US3691105A - Compositions for electrosensitive recording material - Google Patents

Compositions for electrosensitive recording material Download PDF

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Publication number
US3691105A
US3691105A US82855A US8585570A US3691105A US 3691105 A US3691105 A US 3691105A US 82855 A US82855 A US 82855A US 8585570 A US8585570 A US 8585570A US 3691105 A US3691105 A US 3691105A
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US
United States
Prior art keywords
composition
metal
zinc oxide
doped
oxide
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
US82855A
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English (en)
Inventor
Kiyoshi Juna
Noboru Shinada
Masuo Tsuchiya
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Individual
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Individual
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Filing date
Publication date
Priority claimed from JP45039691A external-priority patent/JPS4920099B1/ja
Priority claimed from JP45055947A external-priority patent/JPS4920100B1/ja
Priority claimed from JP45074947A external-priority patent/JPS4920230B1/ja
Application filed by Individual filed Critical Individual
Application granted granted Critical
Publication of US3691105A publication Critical patent/US3691105A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/087—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and being incorporated in an organic bonding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/20—Duplicating or marking methods; Sheet materials for use therein using electric current
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors

Definitions

  • ABSTRACT Compositions for electrosensitive recording material used as recording paper for facsimiles etc. comprise zinc oxide doped with trivalent or tetravalent metal elements and a binder.
  • compositions for an electrosensitive recording material and more particularly to electrosensitive recording material comprising binder and zinc oxide doped with a doner impurity element and, if necessary, metallic soap of fatty acid.
  • compositions to which electric conductivity has been bestowed by adding a conductive material as electrosensitive recording materials.
  • Metals, carbon black or graphite, or electrolytes such as metal chlorides have been used as such additives.
  • these have numerous defects such as being economically disadvantageous when a metal is used; a recording which has sufficient contrast cannot be obtained because the coated film is colored grey when carbon black or graphite is used; and the base material of the electrosensitive recording material is eroded when electrolytes such as metal chlorides are used.
  • the previous electrosensitive recording material had the defect of requiring a higher voltage, for example from to volts, in order to obtain a recording which has sufficient contrast.
  • the object of this invention is to eliminate such defects and provide compositions for electrosensitive recording materials which can respond to recording signals at a lower voltage and faster than the previous electrosensitive recording material, and also by a dry method.
  • This invention relates to the compositions of electrosensitive recording material whose chief components are zinc oxide doped with a donor impurity element and a binder, and, if necessary, a metallic soap of fatty acid.
  • the impurity metal is doped to zinc oxide and made semiconductive.
  • Metals used for this invention are elements which have a higher valence than the valence of zinc the form of zinc oxide and generally, these are trivalent or tetravalent metallic elements and are doped to zinc oxide by heat energy.
  • Elements which are to be doped to zinc oxide must have ionic radius which is smaller than the ionic radius of zinc (0.74A). Calcining with a higher temperature for a longer time is necessary for doping an element having larger ionic radius than that of zinc, and sintering takes place during calcination.
  • Metallic ions which satisfy such condition are trivalent metallic ions such as Co (ionic radius 0.65A,), Ga (0.62A), Al (0.50A), Fe (0.60A) and Cr (0.64A), and tetravalent metallic ions such as Si (0.41A), Ge(0.53A), Ti (0.68A) and Sn (0.71A), and normally, it is preferable to use transition elements.
  • the quantity to be doped to zinc oxide is a range of from 0.005 to 10.0 percent by mole.
  • the specified quantity of zinc oxide and compound of element having an ionic radius smaller than the ionic radius of zinc are mixed and blended,
  • the semiconductive zinc oxide obtained in this invention is dispersed into the binder in a range of from 150 to 1,000 per hundred resin (hereinafter referred in simply as Pl-IR), preferably from 250 to 800 PHR.
  • Pl-IR a range of from 150 to 1,000 per hundred resin
  • Pl-IR preferably from 250 to 800 PHR.
  • the addition and dispersion concentration is less than 150 PHR, the hiding power of the compositions becomes very low.
  • the concentration is more than 100 PHR, the dry film obtained from coating said compositions is markedly brittle and has lower adhesive property.
  • the binder may be one or more resins selected from urea resin (urea-alkyd resin), alkyd resin (oil-free, modified drying 'oil or modified semi-drying oil), melamine resin (melamine-alkyd resin), polyurethane vinyl resin (vinyl chloride-vinyl acetate copolymer), epoxy resin, nitrocellulose lacquer, acryl lacquer and acryl resin.
  • urea resin urea-alkyd resin
  • alkyd resin oil-free, modified drying 'oil or modified semi-drying oil
  • melamine resin melamine-alkyd resin
  • polyurethane vinyl resin vinyl chloride-vinyl acetate copolymer
  • epoxy resin nitrocellulose lacquer
  • acryl lacquer acryl lacquer and acryl resin.
  • a suitable resin selected from the binders abovementioned is dissolved in a suitable organic solvent or mixture thereof to obtain the resin solution, the semiconductive zinc oxide in dispersed into the resin solution with a pebble mill or sand grinder, and then a suitable organic solvent is added for diluting to a viscosity which is suitable for coating on the base material.
  • the quantity of said soap used is a range of from 5 to PHR, preferably from 10 to 60 PHR.
