US3451338A - Thermographic recording system - Google Patents

Thermographic recording system Download PDF

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Publication number
US3451338A
US3451338A US366524A US3451338DA US3451338A US 3451338 A US3451338 A US 3451338A US 366524 A US366524 A US 366524A US 3451338D A US3451338D A US 3451338DA US 3451338 A US3451338 A US 3451338A
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sheet
sheets
particles
reactants
methoxy
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US366524A
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English (en)
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Henry H Baum
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Appvion LLC
NCR Voyix Corp
National Cash Register Co
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NCR Corp
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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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    • 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
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • 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
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • 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

Definitions

  • thermographic method of data-recording and heat-sensitive record sheets comprising chromogenic benzo-indolinospiropyran material and a di-phenol material capable of producing immediate and lasting color when and where the two co-reactant materials are brought into liquid contact, as in a melt.
  • the two described co-reactant materials may be coated in a polymeric film binder on a single base web in interspersion in a single coat or separately incorporated into successive coats, or alternatively the coreactants may be coated on separate base web sheets to provide a co-reactive pair of sheets.
  • This invention relates to temperature-responsive record material, and particularly pertains to sheet material having particles of solid material becoming mobile as a fluid phase in recording processes involving thermographic temperatures with heat applied as radiant energy or conducted energy, the fluid mobile material making contact then or later with proximately-located co-reactant solid particles which also may become mobile as a fluid phase to produce a colored mark, and such mark itself being transferable to an unsensitized sheet either at the time the mark is made, or later.
  • the solid particles provided have a low vapor pressure at temperatures under 60 degrees centigrade (the maximum of living environment), to prevent loss of material by evaporation at room temperature, and will not react on solid-solid contact unless prolonged contact engenders such, so that, if the co-reactant substances are held separated by being on different sheets, the sheets may be brought into contact just before use in a recording operation to make a record by heat application thereto by radiation which produces a thermographic effect, or by conduction in some cases.
  • the particles are isolated against particle contact by their films of material, which will transmit the mobile reactants at the higher-than-60-degree-centigrade recording temperatures, which may range up to 200 degrees centigrade.
  • a thin binder of polymeric film material just sufiicient to physically sheath the particles, is used, to prevent solid-solid contact or low vapor pressure contact and consequent premature coloration.
  • one or the other, or both may have their solid particles of reactant isolated by a binder film material, or a common insert sheet or coating may be used, to separate the sheets.
  • a binder film material or a common insert sheet or coating may be used, to separate the sheets.
  • an over-layer of film may be used to prevent smudging by winding pressure or stack-contact pressures during storage or handling.
  • thermographic temperatures The fluid mobility produced in the reactants by thermographic temperatures is associated with the liquid or vapor state of the material at the high temperature.
  • the preferred color-producing reactants are phenols on one hand and certain photochromic benzo-indolinospiropyran compounds on the other hand.
  • the preferred phenols are the di-phenols, and the preferred benzoindolinospiropyrans have the structure (with additional substitution in at least the 8' position).
  • R, R, and R" are lower alkyl or phenyl groups. Most commonly R, R', and R" are methyl groups and in Table I may be so taken unless some other group is indicated by position number. Useful representative compounds are listed in Table I as follows:
  • the preferred compounds, as well as other indolinobenzospiropyran compounds, are made by previously disclosed methods; for example, the method disclosed in The Journal of the American Chemical Society, volume 81, 5605 (1959), which discloses that the general method for making this class of compounds consists essentially of condensing equi-molar amounts of a salicylaldehyde compound and a Z-methylene-l,3,3-trimethylindoline compound, both materials being so selected as to provide the desired substituent groups at desired positions on the 3 condensation reaction products; the methods disclosed in United States Patents Nos. 2,953,454 and 3,100,778; the conventional methods disclosed in Wizinger and Wenning, Helvetica.
