US3839070A - Pressure sensitive recording system and method of providing a split image therefor - Google Patents

Pressure sensitive recording system and method of providing a split image therefor Download PDF

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Publication number
US3839070A
US3839070A US00275394A US27539472A US3839070A US 3839070 A US3839070 A US 3839070A US 00275394 A US00275394 A US 00275394A US 27539472 A US27539472 A US 27539472A US 3839070 A US3839070 A US 3839070A
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United States
Prior art keywords
percent
reactant
sheet
image
weight
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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
Application number
US00275394A
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English (en)
Inventor
J Martone
R Jablonski
J Kotla
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International Business Machines Corp
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International Business Machines Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by International Business Machines Corp filed Critical International Business Machines Corp
Priority to US00275394A priority Critical patent/US3839070A/en
Priority to FR7322365A priority patent/FR2194158A5/fr
Priority to IT25616/73A priority patent/IT998168B/it
Priority to CA174,772A priority patent/CA1007266A/en
Priority to JP48069980A priority patent/JPS5123201B2/ja
Priority to GB3325473A priority patent/GB1378268A/en
Priority to DE19732337360 priority patent/DE2337360A1/de
Application granted granted Critical
Publication of US3839070A publication Critical patent/US3839070A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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 Corresponding images are provided on adjacent surfaces of two sheets.
  • An encapsulated liquid reactant precursor is supported on one of the surfaces and a co-reactant is coated on the other surface.
  • the adhesion/cohesion characteristics of the co-reactant coating are so adjusted and selected that upon pressure-effected rupture of the particular capsules used, some of the coreactant (as well as some precursor) physically trans fer and the balance of each remains in situ and does not transfer. Substantially identical chemical reactions are thus produced concurrently on both adjacent surfaces to provide corresponding colored images thereon.
  • the mirror image formed on the underside thereof by one of the chemical reactions will be viewable from the top side thereof as a right-readable image upon separation of the sheets.
  • This invention relates to pressure-sensitive recording systems and methods, and more particularly to an improved system of the so-called carbonless type wherein capsules on one sheet containing one liquid reactant are ruptured by pressure to produce a chemical reaction with a co-reactant on another sheet to provide visible images on both such sheets as a result of a partial transfer of the co-reactant as well as the reactant.
  • the porous sheet when compressed, releases a reactant that migrates up through the sheet to make a one-way reaction with a reactive coating at the top of the sheet and a one-way reaction with the adjacent reactively coated surface of another sheet.
  • the colorless marking material produces no image on the underside of the porous sheet.
  • an image is produced concurrently on the adjacent surfaces of two superposed sheets; but in such system the underside of a porous upper sheet is coated with an encapsulated colored marking fluid or colored dye.
  • the images are formed, not by any chemical reaction, but by capsule rupture and release of colored ink or dye in the upper sheet and oneway physical transfer of some of such colored ink or dye to the lower sheet.
  • any inadvertent rupture of the colored-dye-containing capsules prior to superposition of the sheets will produce undesirable marking or smearing.
  • the material used to coat the sheet must provide a low-viscosity ink comprising a solvent capable of penetrating that sheet in such manner and in such quantity as to provide a visible colored mark or a potentially visible mark on the side opposite the coated side.
  • the solvent must be suffi- 5 ciently volatile to limit the migration. Volatile solvents are difficult to retain in capsules.
  • the low viscosity inks will feather out laterally, as well as vertically, as they bleed through the porous sheet; and this will impair legibility and sharpness of the resultant image on the porous sheet.
  • a pressure-sensitive recording system and method embodying an encapsu lated reactant in solution that partially transfers and reacts with a co-reactant that also partially transfers upon rupture of the capsules so as to simultaneously produce a dry right-readable reaction by-product colored image anda dry reaction by-p ro d uct colored mirror image thereof on adjacent surfaces of two sheets as a result of the two-way mutual physical transfer and chemical reaction.
  • the encapsulated reactant and the co-reactant are supported on adjacent surfaces of different sheets. Only some of the co-reactant and some of the reactant physically transfer to the adjacent surface of the other sheet; the balance remains in situ (i.e., on the surface on which it had originally been supported), thus providing colored images by essentially identical chemical reactions on both such surfaces.
  • Such a pressure-responsive recording system is especially desirable in record sets, such as used for gasoline credit sales, wherein a translucent sheet overlies an opaque sheet; in such case, the encapsulated reactant would preferably be applied to the opaque sheet and the coreactant applied to the translucent sheet.
  • FIGS. 1 and 2 are elevational sectional views, to vastly enlarged scale, of a pressure-sensitive recording system embodying the invention and comprising an encapsulated reactant and co-reactant coated on adjacent surfaces of different sheets, FIG. 1 denoting the condition before and FIG. 2 the condition after a mutual partial transfer of reactant and co-reactant produces chemical reactions and corresponding images on both such surfaces.
  • the pressure-sensitive recording system illustrated in FIGS. 1 and 2 comprises a substrate, such as sheet 10, the upper surface of which has a coating 11 or the like.
  • This coating includes a multitude of microscopic pressure-rupturable capsules 12 containing a reactant solution comprising a chemically reactive dye precursor and a solvent.
  • a coating 13 or the like which comprises a color-forming co-reactant for the said dye precursor and is carried by the underside of an overlying substrate, such as a sheet 14.
  • the cobe ofa formulation providing sufficient adhesion to the substrate 14 and cohesion within itself to prevent premature release during normal handling; it must exhibit the proper amount of adhesion to coating 12 to facilireactant coating 13 transferred to sheet 10 chemically tate transfer; and yet coating 13 must have a cohesion reacts with that portion of the released reactant solulow gh to as e that hen a normal degree of lotion which remained in sit on said h t t produce a calized pressure is applied, the forces of adhesion will dry right-reading reaction by-product image 15 correprevail over the forces of cohesion. This combination sponding to the pattern of applied pressure.
