US3721554A - Organic photoconductive materials formed by condensing photoconductive and dyestuff reactants - Google Patents

Organic photoconductive materials formed by condensing photoconductive and dyestuff reactants Download PDF

Info

Publication number
US3721554A
US3721554A US00888886A US3721554DA US3721554A US 3721554 A US3721554 A US 3721554A US 00888886 A US00888886 A US 00888886A US 3721554D A US3721554D A US 3721554DA US 3721554 A US3721554 A US 3721554A
Authority
US
United States
Prior art keywords
colored
photoconductive
substance
materials
color developing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00888886A
Inventor
S Nagashima
K Tsuchiya
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Canon Inc filed Critical Canon Inc
Application granted granted Critical
Publication of US3721554A publication Critical patent/US3721554A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0644—Heterocyclic compounds containing two or more hetero rings
    • G03G5/0661—Heterocyclic compounds containing two or more hetero rings in different ring systems, each system containing at least one hetero ring
    • 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
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0609—Acyclic or carbocyclic compounds containing oxygen
    • 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
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
    • G03G5/0614—Amines
    • G03G5/06142—Amines arylamine
    • 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
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
    • G03G5/0614—Amines
    • G03G5/06142—Amines arylamine
    • G03G5/06144—Amines arylamine diamine
    • 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
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0618—Acyclic or carbocyclic compounds containing oxygen and nitrogen
    • 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
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
    • G03G5/0629—Heterocyclic compounds containing one hetero ring being five-membered containing one hetero atom
    • 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
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
    • G03G5/0631—Heterocyclic compounds containing one hetero ring being five-membered containing two hetero atoms
    • 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
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
    • G03G5/0633—Heterocyclic compounds containing one hetero ring being five-membered containing three hetero atoms
    • 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
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0635—Heterocyclic compounds containing one hetero ring being six-membered
    • G03G5/0637—Heterocyclic compounds containing one hetero ring being six-membered containing one hetero atom
    • 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
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0635—Heterocyclic compounds containing one hetero ring being six-membered
    • G03G5/064—Heterocyclic compounds containing one hetero ring being six-membered containing three hetero atoms
    • 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
    • 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
    • G03G5/0675—Azo dyes
    • G03G5/0677—Monoazo dyes
    • 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
    • G03G5/0675—Azo dyes
    • G03G5/0679—Disazo dyes
    • 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
    • G03G5/12—Recording members for multicolour processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0906—Organic dyes
    • G03G9/0908—Anthracene dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0906—Organic dyes
    • G03G9/091—Azo dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0906—Organic dyes
    • G03G9/0924—Dyes characterised by specific substituents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0926—Colouring agents for toner particles characterised by physical or chemical properties

