US3856554A - Pressure-sensitive carbonless transfer sheet and method for providing a chemically formed image on an untreated substrate - Google Patents

Pressure-sensitive carbonless transfer sheet and method for providing a chemically formed image on an untreated substrate Download PDF

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Publication number
US3856554A
US3856554A US00351710A US35171073A US3856554A US 3856554 A US3856554 A US 3856554A US 00351710 A US00351710 A US 00351710A US 35171073 A US35171073 A US 35171073A US 3856554 A US3856554 A US 3856554A
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United States
Prior art keywords
reactant
percent
image
sheet
pressure
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Expired - Lifetime
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US00351710A
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English (en)
Inventor
R Jablonski
J Martone
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International Business Machines Corp
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International Business Machines Corp
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Application filed by International Business Machines Corp filed Critical International Business Machines Corp
Priority to US00351710A priority Critical patent/US3856554A/en
Priority to FR7407863A priority patent/FR2225293B1/fr
Priority to GB1070274A priority patent/GB1455627A/en
Priority to JP2869074A priority patent/JPS5316728B2/ja
Priority to CA195,379A priority patent/CA1026555A/en
Priority to IT12715/74A priority patent/IT1010743B/it
Priority to DE2418128A priority patent/DE2418128A1/de
Application granted granted Critical
Publication of US3856554A publication Critical patent/US3856554A/en
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
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients

