIII A coating solution is prepared by dissolving about 70 parts Epon 1007, an epoxy resin available from the Shell Chemical Company, in about 80 parts ethyl Cellosolve, an ethylene glycol monoethylether available from the Union Carbide Corporation. To this solution is added about 40 parts Methylon 7520, a phenolic resin available from the General Electric Company, and about 9 parts Uformite F-240, a urea-formaldehyde resin available from the Rohm & Haas Company. The mixture is stirred to insure complete solution. To this solution is added about 20 parts of the vr-form copper phthalocyanine prepared as in Example I. An aluminum substrate is coated with this mixture to a dry film thickness of about 40 microns.
  • the plate is heated to about 180 C. for about 2 hours to cure the resins.
  • the plate is electrostatically charged by means of a corona discharge device operating at a positive potential of about 6,000 volts.
  • the plate is exposed for about 1 second by projection using a blackand-white transparency in a Simmons-Omega D3 Enlarger equipped with an 7/ 4.5 lens and a tungsten light source operating at 2950 K. color temperature.
  • the illumination level at the plate is about 4 foot-candles.
  • the resulting latent electrostatic image is developed by cascading electroscopic marking particles across the surface thereof as described by Walkup in U.S. Pat. 2,618,551.
  • the resulting powder image is electro'statically transferred to a paper receiving sheet as described by Schalfert in U.S.
  • Pat. 2,576,047 The image on the sheet is of good quality and corresponds to the projected image.
  • the plate is then reused by the above-described process until 100 copies are produced.
  • the image on the 100th copy is as of good quality as that produced on the first sheet and corresponds to the projected image.
  • Example IX Example VIII is repeated using the vr-form cobalt phthalocyanine of Example H. Images of good quality corresponding to the originals result in each case. After producing about 150 copies, the images produced in each case appear to be as good a quality as the first reproduced image.
  • Nuclear substituted metal phthalocyanine in the 1rform having an X-ray dilfraction pattern exhibiting strong lines at Bragg angles of 20 equal to about 5.1, 8.8 and 10.0 using CuK;
  • composition of claim 1 wherein said metal is selected from the group consisting of copper and cobalt.
  • a method of preparing wr-form metal phthalocyanine comprising the steps of (a) mixing phthalonitrile in pre-heated alkylalkanolamine solvents adding an anhydrous metal salt, whereby the temperature of the mixture rises to above reflux temperature; and
  • a method of preparing 1r-form metal phthalocyanine comprising the steps of:
  • alkylalkanolamine is 2-dimethylaminoethanol.
  • An electrophotographic plate comprising:
  • metal phthalocyanine is selected from the group consisting of Ir-form copper phthalocyanine, 1r-form cobalt phthalocyanine, and mixtures thereof.
  • An electrophotographic imaging process comprising the steps of:
  • An electrophotographic imaging process comprising the steps of:

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US00145678A 1971-05-21 1971-05-21 Pi-form metal phthalocyanine Expired - Lifetime US3708292A (en)

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AR (1) AR194234A1 (de)
BE (1) BE783793A (de)
BR (1) BR7203164D0 (de)
CA (1) CA996931A (de)
DE (1) DE2218767A1 (de)
FR (1) FR2138730A1 (de)
GB (1) GB1395615A (de)
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Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897249A (en) * 1973-04-09 1975-07-29 Xerox Corp Toners for phthalocyanine photoreceptors
US4108863A (en) * 1976-01-01 1978-08-22 Nippon Shokubai Kagaku Kogyo Co. Ltd. Copper phthalocyanine of novel crystal form
US4666802A (en) * 1986-07-16 1987-05-19 Eastman Kodak Company Photoconductive elements sensitive to infrared radiation having a bromoindium phthalocyanine pigment
US5252417A (en) * 1990-03-20 1993-10-12 Fuji Xerox Co., Ltd. Titanyl phthalocyanine crystal and electrophotographic photoreceptor using the same
US5283145A (en) * 1991-05-01 1994-02-01 Fuji Xerox Co., Ltd. Crystals of dichlorotin phthalocyanine, method of preparing the crystal, and electrophotographic photoreceptor comprising the crystal
US5298617A (en) * 1990-11-22 1994-03-29 Fuji Xerox Co., Ltd. Oxytitaniumphthalocyanine hydrate crystal and electrophotographic photoreceptor using said crystal
US5302479A (en) * 1991-04-26 1994-04-12 Fuji Xerox Co., Ltd. Crystals of hydroxygallium phthalocyanine, method of preparing the crystals, photoconductive material comprising the crystals, and electrophotographic photoreceptor comprising the material
US5304446A (en) * 1991-04-22 1994-04-19 Fuji Xerox Co., Ltd. Hydroxyindium phthalocyanine crystals and electrophotographic photoreceptor
US5308728A (en) * 1991-08-16 1994-05-03 Fuji Xerox Co., Ltd. Dichlorotin phthalocyanine crystal, process for producing the same, and electrophotographic photoreceptor using the same
US5358813A (en) * 1902-01-13 1994-10-25 Fuji Xerox Co., Ltd. Crystals of chlorogallium phthalocyanine and method of preparing them
US5360475A (en) * 1992-10-09 1994-11-01 Fuji Xerox Co., Ltd. Process for preparing hydroxymetal phthalocyanine pigment
US5393629A (en) * 1991-04-26 1995-02-28 Fuji Xerox Co., Ltd. Electrophotographic photoreceptor
US5393881A (en) * 1992-08-26 1995-02-28 Fuji Xerox Co., Ltd. Crystalline forms of hydroxygallium phthalocyanine
US5440029A (en) * 1990-11-28 1995-08-08 Fuji Xerox Co., Ltd. Titanyl phthalocyanine crystal
US5459004A (en) * 1992-03-31 1995-10-17 Fuji Xerox Co., Ltd. Process for preparing hydroxygallium phthalocyanine crystals and electrophotographic photoreceptor using the crystals
US5463044A (en) * 1992-08-26 1995-10-31 Fuji Xerox Co., Ltd. Process for preparing chlorogallium phthalocyanine crystal
US5463043A (en) * 1991-09-27 1995-10-31 Fuji Xerox Co., Ltd. Process for producing a dichlorotin phthalocyanine crystal
US5463041A (en) * 1992-06-17 1995-10-31 Fuji Xerox Co., Ltd. Process for preparing purified hydroxymetal phthalocyanine and electrophotographic photoreceptor using the same
US5495011A (en) * 1992-08-25 1996-02-27 Fuji Xerox Co., Ltd. Process for preparing hydroxygallium phthalocyanine crystal, product thereof and electrophotographic photoreceptor using the same
US5510217A (en) * 1993-01-01 1996-04-23 Fuji Xerox Co., Ltd. Gallium phthalocyanine halide crystals, method for preparing the same and electrophotographic photoreceptor using the same
US5516609A (en) * 1993-04-02 1996-05-14 Fuji Xerox Co., Ltd. Methoxy gallium phthalocyanine compound and electrophotographic photoreceptor using it
US5545733A (en) * 1993-08-12 1996-08-13 Fuji Xerox Co., Ltd. Method for preparing hydroxygallium phthalocyanine crystals and electrophotographic photoreceptor using the crystals
US5588991A (en) * 1994-08-31 1996-12-31 Fuji Xerox Co., Ltd. Process for producing chlorogallium phthalocyanine crystal
US5643703A (en) * 1993-03-25 1997-07-01 Fuji Xerox Co., Ltd. Hydroxygallium phthalocyanine crystal, process for preparing same, and electrophotographic photoreceptor comprising same
US5663327A (en) * 1994-09-30 1997-09-02 Fuji Xerox Co., Ltd. Hydroxygallium phthalocyanine crystal, process for producing the same, and electrophotographic photoreceptor containing the same
US5834149A (en) * 1994-06-06 1998-11-10 Fuji Xerox Co., Ltd. Hydroxygallium phthalocyanine crystals and electrophotographic photoreceptors using same
US6232466B1 (en) 1990-03-20 2001-05-15 Fuji Xerox Co., Ltd Process for preparing titanyl phthalocyanine crystal by solvent treatment of amorphous or quasi-amorphous titanyl phthalocyanine