  • EXAMPLE 11 The 4,7,8-trimethoxy-I,3,3-trimethyl 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 oil and distilled at 153 degrees centigrade/ 0.8 mm. of Hg to give 0.85 mole of 2,3-dimethyl-4,7-dimethoxyindole.
  • the indole (0.85 mole) thus obtained is methylated by being heated at 120 degrees for five hours in 100 milliliters of methanol with 2.55 moles of methyl iodide in a two-liter autoclave.
  • the solid thus obtained is washed with 4 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 of 4,7-dimethoxy-1,3,3-trimethyl-2methyleneindoline.
  • EXAMPLE III The 5-chl0r0-8'-methoxy-1,3,3-trimethyl derivative To one mole of 5-chloro-1,3,3trimethyl-2-methyleneindoline (Soc. Anon. Pour lInd. Chim. A Bale, Heinrich von Diesbach, Swiss 137,943, May 19, 1928) in 200 milliliters 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 140 to 141 degrees centigrade.
  • the particles of sensitizing materials in unreacted colorless state or in reacted colored state may be organized with respect to support material and with respect to markreceiving material in a number of ways to make possible the production of multiple copies at once or serially, or to make recordings, on a single sheet or by use of a master sheet.
  • the preferred support sheet is paper because of its durability, absorbence, light and heat coefficients, opaqueness or translucense as desired, cheapness, and flexibility.
  • film sheets of polymeric material, woven sheets, or bands of laminated materials may be used.
  • the sheet used may be impregnated or coated with the sensitizing materials, such coating or impregnation fitting the proposed use as to depth of penetration of the reactants if penetration is involved, or with respect to the location of the reactants as to the broad surfaces of the sheet, or with respect to amounts and kinds of reactants. If the sheet is of solid film material, it should be penetrable by the fluid state of the reactants, or else the sensitizing materials should be situated at or on the surface of the sheet.
  • the support material can be the surface of a thick plate, or of other more substantial structure than the sheet or plate form, providing that the support material does not act as a heat-sink to any large degree so that it interferes with the production of temperatures necessary to make marks or to transfer marks or marking reactants.
  • the sheets should be as thin as is consistent with the proposed use, and for some purposes may be opaque and for other purposes may be of a translucent character, to enable data recorded on one side to be read from the other side.
  • the support sheet is thin, relatively opaque white paper, and that any written or printed data to be used in conjunction therewith for control of recording be of a marking material that is raised in temperature relatively to the supporting member when both are commonly irradiated by infra-red radiation.
  • the particles of phenol material should be as small in size as is consistent for the necessary resolution and coating propertiessuch as, say, around three microns in average largest dimension-and the particles of chomogenie material should be of similar dimensions, although the size is not critical if the optical effect is sulficiently good with respect to resolution, as may result from the materials having been in mobile condition.
  • the particles preferably should be supplied in such quantity in an area to be served as to give no perception of individual existence. All of the named materials either are colorless (white in powdered form) or have such small coloration in the unreacted form that they may be considered as leuco compounds.
  • the two reactants in unreacted state be on diiferent sheets, insulated by space or an intermediate insulator means until just before use, and separated thereafter if any unreacted materials remain in contact.
  • Either reactant can exist alone on a sheet, or the reactants in reacted colored state can exist together with an unreacted residue, without physical insulation, and even one of the reactants can exist on a sheet in the presence of the reaction product mark without desensitizing the unreacted remaining area.
  • both reactants are on the same sheet, they may be in interspersion or in layers, be one or both on the surface, partly beneath the surface, or entirely beneath the surface of a sheet. If in layers, the reactants with binder materials will not obscure vision of recorded data, as, at points where marks are produced, a fusion of the superimposed materials occurs.
  • FIG. 1 is a schematic diagram of several constructions in cross-section of a sheet supplied with the reacting compound particles, (a) showing a sheet of film material or paper having the reactant particles located on a surface ,in interspersion, (b) showing the color reactant buried unit, and view (b) showing a folded sheet with a severance formation served with an interleaf sheet carrying one of the reactants.
  • FIG. 2 it is assumed that the chromogenic material is not rendered mobile by the temperatures used, but the phenol is transferred;
