US3293055A - Heat sensitive coating composition and copy sheet coated therewith - Google Patents

Heat sensitive coating composition and copy sheet coated therewith Download PDF

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Publication number
US3293055A
US3293055A US331085A US33108563A US3293055A US 3293055 A US3293055 A US 3293055A US 331085 A US331085 A US 331085A US 33108563 A US33108563 A US 33108563A US 3293055 A US3293055 A US 3293055A
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United States
Prior art keywords
copy sheet
mole
sheet
compound
melting point
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US331085A
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English (en)
Inventor
Henry H Baum
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.)
Appvion LLC
NCR Voyix Corp
National Cash Register Co
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NCR Corp
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Publication date
Priority to NL128266D priority Critical patent/NL128266C/xx
Priority to NL283350D priority patent/NL283350A/xx
Priority to BE623057D priority patent/BE623057A/xx
Priority to GB21450/62A priority patent/GB953150A/en
Priority to CH959262A priority patent/CH406257A/fr
Priority to FR910567A priority patent/FR1373659A/fr
Priority to DEN22169A priority patent/DE1208311B/de
Application filed by NCR Corp filed Critical NCR Corp
Priority to US331085A priority patent/US3293055A/en
Application granted granted Critical
Publication of US3293055A publication Critical patent/US3293055A/en
Assigned to APPLETON PAPERS INC. reassignment APPLETON PAPERS INC. MERGER (SEE DOCUMENT FOR DETAILS). FILED 12/1781, EFFECTIVE DATE: 01/02/82 STATE OF INCORP. DE Assignors: GERMAINE MONTEIL COSMETIQUES CORPORATION (CHANGED TO APPLETON PAPERS), TUVACHE, INC.
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Expired - Lifetime legal-status Critical Current

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    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S252/00—Compositions
    • Y10S252/962—Temperature or thermal history
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated

