US3561991A - Transfer record sheet for making multiple copies of a single heat impression - Google Patents

Transfer record sheet for making multiple copies of a single heat impression Download PDF

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Publication number
US3561991A
US3561991A US756008A US3561991DA US3561991A US 3561991 A US3561991 A US 3561991A US 756008 A US756008 A US 756008A US 3561991D A US3561991D A US 3561991DA US 3561991 A US3561991 A US 3561991A
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US
United States
Prior art keywords
coating
sheet
transfer
image
color
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US756008A
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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
Original Assignee
NCR Corp
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Publication date
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Publication of US3561991A publication Critical patent/US3561991A/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.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382Contact thermal transfer or sublimation processes
    • B41M5/38235Contact thermal transfer or sublimation processes characterised by transferable colour-forming materials
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/913Material designed to be responsive to temperature, light, moisture
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24851Intermediate layer is discontinuous or differential
    • Y10T428/24868Translucent outer layer
    • Y10T428/24876Intermediate layer contains particulate material [e.g., pigment, etc.]

Definitions

  • This invention relates to a self-revelation heat-activatable sheet-like transfer printing member comprising a translucent support sheet and a back-coating of heattackifiable transfer ink that normally is solid and normally reveals a light-reflecting surface at the interface of the support sheet and the coating, as viewed from the front uncoated side, but is irreversibly darkened when and where heated to the tackifiable condition.
  • the heattackified coating is an ink-source for making a transfer print against each of a number of light-colored copy-receiving sheets brought into pressure contact therewith in succession.
  • Tackified image areas of this novel sheet stay tacky long after the activating heat has been withdrawn and for some minutes stay tacky while cooled to room tem perature.
  • a tacky area may be used as a pattern ink-source to make successive copies on copy-receiving sheets brought into contact therewith.
  • the persistent tacky state of an area permits a number of images to be made in timed succession, side by side.
  • an image area forms a permanent copy of what has been printed and copied by its contrast with the light background of the untackified areas.
  • the dark image in one form (Type I) of the invention is made by generation of color and in another form (Type II) of the invention is made by solution and liquid migration of inherently color material.
  • Each of the two forms of the invention results in the making of a permanent right-reading image in the sheet-like transfer member itself, and this is the principal novelty of utility and construction provided by the invention.
  • None of the foregoing disclosures in any way show any means for making the heated image ink-source visible from the uncoated side of the transfer sheet as a dark area against a light background.
  • this invention provides a transparent base sheet having a complex coating on one side that ordinarily shows white or light color at the interface of the coating and the base sheet and a dark color at the interface wherever heated to a critical temperature as by a hot printing member.
  • This color may be produced by chemical reaction in situ at the interface by the applied heat, or may be material that migrates to the interface because of the heat, according to the construction of the coating.
  • the color is generated in situ (Type I)
  • small colorless particles of co-reactant color-forming material are dispersed throughout a heat-meltable coating with the retarded solidifying property, said co-reactant particles being brought together in reaction-contact solution when heated to the critical melting temperature.
  • This color appears at the interface, extends directly to the outer surface of the coating, and is transferable to copy paper brought into contact therewith.
  • the transfer material is substantially used up after a number of copies are made in succession. Even though the image temperature drops to room temperature (20 to 25 degrees centigrade), the melted state of the ink-source image persists. Put in other words, hardening of this image area is retarded, even though cooled to room temperature, for a time measured in tens of minutes.
  • the meltable heat-colorable transfer material is coated over a white liquid-penetrable sub-coating.
  • the melted tackified transfer coating When melted to a liquid, the melted tackified transfer coating dissolves dye particles dispersed therein, migrates through the white coating to appear at the inter face, and also is available at the outside surface for contact transfer to a copy sheet by reason of the tackiness.