Definitions

  • ABSTRACT An encapsulated liquid reactant precursor and a coreactant therefor are supported on the under surface of a donor sheet that is placed over an untreated surface (i.e, devoid of reactant precursor and coreactant) of a receptor sheet or other substrate. Upon pressure-effected rupture of the capsules, a substantial amount of both the reactant precursor and the coreactant physically transfers to the untreated surface to provide, as a chemical reaction product, an essentially smudge-free, eradication-resistant, rightreadable image on the untreated receptor surface.
  • This donor transfer sheet and method are especially desirable where the receptor to be imaged is a data processing card or record on which a reactant and/or co-reactant coating could adversely affect processability through data processing equipment; or the receptor to be imaged has a rigid non-flat surface on which a conventional carbonless receptor coating is impractical; or where only a small area of the receptor is to be imaged.
  • This invention relates to pressure-sensitive transfer sheets and methods, and more particularly to an improved transfer sheet of the so-called carbonless type which supports an encapsulated liquid reactant and a co-reactant therefor that, upon rupture of the capsules by application of localized pressure, are adapted to physically transfer to an untreated surface of a substrate to provide a visible, chemical reaction product image on said untreated surface.
  • Applicants have discovered that certain non-obvious advantages over prior art arrangements are achieved by providing a pressure-sensitive donor sheet supporting on one surface thereof both an encapsulated reactant in solution and a distinctive co-reactant therefor, preferably in the form of separate coatings.
  • a pressure-sensitive donor sheet supporting on one surface thereof both an encapsulated reactant in solution and a distinctive co-reactant therefor, preferably in the form of separate coatings.
  • untreated surface means a surface that is devoid of both reactant and co-reactant.
  • Applicants pressure-sensitive carbonless transfer sheet is especially useful in applications where it is undesirable or impractical to have a reactant and/or coreactant coating preapplied to the sheet on which the image is desired; e.g., tabulating cards or the like on which a chemical coating could adversely affect the ability to process the cards through data processing equipment, or articles on which the surface to be imaged is only' a small fraction of the total surface of the article or is irregular in configuration.
  • no chemically reactive coating need be preapplied to the surface to be imaged that would or might change the properties or characteristics of the said surface; and when imaged, the card has a dry, smudge-free chemical reaction product image that does not impair its machine processing ability.
  • a visible mirror image of the image formed on the untreated receptor sheet is provided on the reactant/co-reactant coated surface of the donor sheet; this is useful as a security feature on legal documents, checks, etc. to produce automatically on the coated back of the document a mirror image of the right reading image imprinted on the uncoated face of the document and any alteration ofwhich mirror image can be readily detected.
  • FIGS. 1 and 2 are elevational sectional views, to greatly enlarged scale, of a pressure-sensitive donor sheet embodying the invention and supporting encapsulated reactant and co-reactant coatings for physical transfer to and chemical reaction on the adjacent untreated surface of a receptor sheet.
  • FIG. 1 denotes the condition before and FIG. 2 the condition after the transfer of reactant and co-reactant from the donor sheet to the receptor sheet.
  • sheet 10 is adapted to be placed with its co-reactant coating; 12 face down in intimate physical contact with the untreated somewhat absorptive surface 14 of a receptor substrate, such as a tabulating card or sheet 15.
  • a stylus, imprint member, or the like that exertsat least a preselected magnitude of impact or shear force, sufficient localized pressure is applied to the composite of sheets 10 and 14 to rupture the capsules 13.
  • the receptor surface 14 is somewhat absorptive so that image 16 is actually absorbed into the surface; i.e., it is formed substantially within the receptor surface rather than applied on it, as would be the case if the image were formed solely by physical transfer of a transfer medium. This makes the image 16 essentially erasure and alteration resistant, as well as smear and smudge free.
  • a sufficient proportion of the released reactant solution and co-reactant will generally remain on sheet to chemically react in situ to produce simultaneously on the underside of donor sheet 10 a dry reaction product mirror image 17 of the image 16 produced on sheet 15. In most instances, this mirror image will be an incidential product of the main chemical reaction that produces the right-reading image 16 on the untreated sur face 14. However, in certain applications the creation of such a mirror image may be useful or desirable as a security feature, in that there will be recorded on the underside of sheet 10 a mirror image 17 of the rightreading image 18 imparted on the upper side of sheet 10. This chemically formed mirror image 17 is embedded in the underside of sheet 10, rendering it essentially impossible to alter without such attempted alteration being readily detectable.
  • the pressure-rupturable capsules 13 must be formed of a film forming material that has the requisite properties, including sufficient strength to preclude inadvertent rupture. While many materials might be satisfactory, aldehyde condensation polymers, especially urea formaldehyde condensation polymers, are especially suitable.
  • the capsules are preferably from about 1 to 50 microns in size and formed in any suitable manner already known in the art; e.g., in the manner described in U.S. Pat. Nos. 2,730,457; 3,432,327; 3,5l6,846 or 3,558,341.
  • the capsules contain a liquid reactant precursor; preferably this is in the form of a solution comprising a chemically reactive dye precursor dissolved in an appropriate solvent.
  • a particularly suitable class of reactant precursors are dithiooxamide and its N,N-disubstituted derivatives; of these, the N,N-diorganosubstituted-dithiooxamides, dissolved in organic solvents, are preferred. It will be understood that the solution will preferably contain one or more additional ingredients for specialized purposes such as enhancing storage stability. speed and/or intensity of colorproducing reaction, etc.
  • Applicants improvement resides, primarily, in providing a reactant coating 11 and a co-reactant coating 12 that will physically transfer to an untreated somewhat absorptive surface 14 of a tabulating card 15 or the like, and there chemically react to promptly produce a dry, eradication-resistant image of commercially acceptable intensity and durability that will not impede processing of the card through data processing machines.
  • the combination of chemical reaction and solubility characteristics and absorption characteristics into the cardstock assures that a substantial part of the coreactant coating will transfer with the reactant solution and be absorbed; the remainder of the coating and solution will remain in situ and provide a security feature for applications, such as of the type above described.
  • the reactant coating 11 and co-reactant coating 12 are preferably applied by a conventional coating apparatus before a paper web is severed into sheets 10. Coating 11 is preferably applied, then dried as the web moves in line to a second coating apparatus that applies the coating 12. However, it will be apparent that, if preferred, the coatings 11, 12 may be applied as a composite single coating, rather than sequentially as just described.
  • the capsules are believed to contain solvents of tributyl phosphate and diethyl phthalate and reactive components of N,N-bis(2-octanoyloxyethyl) dithiooxamide coated with a binder containing azinccarboxylate; and the capsule walls are formed of urea formaldehyde resin.
  • the co-reactant coatings 12 were prepared by adding the ingredients specified in Table I to a suitable solvent, such as denatured alcohol. Each mixture was then shaken for 15 minutes by a vibratory paint shaker using steel ballswithin the container to facilitate solution and dispersion. The resulting solution was then applied as a coating over the encapsulated reactant coating 11 and dried to remove the solvent.
  • a suitable solvent such as denatured alcohol
  • the variously coated sheets 10 were then placed, with the co-reactant-coated surface face down, in inti mate physical contact with the untreated surface 14 of tabulating card 15.
  • the cards 15 were then imaged by applying localized pressure to the upper uncoated surface of the sheets 10 using well known techniques such as ball-point pens, pencils, typewriter keys, and imprinting devices employing embossed credit cards.
  • Table I expresses the formulations of the co-reactant coatings 12 of Examples 1 through 4 in terms of percentage by weight of the various ingredients less the volatile solvent which ultimately evaporates.
  • the examples are listed in order of preference; i.e., Example l is preferred.
  • An evaluation of these formulations with respect to image intensity, image development speed and appearance of the coated sheet after imaging are also included in Table l, with the letters E, G, F, P
  • the sodium benzoate is not essential, but is be lieved to contribute to image intensity on the receptor sheet 15.
  • Zinc resinate 10.3 Solvent denatured alcohol (preferably PM 3163, Ashland Chemical Co.)
  • Example 1 the image develops usable intensity more rapidly than that of Example 2, and donor sheet appearance is better. Both exhibit good temperature and environment stability (i.e., shelf life) and produce on card 15, by ingredient transfer and reaction, chemically formed images of commercially acceptable intensity.
  • the nickel (II) chloride provides the metal cation that ultimately complexes with dithiooxamide and/or its derivatives.
  • the sodium ricinoleate provides the anion that combines with the nickel (ll) chloride to form (in part) nickel ricinoleate which is highly soluble in the solvent systemincluded in the capsule fill of the 3M CB sheet.
  • the lithium stearate and stearic acid facilitate release of the imaging materials from the donor sheet.
  • the Santovar A antioxidant confers long term environmental stability to the coating.
  • the amount of sodium ricinoleate is reduced and zinc resinate substituted; in this instance, the zinc resinate pro vides a substance that reacts with the nickel (II) chloride to form (in part) nickel resinate which is highly soluble in the solvent system included in the capsule fill ofthe 3M CB sheet, and it also binds the coating to the substrate and provides coating cohesion.
  • the coated donor sheet 10 is described as imaging an untreated surface 14 of a tabulating card 15, it should be noted that donor sheets having the compositions above described have also been used successfully to image untreated signature panels on credit cards, untreated paper sheets (e.g., bank checks, labels) and painted or coated objects. It is contemplated that, if desired, the donor sheet 10 might also be used to image porous or nonporous receptors which serve as intermediaries from which the image is transferred to another surface.
  • split-image formulations disclosed in the above-identified related application were tested in reactive transfer applications (i.e., imaging an untreated surface), but found to be totally unsuitable.
  • mirror image 17 of the indicia 18 imprinted on the top side of the donor sheet 10 will be formed by chemical reaction on the underside of said donor sheet, this being highly desirable for security feature applications of the type above described.
  • a pressure-sensitive carbonless transfer sheet having a surface supporting a multitude of microscopic pressure-rup'turable capsules containing a reactant solution comprising a precursor taken from the class of dithiooxa'mide and its N,N'di-substituted derivatives, and a solvent and also supporting a co-reactant for the reactant solution, which co-reactant comprises nickel (ll) chloride, sodium ricinoleate and stearic acid,
  • a sheet according to claim 1 wherein upon application of such localized pressure to another surface of the sheet opposite the first-mentioned surface, the remainder of the co -reactant and reactant solution will remain in situ and chemically react to provide on the first-mentioned surface a chemically formed mirror image of the image formed by application of pressure to such other surface.
  • a sheet according to claim 1, wherein the coreactant comprises, by weight, when dried, about 10 30 percent nickel (ll) chloride; -50 percent sodium ricinoleate; 2545 percent stearic acid and lithium stearate as a combined total, but for any percentage selected there being ore stearic acid by weight than lithium stearate; and 2 10 percent anti-oxidant.
  • a sheet according to claim 1, wherein the co reactant consists by weight, when dried, of essentially about 21 percent nickel (ll) chloride; 21 percent sodium ricinoleate; 10 percent lithium stearate; 20 percent stearic acid; 10 percent sodium benzoate; 10 percent zinc resinate; and 8 percent anti-oxidant.
  • a sheet according to claim 1, wherein the coreactant consists by weight, when dried, of essentially about 15 percent nickel (11) chloride; 35 percent sodium ricinoleate; 17 percent lithium stearate; 25 percent stearic acid; and 8 percent anti-oxidant.
  • a sheet according to claim 1, wherein the coreactant consists by weight, when dried, of essentially about 20 percent nickel (ll) chloride; 46 percent sodium ricinoleate; 28 percent stearic acid; and 6 percent anti-oxidant.
  • a sheet according to claim 1, wherein the coreactant consists by weight, when dried, of essentially about 25 percent nickel (l1) chloride; 31 percent sodium ricinoleate; 13 percent lithium stearate; 19 per cent stearic acid; 6 percent sodium benzoate; and 6 percent anti-oxidant.
  • a pressure-sensitive recording system the combination of one member having a substantially flat surface supporting a multitude of microscopic pressurerupturable capsules containing a reactant solution comprising a precursor taken from the class of dithiooxamide and its N,N'di-substituted derivatives, and the co-reactant comprises nickel (II) chloride, sodium ricinoleate and stearic acid, and another member having a somewhat absorptive surface which is devoid of reactant and co-reactant,
  • the reactant solution and co-reactant being adapted, upon application of a localized pressure to said members and consequent rupture of the capsules while said surfaces are superimposed in intimate contact, to cause at least some of the reactant solution to partly dissolve at least some of the coreactant and physically transfer from the flat surface to the absorptive surface and be absorbed therein sufficiently to cause the chemical reaction that occurs between precursor and co-reactant to provide in the absorptive surface a chemically formed image that is immediately dry and essentially smudge-free and erasure resistant.
  • the coreactant comprises, by weight, when dried, about 10-30 percent nickel (ll) chloride; 15-50 percent sodium ricinoleate; 2545 percent stearic acid and lithium stearate with a preponderance of stearic acid; and