Definitions

  • a light-transparent photoconductive material for use in electrophotography is the reaction product obtained by condensing a. an organic photoconductive compound containing an amino and/or hydroxyl group and b. a reactive colored compound containing an active halogen atom; or by condensing v a. an organic photoconductive compound containing an active halogen atom and b. a reactive colored compound containing an amino and/or hydroxyl'group.
  • a negatively charged photoconductive layer is first exposed to the object through a red filter and then developed with a cyancolored toner.
  • the photoconductive layer is then again charged in a negative sense and exposed to the object through a green filter to obtain a negatively charged image which is subsequently developed with a magenta toner. Further, the photoconductive layer is charged negatively, exposed to the object through a blue filter andv developed with a yellow toner.
  • the images toned in cyan color are electrically insulating, they are also charged at the second negative charging and the charged electricity will not disappear at the following exposure to green light so that the images produced by the magenta toner inevitably overlap the images in cyan.
  • the cyan-colored toner is electrically conducting, the cyan images are not at all charged during the second charging process so that, if the images produced by the second exposure with the green light overlap the blue images of the first exposure, the magenta toner will never be attached to the respective part. To overcome the difficulty, the toner has to exhibit photosensitivity in itself.
  • the toner possesses photosensitivity or photoconductivity. If the magenta toner and the yellow toner are not transparent to light, for example, the parts where the images of three colors superimpose each other will not show their mixed color (in other words, will not show blue color at the superimposition of cyan and magenta, not green color at the superimposition of cyan and yellow), but the color of the toner employed afterwards covers the color of the previously applied toner, so that the parts where cyan is superimposed by magenta and by yellow show magenta and ye]- low color, respectively.
  • the toners in either dry or wet process of developing, must be of colored materials having photoconductivity and light transparency to reproduce naturally colored images by electrophotography.
  • the object of this invention is to provide colored or color developing organic photoconductive materials which are transparent to light.
  • An other object of this invention is to provide colored or color developing organic photoconductive materials which do not show blurring and transfer of coloring materials and which can be reproducibly produced with constant color characteristics and which are not influenced by lot-to-lot variation of the contamination of impurities.
  • a further object of this invention is to provide colored or color developing organic photoconductive materials for use in photographic developing having favorable light transparency of which the electrical characteristics are suited especially to the reproduction of multi-colored or naturally colored images.
  • a further object of this invention is to provide a.
  • An other further object of this invention is to provide colored or color developing photosensitive materials for use in electrophotography which have a photosensitive layer containing colored or color developing or? ganic photoconductive materials.
  • the present invention can provide colored organic photoconductive materials for use in electrophotography by the reaction of organic photoconductive sub.- stances with reactive colored components.
  • the reactive colored components refer to reactive coloring materials and reactive color developing components in general.
  • the present invention relates to a procedure for obtaining colored organic photoconductive materials for use in electrophotography by the reaction of organic photoconductive materials with reactive coloring materials, and also to a process for obtaining color developing organic photoconductive materials for use in electrophotography by the reaction of organic photoconductive substances with reactive color developing components.
  • the colored or color developing organic photoconductive materials of this invention can be obtained by chemically combining an organic photoconductive substance having at least one amino or hydroxy group with a coloring or a color developing component having at least one active halogen atom.
  • colored or color developing organic photoconductive materials of this invention can be obtained by chemically combining anorganic photoconductive substance having at least one active halogen atom with a coloring or a color developing component having at least one amino or hydroxyl group.
  • the resulting products of the chemical combination are not only photoconductive but also colored and light-transparent, and the colors on them are free from defects, e.g. they do not become blurred or transferred because the coloring materials are chemically combined, not in the same manner as in a usual dyeing, with the photoconductive substances, and the steadiness of color was maintained for every product owing to the constant ratio of combining molecules in the chemical combination.
  • the color developing organic photoconductive I materials of this invention When employed as materials for photographic developing, they can either be reacted beforehand with a color developing auxiliary to develop coloration, or they are used as they are as materials for developing and are reacted, after developed, with the color developing auxiliary to develop coloration.
  • the colored or color developing organic photoconductive materials may be pulverized in a ball-mill, a roll-mill and an atomizer to use them as toner for use as dry or wet developing agent, or they may be used in combination with other colored substances or vehicle resins, in the case of which the vehicle resins include, for example, rosin and the derivatives thereof, styrene resin, alkyd resin, terpene resin, xylene resin, straight chain hydrocarbon resin, phenol resin, epoxy resin and acrylic resin.
  • These toners may be used as developer for negatively charged images in single or in combination with carrier materials such as glass beads, iron powder and furs.
  • the materials are dispersed in a carrier liquid.
  • a carrier liquid an insulating liquid widely know as carrier liquid for a liquid developer, for example, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons such as pentane, hexane, gasoline, kerosene, mineral spirit, cyclohexane, carbon tetrachloride, perchloroethylene and naphtha and silicone oil waxes may be used and in aspecial case water may be used.
  • binding resin or plasticizer is not required for the organic photoconductive materials having capability of forming films, but use of 30 100 percent by weight of a binding resin is desired for the photoconductive materials which do not have capability of forming films.
  • a plasticizer may be added in the amount of 5 100 percent by weight, alone or in combination with an other photoconductive material, to further improve the quality of the coating films.
  • Binding resins referred to above include, for example, polystyrene resin, polyvinyl chloride, phenol resin, polyvinyl acetate, polyvinyl acetal, epoxy resin, xylene resin, alkyd resin, polycarbonate resin, acrylonitrile styrene resin.
  • supports for the photosensitive materials may be used, for example, metallic plates of aluminum, copper, zinc and silver, papers treated so that solvents could not enter the interior, aluminum laminated paper, filmsof synthetic resins in which a plasticizer is contained, and supports the surfaces of which are coated with a metal, a metal oxide or a metal halide as glass, paper, polyethylene, polypropylene, polyethylene terephthalate, polystyrol, polyvinyl chloride, ethylcellulose, cellulose acetate, polyester films and other synthetic resin films. In general, they should have a surface resistance less than 10 ohms, preferably less than 10 ohms.
  • the films of the photosensitive layer can be formed on the' supports in a conventional manner such as, for example, by use of rolls, wire bars, or air knives.
  • color developing organic photoconductive materials of this invention are generally colorless or lightly colored, they have many advantages over colored organic photoconductive materials when employed as materials for photographic developing or photosensitive materials.
  • the most predominant advantage of the materials of this invention as used for materials of photographic developing is as follows. In case of developing by way of superimposed multi-colored images as described before, for example, if an already colored material for developing is used, the coloration of the first developed image will act as filter in the subsequent exposures, thus significantly decreasing the apparent sensitivity. However, if a color developing organic photoconductive material which is colorless or lightly colored is used, the above described difficulty will be completely eliminated or at least minimized.
  • reaction-of a colored substance with an organic photoconductive compound should be carried out fairly slowly in order that the coloring substance be not decomposed nor faded in the course of reaction.
  • the various conditions of reaction may, however, be freely selected, when a color developing component is used, because the component is usually of a lower molecular weight and more resistant to heat and light than the coloring substances.
  • the condensation reaction of the various active halogens and amines of this invention is preferably performed-in anhydrous media.
  • the condensation reacplayed in the present invention include, for example, 12 the following:
  • the reactive coloring materials having an amino or a hydroxy group or groups include, for example, the following substahces: 0H
  • the reactive color developingcomponents having an N amino or/and a hydroxyl group which are employed in thepresent invention include, for example, the following substances: c1
  • EXAMPLE 1 such a manner that the temperature did not rise above 5C. After the whole volume had been added, the resultant solution was stirred for 30 minutes, and to it a solution of 1.0 mol sodium carbonate in 500ml water was added at the same temperature. After stirred for 3.5 4 hours, the mixture was pouredinto a large amount of water to obtain a magenta-colored photoconductive coloring material. Recrystallization from dioxane gave magenta-colored crystals. Melting point: 245 248C.
  • Example 2 the same treatment as in Example 1 .was followed to obtain a solid yellow substance.
  • EXAMPLE 3 The substance (1.0 mol) of theformula (5) was dissolved in 3 liters of dried dioxane to which 700ml of dried acetone was added. The mixed solution was.
  • EXAMPLE 4 The substance (1.0 mol) of the formula (7) was dis- I solved in a mixture of 3 liters of. dried dioxane and 4 mol of triethylamine. On the other hand, the substance (1 mol) of the formula (49) was dissolved in 4.0 liters of o-dichlorobenzene. Using these solutions, the same treatment as in Example 1 was followed to obtain solid reddish orange matter.
  • EXAMPLE 5 The substance (1.0 mol) of the formula (1 l was dissolved in 3 liters of dried dioxane to which 700ml of dried acetone was added. The solution was thoroughly mixed by stirring and kept at 0 5C.'Next, the substance (0.5 mol) of the formula (43) was dissolved in 3.0 liters of dried dioxane. Using these solutions, the
  • Example 2 same treatment as in Example 1 was followed to obtain a solid yellow substance.
  • EXAMPLE 6 The substance (1.0 mol) of the formula (21) was dissolved in 3 liters of monochlorobenzcne to which 300g cooled, the mixture was filtered and the filtrate wasevaporated to the half volume under reduced pressure. The remainder was added to methyl alcohol to obtain a red photoconductive substance. Recrystallization from a mixture of monochlorobenzene and dioxane gave a red photoconductive substance (m.p: 200C).
  • EXAMPLE 7 The substance (1.0 mol) of the formula (26) was dissolved in 4.0 liters of dioxane to which 320g of triethylamine was added. The mixture was cooled to -5C under agitation. On the other hand, the substance 1.0 mol) of the formula (58') was dissolved in 4.5 liters of dioxane. Using thesesolutions, the same treatment as in Example 6 was followed to obtain a yellowish red organic photoconductive substance.
  • EXAMPLE 8 The substance (1.0 mol) of the formula (59) was dissolved in a mixture of 3.0 liters of monochlorobenzene and 4.0 liters of pyridine. While the solution being stirred at 0 5C, 1.0 mol of the substance'of-the for mula (27) was added. Then the stirring was continued at the elevated temperature 90 95C for 90 minutes to complete the reaction. The whole mixture was then poured into iced hydrochloric acid when a purple solid was separated. After separated by filtration, the solid matter was washed thoroughly with water and dried. Recrystallization from monochlorobenzene gave violet photoconductive powders with the yield 62 65 percent.
  • EXAMPLE 9 The substance (1.0 mol) of the formula (34) was dissolved in 3 liters of dried dioxane to which 700ml of dried acetone was added. The solution was thoroughly mixed by stirring and kept at 5C. 0n the other hand, the substance (1.0 mol) of the formula (61) was dissolved in 3.0 liters of dioxane. Using these solutions, the same treatment as in Example 1 was followed to obtain an orange photoconductivesubstance.
  • EXAMPLE EXAMPLE 1 l The substance (1.0 mol) of the formula (34) was reacted with the substance (1.0 mol) of the formula (67) in the same manner as in Example 10 to obtain an orange photoconductive substance.
  • EXAMPLE 12 The chemically bound colored substances described in Examples 1 through 11 were pulverized into powders of 5p. diameter in average with an atomizer and l 10g, preferably 2 5g, of the powders were mixed thoroughly with 100g of magnetic iron powders (as carrier) of 100 150 mesh in the average diameter of particles. The mixture was adsorbed on a bar magnet to be used as amagnetic brush, with which several time scanning on electrostatic figures produced visible images. The images, when treated by the known process of fixation, were converted into permanent ones.
  • EXAMPLE 13 The chemically bound colored substances (10g) described in Examples 1 through 11 were dispersed with a ball mill in 100ml of insulating liquid such as .herosene and mineral spirit, and 10ml of it was again visible figures, when applied in an appropriate manner such as dipping, rolling or spraying.
  • insulating liquid such as .herosene and mineral spirit
  • EXAMPLE 14 A photosensitive paper for electrophotography prepared by use of zinc oxide and acrylicresin was charged with a corona discharger with the applied voltage 7KV. Then the paper was exposed to a colored figure through a red filter. The electric charge remains on the paper only in the shape of figure which should be colored in blue. The charged figure was developed with the developer for blue color (the liquid photographic developer obtained in Example 3 prepared by adding 1.5 2.0g. of a blue substance in ml of a petroleuin solvent and by dispersing with a ball mill for 15 20 hours) and was fixed.
  • the developer for blue color the liquid photographic developer obtained in Example 3 prepared by adding 1.5 2.0g. of a blue substance in ml of a petroleuin solvent and by dispersing with a ball mill for 15 20 hours
  • the paper After being dried, the paper was again charged with electricity, exposed to a colored figure through a green filter and developed with a developer for magenta color (prepared in the same manner as above using the toner obtained in Example by which process the only part that was sensitive tothe magenta developer appeared in color by the developing. After the figure was fixed, the paper was again electrostatically charged, exposed through a blue filter and developed in the same manner (with a similar developer using the toner prepared in Example 2), by which process the only part that was sensitive to the photographic developer for yellow color appeared. The composite figure: thus obtained almost perfectly reproduced the original figure.
  • the colored organic-photoconductive materials of this invention is employed not only as a toner as above in both wet and dry processes, but also as a suitable developing material to be used for the photoelectrophoretic imaging process.
