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US3239366A - Thermotransfer sheet material and copying systems utilizing same - Google Patents

Thermotransfer sheet material and copying systems utilizing same Download PDF

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Publication number
US3239366A
US3239366A US153806A US15380661A US3239366A US 3239366 A US3239366 A US 3239366A US 153806 A US153806 A US 153806A US 15380661 A US15380661 A US 15380661A US 3239366 A US3239366 A US 3239366A
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United States
Prior art keywords
sheet
heat
thermotransfer
dye
sublimable
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US153806A
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English (en)
Inventor
Robert E Miller
Cheng James Ke-Jen
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 BE625049D priority Critical patent/BE625049A/xx
Priority to NL285755D priority patent/NL285755A/xx
Application filed by NCR Corp filed Critical NCR Corp
Priority to US153806A priority patent/US3239366A/en
Priority to GB41354/62A priority patent/GB973028A/en
Priority to FR915912A priority patent/FR1349982A/fr
Priority to CH1366362A priority patent/CH412950A/fr
Priority to SE12450/62A priority patent/SE325777B/xx
Priority to DE19621421471 priority patent/DE1421471B2/de
Priority to AT913662A priority patent/AT243080B/de
Priority to DK501562AA priority patent/DK140399B/da
Application granted granted Critical
Publication of US3239366A publication Critical patent/US3239366A/en
Priority to NL727212629A priority patent/NL151935B/xx
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.
Anticipated expiration legal-status Critical
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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/38235—Contact thermal transfer or sublimation processes characterised by transferable colour-forming materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/02—Diaryl- or thriarylmethane dyes derived from diarylmethanes
    • 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
    • Y10S101/00—Printing
    • Y10S101/29—Printing involving a color-forming phenomenon
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania

Definitions

  • thermotransfer record copying sheet material to compositions containing sublimable color-forming compounds useful therewith, and to graphic data-copying systems utilizing said sheet material.
  • thermotransfer sheets and to the use of such thermotransfer sheet material coated with sublimable dye, whereby a large number of duplicate or facsimile copies of a graphic original may be produced by thermographic means when the thermotransfer dye material on said transfer sheet is placed in heat-conductive relation with both the graphic original and a suitable receiving sheet and the combination is briefly exposed to intense infra-red irradiation obtained with suitable conventional means.
  • thermotransfer sheet of this invention is utilized in a copying system in which a master sheet having high heat-absorbent areas containing graphic data and low heat-absorbent areas is irradiated with infrared radiation to control the formation of an image on a copy-receiving sheet, the image being formed as a colored image in the form of a condensed sublimate of normally colorless or slightly colored organic dyes which lead themselves to development to a visibly colored form, in some instances by adsorption reaction in the vapor or solid state with acidic surface active adsorbent material, and in other instances by subjecting the condensed sublimate to light predominantly in the ultra-violet region of the spectrum, depending on the organic compound in use.
  • thermographic copying papers and processes have heretofore beeen disclosed, such as the heat-sensitive papers disclosed in United States Patent No. 2,710,263, issued to Bryce L. Clark and Carl S. Miller on June 7, 1955, and the thermographic process disclosed by Carl S. Miller in United States Patent No. 2,740,896, issued April 3, 1956.
  • thermotransfer sheets which utilizes the method of making a copy of a graphic original by thermaltransfer of color-forming compounds coated on a transfer sheet to the surface of a suitably-coated copyreceiving sheet.
  • one disadvantage associated with the use of such prior-art thermotransfer sheets is the relatively small number of copies which can be made with any one transfer sheet.
  • the novel thermotransfer materials of the invention provide an unexpectedly large number of copies by repeated transfers from the same sheet.
  • thermotransfer sheet materials of this invention inhere principally in the thermotransfer composition coated on said sheet material, and particularly in the thermotransferable sublimable dyes and organic compounds and mixtures thereof pres ent in said coated compositions.
  • Typical classes of sublimable dyes and organic compounds having the necessary physical and chemical characteristics to be useful for purposes of this invention include the following: (1) leuco methylene blue dyes, (2) leucauramine compounds, and (3) indolino benzo spiro pyran compounds.
  • the term dye(s) represents and includes any and all of the sublimable color-forming compounds disclosed herein. Even though some of the mentioned compounds may not normally be considered as dyes, they are color-producing, and therefore, from a functional standpoint, they are similar to dyes. It has been found that the dyes comprised in the coating compositions of this invention are transferred or transported from said coating to the surface of the juxtaposed receiving sheet by true sublimation.
  • this phenomenon accounts for the large number of copies obtainable with the novel sheet material, as compared to the limited number obtainable with related prior-art thermotransfer materials, in which the color-producing compounds are first melted or fused, so that transport of said prior-art compounds to the receiving sheet surface is effected while the compounds are in the liquid state.