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  • Color Printing (AREA)
  • Decoration By Transfer Pictures (AREA)
  • Printing Methods (AREA)
  • Credit Cards Or The Like (AREA)
US00351710A 1973-04-16 1973-04-16 Pressure-sensitive carbonless transfer sheet and method for providing a chemically formed image on an untreated substrate Expired - Lifetime US3856554A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US00351710A US3856554A (en) 1973-04-16 1973-04-16 Pressure-sensitive carbonless transfer sheet and method for providing a chemically formed image on an untreated substrate
FR7407863A FR2225293B1 (enrdf_load_stackoverflow) 1973-04-16 1974-02-28
GB1070274A GB1455627A (en) 1973-04-16 1974-03-11 Pressure-sensitive donor sheet
JP2869074A JPS5316728B2 (enrdf_load_stackoverflow) 1973-04-16 1974-03-14
CA195,379A CA1026555A (en) 1973-04-16 1974-03-19 Pressure-sensitive carbonless transfer sheet and method for providing a chemically formed image on an untreated substrate
IT12715/74A IT1010743B (it) 1973-04-16 1974-04-05 Procedimento e carta speciale per il trasferimento di immagini da un foglio all altro senza l impiego di carta carbone
DE2418128A DE2418128A1 (de) 1973-04-16 1974-04-13 Verfahren zur erzeugung eines bildes auf chemischem wege auf einer unbehandelten oberflaeche