Definitions

  • thermo-colorable record copy sheet consisting of a base web, such as paper, coated with a normally substantially colorless coating that assumes a color where heated to temperatures used in ordinary thermographic printing, and to a composition for coating such a sheet.
  • the novel copy sheet is used in contact with a master sheet bearing data in infraredradiation-absorbing characters.
  • the characters Upon the two-sheet systems being generally subjected to infrared radiation, the characters become hot and cause a corresponding colored copy on the copy sheet.
  • the novel copy sheet consists of a thin white sheet of paper coated on one side with a minimal amount of binder containing a profusion of minute interspersed solid particles or reactant materials being a mixture of at least one thermochromic indolinobenzospiropyran derivative having a melting point preferably in the range of 180 degrees Fahrenheit to 330 degrees Fahrenheit, and at least one metallic salt of an organic acid, whereby, upon the coatings being heated to the melting point of either the indolinobenzospiropyran material or the metallic salt, or both, a reaction occurs, forming an intensely-colored metallic complex or complexes.
  • a profusion of minute interspersed solid particles or reactant materials being a mixture of at least one thermochromic indolinobenzospiropyran derivative having a melting point preferably in the range of 180 degrees Fahrenheit to 330 degrees Fahrenheit, and at least one metallic salt of an organic acid, whereby, upon the coatings being heated to the melting point of either the indolinobenzospiropyran
  • the master sheet is placed in contact with the novel copy sheet, and the two-sheet system is exposed to radiation rich in infrared wave lengths. If a positive copy is to be made of the data on the master sheet, the heat induced in the characters is conducted through the base web of the master sheet or through the copy sheet, depending on the arrangement of the sheets, as will be explained, to cause the data to appear in color on the coated surface of the copy sheet.
  • the materials which immediately form the color when the coating is heated are a substituted thermochromic indolinobenzospiropyran compound having the molecular formula 1,3,3-trimethyl-4,7,8-trimethoxy [(Z'H-l benzopyran)- 2,2-indoline] and having the structure and calcium resinate or a mixture of calcium resinate and cobalt naphthenate, which materials develop a dark grayish-blue color on being heated to the melting point of the indolinobenzospiropyran compound, which is in the range of 220 degrees Fahrenheit to 225 degrees Fahrenheit.
  • the metallic salts first were combined together in a ball mill with a water dispersion of a polyvinyl alcohol binder, a surfactant, and water in the following amounts:
  • the ball milling was continued until a fine slurry was formed, which slurry then was combined with a slurry of the indolinobenzospiropyran-containing component made as follows.
  • the indolinobenzospiropyran compound of the coating composition was blended with a binder material, a surfactant, and water in the following amounts:
  • Mixture B Grams 1,3,3-trimethyl-4,7,8 trimethoxy [(2'H-1'- benzopyran)-2,2 indoline] 330.0 Polyvinyl alcohol aqueous solution as specified for Mixture A 785.0 Nonionic surface active agent as specified for Mixture A 1.5
  • Mixture A and Mixture B when mixed together, form a coating composition of 5450.0 grams which may be used as is or as modified by the addition of 50 grams of a bluefluorescing whitener such as disodium-4,4-bis (4,6-dianilino-s-triazine-2-yl'amino)-2,2-stilbene disulfonate, commonly used as a fabric whitener.
  • a bluefluorescing whitener such as disodium-4,4-bis (4,6-dianilino-s-triazine-2-yl'amino)-2,2-stilbene disulfonate, commonly used as a fabric whitener.
  • Water content of the composition it may be varied as desired to meet the flow demands of the paper coater, paper of course being the preferred base web material, although other film-forming materials will do.
  • binder and surfactant materials are not critical, and the person skilled in the paper-coating art will know of many binder substitutes for polyvinyl alcohol, such as methyl cellulose or hydroxy-ethyl cellulose, the criterion being that it be not too absorbent of infrared radiation.
  • the heart of the invention is the presence of minute solid particles of two reactants in close interspersed relation on a surface of a preferably white and noninfrared radiation-absorbent record material sheet, the reactants being so selected that at least one melts and reacts with the other at thermographic copy temperatures, the reaction product being colored and solid at room temperature, one of the reactants being an indolinobenzospiropyran compound and the other reactant being a metallic salt of an organic acid.
  • the color of the reaction product obtained in the thermographic operation is a composite of the color contribution from the indolinobenzospiropyran compound and the cation of the metallic salt.
  • the particular color contribution of the salt has been found to be primarily dependent on the cati-on, since essentially no difference in color is observed by varying the anion associated with any particular cation.
  • the metallic salt cations play a dual role in the color-forming reaction.
  • the cation stabilizes the color produced in the thermographic printing operation by forming a complex or chelate with the spiropyran compound, and, in the next instance, such complex formation results in an ultimate color which incorporates a color contribution from the cation.