  • a greater number of facsimile copies can be made with the thermotransfer sheet material coated with the sublimable dye compositions described herein than with prior materials coated with color-forming compounds which are transferred in the liquid state, since, for each copy made, other factors being equal, a much smaller fraction of the total available dye or color-forming material is transferred to the receiving sheet by the mechanism of sublimation than is transferred by liquid transport.
  • thermotransfer materials of this invention are suitable for use in a number of different copying systems and arrangements, they are preferably used in either a two-sheet or a three-sheet arrangement.
  • the top sheet consists of a thin flexible sheet of infra-red-transmitting, base web material bearing on one surface the graphic data to be copied, the data being present as substantially heat-absorbent characters, such as black heat-absorbent typewritten, drawn, or written characters; and having disposed on the other surface of said sheet a thermotransfer coating including one or more sublimable color-forming dyes.
  • this top sheet is superimposed upon a non-infra-red-absorptive copy-receiving sheet, and the combination, while held in close heat-conductive contact, is moved past a source of heat-producing irradiation, such as an infra-red lamp, so that radiant energy is made to fall on the master sheet at such a rate and at such energy level as to preferentially heat the heat-absorbent printed areas in relation to the light-reflecting areas having no graphic data.
  • a source of heat-producing irradiation such as an infra-red lamp
  • the amount of heat genera-ted by absorption of radiant energy by the heat-absorbent graphic data areas is much greater than the amount absorbed by areas where no graphic data is present, so that the heat so absorbed results in a heat pattern corresponding to the graphic data.
  • Heat from said heated areas, in the form and outline of said heat pattern is transferred by conduction through the intervening base web to the dye coating in areas contiguous and corresponding to said graphic data, causing the dye or dyes contained therein to sublime in small quantity, the sublimate so produced condensing in the form of said heat pattern on the receiving sheet as a colored or latent image, depending on the type of dye and receiver sheet being used.
  • the color of the image so produced ranges from blue to red, the
  • Another object of this invention is to provide a novel composition comprising at least one color-forming compound useful for coating thermotransfer sheet material, said compound being sublimable from a coated sheet used for copying purposes with thermographic copying means.
  • Another object of the invention is to the provision of a thermographic copying system comprising an array of 1) an infra-red-transmitting, low-heat-conductivity master sheet bearing heat-absorbing graphic data on one surface thereof; (2) an infra-red-transmitting sheet coated on one side with a composition including sublimable color-forming material, and (3) a copy-receiving sheet.
  • Yet another object of the invention is to provide a thermographic copying system consisting of two sheets in combination: a first, infra-red-t-ransmitting, sheet having disposed thereon a coating containing a sublimable color-forming compound on one side and heat-absorbent graphic data on the other, and, as a second sheet, a copying-receiving sheet having acidic absorbent particles coated on one side, which side is in heat-conductive contact with the coated side of said first sheet.
  • Still another object of the invention is to provide a thermographic copying system consisting of either a twosheet arrangement or a three-sheet arrangement, wherein said arrangements include one of two species of receiving sheet; that is, either a sheet coated with particles of acid clay absorbent material or like materials, or one which consists of a plainsheet of paper with no absorbent coated thereon, the choice depending on the sublimabledye coated on the transfer sheet and on the end result desired.
  • FIGS. 1, 2, and 3 represent views, in perspective, of
  • FIGS. 4, 5, and 6 represent a related arrangement of sheets for copying graphic data, except that a twosheet system, instead of the three-sheet arrangement of FIGS. 1, 2, and 3, is shown.
  • FIGS. 7, 8, 9, and 10 show another system consisting of a three-ply array of sheets wherein an intermediate sheet coated with a photochromic dye transfers a latent image of graphic data onto a receiving sheet when said graphic data is subjected to infra-red radiation, the latent image being developed to a substantially stable visibly infra-red radiation necessary for the practice of this in FIGS. 1A, 4A, and 7Arepresent cross-sections of the.
  • FIG. 1 there is shown a three-sheet system for copying heat-absorbent graphic .data,-'consisting of an intermediate sheet 21., held in heat-conductive contact between a master sheet 20 and a receiving; sheet 22.
  • the master sheet 20 is an infra-red-transmitting paper web base having disposed .on its surface heat-absorbent graphic data areas 23,'such as carbon ink characters, said master sheet, being overlaidin heat-conductive :contact with the uncoated surface of the intermediate sheet'21.
  • the sheet 21 is'back-coated with a sublimable dye or a composition containing a :sublimable dye, this coating in turn being held in contact with the, coated side of'the receiving sheet 22, which is coatedawith clay particles or equivalent, which particles are acid relative to the sublimable dyes transferred to said sheet.
  • FIG; 2 shows the three-sheet arrangement of FIG. 1 being briefly irradiated with an, intense source. of infrared heat-producing rays provided by a suitable heat lamp. It should be understood that means for providing suitable vention are nowwell known in the art and hence need not be describedherein..