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5358813A (en) * 1902-01-13 1994-10-25 Fuji Xerox Co., Ltd. Crystals of chlorogallium phthalocyanine and method of preparing them
US3897249A (en) * 1973-04-09 1975-07-29 Xerox Corp Toners for phthalocyanine photoreceptors
US4108863A (en) * 1976-01-01 1978-08-22 Nippon Shokubai Kagaku Kogyo Co. Ltd. Copper phthalocyanine of novel crystal form
US4666802A (en) * 1986-07-16 1987-05-19 Eastman Kodak Company Photoconductive elements sensitive to infrared radiation having a bromoindium phthalocyanine pigment
US6232466B1 (en) 1990-03-20 2001-05-15 Fuji Xerox Co., Ltd Process for preparing titanyl phthalocyanine crystal by solvent treatment of amorphous or quasi-amorphous titanyl phthalocyanine
US5252417A (en) * 1990-03-20 1993-10-12 Fuji Xerox Co., Ltd. Titanyl phthalocyanine crystal and electrophotographic photoreceptor using the same
US5298617A (en) * 1990-11-22 1994-03-29 Fuji Xerox Co., Ltd. Oxytitaniumphthalocyanine hydrate crystal and electrophotographic photoreceptor using said crystal
US5440029A (en) * 1990-11-28 1995-08-08 Fuji Xerox Co., Ltd. Titanyl phthalocyanine crystal
US6268096B1 (en) * 1990-11-28 2001-07-31 Fuji Xerox Co., Ltd Titanyl phthalocyanine crystal and electrophotographic photoreceptor using the same
US5304446A (en) * 1991-04-22 1994-04-19 Fuji Xerox Co., Ltd. Hydroxyindium phthalocyanine crystals and electrophotographic photoreceptor
US5302479A (en) * 1991-04-26 1994-04-12 Fuji Xerox Co., Ltd. Crystals of hydroxygallium phthalocyanine, method of preparing the crystals, photoconductive material comprising the crystals, and electrophotographic photoreceptor comprising the material
US5393629A (en) * 1991-04-26 1995-02-28 Fuji Xerox Co., Ltd. Electrophotographic photoreceptor
US5283145A (en) * 1991-05-01 1994-02-01 Fuji Xerox Co., Ltd. Crystals of dichlorotin phthalocyanine, method of preparing the crystal, and electrophotographic photoreceptor comprising the crystal
US5416207A (en) * 1991-08-16 1995-05-16 Fuji Xerox Co., Ltd. Dichlorotin phthalocyanine crystal, process for producing the same, and electrophotographic photoreceptor using the same
US5308728A (en) * 1991-08-16 1994-05-03 Fuji Xerox Co., Ltd. Dichlorotin phthalocyanine crystal, process for producing the same, and electrophotographic photoreceptor using the same
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Also Published As

Publication number Publication date
CA996931A (en) 1976-09-14
DE2218767A1 (de) 1972-12-07
GB1395615A (en) 1975-05-29
IT955644B (it) 1973-09-29
NL7206868A (de) 1972-11-23
FR2138730A1 (de) 1973-01-05
BE783793A (fr) 1972-11-23
BR7203164D0 (pt) 1973-06-14
AR194234A1 (es) 1973-06-29

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