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Application Number Priority Date Filing Date Title
US00351710A US3856554A (en) 1973-04-16 1973-04-16 Pressure-sensitive carbonless transfer sheet and method for providing a chemically formed image on an untreated substrate

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US3856554A true US3856554A (en) 1974-12-24

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US00351710A Expired - Lifetime US3856554A (en) 1973-04-16 1973-04-16 Pressure-sensitive carbonless transfer sheet and method for providing a chemically formed image on an untreated substrate

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US (1) US3856554A (enrdf_load_stackoverflow)
JP (1) JPS5316728B2 (enrdf_load_stackoverflow)
CA (1) CA1026555A (enrdf_load_stackoverflow)
DE (1) DE2418128A1 (enrdf_load_stackoverflow)
FR (1) FR2225293B1 (enrdf_load_stackoverflow)
GB (1) GB1455627A (enrdf_load_stackoverflow)
IT (1) IT1010743B (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4321092A (en) * 1973-07-27 1982-03-23 Kores Holding Zug Ag Pressure-sensitive duplicating material
US4435471A (en) 1981-06-17 1984-03-06 Mitsubishi Paper Mills, Ltd. Transfer-onto-plain paper type of pressure-sensitive copying paper
US4971886A (en) * 1987-08-10 1990-11-20 Brother Kogyo Kabushiki Kaisha Recording medium having heat-sensitive chromogenic material, and image reproducing method by using the medium
WO1999008882A1 (en) * 1997-08-20 1999-02-25 Sergei Evgenievich Lavysh Blank form for official declarations, announcements and letters