  • FIG. 3 represents the copy-receiving sheet 22 with an exact facsimile copy 24 of the original graphic data 23.
  • FIG. 4 there is shown a combination of two sheets useful for. copying andduplicating graphic originals, con
  • FIG- 5 shows the two-sheet system being exposed to intense infra-red radiation in-the manner described in connection with FIG. .2.
  • FIG. 7 there is shown, in perspective, a three-sheet copying system which is identical with the arrangementshown in .FIG. 1 except that the receivingv sheet 42'1consists of plain uncoated web base material,
  • the intermediate transfer sheet 41 is coated with a thin layer including a sublimable photochromicidye;
  • FIG. 8 shows the three-sheet combination of FIG. 7 being subjected tohigh-intensity heat rays, such as infrared rays, generated by the heat lamp shown in the figure.
  • the uncoated receiving. sheet: 42 . is shown with a latent image 44 0f the graphic original on its surface in position for irradiatiomwith an ultraevioletzlight source, said latent image having been obtained by infrared irradiation of the three-sheet arrangement as shown in FIG. 8.
  • the latent image 44 represents an invisible sublimate of photochromic dye transferred to the receiving sheet 42 from the intermediate transfer sheet.
  • the latent image is in the form of the heat pattern generated within the graphic original by irradiation of said original with infra-red rays.
  • FIG. shows the receiving sheet 42 after exposure to ultra-violet light, the exposure having transformed the latent image 44 to a visibly blue colored facsimile copy 45 of the graphic original.
  • FIGS. 7, 8, 9, and 10 Other modifications of the arrangement shown in FIGS. 7, 8, 9, and 10 are also within the purview of this invention.
  • a sublimable-photochromic-dyecoated transfer sheet is used with a clay-coated receiving sheet
  • a visibly colored reddish image Ofthe graphic original is directly obtained on the receiving sheet, instead of a latent image, which is obtained with the uncoated receiving sheet arrangement above described. It is thus possible to obtain facsimile copies of graphic data in contrasting colors on the same receiving sheet by the transfer of photochromic dye to clay-coated sheet areas and to uncoated sheet areas, the former areas providing a reddish-colored image directly and the latter providing a latent image which develops a blue color when subjected to ultra-violet radiation.
  • sublimable dye compositions comprising sublimable photochromic dyes and one or more of the other sublimable dyes of this invention in a copying system including either an uncoated receiving sheet or a clay-coated receiving sheet to obtain graphic copies of varying color composition.
  • compositions comprising sublimable dyes and to set forth the best mode of preparing thermotransfer sheet material including such compositions.
  • thermotransfer sheet material of this invention comprises three dyes or color-forming compounds and is prepared as follows:
  • An aqueous dispersion is prepared by ball-milling a composition consisting of, in parts by weight:
  • a nonylphenoxyethanol surfactant i.e., Triton N-100, a non-ionic surface active agent, and 31 parts of water.
  • the final transfer coating emulsion is prepared by blending the above-described dye dispersion with a binder composition consisting of a mixture of 2.1 parts (dry weight basis) of a 20% aqueous solution of Elvanol 50-42, a high-viscosity, highly-hydrolyzed polyvinyl alcohol, having a viscosity of 35-45 centipoises when measured with a 4% aqueous solution at 20 degrees centigrade by the Hoeppler falling ball method and in which the degree of hydrolysis varies from 97.7 to 98.4%, and 1.05 parts (dry weight basis) of Dow Latex 630, which is a 48% solids styrene-butadiene copolymer latex.
  • the so-prepared blend is then adjusted to about 20% total solids, and, after thorough mixing, the dispersion is ready for coating.
  • thermotransfer sheet A sheet of paper coated with 2.5 pounds per ream (25" x 38 x 500 sheets) of the above composition was used as the thermotransfer sheet in both a three-sheet system and a two-sheet system in accordance with this invention, and, when so utilized with thermographic copying means, each novel thermotransfer sheet readily provided at least sixty and in many instances a greater number of legible and clear facsimile copies of a graphic original on individual attapulgite-clay-coated receiving sheets.
  • EXAMPLE II The composition of this example consists of two colorproducing compounds instead of the three shown in Example I.
  • An aqueous dispersion is prepared by ball-milling the following ingredients, the amounts given as parts by weight:
  • the final coating composition is made by blending therewith the binder composition of Example I in the manner described therein.
  • thermotransfer coating composition consisting of the following materials is prepared, in which the materials are dispersed and/or dissolved in an organic vehicle as follows, all
  • azo-oil Blue Black B a polyazo alkylated naphthol dye, disclosed in United States Patent No. 2,090,938, issued to Karl F. Conrad on August 24, 1937,
  • milled natural rubber Four parts of milled natural rubber is first dissolved in 200 parts of the petroleum solvent, to which have been added the given amounts of lecithin, a dispersing agent,
  • azo oil Blue Black B which serves as a tinting agent 'by incorporating a slight color to the coating and thus aids in distinguishing coated areas from uncoated areas of the base sheet.