  • This process employs photoconductive pigment as toner in place of a socalled light sensitive layer made of a photoconductor.
  • the following example illustrates the case in which the colored organic photoconductive materials of this invention was employed as developer for figure formation in the photoelectrophoretic imaging process.
  • EXAMPLE 15 To a petroleum solvent lsopar-H (commercial name) 12 15 percent by weight of the substance obtained in Example 1 was added and the mixture was treated with a ball mill for 4 5 days to make a dispersoid of micro particles. This was applied on a light transparent electrode in a. thin layer on which was placed an insulating paper and further on it another electrode. While a DC voltage 700V was being applied between the two electrodes, the paper was exposed to a light image through the transparent electrode. A colored image appeared on the surface of the insulating paper and a negative mirror image on the surface of transparent electrode.
  • the colored organic photoconductive materials of this invention can also be effectively employed as a component of the photosensitive layer for electrophotography.
  • n base papers of 60 70g weight per square meter which had been treated with polyvinyl alcohol, the zinc oxide paint above was applied with a roll and dried by hot air.
  • the photosensitivepapers thus prepared are colored magenta.
  • the colored photosensitive paper for electrophotography prepared in this way was electrostatically charged with a corona discharger to which -7KV was applied. Subsequently the paper was exposed to light together with the original figure and by the liquid developing process using pigment-petroleum solvent a positive image was produced.
  • the colored organic photoconductive materials of this invention are especially suited, as the above examples show, to be used for photographic developer and photosensitive materials.
  • the materials of this invention can be naturally used not only alone but also in combination with various known additives or other materials.
  • one or more members selected from the group consisting of pigments, dyestuffs, resins, electrostatic charge controllers, dispersing agents and fixers may be dispersed or dissolved in the materials of this invention.
  • EXAMPLE 17 To the substance (1.0 mol) of the formula (1) were added 3.0 liters of dioxane, 0.3 liter of methylene chloride and further 0.6 mol of a reactive coupler dissolved in 2.0 liters of dioxane. While the mixture being stirred at 10 15C, 2 mols of sodium carbonate dissolved in 300ml of water was added at the same temperature. After stirring was continued for 5 6 hours, the mixture was poured into a large amount of water, when white crystals were precipitated which were then separated by filtration and washed with water.
  • Example 17 was separated by filtration, washed with water, and dissolved in an alcoholic alkali solution to which solution was added a diazonium salt of aniline to obtain a yellow organic photoconductive coloring material.
  • EXAMPLE 19 The substance (1 mol) of the formula (4) was dissolved in a mixture consisting of 2.4 liters of dried benzene, 700ml of dried methylene chloride and dried pyridine. On the other hand, the substance (0.5 mol) of the formula (73) was dissolved in a mixture consisting of 1.5 liters of dried dioxane and 1.5 liters of dried benzene. Using these solutions, the treatment was followed as in Example 17 to obtain the reaction product,
  • Example 17 Further color developing reaction as in Example 17 produced a magentacolored photoconductive coloring material.
  • EXAMPLE 21 The substance (1 mol) of the formula (7) was dissolved in a mixture consisting of 3 liters of dried dioxane and 4 mols of triethylamine, and on the other hand the substance (1 mol) of the formula (77) was dissolved in 4.0 liters of o-dichlorobenzene. Using the two solutions above the treatment was followed as in Example 20 and further the same color developing reaction as in Example 17 was conducted to obtain a blue photoconductive coloring material.
  • EXAMPLE 22 The substance (1 mol) of the formula (13) was dissolved in a mixture consisting of 500ml of dried ether, 2.5 liters of dried dioxane and 4 mols of dried triethylamine and, on the other hand, the substance (1 EXAMPLE 24 To a solution of the substance (1.0 mol) of the formula (21) in 3.0 liters of chlorobenzene and further 310g of triethylamine maintained at C, the substance (l.0 mol) of the formula (77) dissolved in 2.5
  • Example 20 produced white powders which afforded a blue material when treated by the color developing reaction with diethylparamine as in Example 17 and a red material when treated with a diazonium salt of aniline.
  • EXAMPLE 25 To a solution of the substance (1.0 mol) of the formula (26) in 4.0 liters of dioxane and 320g of triethylamine cooled at 0 5C, a solution of the substance mol) of the formula (76) in 2.5 liters of dioxane was added and the mixture was treated as in Example to obtain white powders of the melting point 210 212C. The powders developed yellow coloration when treated with either color developing agent of diethylparamine or diazonium salt.
  • EXAMPLE 28 The substance (1.0 mol) of the formula (85) was dissolved in 5.0 liters of dioxane and 320g of triethylamine and cooled to 0 5C. The substance (1.0 mol) of the formula (32) was added to it under agitation, and the mixture was treated as in Example 26 to give white powders. The color developing reaction with diethylparamine produced yellow coloration.
  • EXAMPLE 30 The intermediate obtained prior to the color developing treatment described in Example 17, that is the reaction product of the substances of the formulas (I) and (72), was thoroughly washed with water and dried. The 5g portion of it was dispersed in 1,000ml of a petroleum solvent (trade mark: Isopar) by treating with a ball mill for 5 hours, to prepare a developing solution.
  • a photosensitive paper for electrophotography which was prepared from zinc oxide and acrylic resin, was electrostatically charged with a corona discharger to which 7KV was applied, and this was exposed to light.
  • the developing treatment with the above developer produced colorless figures at the charged parts.
  • the paper was soaked in a color developing solution as in Example 17, when magentacolored visible figures appeared.
  • the colorless figures formed on the zinc oxide paper were transferred under pressure to a copying paper which had a slightly adhesive surface.- The same color developing reaction as before produced magentacolored visible figures.
  • EXAMPLE 31 The substance obtained prior to the color developing reaction in Example 21 was dispersed in Isopar in the same manner as in Example 30. Following the procedure in Example 30 colorless figures were formed on a zinc oxide paper, which were treated-with a color developing agent either directly or after transferred to a copying paper as in Example 30 to form visible figures in which figures were colored blue.
  • EXAMPLE 32 The substance obtained prior to the color developing reaction in Example 23 was dispersed in Isopar in the same manner as in Example 30. Following the procedure in Example 30, colorless figures were formed on a zinc oxide paper, which were treated with a color developing agent either directly or after transferred to a copying paper as in Example 30 to form visible figures in which figures were colored yellow.
  • EXAMPLE 33 A photosensitive paper for electrophotography prepared from zinc oxide and acrylic resin was electrostatically charged with a corona discharger to which -7K ⁇ was applied. This paper was exposed to an original colored manuscript through a red filter when the electrical charge remains on the paper at those parts of the figures which should be colored blue. These parts were developed with the colorless developer described in Example 31 and the colorless figures were transferred, as in Example 30, by the electrostatic method to a copying paper having a slightly adhesive surface. Then the zinc oxide paper was exposed in the same way through a green filter, treated with a colorless developer described in Example 30 and the colorless figures were transferred to the same copying paper as above.
  • EXAMPLE 34 I The chemically combined colored substances appearing in Example 17 through 29 were separately pulverized with an atomizer into particles of the average diameter 5 of which 1 lg, preferably 2 5g, was thoroughly mixed with 100g of magnetic iron powder (as carrier) of the average particle diameter 100- 150 mesh. The mixture was adsorbed on a bar magnet to be used as a magnetic brush. The electrostatically charged figures were converted into colored visible figures, when scanned above them several times with the brush. The colored figures could be made permanent figures by treating the known method of developing.
  • EXAMPLE 35 A photosensitive paper for electrophotography prepared from zinc oxide and acrylic resin was electrostatically charged with a corona discharger to which 7KV was applied. This paper was exposed to an original colored manuscript through a red filter, when the charge on the paper remains only at those parts of the figures which should be colored blue. These parts prepared by dispersing a mixture of ml of a petroleum solvent and 1.5 2.0g of the toner with a ball mill for 15 20 hours) and fixed. The paper, after being dried, was again charged, exposed-through a green filter and treated with the magenta developing solution (prepared as above from the toner obtained in Example 17) when only those parts were developed which were sensitive to the magenta developer. After fixing, the paper was again charged, exposed through a blue filter and treated with the developer (prepared as above from the toner obtained in Example 23) when only those parts were developed into figures which were sensitive to the yellow developer. The copied figures thus obtained almost reproduced the original manuscript.
  • the colored organic photoconductive materials of the present invention are not only used as toner materials in both dry and wet processes, but also suitable to the developing materials for figure formation in electrophoresis.
  • the present method employs a photoconductive pigment as toner instead of using a so-called photoconductive photosensitive layer.
  • the materials of this invention exhibit very excellent quality when used for the photoelectrophoretic imag- EXAMPLE 37
  • the substance obtained in Example 17 was added to a petroleum solvent, Isopar-l-l (commercial name), in the amount of 12- l5percent by weight and dispersed by treating-with a ball mill for 4 5 days to make a microdispersoid. This was applied on a light ti'ansparent electrode in a thin layer and an insulating paper was placed on it and then another electrode further on them. They were exposed to a light image while a DC voltage, 700V, was being applied between the two electrodes. A colored image which corresponded to the light image was obtained on the insulating paper and a negative mirror image on the surface of the transparent electrode.
  • the colordeveloping organic photoconductive materials of this invention can also be used effectively for a component of the photosensitive layer for elec tropho tography.
  • color developing photoconductive materials of this invention are photoconductive by themselves, they can be employed to make copying papers for electrophotography when applied on a supporting base such as paper, either alone or in combination with other photoconductive EXAMPLE 38
  • a supporting base such as paper, either alone or in combination with other photoconductive EXAMPLE 38
  • the zinc oxide paint thus prepared was then applied with a roller onto paper of 60 70g weight per square meter to which polyvinyl alcohol had been applied to the surface, and the product was dried with hot air.
  • the photosensitive paper thus obtained was colored in magenta color.
  • This colored photosensitive paper for electrophotography was electrostatically charged with a corona discharger to which 7KV was applied, exposed to light together with aphotographic manuscript, and treated with a liquid developer containing a pigment and a petroleum solvent to produce a positive figure.
  • the colored organic photoconductive substances of this invention are also characterized by producing different colors by being treated with different color developing agents. This fact is illustrated by the following examples.
  • EXAMPLE 39 The substance (1 mol) of the formula (1) was dissolved. in 3 liters of dried benzene to which 700 ml of dried pyridine was thenadded. The mixture was thoroughly mixed by stirring and maintained at 5C.
  • the reactive coupler (0.6 mol) of the formula (72) was dissolved in liters of dried benzene and 1.5 liters of dried dioxane. This solution was added in small increments to the former solution in such a way that the temperature did not rise above C. After the total volume had been added, the temperature was gradually raised up to 90 95C under agitation, after 2 hours allowed to cool and then poured into ice-cooled hydrochloric acid to make a slightly acid solution, when immediately the reaction product was precipitated. This was separated by filtration, thoroughly washed with water and dried.
  • the condensed solution (5g) thus prepared of the color developing colorless developer was dispersed in 1,000ml of a petroleum solvent, Isopar, to obtain the color developing colorless developer.
  • This developer exhibited magenta color when treated with dimethylparamine or diethylparamine, and yellow color when treated with diazonium salt.
  • EXAMPLE 40 The reaction product obtained in Example 21 (the substance before submitted to the color developing reaction) was dispersed as in Example 39 together with alkyd or rosin and 5g of the concentrated color developing agent for photographic developer thus prepared was dispersed in 1,000ml of Isoper to obtain a color developing colorless developer. This agent developed blue and red colors when treated with dimethyl and diethylparamines, respectively.
  • EXAMPLE 41 A commercial zinc oxide copying paper was charged and exposed, as in Example 36, and developed with the colorless developer obtained in Example 39, and then with the developer for color developing in the same manner as in Example 17 to obtain magenta-colored figures.
  • EXAMPLE 42 A mixture consisting of 50g of the colorless photoconductive substance obtained in Example 17 (the substance before submitted to the color developing reaction), 8g of styrene resin and 10g of methyl acrylate ester resin was dissolved in 40g of methyleth ylketone and 30g of dimethylformamide. The resulting mixture was applied to 15 18 pthickness to a high quality paper the surface of which had been processed with polyvinyl alcohol. The prepared photoconductive paper .was electrostatically charged with a corona discharger to which 7KV was applied, and then exposed to light.
  • EXAMPLE 43 v The color developing photoconductive substance (50g) obtained in Example 17 was mixed with 8g of polyvinyl butylate and 10g of acrylic acid-vinyl acetate (inthe association ratio 1 1), and was dissolved in a mixture of 140g of methylet hylketone and 130g of dimethylformamide. This was applied to 15 18p. thickness to a high quality paper the surface of which had been treated with oilyvinyl alcohol. The prepared photosensitive paper was electrostatically charged with a corona discharger, to which +7KV was applied, and exposed to light.
  • the color developing substance (10g) prepared from the substances of the formula (7) and of the formula (77) was dissolved in 30g of polyvinyl butylate and the mixture was dispersed for 8 hours with a ball mill to obtain a concentrated developer.
  • the 10g portion of the developer was dispersed in 2,000ml of lsopar, with which the above exposed paper was developed to obtain white figures.
  • the base of the photosensi tive paper was colored in magenta color and the figures in cyan.
  • the color developing organic photoconductive materials of this invention are especially suitable to developing or photosensitive materials.
  • the materials of this OH invention can be used not only alone, but in combina- I I tion with various known additives or other materials.
  • one or more pigments, dyestuffs, resins, l and and charge controllers, dispersers, fixers, sensitizers and desensitizers may be dispersed or dissolved in the materials of this invention.
  • N 01 What is claimed is: 1. A light transparent photoconductive material for f ff and use in electrophotography which is the reaction product obtained by condensing ⁇ C a.