  • the action of the cations is the same whether the spiropyran compound or the metallic salt has the lower melting point. In either case, all that is required to form a stable colored image on the copy sheet is that a concentration of metallic cations, at least divalent and suitable for complex formation, be present in a mobile or dissolved form, so as to react with available dispersed or liquid spiropyran material.
  • the rate of color formation bears a direct relation to the melting point of the colorforming ingredients; the lower the melting point, the faster the rate of color formation. This is true whether the lower-melting material is metallic salt or the spiropyran material.
  • the coating composition is applied to the chosen surface in any of the conventional paper-coating methods of rolling, brushing, spraying, and the like, so that the dried film is of the order of 0.0005 inch in thickness.
  • novel sheet is shown in the drawing in the two major forms of use with a master sheet, to give positive copies, together with a much-enlarged fragmentary crosssection of the novel copy sheet, showing in exaggerated diagrammatic form the disposition of its elements.
  • FIG. 1 represents the copy sheet 21 with its uncoated back surface against a data-bearing surface of a master sheet 22.
  • the infra-red radiation comes from above and passes through the temperature-colorable coating and the base web of the copy sheet to heat the data characters on the upper surface of the master sheet.
  • the heat is conducted back through the base web of the copy sheet to effect a positive colored copy of the data in the coating of said copy sheet.
  • the base web of the copy sheet should be thin, so that the energy of the applied radiation necessary to cause a copy of the data will be insufficient to heat the characters 23 on the bot tom of the master sheet to a temperature to interfere by heat conduction back through the master sheet and the base web of the copy sheet.
  • a master sheet having data printed on both sides may be used with the novel copy sheet to reproduce the data on but one side.
  • the thickness, the translucence, and the heat conductance of the master sheet are not of first importance, as the applied radiation may be judiciously used to copy only that data in contact with the base web of the copy sheet. It is to be understood that FIG.
  • 1 is diagrammatical as to dimensions and shows a flood-source of infrared radiation, whereas it is possible to move an infrared light source of spot or linear section over the copy paper, irradiating it in its various areas in sequence; or, on the other hand, the system of copy sheet and master sheet may be moved with respect to a stationary source of infrared radiation whose scope is less than the area of the sheets themselves.
  • FIG. 2 shows the arrangement of the two sheets 21 and 22, given a subscript a, where the copy sheet is on the bottom, with the temperature-colorable coating against the rear surface of the master sheet.
  • the infrared radiation impinges directly against the data characters, and the induced heat passes through to cause corresponding coloration of the coating on the copy sheet.
  • the master sheet must pass the induced heat by conduction and should be relatively thin and of suitable heat-conducting material, Obviously, the system of FIG. 2 is not adapted to copy a master sheet bearing infrared-radiationabsorbing data on both sides. Also, in the system of FIG. 2, the heat and radiation transductance characteristics of the base web of the copy sheet are unimportant.
  • FIG. 3 is a diagrammatic section through a part of a copy sheet, showing the relative disposition of the base web, the coating, and the elements in the coating.
  • the dimensions and the proportions of the elements are greatly out of proportion, as the particles of reactant are very small and are in close interspersed profusion, so that, in the preferred form, when the indolinobenzospiropyran compound particles melt, they make contact with the metallic salt particles.
  • the binder constitutes about fifteen percent thereof, by weight.
  • EXAMPLE I The 4,7,8-trimeth0xy derivative.-One mole of 2,5- dimethoxyaniline, one mole of acetoin, and four moles of zinc chloride are placed in a two-liter flask and heated to 160 degrees centigrade for one hour. The reaction mixture is cooled, washed several times with water, and extracted with ether. The ether is evaporated off and distilled at 153 degrees centigrade/0.8 min. of Hg to give 0.85 mole of 2,3-dimethyl-4,7-dimethoxyindole.
  • T-he indole (0.85 mole) thus obtained is methylated by being heated at 120 degrees for five hours in 100 ml. of methanol with 2.55 moles of methyl iodide in a twoliter autoclave.
  • the solid thus obtained is washed with acetone, decomposed with base, extracted with ether, and distilled at 142 degrees centigrade/ 1.5-2.0 mm. of Hg to give 0.4 mole or 4,7-dimethoxy-1,3,3-trimethyl-2- methyleneindoline.
  • EXAMPLE II The 6'-chlor0-8'-methoxy derivative.A solution of one IITlOlC of 3-methoxysalicyladehyde (Tiemann, Koppe, Ber. 14, 2021 (1881)) in 700 ml. of glacial acetic acid is bubbled with chlorine, the temperature of the solution being held below 20 degrees centigrade, until a yellow precipitate separates. The precipitate is recrystallized from ethanol to give 0.40 mole of -chloro-3-rnethoxysalicylaldehyde with a melting point of 117 to 118 degrees centigrade.
  • EXAMPLE III The 1 phenyl-8'-meth0xy derivative.To one mole of 1-phenyl-3,3,-dimethyl 2 methyleneindoline (Brunner, Ber. 31, 1943 (1898)) in 200 ml. of ethanol is added one mole of 3-methoxysalicylaldehyde (Tiemann, Koppe, Ber. 14, 2021 (1881) The mixture is refluxed for two hours, filtered hot, cooled, and filtered a second time. The precipitate is recrystallized from ethanol to give 0.90 mole of White crystals, melting point 163 to 164 degrees centigrade.