  • the coloring compounds or dyes are then added, and, after thorough mixing, the dispersion is applied as a coating on suitable web stock, such as Nekoosa bond paper, in an amount ranging from about two to'three pounds per ream of 25'' x 38 x 500 sheets.
  • the coating is applied to the transfer base by any suitable conventional technique, and the applied coating then is dried by passing the coated medium through a heated tunnel or the like to evaporate the solvent.
  • a transfer coating emulsion containing a photochromic dye is prepared by. ball-milling a 3% aqueous dispersion of the photochromic dye of Example I with a 2% aqueous binder solution of DX843-11, a polyethylenemaleic anhydride copolyrner having a specific viscosity of 1.0 as a
  • a thermotransfer composition containing the photo- 'chr'omic dye of Example I but having no binder is prepared by evaporating the acetone solvent from a paper base transfer medium coated with a saturated acetone solution of said photochromic dye.
  • the preferred dyes or color-forming compounds disclosed in the foregoing examples may be substituted with other compounds selected from the same or related class of compounds.
  • Examples of compounds from each class which have been found to be particularly suitable include the following:
  • R R andR are selected from the group consisting of (a) R; is N0 and R and R are hydrogen, (b) R, and R4 are hydrogen and R is N0 (c) R and R are hydrogen and R jis OCH ,(d) R is hydrogen, R is N0 R5 is OCH (e), Rg is Cl,-Ri, and R are both N0 (f) R is hydrogen,'R is Br, and R is N0 (g) R, is Cl, R is hydrogen, and R .is N0 (h), R 'is Cl, R
  • thermotransferable compositions of this invention may comprise one or more dyes from .eachof the dyes of Groups I, II, and III above, one or more dyes selected. from each of the dyes of Groups I and II or Groups I and III, or one or more dy'es from Group. III.
  • cauramine group are disclosedinz'United States Letters Patent Nos. 2,828,341and 2,828,342,'issued to Clyde S.
  • the polymeric binder material of this in-- Vention comprise a blend of a hydrophilic synthetic polymer and a rubbery copolyrner -latex,.such as the polymer blend of Examples I and II.
  • a hydrophilic synthetic polymer such as the polymer blend of Examples I and II.
  • other polymeric materials may be substituted for'the preferred binder compositions.
  • examples of such other materials 1 include hydrophilic polyvinyl alcoholwithout the added I copolyrner latex, and hydrophilic copolymers of: polyethylenemaleic anhydride, as well as other known copolymers having similar characteristics.
  • the binder may also comprise polymers. of natural origin, such as gelatin, gum arabic, and the like.
  • the ratio, on a'weight basis, of the amount of leuco methylene blue dye to the amount of dye from either of the other two classes of dyes may vary from about 1.5:1 to 4:1.
  • the preferred transfer compositions include a leuco methylene blue derivative, preferably an iso alkyl derivative having four or five carbon atoms attached to the 10 position on the phenothiazine group, in combination with one or more dyes from the other previouslydisclosed classes of dyes.
  • Thermotransfer compositions containing such leuco methylene blue derivatives provide permanent copies of graphic matter; i.e., which remain stable indefinitely against the effects of heat and light. Some tendency of the graphic copy to fade, however, is observed in copies prepared with sublimable dye compositions in which leuco methylene blue derivatives have been excluded, the degree of fading, of course, varying with the dye and the type of receiving sheet.
  • compositions of Examples IV and V in both of which the only color-forming compound is a photochromic dye, the other compositions all contain the preferred isovaleryl derivative of leuco methylene blue.
  • thermotransfer sheets in which the preferred leuco methylene blue derivatiesi.e., l-isovaleryl, lO-isobutyryl, and 10-pivalyl-have been replaced by the other derivatives of this class specified aboveie, the -acetyl, IO-propionyl, and 10-phenyl acetyl derivatives-copies made with sheets containing the former preferred derivatives have much greater stability to color change,
  • thermotransfer record sheet material adapted for making copies of heat-absorbing graphic data onto receiving sheet material by subjecting said graphic data to heat-producing irradiation while said data is held in heatconductive relation with said thermotransfer and receiving sheet materials, the thermotransfer sheet material comprising (1) a flexible infra-red-transmitting supporting web base, and
  • a thin layer containing sublimable dye coated on one side of said base comprising a mixture of sublimable fine solid particles of (a) a leuco methylene blue dye, (b) a leucauramine compound, and (c) a 1,3,3-trimethyl spiro [(2H'1-benzopyran)-2, 2'-indoline] compound.