Abstract

A light-transparent photoconductive material for use in electrophotography is the reaction product obtained by condensing A. AN ORGANIC PHOTOCONDUCTIVE COMPOUND CONTAINING AN AMINO AND/OR HYDROXYL GROUP AND B. A REACTIVE COLORED COMPOUND CONTAINING AN ACTIVE HALOGEN ATOM; OR BY CONDENSING A. AN ORGANIC PHOTOCONDUCTIVE COMPOUND CONTAINING AN ACTIVE HALOGEN ATOM AND B. A REACTIVE COLORED COMPOUND CONTAINING AN AMINO AND/OR HYDROXYL GROUP.

Description

Nagashima et al.
ORGANIC PHOTOCONDUCTIVE MATERIALS FORMED BY CONDENSING- PHOTOCONDUCTIVE AND DYESTUFF REACTANTS Inventors: Shinichiro Nagashima, Kaichi Tsuchiya, both of Tokyo, Japan Assignee: Canon Inc., Tokyo, Japan Filed: Dec. 29, 1969 App1.No.: 888,886
u.s. c1. ..96/l.5, 260/249.5, 260/249.6, 260/249.8
1m. Cl. ..G03g 5/04 Field Of Search ..8/8.1 E; 260/249.5, 249.6, 260/249.8; 296/15 I References Cited UNITED STATES PATENTS 3/1954 Scalera et 1. ..260/249 ]March 20, 1973 2,950,196 8/1960 Carroll et a1. ..96/100 3,054,795 9/ 1962 Staeuble et a1. ..260/249 3,060,180 10/ 1962 Staeuble et a1. 260/249 3,157,651 11/1964 Atkinson et a1. .260/248 1,663,474 3/ 1928 Ackermann ..8/1 E 3,261,826 7/1966 Andrew ..260/153 Primary Examiner-John C. Cooper, III
Attorney- McGlew and Toren ABSTRACT A light-transparent photoconductive material for use in electrophotography is the reaction product obtained by condensing a. an organic photoconductive compound containing an amino and/or hydroxyl group and b. a reactive colored compound containing an active halogen atom; or by condensing v a. an organic photoconductive compound containing an active halogen atom and b. a reactive colored compound containing an amino and/or hydroxyl'group.
3 Claims, No Drawings ORGANIC PHOTOCONDUCTIVE MATERIALS FORMED BY CONDENSING PHOTOCONDUCTIVE AND DYESTUFF REACTANTS FIELD OF INVENTION The present invention 'relates to novel colored or color developing organic photoconductive materials which are useful as developing or photosensitive materials in electrophotography or related techniques.
BACKGROUND INFORMATION AND PRIOR ART The present inventors, who have investigated the.
reproduction of multi-colored or naturally colored images as one of the aims in electrophotography, obtained good results when they used colored organic photoconductive materials as toner in the production of superimposed images.
For example, in the reproduction of naturally colored images on a panchromatically sensitized zinc oxide photoconductive layer, a negatively charged photoconductive layer is first exposed to the object through a red filter and then developed with a cyancolored toner.
The photoconductive layer is then again charged in a negative sense and exposed to the object through a green filter to obtain a negatively charged image which is subsequently developed with a magenta toner. Further, the photoconductive layer is charged negatively, exposed to the object through a blue filter andv developed with a yellow toner.
In this case, if the images toned in cyan color are electrically insulating, they are also charged at the second negative charging and the charged electricity will not disappear at the following exposure to green light so that the images produced by the magenta toner inevitably overlap the images in cyan. On the other hand, however, if the cyan-colored toner is electrically conducting, the cyan images are not at all charged during the second charging process so that, if the images produced by the second exposure with the green light overlap the blue images of the first exposure, the magenta toner will never be attached to the respective part. To overcome the difficulty, the toner has to exhibit photosensitivity in itself.
For obtaining satisfactory results it is, however, not sufficient that the toner possesses photosensitivity or photoconductivity. If the magenta toner and the yellow toner are not transparent to light, for example, the parts where the images of three colors superimpose each other will not show their mixed color (in other words, will not show blue color at the superimposition of cyan and magenta, not green color at the superimposition of cyan and yellow), but the color of the toner employed afterwards covers the color of the previously applied toner, so that the parts where cyan is superimposed by magenta and by yellow show magenta and ye]- low color, respectively.
In conclusion, the toners, in either dry or wet process of developing, must be of colored materials having photoconductivity and light transparency to reproduce naturally colored images by electrophotography.
Organic photoconductive materials colored with a coloring material and meeting the above requirements have previously been investigated. But the lot-to-lot variation of the coloring materials with respect to purity, solubility etc. often resulted in fluctuation in the quality of product, and therefore reproducible and continuous production of the developers was very difficult. It was also found that the coloring materials in the developed images becameblurred during storage and have a tendency to transfer to other matter.
The present inventors continued their effort to eliminate these defects and finally arrived at the present invention.
I SUMMARY OF INVENTION 'The object of this invention is to provide colored or color developing organic photoconductive materials which are transparent to light.
An other object of this invention is to provide colored or color developing organic photoconductive materials which do not show blurring and transfer of coloring materials and which can be reproducibly produced with constant color characteristics and which are not influenced by lot-to-lot variation of the contamination of impurities.
A further object of this invention is to provide colored or color developing organic photoconductive materials for use in photographic developing having favorable light transparency of which the electrical characteristics are suited especially to the reproduction of multi-colored or naturally colored images.
A further object of this invention is to provide a.
process for producing visible images by employing color developing organic photoconductive materials as materials for photographic developing and making them to react with a color developing auxiliary after the developing process.
An other further object of this inventionis to provide colored or color developing photosensitive materials for use in electrophotography which have a photosensitive layer containing colored or color developing or? ganic photoconductive materials.
The present invention can provide colored organic photoconductive materials for use in electrophotography by the reaction of organic photoconductive sub.- stances with reactive colored components. The reactive colored components refer to reactive coloring materials and reactive color developing components in general.
In other words, the present invention relates to a procedure for obtaining colored organic photoconductive materials for use in electrophotography by the reaction of organic photoconductive materials with reactive coloring materials, and also to a process for obtaining color developing organic photoconductive materials for use in electrophotography by the reaction of organic photoconductive substances with reactive color developing components.
. The colored or color developing organic photoconductive materials of this invention can be obtained by chemically combining an organic photoconductive substance having at least one amino or hydroxy group with a coloring or a color developing component having at least one active halogen atom.
Further the colored or color developing organic photoconductive materials of this invention can be obtained by chemically combining anorganic photoconductive substance having at least one active halogen atom with a coloring or a color developing component having at least one amino or hydroxyl group.
The resulting products of the chemical combination are not only photoconductive but also colored and light-transparent, and the colors on them are free from defects, e.g. they do not become blurred or transferred because the coloring materials are chemically combined, not in the same manner as in a usual dyeing, with the photoconductive substances, and the steadiness of color was maintained for every product owing to the constant ratio of combining molecules in the chemical combination.
When the color developing organic photoconductive I materials of this invention are employed as materials for photographic developing, they can either be reacted beforehand with a color developing auxiliary to develop coloration, or they are used as they are as materials for developing and are reacted, after developed, with the color developing auxiliary to develop coloration.
The colored or color developing organic photoconductive materials may be pulverized in a ball-mill, a roll-mill and an atomizer to use them as toner for use as dry or wet developing agent, or they may be used in combination with other colored substances or vehicle resins, in the case of which the vehicle resins include, for example, rosin and the derivatives thereof, styrene resin, alkyd resin, terpene resin, xylene resin, straight chain hydrocarbon resin, phenol resin, epoxy resin and acrylic resin. These toners may be used as developer for negatively charged images in single or in combination with carrier materials such as glass beads, iron powder and furs.
When the organic photoconductive materials are used as wet developing agent, the materials are dispersed in a carrier liquid. For the carrier liquid, an insulating liquid widely know as carrier liquid for a liquid developer, for example, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons such as pentane, hexane, gasoline, kerosene, mineral spirit, cyclohexane, carbon tetrachloride, perchloroethylene and naphtha and silicone oil waxes may be used and in aspecial case water may be used.
When the colored or color developing organic photoconductive materials of this invention are utilized as the photosensitive materials for use in electrophotography, binding resin or plasticizer is not required for the organic photoconductive materials having capability of forming films, but use of 30 100 percent by weight of a binding resin is desired for the photoconductive materials which do not have capability of forming films. In this case, a plasticizer may be added in the amount of 5 100 percent by weight, alone or in combination with an other photoconductive material, to further improve the quality of the coating films.
Binding resins referred to above include, for example, polystyrene resin, polyvinyl chloride, phenol resin, polyvinyl acetate, polyvinyl acetal, epoxy resin, xylene resin, alkyd resin, polycarbonate resin, acrylonitrile styrene resin.
As supports for the photosensitive materials may be used, for example, metallic plates of aluminum, copper, zinc and silver, papers treated so that solvents could not enter the interior, aluminum laminated paper, filmsof synthetic resins in which a plasticizer is contained, and supports the surfaces of which are coated with a metal, a metal oxide or a metal halide as glass, paper, polyethylene, polypropylene, polyethylene terephthalate, polystyrol, polyvinyl chloride, ethylcellulose, cellulose acetate, polyester films and other synthetic resin films. In general, they should have a surface resistance less than 10 ohms, preferably less than 10 ohms.