  • EXAMPLE V The 1-is0amyl-8-meth0xy derivative.
  • One mole of l-isoamylaniline, one mole of acetoin, and 4 moles of zinc chloride are placed in a two-liter flask and heated to 160 degrees centigrade for one hour.
  • the reaction mixture is cooled, washed several ti-mes with water, and extracted with ether.
  • indole salt 0.8 mole of the indole is methylated in ml. of methanol with 1.6 moles of methyl iodide in a two-liter autoclave at degrees centigrade for five hours to provide the indole salt.
  • the salt is Washed with acetone, decomposed with base, extracted with ether, and distilled at 98 to 107 degrees centigrade/0.7 mm. of Hg to give 0.56 mole of 1-isoamyl-3,3-dimethyl-2-tmethyleneindoline.
  • EXAMPLE VI The 8-etlz0xy derivative-To one mole of 1,3,3-trimethyl-Z-methyleneindoline (Brunner, Ber. 31, 1943 (1898)) in 200 ml. of ethanol is added one mole of 3- ethoxysalicylaldehyde (Davies, 1. Chem. Soc. 123 1587 (1923)). The mixture is refluxed for two hours, filtered hot, cooled, and filtered a second time. The precipitate is recrystallized from ethanol to give 0.85 mole of white crystals, melting point 83 to 85 degrees centigrade.
  • EXAMPLE VII The 5-chlor0-8-eth0xy derivative-To one mole of 5 chloro 1,3,3 trimethyl 2 methyleneindoline (Soc. Anon. Pour lInd. Chim. A Bale, Heinrich von Diesbach, Swiss 137,943, May 19, 1928) in 200 ml. of ethanol is added one mole of 3-ethoxysalicylaldel1yde (Davies, J. Chem. Soc. 123, 1587 (1923)). The mixture is refluxed for two hours, filtered hot, cooled, and filtered a second time. The precipitate is recrystallized from ethanol to give 0.80 mole of white powder, melting point 144 to 145 degrees centigrade.
  • the metallic salt anions may be, for example, acetates, naphthenates, stearates, ricinoleates, oleates, and the like, the latter two classes having exceptionally low melting points.
  • metallic salts suitable for use in the invention have a cation which is at least divalent and an organic anion including at least carbon, hydrogen, and oxygen and preferably so selected that the melting point of the salt ranges from a low of about 75 degrees centigrade to a high of about 250 degrees centigrade.
  • metallic salts of the type just described are the preferred salts of the invention, any salt which can provide a multivalent cation in a milieu of spiropyran material and which has a melting point of at least 65 degrees centigrade may be used in the present invention.
  • the metallic salts tint the coating of the copy sheet slightly, as, for instance, while zinc resinate or acetate is white, the manganese salts are brown, the magnesium salts are light brown, the aluminum salts are light yellow, the lead salts are white, the copper salts are green, and the cobalt salts are purple, but, when used in small quantities in the coating, the colored salts are not of an objectionable nature, as their tinctorial effect is small.
  • the novel copy sheet While emphasis has been placed on the copying of data by infrared thermography, the novel copy sheet also is responsive to hot stylus writing, as commonly used in graph tracings of recording machines, or it may be used in conjunction with any other heat-recording instrumentality, such as hot type.
  • two metallic salts may be used in the coating, but such is not to be deemed limited to two.
  • the invention also admits of the use of two or more of the indolinobenzospiropyran compounds in conjunction with one or more of the metallic salts, to give a mixed color effect, or a particular desired coloring temperature.
  • a record copy sheet consisting of a base web having on a surface thereof a temperature-colorable coating including a profusion of minute solid particles of two kinds in intimate interspersion, one kind of said particle being a metallic salt of an organic acid, the metallic cation being at least divalent and the melting point of the salt being at least 65 degrees centrigrade, and the other kind of particle being at least one indolinobenzospiropyran compound, said compound having an oxygen-containing radical at the 8' position selected from the group consisting of -NO OCH and OC H 2.
  • a coating composition dryable on a recording surface to form a temperature-colorable film consisting of an aqueous slurry of finely-ground entities of (a) a metallic salt of an organic acid, the metallic cation being at least divalent and the melting point of the salt being at least 65 degrees centigrade,
  • said compound having an oxygen-containing radical at the 8 position selected from the group consisting of NO OCH and -OC H and (c) a water-soluble film-forming binder material.
  • the coating composition of claim 8 in which the solids constitute about 20 percent by weight thereof, approximately 50 percent of which is metallic salts, 30 percent indolinobenzospiropyran compound, and 15 percent binder.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Color Printing (AREA)
US331085A 1961-10-05 1963-12-12 Heat sensitive coating composition and copy sheet coated therewith Expired - Lifetime US3293055A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
NL283350D NL283350A (xx) 1961-10-05
BE623057D BE623057A (xx) 1961-10-05
NL128266D NL128266C (xx) 1961-10-05
GB21450/62A GB953150A (en) 1961-10-05 1962-06-04 A temperature-colourable record copy sheet
CH959262A CH406257A (fr) 1961-10-05 1962-08-14 Feuille de reproduction colorable thermiquement
FR910567A FR1373659A (fr) 1961-10-05 1962-09-27 Feuille de reproduction colorée thermiquement
DEN22169A DE1208311B (de) 1961-10-05 1962-10-03 Thermographisches Aufzeichnungskopierblatt
US331085A US3293055A (en) 1961-10-05 1963-12-12 Heat sensitive coating composition and copy sheet coated therewith