  • thermotransfer sheet of claim 1 wherein (l) the base material is a thin infra-red-transmitting flexible paper web and (2) the thin layer on said base material comprises a polymeric binder having homogeneously disperse-d therein a sublimable mixture of fine particles of (a) a leuco methylene blue compound of the formula III-11 2 (CH3) 2N wherein R is selected from the group consisting of:
  • R R and R are selected from the group consisting of (a) R; is N0 and R and R are hydrogen, (b) R, and R are hydrogen and R is N0 (c) R and R are hydrogen and R is OCH (d) R is hydrogen, R is N02, R5 is OCH3, (e) R3 is C1, R4 and R5 are N0 (f) R is hydrogen, R is Br, and R is N0 (g) R is Cl, R is hydrogen and R is N0 (h) R is Cl, R is N0 and R is hydrogen, (i) R is Cl, R is Br, and R is N0 and (1') R is Cl, R is N0 and R is OCH 3.
  • R R and R are selected from the group consisting of (a) R; is N0 and R and R are hydrogen, (b) R, and R are hydrogen and R is N0 (c) R and R are hydrogen and R is OCH (d) R is hydrogen, R is N02, R5 is OCH3, (e) R3 is C1, R4 and
  • thermotransfer record sheet material adapted for making copies of heat-absorbing graphic data onto receiving sheet material by subjecting said graphic data to heat-producing irradiation while said data is held in heatconductive relation with said thermotransfer and receiving sheet materials, the thermotransfer sheet material comprising (1) A flexible infra-red-transmitting supporting Web base, and
  • a layer containing sublimable dye coated on one side of said base comprising a mixture of sublimable fine particles of (a) "a leuco methylene blue dye, and (b) a 1,3,3-trimethyl-spiro- [(2H-1'-benzopyran)-2,2'-indoline] compound homogeneously dispersed in a binder.
  • thermotransfer sheet of claim 4 wherein the layer coated on the base material comprises amixture of fine particles of (a) a leuco methylene bluecompound Of the formula (CHa)zN S N(CH3)2 Where R is selected from the group consisting of isobutyryl, isovaleryl, pivalyl, acetyl, propionyl, and phenyl acetyl; and (b) a photochromic compound of the formula in 1130 on;
  • R R4, and R are selected from the group consisting of (a) R is N and R and R are hydrogen,
  • the ,thermotransfer :sheet material comprising (1) A-flexible infrared-transmitting supporting web base, and r V i (2) A thin layer containing sublimable dye coated on one side of said base, said layer comprising amixture of sublimable fine particles of '(a) -a leuco methylene blue dye,'and (b) a leucauramine com pound, said sublimable fine particlesbein-g homogeneoiisly dispersed in a binder;
  • thermotransfer sheet of claim 6' wherein the layer coated on the base material comprises a mixture of fine particles of (a) a leuco-methylene blue dye of the formula I r (CH3) 2N. S N (CH3) 2 i wherein sR is selectedfromithegroup consisting of isobutyryl, isovaleryl, pivalyl, acetyl,propionyl, and phenyl acetyl; and (b) a leucauramine compound of the formula:
  • a flexible non-infra-red-absorptive :thermotransfer f 7 sheet consisting of a Web base coated on oneside with R; is NOQ, and R5 a thin layer comprising sublimable dye, said layer comprising a mixture of sublimable fine solid particles of (a) a leuco methylene blue dye, (b) a leucauramine compound, and (c) a 1,3,3-trimethylspiro-[2'H-l'-benzopyran)-2,2'-indoline] compound, and (3) a flexible non-infra-red-absorptive web base receiving sheet coated on one side with fine particles of acidic adsorbent material, said layer of sublimable dye overlaying said particles of adsorbent material, so that irradiation of the graphic data areas with infra-red rays of suitable duration and energy generates heat in said graphic data areas and, by heat conduction through the supporting web base of sheets 1 and 2 above, forms
  • thermotransfer copying system of claim 9 in which the coating containing sublimable dye consists of (1) a polymeric binder, and, homogeneously dispersed therein, (2) a sublimable mixture of fine particles of (a) a leuco methylene blue compound of the formula wherein R is selected from the group consisting of isobutyryl, isovaleryl, pivalyl, acetyl, propionyl, and phenyl acetyl; (b) a leucauramine compound of the formula III-11 Br II N (CHM and (c) a photochromic spiro-pyran compound of the formula (III) H wherein R R and R are selected from the group consisting of (a) R; is N0 and R and R are hydrogen, (b) R and R are hydrogen and R is N0 (c) R and R are hydrogen and R is OCH (d) R is hydrogen, R is N0 R is OCH (e) R is C1, R and R are both N0 (f) R;,
  • thermotransfer copying system of claim 12 wherein the thin sublimable dye layer comprises a polymeric binder having homogeneously dispersed therein a sublimable mixture of fine particles of (a) a leuco methylene blue compound of the formula (CH3)2N S N(CHa)n wherein R is selected from the group consisting of isobutyryl, isovaleryl, pivalyl, acetyl, propionyl, and phenyl acetyl; (b) a leucauramine compound of the formula wherein R is selected from the group consisting of;-
  • thermotr-ansfer copying system consisting of a three-sheet array in heat-conductive relation adapted for making colored copies of heat-absorptive graphic matter, comprising, in order,
  • an infra-red-transmitting master sheet having heatabsorptive graphic data areas on one surface therei (2 aflexiblenoninfra-red-absorptive therinotransfer sheet consisting ofa web base coated on one side with 'a thinilayer comprising a sublimable indolino benzo spiro pyran dye, and Y (3) a flexible base web receiving sheet,
  • said layer of sublimable dye overlying said base'web receiving sheet, so that irradiation of the graphic data areas with infra-red rays of suitable duration and energy gene cratesheat in said graphic areas and by heat conduction through the supporting web base of sheets 1 and 2 forms a heatpattern in an area of the dye layer corresponding to the heat-energy-absorbing, areas of said graphic data,
  • said heat causes a :small fractionof sublimable dye in the heated area to sublime and then condense on the receiving sheet as an invisible latent image of said graphic data, said latent image being developed to a distinctive color by brief exposure to, ultra-violet light.