  • FIG. 1 shows, in FIG. 1, a diagrammatic sketch of a heat-sensitive transparent base web transfer sheet of Type I, in which the transfer coating has dispersed in it particles of colorless chromogenic material and colorless particles of co-reactant to generate color, where melted, and
  • FIG. 2 is a diagrammatic sketch of a transparent base Web sheet of Type II with a transfer coating of particles of dye soluble in the melted transfer coating material.
  • the chief non-color components are a resin and a plasticizer which, once melted together at a critical temperature above normal room temperature, form a mixture which has a congealing temperature lower than the critical temperature and a delayed or retarded hardening characteristic.
  • the eligible support sheet material may be either translucent paper or a film of polymeric material thin enough to yield to marking pressures necessary to transfer the coating material and resistant to attack by the coating slurry liquid.
  • Ordinary carbonizing tissue paper is translucent enough to show a mark of blackish hue against a light background.
  • Commercial onion-skin paper likewise works well.
  • a five-pound sheet per ream of 500 sheets equaling 3,300 square feet is about minimum weight for tissue paper for transfer coatings. If polymeric film sup port sheet material is used, one with greater transparency than thin paper will yield prints more easily seen. Other than for these qualities, the nature of the base sheet is unimportant if it readily conducts heat of an applied hot printing member.
  • polymeric material may be mentioned, as eligible, films of cellulose acetate, cellulose acetate butyrate, cellophane, polyester, polyethylene, polyethylene terephthalate (Mylar), and equivalents. All such base sheets may be tinted lightly with transparent colors if desired.
  • the materials are so chosen that the re-hardening is retarded long enough to allow repeated transfer images to be made on plain copy sheets brought into contact with the melted image surface, the coating being used up incrementally until exhausted or else re-hardened by passage of time and heat loss, which may occur in ten to twenty minutes at room temperature.
  • the liquid used in the composition of materials used for coating the transparent support sheet should not dissolve the color-reactant materials or the colored materials lest a premature all-over coloring occur by reaction or liquid transportation of the coloring materials to make reaction contact, or by solution.
  • the color reactants of Type I and the dyes of Type II should dissolve in the melt but not in the vehicle used in the coating slurry. Therefore the liquid coating vehicle of choice is made with the purpose in mind of avoiding premature coloring, and the coating composition is unique in that respect over anything shown in the prior art and therefore is itself claimed as an aspect of the invention.
  • Example 1 This is a Type I coating and constitutes the preferred form of the invention. It is to be coated as a liquid slurry on 5 to pounds per ream weight of 3,300 square feet of translucent onion skin paper of smooth finish.
  • the liquid of the slurry is not a solvent for the particulate co-reactant color-formers, which are bis-phenol A and crystal violet lactone, which latter is 3,3 bis (p-dimethylaminophenyl)-6-dimethyl amino phthalide and which is normally white but turns dark blue on reaction contact with a suitable acidic substance.
  • the coating composition itself employs a dryable liquid vehicle of isoparaffinic constituents of inert properties and high evaporation rates.
  • the vehicle may be purchased under the trade name Isopar, sold by Humble Oil and Refining Company, of Houston, Tex., United States of America. Their Grade E has been found suitable as the vehicle for the dispersion of the color-forming materials bis-phenol A as the acid and crystal violet lactone as the base chromogenic reactant. They do not form reaction contact in the Isopar E, the vehicle evaporating without odor sufficiently rapidly to permit the coating to be applied to the base sheet and dried on conventional paper-coating apparatus. Of course, any fast-drying inert liquid vehicle may be substituted therefor, as it acts only as a liquid vehicle. Crystal violet lactone may be made according to directions given in United States Pat. Re. 23,024, issued Aug.
  • the color-forming chromogenic colorless dye precursors may be chosen from many colorless diaryl phthalides, leucauramines, acyl auramines, unsaturated aryl ketones, basic mono azo dyes, colorless Rhodamine 5 lactams, polyaryl carbinols, and 8 methoxy benzoindolinospiropyrans mentioned in said last-named application and patent.
  • colorants are not critical and does not form an important part of the invention, which is to provide a combination of such reactant material particles interspersed in a composition which when dried on a substrate of transparent or translucent propertties will, upon being impressed by a hot printing member, yield a tacky reusable colored ink-source pattern which is visible from the uncoated side of the support sheet.