The films of the photosensitive layer can be formed on the' supports in a conventional manner such as, for example, by use of rolls, wire bars, or air knives.
Since the color developing organic photoconductive materials of this invention are generally colorless or lightly colored, they have many advantages over colored organic photoconductive materials when employed as materials for photographic developing or photosensitive materials.
The most predominant advantage of the materials of this invention as used for materials of photographic developing is as follows. In case of developing by way of superimposed multi-colored images as described before, for example, if an already colored material for developing is used, the coloration of the first developed image will act as filter in the subsequent exposures, thus significantly decreasing the apparent sensitivity. However, if a color developing organic photoconductive material which is colorless or lightly colored is used, the above described difficulty will be completely eliminated or at least minimized.
When these colorless or lightly colored materials are used for photosensitive materials, unfavorable effects on sensitivity to light and color could not be observed.
0n the other hand, in synthesizing photoconductive materials, the reaction-of a colored substance with an organic photoconductive compound should be carried out fairly slowly in order that the coloring substance be not decomposed nor faded in the course of reaction. The various conditions of reaction may, however, be freely selected, when a color developing component is used, because the component is usually of a lower molecular weight and more resistant to heat and light than the coloring substances.
The condensation reaction of the various active halogens and amines of this invention is preferably performed-in anhydrous media. The condensation reacplayed in the present invention include, for example, 12 the following:
-NHz I I NH: 5 \N (!]HCH2 HzN NH:
-OHCH \1 I A, NHZ HzN 1 l i) 8) 0 0H 0H, I I
l OH 1 (20) HzN-@C=CNH1 a m-e m 3 Q \g/ \N 5 7 mcocl (a1) w g N L H 10 a at N 7 Aw ---fi v" 'v-T- m l -Q a s 0001 (33) Br Br H 001 H5Cz \C2H6 l m, l L OH H N The reactive coloringmaterials or compounds having an active halogen atom or atoms, which may be em- (25) ployed in the presentinvention, include the following H10 CH1 substances:
H3O H:
N N /CH3 c1 J-NH- -c=1-z -N H N 5:0 0H; (26) /N\ 40 v l 3 01 N H3O \s 4s The photoconductlve substances havmg an actlve halogen atom or atoms include, for example, following 1 $1 substances: Cl-k J-NH-Q N C-N V I I I 0C] (28) v N H (2 I (as) 01 OH C 0 Cl 7 o v v (60) 1 CS1 OH 01 OH (as) H (51 W V v Cl0C-N=Nl(flJ-CH;
N01 01 0:2) N l CH F:
(6 I The reactive coloring materials having an amino or a hydroxy group or groups include, for example, the following substahces: 0H
K/] (59) 1 O 17H:
0 ONH- I N=NCOGl 4o 60) 5 111 I A AOOH 1 l coNI-I- CF K Q 1 5 I 4 NH: (61) H I v H,c0- N=N-o-c-Nm U54) I N0: a .H
i N: @0001 50 N -CO(|JHCONH NH: 1
(64) 0011: Cl J'NII-' -CII- NIICO- on, a
68 v H3O 0'N=NO H c1 1 (m) I ClCH C IhNI-ISOQNIICOCIIzCOOCHa (69) 0 1 1mm:
ClCH2CHz-NH-SO2 (is) I cicrncmmI socoNH p -cm I v I bl =0 40 l i l (),N VNQN ()H QC l I Examples of reactive color developing components (79) C1O2s having an active halogen atom or atoms, which are employed in the present invention include, for example, V OR the following substances: s
v C0NH(CH2)NHC0 N N c1 c1 LNHfi-C Iz The reactive color developingcomponents having an N amino or/and a hydroxyl group which are employed in thepresent invention include, for example, the following substances: c1
N v A 73) (I31 I H2(|3---l|'|J-NH2 o=c N A 11 I I Cl l NH 5 (81) 1121C fi-NHz COONH1. (83) I @COCHzCONH-QNH:
o=o /N The present invention will be illustrated below with reference to examples, but these examples do not restrict the invention.
Examplesof reactions of reactive coloring materials having an active halogen atom or atoms with organic v photoconductive substances having an amino or hydroxyl group or groups.
EXAMPLE 1 such a manner that the temperature did not rise above 5C. After the whole volume had been added, the resultant solution was stirred for 30 minutes, and to it a solution of 1.0 mol sodium carbonate in 500ml water was added at the same temperature. After stirred for 3.5 4 hours, the mixture was pouredinto a large amount of water to obtain a magenta-colored photoconductive coloring material. Recrystallization from dioxane gave magenta-colored crystals. Melting point: 245 248C.
- EXAMPLE 2 The substance (1.0 mol)'of the formula (4) was dismula (36) was dissolved in 3.0 liters of dried dioxane,
the same treatment as in Example 1 .was followed to obtain a solid yellow substance.
EXAMPLE 3 The substance (1.0 mol) of theformula (5) was dissolved in 3 liters of dried dioxane to which 700ml of dried acetone was added. The mixed solution was.
thoroughly mixed by stirring and kept at 0 5C. The substance (0.5 mol) of the formula (41) was dissolved in 3.0 liters of dioxane. Using the solutions, the same treatment as in Example 1 was followed to obtain a solid blue substance;
EXAMPLE 4 The substance (1.0 mol) of the formula (7) was dis- I solved in a mixture of 3 liters of. dried dioxane and 4 mol of triethylamine. On the other hand, the substance (1 mol) of the formula (49) was dissolved in 4.0 liters of o-dichlorobenzene. Using these solutions, the same treatment as in Example 1 was followed to obtain solid reddish orange matter.
EXAMPLE 5 The substance (1.0 mol) of the formula (1 l was dissolved in 3 liters of dried dioxane to which 700ml of dried acetone was added. The solution was thoroughly mixed by stirring and kept at 0 5C.'Next, the substance (0.5 mol) of the formula (43) was dissolved in 3.0 liters of dried dioxane. Using these solutions, the
same treatment as in Example 1 was followed to obtain a solid yellow substance.
EXAMPLE 6 The substance (1.0 mol) of the formula (21) was dissolved in 3 liters of monochlorobenzcne to which 300g cooled, the mixture was filtered and the filtrate wasevaporated to the half volume under reduced pressure. The remainder was added to methyl alcohol to obtain a red photoconductive substance. Recrystallization from a mixture of monochlorobenzene and dioxane gave a red photoconductive substance (m.p: 200C).
EXAMPLE 7 The substance (1.0 mol) of the formula (26) was dissolved in 4.0 liters of dioxane to which 320g of triethylamine was added. The mixture was cooled to -5C under agitation. On the other hand, the substance 1.0 mol) of the formula (58') was dissolved in 4.5 liters of dioxane. Using thesesolutions, the same treatment as in Example 6 was followed to obtain a yellowish red organic photoconductive substance.
Examples of reactions of an organic photoc onductive substance having an active halogen atom or atoms with a reactive coloring material having an amino or a hydroxyl group of groups.
EXAMPLE 8 The substance (1.0 mol) of the formula (59) was dissolved in a mixture of 3.0 liters of monochlorobenzene and 4.0 liters of pyridine. While the solution being stirred at 0 5C, 1.0 mol of the substance'of-the for mula (27) was added. Then the stirring was continued at the elevated temperature 90 95C for 90 minutes to complete the reaction. The whole mixture was then poured into iced hydrochloric acid when a purple solid was separated. After separated by filtration, the solid matter was washed thoroughly with water and dried. Recrystallization from monochlorobenzene gave violet photoconductive powders with the yield 62 65 percent.
EXAMPLE 9 The substance (1.0 mol) of the formula (34) was dissolved in 3 liters of dried dioxane to which 700ml of dried acetone was added. The solution was thoroughly mixed by stirring and kept at 5C. 0n the other hand, the substance (1.0 mol) of the formula (61) was dissolved in 3.0 liters of dioxane. Using these solutions, the same treatment as in Example 1 was followed to obtain an orange photoconductivesubstance.
EXAMPLE EXAMPLE 1 l The substance (1.0 mol) of the formula (34) was reacted with the substance (1.0 mol) of the formula (67) in the same manner as in Example 10 to obtain an orange photoconductive substance.
Examples will be shown below in which the colored organic photoconductive materials of the present invention are used as developing materials for electrophotography.
EXAMPLE 12 The chemically bound colored substances described in Examples 1 through 11 were pulverized into powders of 5p. diameter in average with an atomizer and l 10g, preferably 2 5g, of the powders were mixed thoroughly with 100g of magnetic iron powders (as carrier) of 100 150 mesh in the average diameter of particles. The mixture was adsorbed on a bar magnet to be used as amagnetic brush, with which several time scanning on electrostatic figures produced visible images. The images, when treated by the known process of fixation, were converted into permanent ones.
EXAMPLE 13 The chemically bound colored substances (10g) described in Examples 1 through 11 were dispersed with a ball mill in 100ml of insulating liquid such as .herosene and mineral spirit, and 10ml of it was again visible figures, when applied in an appropriate manner such as dipping, rolling or spraying.
EXAMPLE 14 A photosensitive paper for electrophotography prepared by use of zinc oxide and acrylicresin was charged with a corona discharger with the applied voltage 7KV. Then the paper was exposed to a colored figure through a red filter. The electric charge remains on the paper only in the shape of figure which should be colored in blue. The charged figure was developed with the developer for blue color (the liquid photographic developer obtained in Example 3 prepared by adding 1.5 2.0g. of a blue substance in ml of a petroleuin solvent and by dispersing with a ball mill for 15 20 hours) and was fixed. After being dried, the paper was again charged with electricity, exposed to a colored figure through a green filter and developed with a developer for magenta color (prepared in the same manner as above using the toner obtained in Example by which process the only part that was sensitive tothe magenta developer appeared in color by the developing. After the figure was fixed, the paper was again electrostatically charged, exposed through a blue filter and developed in the same manner (with a similar developer using the toner prepared in Example 2), by which process the only part that was sensitive to the photographic developer for yellow color appeared. The composite figure: thus obtained almost perfectly reproduced the original figure.
The colored organic-photoconductive materials of this invention is employed not only as a toner as above in both wet and dry processes, but also as a suitable developing material to be used for the photoelectrophoretic imaging process. This process employs photoconductive pigment as toner in place of a socalled light sensitive layer made of a photoconductor.
The following example illustrates the case in which the colored organic photoconductive materials of this invention was employed as developer for figure formation in the photoelectrophoretic imaging process.