  • FIG. 3 shows both reactants on the rear surface of a sheet bearing thermographically-responsive data on the front surface, so that heat engendered by infra-red radiation striking the data heats it, which heat turns the materials on the rear surface to a pattern of colored mobile fluid which is transferred to a plain sheet of paper placed in contact therewith;
  • FIG. 4 shows an overlying sheet of paper having a mirror-image of data recorded in terms of one or both of the reactants on the rear surface of a sheet, so that it may be passed to a plain sheet in a mobile fluid phase by a heat press; the plain sheet also may be supplied with one of the necessary reactants if it is missing, by intention, from the overlying sheet.
  • the reactant material is to be applied to a base sheet as a solution, it should not come into contact in the liquid solution state with the other reactant, because color will be produced prematurely.
  • the reactants may be applied as solutions and dried.
  • the preferred form of applying the reactant materials is by coating anon-solvent liquid dispersion thereof on the base sheet.
  • a protective overcoating of film material of one to two pounds per ream of 25-inch by 38-inch sheets is applied to the active surfaces.
  • a protective coating composition the following is specified:
  • sheets I, II and III are those illustrated in the drawings.
  • the sheets so designated may have a light coating weight (sheets IA, IIA, and IHA) for use as receiving or copy sheets or a heavier coating weight (sheets IB, IIB and IIIB) for use as transfer sheets.
  • sheet I sheet II, or sheet 111 is used to designate the sheets in cases where it is not necessary or appropriate to designate the coating weight.
  • the A and B designations are added where the coating weight of the sheet is relevant to the discusslon.
  • a coating material which is applied to paper in an amount to yield a coating of two to three pounds per ream, dried weight, for use as a heat-responsive copy sheet (sheet IIIA). If a reflex copy system is used-that is, where the sheet must be penetrated by infra-red 1ighta thin paper base sheet is used. For use as a transfer sheet (sheet IIIB), three to five pounds, dried weight, of coating per ream is used.
  • a protective overcoating should be used with these sheets when they are in close storage.
  • Equivalent binder materials Equivalents for hydroxyethylcellulose as binder materials are:
  • sheets I and II are placed in face-to-face relation, and either can be the copy sheet.
  • the original data is pre-recorded on the uncoated side of the selected sheet to provide thermographic responsive representation of the data.
  • the copy will appear on the coated surface of both sheets.
  • the infra-red radiation in the interests of efliciency, should be applied directly to the thermographically responsive data. It is thus to be noted that either sheet I or sheet II can be a'copy-receiving sheet; in this instance,
  • sheet II has a mirror-image of the data. If the copy made is to be transferred, then the heavier coatings should be used, typified by specified sheets IA and HA. Direct reading images and mirror-images, therefore, may be made according to the arrangement of sheets with respect to each other, and the applied energy, according to the well-known optical and transfer laws governing copying procedures.
  • sheet III This sheet III may be used alone as a copy-receiving sheet by being served with a pattern of heat from front or back, as by thermographic original document, by trace of a hot stylus, by hot type, or by any other means giving a differential heat pattern.
  • the sheet may be used for a transfer sheet to produce multiple copies on plain surfaces of any sort, such as bond paper, newsprint, cloth, film, and the like, as long as the pattern of heat is present to control the transfer.
  • any sort such as bond paper, newsprint, cloth, film, and the like
  • the missing reactant may be supplied by means of an interleaved sheet, as shown in FIG. 2b.
  • Sheet III as a master sheet (direct) Sheet III, as the more heavily coated sheet (sheet IIIB), has the data to be recorded printed on the uncoated side.
  • the coated side is placed against plain paper to form a record pair, which is passed by a light source of infrared wave length, so that the radiation directly strikes the printing. A copy of the recorded data will appear on the plain paper. This can be repeated until the coating is exhausted.
  • sheet III or sheets I and II
  • sheet III or sheets I and II
  • the heavier coated sheet I'IIB is written on with thermographic ink directly on the coated side.
  • a piece of plain paper is placed in contact with the writing on sheet II IB to form a pair, and the pair is subjected to infrared radiation. This puts a colored mirror-image of the recorded data on the plain paper.
  • This plain sheet then may be used over and over against successive sheets of plain paper, and each pair is subjected to a hot press to transfer the colored image in direct reading form.
  • a sheet IA has recording on its coated side in terms of thermographic ink, and a pair is formed by contact of a plain sheet of paper placed thereagainst and subjected to infra-red radiation, the mirror-image of the recorded data will appear on the plain sheet in mirrorimage form. This mirror-image then is transferred to the coated surface of a sheet ⁇ [I and subjected to application of heat by use of a hot plate. The direct reading image will appear on sheet H, and this operation may be repeated with other type II sheets until the pattern of material is exhausted.