  • thermotransfer copying system of claim 15 wherein the sublimable dye is homogeneously dispersed in a polymeric binder coated on said base, and said dye is a compound having thecformula (III) 1130 CH:
  • R R4, and R are selected from .the group consisting of (a) R; is .NO andR and R are hydrogen, a (b) R and R are hydrogen and R is N0 (0) R3 and R are hydrogen and R is OCH (d) R is hydrogen, R
  • thermotransfer copying system consisting of a two-sheet array in heat-conductive relation adapted for making colored copies of heat-absorptive graphic data, comprising, in order,
  • thermotransfer copying system of claim'11' wherein the sublimable dye is homogeneously dispersed in a polymeric binder coated on said base, and said dye is a compound having the formula HaC wherein R R and R5 are selected from thelgroup con- 17 R and R are hydrogen and R is N (c) R and R are hydrogen and R is OCH ((1) R is hydrogen, R is N0 R is OCH (e) R is Cl, R and R are both N0 (f) R is hydrogen, R is Br, and R is N0 (g) R is C1, R is hydrogen and R is N0 (h) R is Cl, R is N0 and R is hydrogen, (i) R is Cl, R is Br, and R is N0 and (j) R, is Cl, R is N0 and R is OCH 19.
  • a thermotransfer copying system consisting of a three-sheet array in heat-conductive relation adapted for making colored copies of heat-absorptive graphic matter, comprising, in order,
  • thermotransfer sheet consisting of a web base coated on one side with a thin layer comprising sublimable dye, said layer consisting of a mixture of sublimable fine particles of (a) a leuco methylene blue dye, and' (b) a leucauramine dye, said sublimable fine particles being homogeneously dispersed in a binder, and
  • thermotransfer copying system consisting of a three-sheet array in heat-conductive relation adapted for making colored copies of heat-absorptive graphic matter, comprising, in order,
  • thermotransfer sheet consisting of a web base coated on one side with a thin layer comprising sublimable dye, said layer consisting of a mixture of sublimable fine par- 2 ticles of (a) a leuco methylene blue dye, and (b) a 1,3,3 trimethyl spiro [(2H-1'-benzopyran)-2,2- indoline] compound, said sublimable fine particles being homogeneously dispersed in a binder, and
  • thermotransfer copying system consisting of a three-sheet array in heat-conductive relation adapted for making colored copies of heat-absorptive graphic matter, comprising, in order,
  • thermotransfer sheet consisting of a web base coated on one side with a thin layer comprising sublimable dye, said layer consisting of fine solid particles of a 1,3,3-
  • thermotransfer copying system consisting of a two-sheet array in heat-conductive relation adapted for making colored copies of heat-absorptive graphic data, comprising, in order,
  • a flexible master sheet consisting of an infra-redtransmitting web base having heat-absorbent graphic data areas disposed on its outer surface, and a thin layer comprising sublimable dye coated on the opposite surface ,said layer comprising a mixture of fine particles of (a) a sublimable leuco methylene blue dye, and ('b) a sublimable leucauramine compound, said particles being homogeneously dispersed in a binder, and
  • said adsorbent material held in contact with said sub limable dye, so that irradiation of said graphic areas with infra-red rays of suit-able duration and energy generates heat in said graphic areas and by heat conduction through the master sheet supporting web base 1 forms a heat pattern in an area of the dye layer corresponding to the heat-energy-absorbing areas of said graphic data, whereupon said heat causes a small fraction of sublimable dye in the heated area to sublime and then condense on the receiving sheet acidic particles as a visible colored facsimile of the original graphic data.