  • the preferred composition is made of three dispersions, A, B, and C, and a solution D.
  • Dispersion A Eighteen grams of finely-divided crystal violet lactone is dispersed in a solution of 2 grams of Piccotex resin in 30 grams of Isopar E.
  • Isopar E is an isoparafiinic hydrocarbon fraction of boiling point range of 240 to 290 degrees Fahrenheit and 99% isoparafiinic content, sold by Humble Oil and Refining Company, of Houston, Tex., United States of America.
  • Piccotex is a styrene homolog copolymer resin, obtainable from Pennsylvania Industrial Chemical Corporation, of Clairton, Pa, United States of America, which in Grade 100 has a normal softening point of 100 degrees Centigrade and which is modified by the plasticizer in Dispersion C upon melting therewith.
  • Dispersion B Eighteen grams of finely-divided bis-phenol A is dispersed in a solution of 2 grams of the specified Piccotex dissolved in 30 grams of the specified Isopar E.
  • Dispersion C Eighteen grams of finely-divided Santicizer 3, which is a plasticizer of the structure and of the formula N-ethyl-para-toluene sulfonamide, obtainable from Monsanto Chemical Company, St. Louis, Mo., United States of America, is dispersed in 30 grams of Isopar E. Suitable plasticizer equivalents may be used to adjust the softening point of the dried coating, of which it forms a part when dried, to yield a transferable tacky condition thereof on application of printing temperature.
  • Solution D 7.5 grams of Vistanex, an adhesive polyisobutylene, available from Enjay Chemical Company, a Division of Humble Oil and Refining Company, of 60 W. 4th St., New York, N.Y., United States of America, is dissolved in 92.5 grams of Isopar E. This serves, when dried, as
  • the coating mixture is:
  • Dispersion A 1.5 parts by weight of Dispersion A 7.1 parts by weight of Dispersion B part by weight of Dispersion C 7.5 parts by weight of Solution D.
  • the dried 10-pound coating composition is Percentage Crystal violet lactone 5.4 Bis-phenol A 25.6 Santicizer #3 54.0 Piccotex 100 9.4 Vistanex 5.6
  • This coated sheet subject to an applied printing member having a temperature of 200 to 300 degrees Fahrenheit for a fraction of a second, melts the dried coating, causing it to assume a dark-blue-colored state throughout the coating layer in the heat image area, and this area is apparent, or self-revealing, as viewed through the translucent or transparent support sheet and remains soft and tacky for ten to twenty minutes, during which time copies of the printed data may be taken from the soft area by copy sheets pressed directly thereagainst.
  • the yield of color may not be fully developed by the fluid contact between the co-reactants in the tacky warm areas, it may be wise in some instances to sensitize the copy-receiving sheet with an acid substance, such as bis-phenol A or attapul ite, to develop any unreacted chromogenic material that has not assumed the colored state.
  • an acid substance such as bis-phenol A or attapul ite
  • Example 2 This Example 2 is a Type I coating in which a Dispersion E is provided to be used with Dispersions B and C and Solution D of Example 1 to form a coating slurry.
  • Dispersion E Eighteen gams of 6'-chloro, 8-methoxy derivative of 1,3,3-trimethylindolinebenzopyrylospiropyran having the structure is dissolved in grams of Isopar E.
  • the slurry is composed of 3.8 parts by weight of Dispersion E, 5.8 parts by weight of Dispersion B, 15 parts by weight of Dispersion C, and 7.5 parts by weight of Solution D. This is coated on suitable transparent or translucent substrate sheet material at a rate to yield a dry coating of 10 pounds per specified ream of 3,300 square feet, having the composition Percent by weight Benzospiran compound 10.1 Bis-phenol A 20.9 Santicizer 3 54.0 Piccotex 100 9.4 Vistanex 5.6
  • This coating also is normally white but turns dark blue and softens to transfer consistency with the property of retarded hardening upon being heated for a fraction of a second to from 200 to 300 degrees Fahrenheit.
  • This example merely substitutes a requisite amount of the benzospiran compound of basic properties and normally colorless state for the crystal violet lactone of Example 1.
  • Example 3 For this example, a coating slurry is made according to Example 1, with an amount of Rhodamine [3 Lactam in place of the crystal violet lactone of Example 1 on an equal weight-for-weight basis. This yields red marks instead of the dark blue marks of Examples 1 and 2.
  • Example 4 This example is a Type II coating on the transparent or translucent sheet material wherein the light color of the interface is caused not by dispersed particles of coreactant colorless materials in a meltable binder, but by dispersed particles of white-light-refiectant inert material dispersed in a suitable binder material which is coated as a sub-coating.
  • An Overcoating is applied to the sub-coating that is pigmented or colored otherwise and softenable to a tacky, transferable condition to the degree of fluidity that permits the pigment or coloring material to dissolve in it and to strike through the sub-coating and appear as a colored area against a light background as viewed from the uncoated side.