  • a sheet I'IA has a recording on its coated surface in terms of thermographic ink and is pressed against a sheet I type coated surface and the pair is subjected to infrared radiation, it forms a mirror-image master sheet, which may be used to transfer the data to a type I sheet successively until the mirror-image is exhausted.
  • the reactant materials in whole, or in part may be placed within the boundaries of a sheet, and such placement may be made by mixing particles of the reactant in the head-box furnish of a paper-making machine, or coated on a wet sheet of paperstock furnish before the drying of it to a completed paper sheet.
  • the amount and the depth of distribution of the buried particles all have a bearing on the effectiveness 13 of such sheets, and optimum conditions quantitatively can be determined for a particular base sheet, energy source, and other variable factors by empirical test, all well within the skill of one familiar with the art.
  • a record member including a support sheet having a record surface of solid particles of phenol material as a first reactant and solid particles of chromogenic benzoindolinospiropyran material as a second reactant which is colora'ble on reaction contact with the phenol material, said particles of phenol and chromogenic material reactants producing color by at least one of the reactants becoming mobile as a fluid phase at temperatures associated with thermographic phenomena, said solid phenol particles being insulated from solid contact with the proximate solid particles of chromogenic material by a thin polymeric material film that is pervious to the thermographically-produced mobile phases of the reactant materials.
  • a record member including a support sheet having a record surface of minute particles of phenol material which are solid at the maximum living environment temperature (60 degrees centigrade) and having a mobile fluid phase in marking quantity at the higher temperatures encountered in thermographic phenomena, and proximately positioned in contiguity to, but spaced apart from, the particles of phenol by a polymeric material film, an equivalent, from a reaction standpoint, amount of solid particles of chromogenic material of the benzo-indolinospiropyran type also being solid at temperatures below 60 degrees centigrade and having a mobile fluid phase at temperatures associated with thermographic phenomena, said polymeric material affording isolation of the solid particles of chromogenic material from the solid particles of phenol but passing either kind of particles material in the mobile fluid state phase produced by thermographic temperatures.
  • a sheet of record material having on a surface thereof a visually continuous coating of the reaction prod not of a di-phenol compound and a benzo-indolinospiropyran compound, said reaction product being convertible to a mobile fluid phase by temperatures associated with thermography.
  • a sheet of record material having on a surface thereof a heat-transferable coating of the reaction product of a di-phenol compound and a benzo-indolinospiropyran compound arranged in data-representing configuration.
  • a sheet of record material having on a surface thereof a heat-transferable coating of the reaction product of a phenol compound and a benzo-indolinospiropyran compound.
  • a method of making copies of recorded data on plain paper including the steps of forming on a surface of a proposed master sheet the mirrro-image of the data in terms of the reaction product of a phenol compound and a benzo-indolinospiropyran compound; placing the mirror-image surface against a plain paper sheet to form a contact pair; and applying heat to the pair sufficient to form a mobile fluid phase of the reaction product image and to transfer such a portion of said fluid phase to the plain paper as adheres thereto.
  • a pair of record material sheets operable in faceto-face contact each sheet being supplied with material in solid form which turns to a mobile fluid phase at temperatures associated with thermographic phenomena and the material on one sheet reacting on contact with the material on the other sheet, if only one of the materials is in a fluid state, to produce a distinctive color, one of the component materials being a phenol compound and the other material being a chromogenic benzo-indolin0- spiropyran compound, both materials being in solid state below 60 degrees centigrade.
  • a master sheet for use in controlling and supplying material for the production of multiple copies of data on successively presented sheets of copy record material brought into contact therewith, said master sheet having on the contacting surface a transfer coating including a finely interspersed juxtaposed array of particles including a phenol compound and a benzo-indolinospiropyran compound which react at thermographic temperatures to produce a marking material capable of transfer to a copyreceiving sheet.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Color Printing (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
US366524A 1964-05-11 1964-05-11 Thermographic recording system Expired - Lifetime US3451338A (en)