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Application Number Priority Date Filing Date Title
US14324261A 1961-10-05 1961-10-05
US331085A US3293055A (en) 1961-10-05 1963-12-12 Heat sensitive coating composition and copy sheet coated therewith

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US3293055A true US3293055A (en) 1966-12-20

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US (1) US3293055A (xx)
BE (1) BE623057A (xx)
CH (1) CH406257A (xx)
DE (1) DE1208311B (xx)
GB (1) GB953150A (xx)
NL (2) NL283350A (xx)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3421894A (en) * 1966-01-13 1969-01-14 Ncr Co Recording process utilizing 6'-nitro-1,3,3 - trimethyl-benzoindolinospiropyran dispersed in heat-meltable wax
US4151748A (en) * 1977-12-15 1979-05-01 Ncr Corporation Two color thermally sensitive record material system
US4620941A (en) * 1983-11-04 1986-11-04 Sakura Color Products Corporation Thermochromic compositions
US4808565A (en) * 1986-08-14 1989-02-28 Minnesota Mining And Manufacturing Company Thermal imaging material
US4829046A (en) * 1987-10-15 1989-05-09 Minnesota Mining And Manufacturing Company Positive-acting thermographic materials
US4902668A (en) * 1988-08-25 1990-02-20 Minnesota Mining And Manufacturing Company Pressure sensitive carbonless imaging system incorporating uncolored ferric organophosphates and colored chelates
US4902667A (en) * 1988-08-25 1990-02-20 Minnesota Mining And Manufacturing Company Pressure sensitive carbonless imaging system incorporating uncolored ferric organophosphates and uncolored chelates
US4910186A (en) * 1987-10-15 1990-03-20 Minnesota Mining And Manufacturing Company Positive-acting thermographic materials
US5310611A (en) * 1991-10-04 1994-05-10 Oki Electric Industry Co., Ltd. Thermoreversible recording material, thermoreversible recording medium and recording method
US5782969A (en) * 1995-04-20 1998-07-21 Nissho Iwai Bentonite Co., Ltd. Ionic spiropyran and photochromic clay conjugate comprising the same
US6696229B1 (en) 1999-07-08 2004-02-24 Kromotek, Ltd. Dry photographic printing process
US20060068315A1 (en) * 2004-09-30 2006-03-30 Gore Makarand P Color forming compositions and associated methods
US20060290769A1 (en) * 2005-06-23 2006-12-28 Polaroid Corporation Print head pulsing techniques for multicolor printers
US20070092845A1 (en) * 2005-10-24 2007-04-26 Gore Makarand P Image recording media and image layers
US20080225308A1 (en) * 2003-02-25 2008-09-18 Zink Imaging, Llc Image stitching for a multi-head printer
US20080238967A1 (en) * 2001-05-30 2008-10-02 Zink Imaging, Llc Print head pulsing techniques for multicolor printers
US8377844B2 (en) 2001-05-30 2013-02-19 Zink Imaging, Inc. Thermally-insulating layers and direct thermal imaging members containing same

Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
US3445261A (en) * 1965-10-23 1969-05-20 Ncr Co Heat-sensitive record material
FR2272082B1 (xx) 1974-05-24 1978-08-11 Issec
FR2508384B1 (fr) * 1981-06-24 1986-06-20 Aussedat Rey Nouveaux developpeurs de couleur, compositions d'enregistrement thermographique les contenant et supports correspondants
FR2530191B1 (fr) * 1982-07-16 1986-11-21 Aussedat Rey Nouveaux developpeurs de couleur a base de saccharine et/ou de derives de saccharine, compositions d'enregistrement thermographique les contenant et supports correspondants

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US2663655A (en) * 1952-05-15 1953-12-22 Minnesota Mining & Mfg Heat-sensitive copying paper
US2940866A (en) * 1957-04-10 1960-06-14 Sperry Rand Corp Heat sensitive copy sheet
US2953454A (en) * 1957-04-23 1960-09-20 Ncr Co Phototropic data storage capsules and base coated therewith
US2967785A (en) * 1959-08-14 1961-01-10 Eastman Kodak Co Thermographic copying material
US3020171A (en) * 1960-08-26 1962-02-06 Ncr Co Pressure-sensitive record and transfer sheet material
US3231584A (en) * 1959-07-16 1966-01-25 Ncr Co 1-phenyl-3, 3-dimethylspiro[(2'h-1'-benzopyran)-2', 2'-indoline] compound