  • Overcoat B Percent by weight Santicizer #3 64 Methylene Blue SP 5 Nigrosine Base 2R 5 Armid HT 1 Vistanex 10 Piccotex 15 This is applied in Iso-par E as a 30% solids slurry.
  • Undercoat A is applied first, allowed to dry, and then overcoated with Composition B, which, when dried, leaves ten pounds per specified ream dry weight.
  • the second coating slurry will not penetrate the first coating.
  • a heated printing instrument applied for a fraction of a second to bring the heated area to between 200 and 300 degrees Fahrenheit will, because of the melting and solubilizing of the materials, make corresponding black marks seen through the base sheet and yield a transferable source of black fluid ink to make repeated copies to the number of six or eight on plain paper if used within ten minutes or so.
  • Allowance for ambient temperature and heat-sink properties of the hot impression means must be taken into account in compounding the various compositions, which may be varied slightly to meet the conditions of use and the differences made necessary by the use of substantially equivalent materials as to function.
  • plasticizer determines the melting point range of the coating and is so made that the coating begins to soften at about 110 degrees Fahrenheit, although this may be adjusted upwardly or downwardly to suit the conditions of use.
  • a hot printing member to bring the coating a temperature of 200 to 300 degrees Fahrenheit is quite adequate for the specified materials, and this is under the disintegration temperature of most eligible sheet support materials.
  • a heat-image-revealing heat-activated transfer sheet for use with a hot imaging printing member for making a printed transfer image on each of a succession of copy sheets brought into contact therewith, the sheet consisting of a substantially visible-light-transparent support sheet web-material adapted to application on one sheet surface of a hot heat-imaging printing member and coated on the other sheet surface with a solid potential ink source coating that is, at normal room temperature, substantially colorless, light reflecting and solid, that is meltable to a tacky transfer condition when a printing member of substantially higher than room temperature is applied to the uncoated side of the support web material, the melted coating staying so melted for a period measured in tens of minutes after the printing member is withdrawn and the normal room temperature of the coating has been resumed by cooling, the coating being characterized by containing potential coloring material that develops color on the coatings becoming melted and in that capacity acting as a solvent for the potential coloring material, said potential coloring material being insoluble in said coating as applied, which color, when developed, can be seen as an image of the
  • color-reactant particles are particles of crystal violet lactone and particles of 4,4-isopropilidene diphenol dispersed in a resin-plasticizer mixture, said particles giving the coating a normal white light reflectance and which coating turns to a dark blue reflectance upon being heated to the melting point and remains the dark blue state after solidification.
  • the coating comprises a sub-coating consisting of a dispersion of a particulate white pigment in plasticized half-second cellulose acetate butyrate; and an overcoating of fine solid particles of intense soluble dye dispersed in a meltable dried coating of resin plasticized with the half-second cellulose acetate butyrate of the retarded solidification property, the dye particles solubilizing in the melt areas wherein the hot image is impressed to yield a dark color which will penetrate the sub-coating to reveal the image at the interface as seen through the support web and to provide a tacky transfer coating.
  • a heat-activated transfer sheet consisting of a substantially white solid coating supported on one surface of a translucent base sheet, the white coating comprising a colorless resin, a colorless heat-meltable plasticizer therefor, and small particles of color former, the color former particles being soluble in the resin-plasticizer melt formed when a hot printing member is applied to the uncoated surface of the base sheet, to form color, but being insoluble in said resin plasticizer material as applied, the plasticizer being selected to melt at the temperature induced in it by the hot printing member and to dissolve the resin, the colored printing-member-melted area being visible through the uncoated surface of the base sheet and the melted coating being a tacky colored ink reservoir available to make copies on each of a succession of copy sheets brought into contact with the melted image area material.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Color Printing (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Coloring (AREA)
US756008A 1968-08-28 1968-08-28 Transfer record sheet for making multiple copies of a single heat impression Expired - Lifetime US3561991A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US75600868A 1968-08-28 1968-08-28