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BE (1) BE663661A (xx)
CH (1) CH444197A (xx)
DE (1) DE1251348B (xx)
DK (1) DK125273B (xx)
GB (1) GB1053905A (xx)
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Cited By (23)

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US3535139A (en) * 1966-11-17 1970-10-20 Pilot Pen Co Ltd Pressure-sensitive copying papers
US3619239A (en) * 1968-12-10 1971-11-09 Fuji Photo Film Co Ltd Pressure sensitive copying paper
US3649357A (en) * 1967-01-23 1972-03-14 Mead Corp Production of colored images on paper bases
US3887808A (en) * 1972-06-26 1975-06-03 Agfa Gevaert Thermoimaging process utilizing a photochromic material containing a spiropyran, a polyhalogenated hydrocarbon, a thiol compound and a polyvinylcarbazole
US3937864A (en) * 1972-09-04 1976-02-10 Mitsubishi Paper Mills, Ltd. Heat-sensitive recording sheets having improved stability
US3950600A (en) * 1973-07-27 1976-04-13 Ing. C. Olivetti & C., S.P.A. Thermosensitive element, and its employ in the thermographic reproduction or record systems
US3964911A (en) * 1972-12-22 1976-06-22 La Cellophane Photographic reproduction processes using diazonium salts and substituted spiro[benzopyrane]
US3988501A (en) * 1971-11-29 1976-10-26 Ing. C. Olivetti & C., S.P.A. Thermosensitive element for thermographic reproduction or registration systems
US4138522A (en) * 1974-09-17 1979-02-06 Fuji Photo Film Co., Ltd. Color image forming system including a layer formed from a dried residue of a developing ink containing a polyester resin binder
US4151748A (en) * 1977-12-15 1979-05-01 Ncr Corporation Two color thermally sensitive record material system
US4171980A (en) * 1975-04-24 1979-10-23 La Cellophane Photosensitive compositions and recording materials and processes utilizing same
US4246318A (en) * 1979-04-09 1981-01-20 Appleton Papers Inc. Thermally-responsive record material
US4321309A (en) * 1979-06-01 1982-03-23 Sanyo-Kokusaku Pulp Co., Ltd. Heat-sensitive recording material
US4387153A (en) * 1981-04-13 1983-06-07 Mecanorma S.A. Dry transfer process which employs ultraviolet light and photosensitive materials
US4439512A (en) * 1975-12-05 1984-03-27 La Cellophane Chromogenic compositions containing stabilized phenolic coupler compounds, recording materials and processes utilizing same
US4453744A (en) * 1981-06-15 1984-06-12 Ciba-Geigy Corporation Pressure-sensitive or heat-sensitive recording material
US4536779A (en) * 1982-12-10 1985-08-20 Ciba-Geigy Corporation Heat-sensitive recording material
US4620941A (en) * 1983-11-04 1986-11-04 Sakura Color Products Corporation Thermochromic compositions
FR2592158A1 (fr) * 1984-06-26 1987-06-26 Pilot Ink Co Ltd Composition indiquant la temperature de maniere reversible.
US5098806A (en) * 1989-09-22 1992-03-24 Board Of Regents, The University Of Texas System Photosensitive elements based on polymeric matrices of diacetylenes and spiropyrans and the use thereof as coatings to prevent document reproduction
US5310611A (en) * 1991-10-04 1994-05-10 Oki Electric Industry Co., Ltd. Thermoreversible recording material, thermoreversible recording medium and recording method
US5364739A (en) * 1992-02-13 1994-11-15 Board Of Regents, The University Of Texas System Nonsilver x-ray recording process
US5919404A (en) * 1997-04-23 1999-07-06 The Pilot Ink Co., Ltd. Reversible thermochromic compositions