EXAMPLE 15 To a petroleum solvent lsopar-H (commercial name) 12 15 percent by weight of the substance obtained in Example 1 was added and the mixture was treated with a ball mill for 4 5 days to make a dispersoid of micro particles. This was applied on a light transparent electrode in a. thin layer on which was placed an insulating paper and further on it another electrode. While a DC voltage 700V was being applied between the two electrodes, the paper was exposed to a light image through the transparent electrode. A colored image appeared on the surface of the insulating paper and a negative mirror image on the surface of transparent electrode.
The colored organic photoconductive materials of this invention can also be effectively employed as a component of the photosensitive layer for electrophotography. V
Recently, colored copy papers are often used for duplicate purpose in offices dependently on the use or content of the duplicates. Since the colored organic photoconductive materials of this invention exhibit photoconductivity for themselves, they can be em- EXAMPLE 16 To 10 parts of the colored organic photoconductive substance obtained in Example 1 were added 80 parts of dioxane, 60 parts of dimethylformamide, and 30 parts of methylcellosolve and further 28 parts of zinc oxide, and the whole mixture was treated for 4.0 4.5
hours with a ball mill to make a dispersoid.
n base papers of 60 70g weight per square meter which had been treated with polyvinyl alcohol, the zinc oxide paint above was applied with a roll and dried by hot air. The photosensitivepapers thus prepared are colored magenta. The colored photosensitive paper for electrophotography prepared in this way was electrostatically charged with a corona discharger to which -7KV was applied. Subsequently the paper was exposed to light together with the original figure and by the liquid developing process using pigment-petroleum solvent a positive image was produced.
The colored organic photoconductive materials of this invention are especially suited, as the above examples show, to be used for photographic developer and photosensitive materials. In these cases, the materials of this invention can be naturally used not only alone but also in combination with various known additives or other materials. For example, one or more members selected from the group consisting of pigments, dyestuffs, resins, electrostatic charge controllers, dispersing agents and fixers may be dispersed or dissolved in the materials of this invention.
In the next place, examples of the reactions of organic photoconductive substance containing amino or hydroxyl group or groups with reactive color developing components containing active halogen atom or atoms will be shown.
EXAMPLE 17 To the substance (1.0 mol) of the formula (1) were added 3.0 liters of dioxane, 0.3 liter of methylene chloride and further 0.6 mol of a reactive coupler dissolved in 2.0 liters of dioxane. While the mixture being stirred at 10 15C, 2 mols of sodium carbonate dissolved in 300ml of water was added at the same temperature. After stirring was continued for 5 6 hours, the mixture was poured into a large amount of water, when white crystals were precipitated which were then separated by filtration and washed with water. To the alcoholic alkali solution of the crystals, 50ml of a 2percent solution of potassium ferricyanide and then 55ml of a 3 percent solution of dimethylparamine were added to obtain a magentacolored matter. Filtration, thorough washing with water, and drying gave a photoconductive coloring material.
EXAMPLE 18 Example 17 was separated by filtration, washed with water, and dissolved in an alcoholic alkali solution to which solution was added a diazonium salt of aniline to obtain a yellow organic photoconductive coloring material.
EXAMPLE 19 The substance (1 mol) of the formula (4) was dissolved in a mixture consisting of 2.4 liters of dried benzene, 700ml of dried methylene chloride and dried pyridine. On the other hand, the substance (0.5 mol) of the formula (73) was dissolved in a mixture consisting of 1.5 liters of dried dioxane and 1.5 liters of dried benzene. Using these solutions, the treatment was followed as in Example 17 to obtain the reaction product,
which was then treated in the same manner as in Example 18 to give a red organic photoconductive coloring material.
' EXAMPLE 20 The substance (1.0 mol) of the formula (5) was dissolved in a mixture consisting of 3 liters of dried toluene and 4 mols of triethylamine, and on the other hand the substance (0.5 mol) of the formula (78) was dissolved in a mixture consisting of 2.5 liters of dioxane and 800ml of benzene. The latter solution was added to the former while the temperature was maintained at 0 5C. Subsequently the temperature was raised to C where the reaction was continued for 2 hours. The mixture was added to an ice-cooled hydrochloric acid and the precipitate formed was filtered,
thoroughly washed with water and purified by recrystallization from dioxane. Further color developing reaction as in Example 17 produced a magentacolored photoconductive coloring material.
EXAMPLE 21 The substance (1 mol) of the formula (7) was dissolved in a mixture consisting of 3 liters of dried dioxane and 4 mols of triethylamine, and on the other hand the substance (1 mol) of the formula (77) was dissolved in 4.0 liters of o-dichlorobenzene. Using the two solutions above the treatment was followed as in Example 20 and further the same color developing reaction as in Example 17 was conducted to obtain a blue photoconductive coloring material.
EXAMPLE 22 EXAMPLE 23 The substance (1 mol) of the formula (13) was dissolved in a mixture consisting of 500ml of dried ether, 2.5 liters of dried dioxane and 4 mols of dried triethylamine and, on the other hand, the substance (1 EXAMPLE 24 To a solution of the substance (1.0 mol) of the formula (21) in 3.0 liters of chlorobenzene and further 310g of triethylamine maintained at C, the substance (l.0 mol) of the formula (77) dissolved in 2.5
liters of dioxane was added under stirring at the same temperature 0' 5C. The same treatment as in ,.Example 20 produced white powders which afforded a blue material when treated by the color developing reaction with diethylparamine as in Example 17 and a red material when treated with a diazonium salt of aniline.
EXAMPLE 25 To a solution of the substance (1.0 mol) of the formula (26) in 4.0 liters of dioxane and 320g of triethylamine cooled at 0 5C, a solution of the substance mol) of the formula (76) in 2.5 liters of dioxane was added and the mixture was treated as in Example to obtain white powders of the melting point 210 212C. The powders developed yellow coloration when treated with either color developing agent of diethylparamine or diazonium salt.
The following examples show reactions of organic photoconductive substances containing active halogen atom or atoms with reactive color developing components containing amino or hydroxyl group or groups.
EXAMPLE 26 To a solution of the substance (1.0 mol) of the formula (80) in 3.0 liters of monochlorobenzene and 3.5 liters of dioxane, 350g of triethylamine was added under agitation and the mixture was cooled to 0 5C.
, Subsequent addition of the substance (1.0 mol) of the EXAMPLE 27 To a solution of the substance (1.0 mol) of the formula (83) in 4.0 liters of dioxane, 320g of triethylamine was added. This was treated with the substance (1.0 mol) of the formula (32) in the same manner as in Example 26 gave white powders. The color developing reaction of the powders as in Example 17 afforded a photoconductive coloring material.
EXAMPLE 28 The substance (1.0 mol) of the formula (85) was dissolved in 5.0 liters of dioxane and 320g of triethylamine and cooled to 0 5C. The substance (1.0 mol) of the formula (32) was added to it under agitation, and the mixture was treated as in Example 26 to give white powders. The color developing reaction with diethylparamine produced yellow coloration.
EXAMPLE 29 To a solution of the substance (1.0 mol) of the formula (84) in 5.0 liters of dioxane, 320g of triethylamine was added and the mixture was cooled at 0 5C. Addition to it of the substance (1.0 mol) of the formula (32) under agitation and the same treatment as in Example 26 produced white powders. The color developing reaction with diethylparamine and a diazonium salt of aniline exhibited magenta and yellow coloration, respectively.
Examples will be shown below in which the color developing organic photoconductive materials of this invention were employed as developing materials for electrophotography.
EXAMPLE 30 The intermediate obtained prior to the color developing treatment described in Example 17, that is the reaction product of the substances of the formulas (I) and (72), was thoroughly washed with water and dried. The 5g portion of it was dispersed in 1,000ml of a petroleum solvent (trade mark: Isopar) by treating with a ball mill for 5 hours, to prepare a developing solution. On the other hand, a photosensitive paper for electrophotography, which was prepared from zinc oxide and acrylic resin, was electrostatically charged with a corona discharger to which 7KV was applied, and this was exposed to light. The developing treatment with the above developer produced colorless figures at the charged parts. The paper was soaked in a color developing solution as in Example 17, when magentacolored visible figures appeared. Alternatively, the colorless figures formed on the zinc oxide paper were transferred under pressure to a copying paper which had a slightly adhesive surface.- The same color developing reaction as before produced magentacolored visible figures.
EXAMPLE 31 The substance obtained prior to the color developing reaction in Example 21 was dispersed in Isopar in the same manner as in Example 30. Following the procedure in Example 30 colorless figures were formed on a zinc oxide paper, which were treated-with a color developing agent either directly or after transferred to a copying paper as in Example 30 to form visible figures in which figures were colored blue.
EXAMPLE 32 The substance obtained prior to the color developing reaction in Example 23 was dispersed in Isopar in the same manner as in Example 30. Following the procedure in Example 30, colorless figures were formed on a zinc oxide paper, which were treated with a color developing agent either directly or after transferred to a copying paper as in Example 30 to form visible figures in which figures were colored yellow.
EXAMPLE 33 A photosensitive paper for electrophotography prepared from zinc oxide and acrylic resin was electrostatically charged with a corona discharger to which -7K\ was applied. This paper was exposed to an original colored manuscript through a red filter when the electrical charge remains on the paper at those parts of the figures which should be colored blue. These parts were developed with the colorless developer described in Example 31 and the colorless figures were transferred, as in Example 30, by the electrostatic method to a copying paper having a slightly adhesive surface. Then the zinc oxide paper was exposed in the same way through a green filter, treated with a colorless developer described in Example 30 and the colorless figures were transferred to the same copying paper as above. Finally the zinc oxide paper was exposed through a blue filter, developed with the colorless developer described in Example 32 when only those parts of the figures which should be colored yellow were developed. These figures were similarly transferred to the above copying paper. Thus, the figures which should be colored blue, red and yellow were superimposedly obtained on a single paper. By the color developing reaction with dimethylparamine as conducted in Example 17, the figures were colored blue, red and yellow corresponding to the above treatments, giving the same colored figures as in the original manuscript.