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US2663655A (en) * 1952-05-15 1953-12-22 Minnesota Mining & Mfg Heat-sensitive copying paper
US2940866A (en) * 1957-04-10 1960-06-14 Sperry Rand Corp Heat sensitive copy sheet
US2953454A (en) * 1957-04-23 1960-09-20 Ncr Co Phototropic data storage capsules and base coated therewith
US3231584A (en) * 1959-07-16 1966-01-25 Ncr Co 1-phenyl-3, 3-dimethylspiro[(2'h-1'-benzopyran)-2', 2'-indoline] compound
US2967785A (en) * 1959-08-14 1961-01-10 Eastman Kodak Co Thermographic copying material
US3020171A (en) * 1960-08-26 1962-02-06 Ncr Co Pressure-sensitive record and transfer sheet material

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3421894A (en) * 1966-01-13 1969-01-14 Ncr Co Recording process utilizing 6'-nitro-1,3,3 - trimethyl-benzoindolinospiropyran dispersed in heat-meltable wax
US4151748A (en) * 1977-12-15 1979-05-01 Ncr Corporation Two color thermally sensitive record material system
FR2415009A1 (fr) * 1977-12-15 1979-08-17 Appleton Paper Inc Support thermosensible d'enregistrement
US4620941A (en) * 1983-11-04 1986-11-04 Sakura Color Products Corporation Thermochromic compositions
US4808565A (en) * 1986-08-14 1989-02-28 Minnesota Mining And Manufacturing Company Thermal imaging material
US4829046A (en) * 1987-10-15 1989-05-09 Minnesota Mining And Manufacturing Company Positive-acting thermographic materials
US4910186A (en) * 1987-10-15 1990-03-20 Minnesota Mining And Manufacturing Company Positive-acting thermographic materials
US4902668A (en) * 1988-08-25 1990-02-20 Minnesota Mining And Manufacturing Company Pressure sensitive carbonless imaging system incorporating uncolored ferric organophosphates and colored chelates
US4902667A (en) * 1988-08-25 1990-02-20 Minnesota Mining And Manufacturing Company Pressure sensitive carbonless imaging system incorporating uncolored ferric organophosphates and uncolored chelates
US5310611A (en) * 1991-10-04 1994-05-10 Oki Electric Industry Co., Ltd. Thermoreversible recording material, thermoreversible recording medium and recording method
US5782969A (en) * 1995-04-20 1998-07-21 Nissho Iwai Bentonite Co., Ltd. Ionic spiropyran and photochromic clay conjugate comprising the same
US6696229B1 (en) 1999-07-08 2004-02-24 Kromotek, Ltd. Dry photographic printing process
US8377844B2 (en) 2001-05-30 2013-02-19 Zink Imaging, Inc. Thermally-insulating layers and direct thermal imaging members containing same
US8098269B2 (en) 2001-05-30 2012-01-17 Zink Imaging, Inc. Print head pulsing techniques for multicolor printers
US20080238967A1 (en) * 2001-05-30 2008-10-02 Zink Imaging, Llc Print head pulsing techniques for multicolor printers
US7791626B2 (en) 2001-05-30 2010-09-07 Zink Imaging, Inc. Print head pulsing techniques for multicolor printers
US8345307B2 (en) 2003-02-25 2013-01-01 Zink Imaging, Inc. Image stitching for a multi-head printer
US20080225308A1 (en) * 2003-02-25 2008-09-18 Zink Imaging, Llc Image stitching for a multi-head printer
US7808674B2 (en) 2003-02-25 2010-10-05 Zink Imaging, Inc. Image stitching for a multi-head printer
US8072644B2 (en) 2003-02-25 2011-12-06 Zink Imaging, Inc. Image stitching for a multi-head printer
US20060068315A1 (en) * 2004-09-30 2006-03-30 Gore Makarand P Color forming compositions and associated methods
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DE1208311B (de) 1966-01-05
NL283350A (xx)
NL128266C (xx)
BE623057A (xx)
CH406257A (fr) 1966-01-31
GB953150A (en) 1964-03-25

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