  • thermotransfer copying system consisting of a two-sheet array in heat-conductive relation adapted for making colored copies of heat-absorptive graphic data, comprising, in order,
  • a flexible master sheet consisting of an infra-redtransmitting web base having heat-absorbent graphic data areas disposed on its outer surface, and a thin layer comprising sublimable dye coated on the opposite surface, said layer comprising a mixture of fine solid particles of (a) a leuco methylene blue dye, and (b) a 1,3,3-trimethyl spiro [(2H-1'-benzopyran)- 2,2'-indoline] compound, said particles being homogeneously dispersed in a binder, and
  • said adsorbent material held in contact with said sublimable dye, so that irradiation of said graphic areas with infra-red rays of suitable duration and energy generates heat in said graphic areas and by heat conduction through the master sheet supporting web base 1 forms a heat pattern in an area of the dye layer corresponding to the heat-energy-absorbing areas of said graphic data, whereupon said heat causes a small fraction of sublimable dye in the heated area to sublime and then condense on the receiving sheet acidic particles as a visible colored facsimile of the original graphic data.
  • thermotransfer copying system consisting of a two-sheet array in heat-conductive relation adapted for making colored copies of heat-absorptive graphic data, comprising, in order,

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Color Printing (AREA)
US153806A 1961-11-21 1961-11-21 Thermotransfer sheet material and copying systems utilizing same Expired - Lifetime US3239366A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
BE625049D BE625049A (de) 1961-11-21
NL285755D NL285755A (de) 1961-11-21
US153806A US3239366A (en) 1961-11-21 1961-11-21 Thermotransfer sheet material and copying systems utilizing same
GB41354/62A GB973028A (en) 1961-11-21 1962-11-01 Thermographic copying system
CH1366362A CH412950A (fr) 1961-11-21 1962-11-20 Feuille pour l'obtention de copies par transfert thermique
SE12450/62A SE325777B (de) 1961-11-21 1962-11-20
FR915912A FR1349982A (fr) 1961-11-21 1962-11-20 Matériau d'enregistrement en feuille
DE19621421471 DE1421471B2 (de) 1961-11-21 1962-11-20 Thermokopieverfahren
AT913662A AT243080B (de) 1961-11-21 1962-11-21 Thermographisches Kopierblatt
DK501562AA DK140399B (da) 1961-11-21 1962-11-21 Kopieringsark til brug ved termokopiering.
NL727212629A NL151935B (nl) 1961-11-21 1972-09-18 Werkwijze voor het vervaardigen van kopieen van warmte-absorberende grafische tekens op velvormig afdrukmateriaal.

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AT (1) AT243080B (de)
BE (1) BE625049A (de)
CH (1) CH412950A (de)
DE (1) DE1421471B2 (de)
DK (1) DK140399B (de)
GB (1) GB973028A (de)
NL (1) NL285755A (de)
SE (1) SE325777B (de)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3451338A (en) * 1964-05-11 1969-06-24 Ncr Co Thermographic recording system
US3481760A (en) * 1964-04-13 1969-12-02 Minnesota Mining & Mfg Thermographic copying sheets
US3525630A (en) * 1967-12-06 1970-08-25 Ncr Co Colorless ink to give black print
US3539375A (en) * 1966-06-01 1970-11-10 Ncr Co Thermo-responsive record sheet
US3619239A (en) * 1968-12-10 1971-11-09 Fuji Photo Film Co Ltd Pressure sensitive copying paper
EP0097493A1 (de) * 1982-06-17 1984-01-04 Matsushita Electric Industrial Co., Ltd. Getrocknetes Übertragungsblatt für wärmeempfindliches Aufzeichnungsverfahren und Vorrichtung zur wärmeempfindlichen Aufzeichnung
US4523402A (en) * 1981-11-09 1985-06-18 Dobson Charles Edward Sign construction
US4675161A (en) * 1982-12-29 1987-06-23 Sakata Shokai, Ltd. Indicator for detection of thermal history
US4880667A (en) * 1985-09-24 1989-11-14 Ppg Industries, Inc. Photochromic plastic article and method for preparing same
US5133819A (en) * 1990-05-01 1992-07-28 Marjorie Croner Process for producing decorative articles
US5699182A (en) * 1995-05-25 1997-12-16 Xytronyx, Inc. Light fatigue resistant photochromic formulations
CN104442059A (zh) * 2014-11-21 2015-03-25 杨又华 一种转印工艺片材生产改良方法
US20150308907A1 (en) * 2014-04-23 2015-10-29 The Boeing Company Witness Material and Method for Monitoring the Environmental History of an Object
US9372177B2 (en) 2013-03-15 2016-06-21 The Boeing Company Method and system for detecting exposure of composites to high-temperature