  • the (to-reactant coating 13 is preferably applied by a 15, 16 will b d d concurrently on dj t conventional coating apparatus before the paper web faces of both sheets l0, 14 by the two-way mutual pariS Severed o ee 14- tial physical transfer and chemical interaction of reac- NOW at t e general nature Of the invention has tant and co-reactant.
  • the overlyeactants that have been used successfully in appliing sheet 14 is preferably sufficiently transparent (e.g., cants split image pressure-sensitive recording systranslucent) so that the mirror image provided on the e and methodunderside of said sheet will be viewable from the top EXAMPLES side of the sheet as a right-reading image when the in each of the following tabulated Examples 1-6, a sheets l0, 14 are separated.
  • the pressure-rupturable capsules 12 may be formed pany, e cap ules 12 form ng pa t thereof are known from any film forming material that is sufficiently to contain dithiooxamide or one of its N,N-distrong to preclude inadvertent rupture.
  • the capsules are believed to contain solpolymers, are especially suitable.
  • the capsules are vents of tributyl phosphate and diethyl phthalate and preferably from about 1 to 50 microns in size and reactive components of N,N-bis(2-octanoyloxyethyl) formed in any suitable manner already known in the dithiooxamide coated with a binder containing a zincart; e.g., in the manner described in U.S. Pat. No.
  • the formaldehyde resin. capsules contain a liquid reactant precursor; preferably The co-reactant coatings 13 were prepared by adding this is in the form of a solution comprising a chemically the ingredients specified in Table l to a suitab e o reactive dye precursor dissolved in a volatile solvent.
  • a preferably denatured alcohol such as that designated as particularly suitable class of reactant precursors are di- PM 3163 and marketed by Ashland Chemical Co.
  • Table l expresses the formulations of the co-reactant when it reacts chemically with the particular reactant coatings 13 of Examples 1 through 6 in terms of perin the capsule 12, but also exhibits proper adhesion/- eentage by weight of the various ingredients less the cohesion characteristics. That is, the coating 13 must volatile solvent which ultimately evaporates.
  • the nickel (ll) chloride provides the metal cation that ultimately complexes with dithiooxamide and/or its derivatives.
  • the zinc resinate provides a substance that reacts with the nickel chloride to form (in part) nickel resinate which is highly soluble in the solvent system included in the capsule fill of the 3M CB sheet; it also binds the coating to the substrate and provides coating cohesion.
  • the lithium stearate causes a reasonably bal- 2Q anced split of the image between the mating sheets, provides coating cohesion and increased image intensity, and also renders the applied coating semi-opaque to increase image contrast.
  • the three ingredients just specified are very important in assuring the split image according to the invention; whereas the sodium benzoate is considered highly desirable, though not essential,
  • Examples 1-6 The six formulations of Examples 1-6 were found to exhibit the following functional requirements that are 3 essential to commercial acceptability; good image visual intensity on both plies, good imaging speed, and good environmental stability. They were also found suitable for imaging by either pens or credit card imprinters. 3 5
  • Example 1 The formulation that produces the optimum blend of the aforementioned functional requirements necessary for commercial acceptance was that of Example 1, which is therefore repeated below as the preferred formulation.
  • commercially acceptable (though not necessarily optimum) coreactant coatings may be obtained by employing the named ingredients within the ranges specified below:
  • Example 1 While applicants do not know the precise reason why the specific formulation of Example 1 is superior to that of the others, they believe, on the basis of their findings, that it possesses the optimum balance of adhesion/cohesion forces and chemical reactivity.
  • Examples l-6 do not constitute all of the formulations prepared and evaluated.
  • Other formulations were prepared and evaluated which included one or more of the ingredients listed for Examples l-6, together with nickel resinate, nickel stearate, stearic acid, and others in varying amounts; but the evaluations made on such other formulations showed that they were generally unsuitable for commercial acceptability, except for one formulation in which silica and sodium benzoate were included.
  • the silica merely supplemented and served the same function as the lithium stearate in enhancing image contrast in the translucent sheet 14, but it could not replace the lithium stearates function of also increasing image intensity.
  • the zinc resinate serves as the binder
  • the propyl gallate and tannic acid serve as the co-reactant for the encapsulated precursor
  • the silica facilitates a splitting of the image between the mating sheets and also renders the coating semi-opaque thereby increasing image contrast.
  • EXAMPLE 8 An encapsulated donor sheet currently being offered for sale in the United States by The Pilot Pen Company, Ltd., Tokyo, Japan, was used to constitute the substrate 10 and encapsulated coating 11. While the specific formulation of the encapsulated coating is not known, it is believed to be in accord with the teachings of Exampie 3 of U.S. Pat. No. 3,432,327.
  • the propyl gallate and tannic acid serve as the co-reactant for the encapsulated precursor
  • the polyvinylpyrrolidone and to some extent the waxes serve as the binder
  • the waxes and the silica facilitate splitting of the image, with the silica also serving to enhance image contrast.
  • a pressure-sensitive recording system comprising one sheet having a surface supporting a multitude of microscopic pressure-rupturable capsules containing a reactant solution comprising a chemically reactive dye precursor and a solvent, and
  • the particular one of said sheets having said other of said surfaces being sufficiently transparent so that upon separation of the sheets the mirror image will be viewable as a right readable image from the reverse side of such particular sheet without bleed through of reaction product to said reverse side.
  • the reactant solution comprising a precursor taken from the class of dithiooxamide and its N,Ndi-substituted derivatives, and the co-reactant comprising by weight, when dried, about 22-37 percent nickel (Il) chloride; about 9-21 percent zinc resinate; about 31-45 percent lithium stearate; and about 5-19 percent sodium benzoate.
  • a system according to claim 1, wherein the co reactant comprises by weight, when dried, essentially about 55 percent propyl gallate; 6 percent tannic acid; 6 percent polyvinylpyrrolidone; 16 percent oxazoline wax; and 17 percent silica.
  • the coreactant comprises by weight, when dried, essentially about 27 percent zinc resinate; 27 percent propyl gallate; 9 percent tannic acid; and 37 percent colloidal sil- 5.
  • the solution comprises a precursor taken from the class of dithiooxamide and its N,Ndi-substituted derivatives, and the co-reactant comprises nickel (ll) chloride, zinc resinate, lithium stearate and sodium benzoate.
  • a system according to claim 1, wherein the coreactant comprises by weight, when dried, 22-37 percent nickel (ll) chloride; 9-21 percent zinc resinate; 31-45 percent lithium stearate; and 5-19 percent sodium benzoate.