  • the quantity is smaller than 5 PER, it is necessary to apply high voltage, and the dry film obtained is rough and has poor flexibility.
  • the quantity is larger than 80 Pl-lR, it is also necessary to apply high voltage, and the adhesion of the dry film obtained is poor.
  • EXAMPLE 1 500 g of zinc oxide doped with aluminum (1.0 mole as aluminum oxide), 40 g of Versamid No. 100 (polyamide resin manufactured by General Mills C0.), 150 g of isopropyl alcohol and 150 g of toluene were charged into a pebble mill and dispersed for 20 hours. Then the mixture was removed from the ball mill, and 60 g of Epon No. 1004 (epoxy resin manufactured by Shell Chemical Co.) and 40 g of methyl ethyl ketone were mixed to prepare the composition. This composition was coated with a bar coater to a dry film thickness of about 10 microns on a conductive material laminated and vapor-deposited with tin. In two cases, 8 volts were applied while moving said coated material, and a mark having favorable contrast was obtained.
  • Epon No. 1004 epoxy resin manufactured by Shell Chemical Co.
  • EXAMPLE2-9 Materials with compositions indicated in the following table were coated in a similar manner as in Example 1 on a conductive material laminated with aluminum. Each 500 g of zinc oxide was doped with each of the following donor impurities.
  • Example Semiconductive No. Zinc Oxide (PHR) Voltage (V) EXAMPLE 11 500 g of zinc oxide doped with iron (0.8 mole as iron oxide), 70 g of Epon No. 1007 and 50 g of methyl ethyl ketone were charged into a pebble mill and dispersed for hours. Then the mixture was removed from the ball mill; and 30 g of Versamid No. 100, 150 g of isopropyl alcohol and 150 g of toluene were added to prepare the composition.
  • This composition was coated with a bar coater to a dry film thickness of about 10 microns a conductive material laminated with aluminum. 8 volts were applied while moving said coated material and a mark having favorable contrast was obtained.
  • EXAMPLE 12- 19 Materials with compositions indicated below were coated in a similar manner as in Example 1 1 a conductive material laminated with zinc.
  • thermosetu'ng acrylic resin manufactured by Hitachi Chemical Co., Japan.
  • EXAMPLE 20 500 g of zinc oxide doped with titanium (0.05 mole as TiO g of Lustrasol A-809 (Acryl resin manufactured by Japan Reichhold C0.), g of butyl acetate and 70 g of toluene were charged into a pebble mill and dispersed for 20 hours, 10 g of aluminum oleate was added and mixed for 1 hour more, then the mixture was removed from the ball mill and a quantity of polyisocyanate, for example XDI (xylene diisocyanate) which is equivalent to the hydroxyl value of Lustrasol A-809 was added to prepare the composition.
  • TiO g of Lustrasol A-809 Acryl resin manufactured by Japan Reichhold C0.
  • This composition was coated with a bar coater to a dry film thickness of about 10 microns on a conductive material laminated with aluminum. 6.5 volts was applied while moving said coated material, and a mark having favorable contrast was obtained.
  • EXAMPLE 21 A composition was prepared by the same procedure as Example using 40 g of zinc stearate in place of aluminum oleate as the metal soap of fatty acid and 5 volts was applied through the film formed on the aluminum layer by the same method. A record having favorable contrast was obtained.
  • EXAMPLE 22 A composition was prepared by the same procedure as Example 20 using 60 g of copper palrnitate in place of aluminum oleate as the metal soap of fatty acid and 6 volts was applied through the film formed on the aluminum layer by the same method. A record having favorable contrast was obtained.
  • a composition for an electrosensitive recording material which comprises zinc oxide doped with an oxide of a donor impurity metal having an ionic radius of less than 0.74 Angstrom units and selected from the trivalent or tetravalent metals, the zinc oxide doped component being dispersed in a binder in an amount from 150 to 1,000 parts by weight of the zinc oxide doped component per 100 parts by weight of the binder.
  • composition of claim 1 wherein the donor impurity metal is a trivalent metal selected from the group consisting of cobalt, gallium, aluminum, mercury, iron and chromium, and in which the zinc oxide is doped with the oxide of such metal in an amount of from 0.005 to 10.0 molar percent thereof.
  • composition of claim 1 wherein the donor impurity metal is a tetravalent metal selected from the group consisting of silicon, germanium, titanium and tin, and in which the zinc oxide is doped with the oxide of such metal in an amount of from 0.005 to 10.0 molar percent thereof.
  • composition of claim 1 further including as a plasticizer for the composition a metallic soap of a fatty acid having eight to 18 carbon atoms, in an amount of from 5 to parts by weight per parts of the binder for the composition.
  • composition of claim 4 wherein the donor impurity is a trivalent metal selected from the group consisting of cobalt, gallium, aluminum, mercury, iron and chromium, and in which the zinc oxide is doped with the oxide of such metal in an amount of from 0.005 to 10.0 molar percent thereof.
  • composition of claim 4 wherein the donor impurity metal is a tetravalent metal selected from the group consisting of silicon, germanium, titanium and tin, and in which the zinc oxide is doped with the oxide of such metal in an amount of from 0.005 to 10.0 molar percent thereof.
  • composition of claim 4 wherein the metallic soap is an aluminum, copper, zinc, lead, iron, magnesium, cobalt, barium, nickel or lithium salt of a fatty acid selected from palmitic acid, oleic acid, stearic acid, lauric acid and caprylic acid.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Paper (AREA)
  • Inorganic Insulating Materials (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
US82855A 1970-05-12 1970-10-21 Compositions for electrosensitive recording material Expired - Lifetime US3691105A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP45039691A JPS4920099B1 (enExample) 1970-05-12 1970-05-12
JP45055947A JPS4920100B1 (enExample) 1970-06-29 1970-06-29
JP45074947A JPS4920230B1 (enExample) 1970-08-28 1970-08-28