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4123580A (en) * 1977-06-23 1978-10-31 Minnesota Mining And Manufacturing Company Color source sheet with rubber binder
US4614521A (en) * 1984-06-06 1986-09-30 Mitsubishi Chemical Industries Limited Transfer recording method using reactive sublimable dyes

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2503759A (en) * 1947-08-16 1950-04-11 Eastman Kodak Co Evaporography
US2770534A (en) * 1949-03-16 1956-11-13 Printing Arts Res Lab Inc Method and material for making overlay masks
US2828341A (en) * 1955-11-01 1958-03-25 Ncr Co N-halophenyl derivatives of leucauramine
US2939009A (en) * 1956-02-01 1960-05-31 Jack M Tien Thermotransfer duplicating process
US2978462A (en) * 1959-06-19 1961-04-04 Ncr Co Derivatives of 3'-methyl-spiro (2h-1-beta-naphthopyran-2', 2'-[2'h-1' benzopyran])
US2983756A (en) * 1958-05-13 1961-05-09 Allied Chem Aliphatic amino derivatives of bis (p-dialkylaminophenyl) methane
US3020171A (en) * 1960-08-26 1962-02-06 Ncr Co Pressure-sensitive record and transfer sheet material
US3034917A (en) * 1958-08-26 1962-05-15 Caribonum Ltd Transfer sheet coated with stabilized colorless leucauramine derivative
US3035935A (en) * 1958-12-01 1962-05-22 Wagner Guenter Hectographic coloring paper having a transfer coat containing lower alkyl mercapto triphenyl carbinol

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2503759A (en) * 1947-08-16 1950-04-11 Eastman Kodak Co Evaporography
US2770534A (en) * 1949-03-16 1956-11-13 Printing Arts Res Lab Inc Method and material for making overlay masks
US2828341A (en) * 1955-11-01 1958-03-25 Ncr Co N-halophenyl derivatives of leucauramine
US2939009A (en) * 1956-02-01 1960-05-31 Jack M Tien Thermotransfer duplicating process
US2983756A (en) * 1958-05-13 1961-05-09 Allied Chem Aliphatic amino derivatives of bis (p-dialkylaminophenyl) methane
US3034917A (en) * 1958-08-26 1962-05-15 Caribonum Ltd Transfer sheet coated with stabilized colorless leucauramine derivative
US3035935A (en) * 1958-12-01 1962-05-22 Wagner Guenter Hectographic coloring paper having a transfer coat containing lower alkyl mercapto triphenyl carbinol
US2978462A (en) * 1959-06-19 1961-04-04 Ncr Co Derivatives of 3'-methyl-spiro (2h-1-beta-naphthopyran-2', 2'-[2'h-1' benzopyran])
US3020171A (en) * 1960-08-26 1962-02-06 Ncr Co Pressure-sensitive record and transfer sheet material

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3481760A (en) * 1964-04-13 1969-12-02 Minnesota Mining & Mfg Thermographic copying sheets
US3451338A (en) * 1964-05-11 1969-06-24 Ncr Co Thermographic recording system
US3539375A (en) * 1966-06-01 1970-11-10 Ncr Co Thermo-responsive record sheet
US3525630A (en) * 1967-12-06 1970-08-25 Ncr Co Colorless ink to give black print
US3619239A (en) * 1968-12-10 1971-11-09 Fuji Photo Film Co Ltd Pressure sensitive copying paper
US4523402A (en) * 1981-11-09 1985-06-18 Dobson Charles Edward Sign construction
EP0097493A1 (de) * 1982-06-17 1984-01-04 Matsushita Electric Industrial Co., Ltd. Getrocknetes Übertragungsblatt für wärmeempfindliches Aufzeichnungsverfahren und Vorrichtung zur wärmeempfindlichen Aufzeichnung
US4675161A (en) * 1982-12-29 1987-06-23 Sakata Shokai, Ltd. Indicator for detection of thermal history
US4880667A (en) * 1985-09-24 1989-11-14 Ppg Industries, Inc. Photochromic plastic article and method for preparing same
US5133819A (en) * 1990-05-01 1992-07-28 Marjorie Croner Process for producing decorative articles
US5699182A (en) * 1995-05-25 1997-12-16 Xytronyx, Inc. Light fatigue resistant photochromic formulations
US9372177B2 (en) 2013-03-15 2016-06-21 The Boeing Company Method and system for detecting exposure of composites to high-temperature
US20150308907A1 (en) * 2014-04-23 2015-10-29 The Boeing Company Witness Material and Method for Monitoring the Environmental History of an Object
US9970833B2 (en) * 2014-04-23 2018-05-15 The Boeing Company Witness material and method for monitoring the environmental history of an object
CN104442059A (zh) * 2014-11-21 2015-03-25 杨又华 一种转印工艺片材生产改良方法

Also Published As

Publication number Publication date
CH412950A (fr) 1966-05-15
DE1421471B2 (de) 1971-08-12
SE325777B (de) 1970-07-06
AT243080B (de) 1965-10-25
BE625049A (de)
DK140399B (da) 1979-08-20
DK140399C (de) 1980-01-14
GB973028A (en) 1964-10-21
NL285755A (de)
DE1421471A1 (de) 1968-10-10

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