EXAMPLE 34 I The chemically combined colored substances appearing in Example 17 through 29 were separately pulverized with an atomizer into particles of the average diameter 5 of which 1 lg, preferably 2 5g, was thoroughly mixed with 100g of magnetic iron powder (as carrier) of the average particle diameter 100- 150 mesh. The mixture was adsorbed on a bar magnet to be used as a magnetic brush. The electrostatically charged figures were converted into colored visible figures, when scanned above them several times with the brush. The colored figures could be made permanent figures by treating the known method of developing.
EXAMPLE 35 EXAMPLE 36 A photosensitive paper for electrophotography prepared from zinc oxide and acrylic resin was electrostatically charged with a corona discharger to which 7KV was applied. This paper was exposed to an original colored manuscript through a red filter, when the charge on the paper remains only at those parts of the figures which should be colored blue. These parts prepared by dispersing a mixture of ml of a petroleum solvent and 1.5 2.0g of the toner with a ball mill for 15 20 hours) and fixed. The paper, after being dried, was again charged, exposed-through a green filter and treated with the magenta developing solution (prepared as above from the toner obtained in Example 17) when only those parts were developed which were sensitive to the magenta developer. After fixing, the paper was again charged, exposed through a blue filter and treated with the developer (prepared as above from the toner obtained in Example 23) when only those parts were developed into figures which were sensitive to the yellow developer. The copied figures thus obtained almost reproduced the original manuscript.
The colored organic photoconductive materials of the present invention are not only used as toner materials in both dry and wet processes, but also suitable to the developing materials for figure formation in electrophoresis. The present method employs a photoconductive pigment as toner instead of using a so-called photoconductive photosensitive layer.
The materials of this invention exhibit very excellent quality when used for the photoelectrophoretic imag- EXAMPLE 37 The substance obtained in Example 17 was added to a petroleum solvent, Isopar-l-l (commercial name), in the amount of 12- l5percent by weight and dispersed by treating-with a ball mill for 4 5 days to make a microdispersoid. This was applied on a light ti'ansparent electrode in a thin layer and an insulating paper was placed on it and then another electrode further on them. They were exposed to a light image while a DC voltage, 700V, was being applied between the two electrodes. A colored image which corresponded to the light image was obtained on the insulating paper and a negative mirror image on the surface of the transparent electrode. v
The colordeveloping organic photoconductive materials of this invention can also be used effectively for a component of the photosensitive layer for elec tropho tography.
Recently colored copying papers are often preferred in offices to classify the copies more easily depending on use and purpose of the copies. Since the color developing photoconductive materials of this invention are photoconductive by themselves, they can be employed to make copying papers for electrophotography when applied on a supporting base such as paper, either alone or in combination with other photoconductive EXAMPLE 38 To 10 parts of the color developing organic photoconductive substance obtained in Example 17, 5 parts of copolymerized resin of styrene and butadiene, 80 parts of dioxane, 60 parts of dimethylformamide, 30 parts of methylcellosolve and 28 parts of zinc oxide were added. The mixture was treated with a ball mill for 4.0 4.5 hours. The zinc oxide paint thus prepared was then applied with a roller onto paper of 60 70g weight per square meter to which polyvinyl alcohol had been applied to the surface, and the product was dried with hot air. The photosensitive paper thus obtained was colored in magenta color. This colored photosensitive paper for electrophotography was electrostatically charged with a corona discharger to which 7KV was applied, exposed to light together with aphotographic manuscript, and treated with a liquid developer containing a pigment and a petroleum solvent to produce a positive figure.
The colored organic photoconductive substances of this invention are also characterized by producing different colors by being treated with different color developing agents. This fact is illustrated by the following examples.
EXAMPLE 39 The substance (1 mol) of the formula (1) was dissolved. in 3 liters of dried benzene to which 700 ml of dried pyridine was thenadded. The mixture was thoroughly mixed by stirring and maintained at 5C. On the other hand, the reactive coupler (0.6 mol) of the formula (72) was dissolved in liters of dried benzene and 1.5 liters of dried dioxane. This solution was added in small increments to the former solution in such a way that the temperature did not rise above C. After the total volume had been added, the temperature was gradually raised up to 90 95C under agitation, after 2 hours allowed to cool and then poured into ice-cooled hydrochloric acid to make a slightly acid solution, when immediately the reaction product was precipitated. This was separated by filtration, thoroughly washed with water and dried.
A mixture consisting of 5 g of the above product, 0.5g of linseed oil denatured alkyd resin, 0.5g of phenol denatured rosin and 10g of toluene was dispersed with a ball mill for 8 hours. The condensed solution (5g) thus prepared of the color developing colorless developer was dispersed in 1,000ml of a petroleum solvent, Isopar, to obtain the color developing colorless developer. This developer exhibited magenta color when treated with dimethylparamine or diethylparamine, and yellow color when treated with diazonium salt.
EXAMPLE 40 The reaction product obtained in Example 21 (the substance before submitted to the color developing reaction) was dispersed as in Example 39 together with alkyd or rosin and 5g of the concentrated color developing agent for photographic developer thus prepared was dispersed in 1,000ml of Isoper to obtain a color developing colorless developer. This agent developed blue and red colors when treated with dimethyl and diethylparamines, respectively.
EXAMPLE 41 A commercial zinc oxide copying paper was charged and exposed, as in Example 36, and developed with the colorless developer obtained in Example 39, and then with the developer for color developing in the same manner as in Example 17 to obtain magenta-colored figures.
EXAMPLE 42 A mixture consisting of 50g of the colorless photoconductive substance obtained in Example 17 (the substance before submitted to the color developing reaction), 8g of styrene resin and 10g of methyl acrylate ester resin was dissolved in 40g of methyleth ylketone and 30g of dimethylformamide. The resulting mixture was applied to 15 18 pthickness to a high quality paper the surface of which had been processed with polyvinyl alcohol. The prepared photoconductive paper .was electrostatically charged with a corona discharger to which 7KV was applied, and then exposed to light. On the other hand, 10g of titanium oxide and 20g of styrene resin was added to 50g of xylene and the mixture was dispersed for 8 hours with a ball mill, from which the resulting concentrated developing agent (10g) was dispersed in 2,000ml of Isopar as carrier. The white developer thus prepared was used to develop the above exposed photosensitive paper to obtain white figures. After complete melting of styrene resin and fixing, the color developing reaction was conducted as in Example 17 to develop magenta-colored figures in addition to white figures.
EXAMPLE 43 v The color developing photoconductive substance (50g) obtained in Example 17 was mixed with 8g of polyvinyl butylate and 10g of acrylic acid-vinyl acetate (inthe association ratio 1 1), and was dissolved in a mixture of 140g of methylet hylketone and 130g of dimethylformamide. This was applied to 15 18p. thickness to a high quality paper the surface of which had been treated with oilyvinyl alcohol. The prepared photosensitive paper was electrostatically charged with a corona discharger, to which +7KV was applied, and exposed to light. The color developing substance (10g) prepared from the substances of the formula (7) and of the formula (77) was dissolved in 30g of polyvinyl butylate and the mixture was dispersed for 8 hours with a ball mill to obtain a concentrated developer. The 10g portion of the developer was dispersed in 2,000ml of lsopar, with which the above exposed paper was developed to obtain white figures. By being heated to 60 C and treated to develop colors in the same manner as in Example 17, the base of the photosensi tive paper was colored in magenta color and the figures in cyan.
As is evident in the above examples, the color developing organic photoconductive materials of this invention are especially suitable to developing or photosensitive materials. Naturally the materials of this OH invention can be used not only alone, but in combina- I I tion with various known additives or other materials. For example, one or more pigments, dyestuffs, resins, l and and charge controllers, dispersers, fixers, sensitizers and desensitizers may be dispersed or dissolved in the materials of this invention. N 01 What is claimed is: 1. A light transparent photoconductive material for f ff and use in electrophotography which is the reaction product obtained by condensing \C a. an organic photoconductive compound selected 1 from the group consisting of photoconductive polycyclic aromatic compounds having an amino 1 5 t i substituent, and photoconductive pol c li b. a reactive colored compound containing an active matic compounds having a hydroxyl substituent, halogel] atom and bemg Selected from the group and consisting of b. a colored substance selected from the group consisting of compounds 35-44 of the specification. Cl 2. A light-transparent photoconductive material for use in electrophotography which is the reaction product obtained by condensing v T /0 Ha a. an organic photoconductive polycyclic aromatic 4 01k )NHC-C=N-N compound containing an amino and/or hydroxyl N l; 4 group and being selected from the group consisting of:
N=N-C Cl-K J-NH N= Q N NH: Q Q l A HZN \N Cl-L J-NH i 1 IN /CH! 01% )NH -so,NII-0c=N@-N N l l N 0:0 on,
and
01 NH I I (\N (EH:
3. A material as claimed in claim 2, wherein compound (a) is the compound of formula (1) of the specification while compound (b) is the compound of formula (35 )ofthe specification.
l I I