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JPS5337943B2 (xx) * 1973-01-24 1978-10-12
CH578432A5 (xx) * 1973-03-05 1976-08-13 Ciba Geigy Ag
FR2272082B1 (xx) 1974-05-24 1978-08-11 Issec
US4625027A (en) * 1982-10-25 1986-11-25 Ciba-Geigy Corporation Bisquinazolines useful in color former systems
JPS59165687A (ja) * 1983-03-10 1984-09-18 Ricoh Co Ltd 感熱記録材料
DE3940480A1 (de) * 1989-12-07 1991-06-13 Bayer Ag Chromogene enaminverbindungen, ihre herstellung und verwendung als farbbildner
DE59309872D1 (de) * 1992-03-13 1999-12-23 Ciba Sc Holding Ag Chromogene Lactamverbindungen, ihre Herstellung und Verwendung
DE59306627D1 (de) * 1992-03-17 1997-07-10 Ciba Geigy Ag Fluoran Farbbildner

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US2967785A (en) * 1959-08-14 1961-01-10 Eastman Kodak Co Thermographic copying material
US3239366A (en) * 1961-11-21 1966-03-08 Ncr Co Thermotransfer sheet material and copying systems utilizing same
US3244550A (en) * 1961-08-31 1966-04-05 Burroughs Corp Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking
US3262386A (en) * 1959-11-23 1966-07-26 Little Inc A Duplicating method
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US2967785A (en) * 1959-08-14 1961-01-10 Eastman Kodak Co Thermographic copying material
US3262386A (en) * 1959-11-23 1966-07-26 Little Inc A Duplicating method
US3244550A (en) * 1961-08-31 1966-04-05 Burroughs Corp Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking
US3239366A (en) * 1961-11-21 1966-03-08 Ncr Co Thermotransfer sheet material and copying systems utilizing same
US3280735A (en) * 1964-04-13 1966-10-25 Minnesota Mining & Mfg Heat-copying process

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3535139A (en) * 1966-11-17 1970-10-20 Pilot Pen Co Ltd Pressure-sensitive copying papers
US3649357A (en) * 1967-01-23 1972-03-14 Mead Corp Production of colored images on paper bases
US3653945A (en) * 1967-01-23 1972-04-04 Mead Corp Production of reactant sheets for developing colorless dye images
US3619239A (en) * 1968-12-10 1971-11-09 Fuji Photo Film Co Ltd Pressure sensitive copying paper
US3988501A (en) * 1971-11-29 1976-10-26 Ing. C. Olivetti & C., S.P.A. Thermosensitive element for thermographic reproduction or registration systems
US3887808A (en) * 1972-06-26 1975-06-03 Agfa Gevaert Thermoimaging process utilizing a photochromic material containing a spiropyran, a polyhalogenated hydrocarbon, a thiol compound and a polyvinylcarbazole
US3937864A (en) * 1972-09-04 1976-02-10 Mitsubishi Paper Mills, Ltd. Heat-sensitive recording sheets having improved stability
US3964911A (en) * 1972-12-22 1976-06-22 La Cellophane Photographic reproduction processes using diazonium salts and substituted spiro[benzopyrane]
US3950600A (en) * 1973-07-27 1976-04-13 Ing. C. Olivetti & C., S.P.A. Thermosensitive element, and its employ in the thermographic reproduction or record systems
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US4439512A (en) * 1975-12-05 1984-03-27 La Cellophane Chromogenic compositions containing stabilized phenolic coupler compounds, recording materials and processes utilizing same
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FR2592158A1 (fr) * 1984-06-26 1987-06-26 Pilot Ink Co Ltd Composition indiquant la temperature de maniere reversible.
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Also Published As

Publication number Publication date
DE1251348B (xx)
GB1053905A (xx)
SE321853B (xx) 1970-03-16
NL6505979A (xx) 1965-11-12
BE663661A (xx) 1965-09-01
DK125273B (da) 1973-01-29
CH444197A (fr) 1967-09-30

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