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US3561991A true US3561991A (en) 1971-02-09

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US756008A Expired - Lifetime US3561991A (en) 1968-08-28 1968-08-28 Transfer record sheet for making multiple copies of a single heat impression

Country Status (7)

Country Link
US (1) US3561991A (fr)
AT (1) AT294863B (fr)
BE (1) BE737421A (fr)
CH (1) CH495851A (fr)
DE (1) DE1942959B2 (fr)
FR (1) FR2017058A1 (fr)
GB (1) GB1265527A (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3908063A (en) * 1974-09-27 1975-09-23 Monarch Marking Systems Inc Novel transfer elements from porous alkenyl aromatic films
US3918895A (en) * 1972-10-09 1975-11-11 Dainippon Printing Co Ltd Transfer printing method
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
US4032690A (en) * 1975-01-24 1977-06-28 Mitsubishi Paper Mills, Ltd. Thermosensitive recording material
US4523207A (en) * 1983-03-30 1985-06-11 Ncr Corporation Multiple copy thermal record sheet
US4853256A (en) * 1986-08-14 1989-08-01 Ncr Corporation Two ply thermal paper and method of making
US5006863A (en) * 1987-07-06 1991-04-09 Ncr Corporation Multiple copy thermal imaging

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4783360A (en) * 1985-07-22 1988-11-08 Canon Kabushiki Kaisha Thermal transfer material
GB2178553B (en) * 1985-07-29 1990-01-04 Canon Kk Thermal transfer material

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3918895A (en) * 1972-10-09 1975-11-11 Dainippon Printing Co Ltd Transfer printing method
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
US3908063A (en) * 1974-09-27 1975-09-23 Monarch Marking Systems Inc Novel transfer elements from porous alkenyl aromatic films
US4032690A (en) * 1975-01-24 1977-06-28 Mitsubishi Paper Mills, Ltd. Thermosensitive recording material
US4523207A (en) * 1983-03-30 1985-06-11 Ncr Corporation Multiple copy thermal record sheet
US4853256A (en) * 1986-08-14 1989-08-01 Ncr Corporation Two ply thermal paper and method of making
US5006863A (en) * 1987-07-06 1991-04-09 Ncr Corporation Multiple copy thermal imaging

Also Published As

Publication number Publication date
DE1942959A1 (de) 1970-04-30
GB1265527A (fr) 1972-03-01
AT294863B (de) 1971-12-10
CH495851A (fr) 1970-09-15
DE1942959C3 (fr) 1979-04-05
BE737421A (fr) 1970-01-16
DE1942959B2 (de) 1978-08-10
FR2017058A1 (fr) 1970-05-15

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AS Assignment

Owner name: APPLETON PAPERS INC.

Free format text: MERGER;ASSIGNORS:TUVACHE, INC.;GERMAINE MONTEIL COSMETIQUES CORPORATION (CHANGED TO APPLETON PAPERS);REEL/FRAME:004108/0262

Effective date: 19811215