Claims (2)

  1. 2. A light-transparent photoconductive material for use in electrophotography which is the reaction product obtained by condensing a. an organic photoconductive polycyclic aromatic compound containing an amino and/or hydroxyl group and being selected from the group consisting of:
  2. 3. A material as claimed in claim 2, wherein compound (a) is the compound of formula (1) of the specification while compound (b) is the compound of formula (35) of the specification.
US00888886A 1969-12-29 1969-12-29 Organic photoconductive materials formed by condensing photoconductive and dyestuff reactants Expired - Lifetime US3721554A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US88888669A 1969-12-29 1969-12-29

Publications (1)

Publication Number Publication Date
US3721554A true US3721554A (en) 1973-03-20

Family

ID=25394104

Family Applications (1)

Application Number Title Priority Date Filing Date
US00888886A Expired - Lifetime US3721554A (en) 1969-12-29 1969-12-29 Organic photoconductive materials formed by condensing photoconductive and dyestuff reactants

Country Status (1)

Country Link
US (1) US3721554A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4165985A (en) * 1978-05-24 1979-08-28 Eastman Kodak Company Electrophotosensitive materials for migration imaging processes
US4251609A (en) * 1979-04-09 1981-02-17 Eastman Kodak Company Isoquinolinedione photoelectrophoretic materials for imaging processes
US4503224A (en) * 1979-07-07 1985-03-05 Bayer Aktiengesellschaft Halogenotriazinyl dyestuffs
US20060106074A1 (en) * 2001-11-28 2006-05-18 Peter Bernstein Er-b-selective ligands

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4165985A (en) * 1978-05-24 1979-08-28 Eastman Kodak Company Electrophotosensitive materials for migration imaging processes
US4251609A (en) * 1979-04-09 1981-02-17 Eastman Kodak Company Isoquinolinedione photoelectrophoretic materials for imaging processes
US4503224A (en) * 1979-07-07 1985-03-05 Bayer Aktiengesellschaft Halogenotriazinyl dyestuffs
US20060106074A1 (en) * 2001-11-28 2006-05-18 Peter Bernstein Er-b-selective ligands

Similar Documents

Publication Publication Date Title
US4012376A (en) Photosensitive colorant materials
US3852208A (en) Photoconductive toner composition
GB2084605A (en) Phthalocyanine pigments
US4146707A (en) Heterocyclic ethenyl or vinyl heterocyclic or aromatic compounds for migration imaging processes
US4175956A (en) Electrophotosensitive materials for migration imaging processes
US3933664A (en) Organic photoconductive toner materials
US3844781A (en) Organic photoconductive materials
US3890146A (en) Organic photoconductive materials derived from reacting a photoconductive compound with a color compound
US4238562A (en) Light transmission particle for forming color image
US4191566A (en) Electrophotographic imaging process using anthraquinoid black pigments or metal complexes
US4197120A (en) Electrophoretic migration imaging process
US3721554A (en) Organic photoconductive materials formed by condensing photoconductive and dyestuff reactants
US5273853A (en) Black photoconductive toner having sensitivity to light in the wavelength range of semiconductor lasers
JPS6045253A (en) Photosensitive electrophotographic plate containing squaric acid methine dye dispersing in binder
JPS5921022B2 (en) print version
US3509146A (en) Process of preparing phthalocyanine and heterocyclic analogues
DE2717007C2 (en)
US4282354A (en) Electrophoretic migration imaging process
US3567438A (en) Organic photoconductors sensitized with pyrylium cyanine dyes
US4142890A (en) Photosensitive trans-epindolidione pigment for migration imaging processes
US4331751A (en) Electrically photosensitive materials and elements for photoelectrophoretic imaging processes
US3951654A (en) Method for enhancement in the rate and efficiency of photodischarge of electrostatographic imaging members comprising phthalocyanine
US4017311A (en) Photoelectrophoretic imaging suspension
US3867141A (en) Photoelectric and electrophotographic pigments comprising derivatives of condensed polycyclic aromatic hydrocarbon aldehydes
US3865587A (en) Electrophographic bichargeable materials and process