Publications (1)

Publication Number Publication Date
US3691105A true US3691105A (en) 1972-09-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
US82855A Expired - Lifetime US3691105A (en) 1970-05-12 1970-10-21 Compositions for electrosensitive recording material

Country Status (11)

Country Link
US (1) US3691105A (enExample)
BE (1) BE766993A (enExample)
CA (1) CA951507A (enExample)
CH (1) CH533323A (enExample)
ES (1) ES390747A1 (enExample)
FR (1) FR2095571A5 (enExample)
GB (1) GB1337427A (enExample)
NL (1) NL7104851A (enExample)
NO (1) NO132168C (enExample)
SE (1) SE362611B (enExample)
SU (1) SU508234A3 (enExample)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4279961A (en) * 1979-04-20 1981-07-21 Kanzaki Paper Manufacturing Co., Ltd. Electrostatic record material
WO1984002030A1 (en) * 1982-11-17 1984-05-24 Chevron Res Electroactive polymers
US4519937A (en) * 1981-09-21 1985-05-28 Chevron Research Company Electroactive polymers
US4579679A (en) * 1981-05-18 1986-04-01 Chevron Research Company Electroactive polymers

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2887632A (en) * 1952-04-16 1959-05-19 Timefax Corp Zinc oxide semiconductors and methods of manufacture
US3128204A (en) * 1956-11-14 1964-04-07 Agfa Ag Process of preparing photoconductive layers for electrophotography
US3138547A (en) * 1959-10-23 1964-06-23 Minnesota Mining & Mfg Electrosensitive recording sheets
US3212890A (en) * 1955-09-30 1965-10-19 Minnesota Mining & Mfg Photoconductive element for use in electrophotography containing a heavy metal soap of a long chain fatty acid; and process for using same
US3411948A (en) * 1964-04-08 1968-11-19 Hewlett Packard Co Electrosensitive recording medium
US3547627A (en) * 1966-05-02 1970-12-15 Xerox Corp Lithographic printing master and method employing a crystalline photoconductive imaging layer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2887632A (en) * 1952-04-16 1959-05-19 Timefax Corp Zinc oxide semiconductors and methods of manufacture
US3212890A (en) * 1955-09-30 1965-10-19 Minnesota Mining & Mfg Photoconductive element for use in electrophotography containing a heavy metal soap of a long chain fatty acid; and process for using same
US3128204A (en) * 1956-11-14 1964-04-07 Agfa Ag Process of preparing photoconductive layers for electrophotography
US3138547A (en) * 1959-10-23 1964-06-23 Minnesota Mining & Mfg Electrosensitive recording sheets
US3411948A (en) * 1964-04-08 1968-11-19 Hewlett Packard Co Electrosensitive recording medium
US3547627A (en) * 1966-05-02 1970-12-15 Xerox Corp Lithographic printing master and method employing a crystalline photoconductive imaging layer

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4279961A (en) * 1979-04-20 1981-07-21 Kanzaki Paper Manufacturing Co., Ltd. Electrostatic record material
US4579679A (en) * 1981-05-18 1986-04-01 Chevron Research Company Electroactive polymers
US4519937A (en) * 1981-09-21 1985-05-28 Chevron Research Company Electroactive polymers
WO1984002030A1 (en) * 1982-11-17 1984-05-24 Chevron Res Electroactive polymers
US4519938A (en) * 1982-11-17 1985-05-28 Chevron Research Company Electroactive polymers

Also Published As

Publication number Publication date
SE362611B (enExample) 1973-12-17
NO132168B (enExample) 1975-06-16
SU508234A3 (ru) 1976-03-25
BE766993A (fr) 1971-10-01
NL7104851A (enExample) 1971-11-16
GB1337427A (en) 1973-11-14
DE2121597A1 (de) 1971-12-23
ES390747A1 (es) 1974-11-16
NO132168C (enExample) 1975-09-24
DE2121597B2 (de) 1974-10-31
FR2095571A5 (enExample) 1972-02-11
CH533323A (fr) 1973-01-31
CA951507A (en) 1974-07-23

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