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4111462A (en) * 1975-07-15 1978-09-05 Minnesota Mining And Manufacturing Company Latent, sensitizing ink
US4622282A (en) * 1985-02-20 1986-11-11 The Mead Corporation Photographic method for forming images on plain paper
US4701397A (en) * 1986-02-26 1987-10-20 The Mead Corporation Method for forming images on plain paper and an imaging sheet useful therein
JPH0311786A (ja) * 1989-06-09 1991-01-21 Ibiden Co Ltd プリント配線板

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711375A (en) * 1951-08-24 1955-06-21 Ncr Co Pressure sensitive manifold sheet
US2872863A (en) * 1954-12-02 1959-02-10 Columbia Ribbon & Carbon Hectograph duplicating
US2932582A (en) * 1959-02-04 1960-04-12 Ncr Co Pressure sensitive transfer record sheet
US3020171A (en) * 1960-08-26 1962-02-06 Ncr Co Pressure-sensitive record and transfer sheet material
US3088028A (en) * 1959-02-06 1963-04-30 Columbia Ribbon & Carbon Duplication with heat-meltable solvent for hectographic coloring material
US3287154A (en) * 1963-04-24 1966-11-22 Polaroid Corp Pressure responsive record materials
US3305382A (en) * 1964-01-02 1967-02-21 Ibm Pressure sensitive transfer sheet
US3558341A (en) * 1968-04-01 1971-01-26 Ncr Co Pressure-sensitive record material
US3697323A (en) * 1971-01-06 1972-10-10 Ncr Co Pressure-sensitive record material

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711375A (en) * 1951-08-24 1955-06-21 Ncr Co Pressure sensitive manifold sheet
US2872863A (en) * 1954-12-02 1959-02-10 Columbia Ribbon & Carbon Hectograph duplicating
US2932582A (en) * 1959-02-04 1960-04-12 Ncr Co Pressure sensitive transfer record sheet
US3088028A (en) * 1959-02-06 1963-04-30 Columbia Ribbon & Carbon Duplication with heat-meltable solvent for hectographic coloring material
US3020171A (en) * 1960-08-26 1962-02-06 Ncr Co Pressure-sensitive record and transfer sheet material
US3287154A (en) * 1963-04-24 1966-11-22 Polaroid Corp Pressure responsive record materials
US3305382A (en) * 1964-01-02 1967-02-21 Ibm Pressure sensitive transfer sheet
US3558341A (en) * 1968-04-01 1971-01-26 Ncr Co Pressure-sensitive record material
US3697323A (en) * 1971-01-06 1972-10-10 Ncr Co Pressure-sensitive record material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4321092A (en) * 1973-07-27 1982-03-23 Kores Holding Zug Ag Pressure-sensitive duplicating material
US4435471A (en) 1981-06-17 1984-03-06 Mitsubishi Paper Mills, Ltd. Transfer-onto-plain paper type of pressure-sensitive copying paper
US4971886A (en) * 1987-08-10 1990-11-20 Brother Kogyo Kabushiki Kaisha Recording medium having heat-sensitive chromogenic material, and image reproducing method by using the medium
WO1999008882A1 (en) * 1997-08-20 1999-02-25 Sergei Evgenievich Lavysh Blank form for official declarations, announcements and letters

Also Published As

Publication number Publication date
JPS5316728B2 (enrdf_load_stackoverflow) 1978-06-03
FR2225293B1 (enrdf_load_stackoverflow) 1979-01-26
IT1010743B (it) 1977-01-20
DE2418128A1 (de) 1974-10-24
FR2225293A1 (enrdf_load_stackoverflow) 1974-11-08
GB1455627A (en) 1976-11-17
JPS501816A (enrdf_load_stackoverflow) 1975-01-09
CA1026555A (en) 1978-02-21

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