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US00275394A 1972-07-26 1972-07-26 Pressure sensitive recording system and method of providing a split image therefor Expired - Lifetime US3839070A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US00275394A US3839070A (en) 1972-07-26 1972-07-26 Pressure sensitive recording system and method of providing a split image therefor
FR7322365A FR2194158A5 (fr) 1972-07-26 1973-06-13
IT25616/73A IT998168B (it) 1972-07-26 1973-06-20 Sistema di registrazione perfezionato
CA174,772A CA1007266A (en) 1972-07-26 1973-06-22 Pressure sensitive recording system and method of providing a split image therefor
JP48069980A JPS5123201B2 (fr) 1972-07-26 1973-06-22
GB3325473A GB1378268A (en) 1972-07-26 1973-07-12 Pressure sensitive recording medium
DE19732337360 DE2337360A1 (de) 1972-07-26 1973-07-23 Druckempfindliches aufzeichnungssystem und verfahren zur erzeugung von splitbildern

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00275394A US3839070A (en) 1972-07-26 1972-07-26 Pressure sensitive recording system and method of providing a split image therefor

Publications (1)

Publication Number Publication Date
US3839070A true US3839070A (en) 1974-10-01

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US00275394A Expired - Lifetime US3839070A (en) 1972-07-26 1972-07-26 Pressure sensitive recording system and method of providing a split image therefor

Country Status (7)

Country Link
US (1) US3839070A (fr)
JP (1) JPS5123201B2 (fr)
CA (1) CA1007266A (fr)
DE (1) DE2337360A1 (fr)
FR (1) FR2194158A5 (fr)
GB (1) GB1378268A (fr)
IT (1) IT998168B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4882211A (en) * 1988-08-03 1989-11-21 Moore Business Forms, Inc. Paper products with receptive coating for repositionable adhesive and methods of making the products

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS608960B2 (ja) * 1978-06-28 1985-03-06 内外インキ製造株式会社 感圧複写紙
JP2535383B2 (ja) * 1988-06-24 1996-09-18 新王子製紙株式会社 改竄防止用感圧複写シ―ト

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2588572A (en) * 1947-09-23 1952-03-11 Potteiger Roy Victor Method of making mechanical negatives for photocopies
US2810661A (en) * 1954-05-20 1957-10-22 Columbia Ribbon Carbon Mfg Transfer sheet
US2872863A (en) * 1954-12-02 1959-02-10 Columbia Ribbon & Carbon Hectograph duplicating
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
US3241996A (en) * 1962-10-10 1966-03-22 Polaroid Corp Heat-sensitive copy sheet system and process of copying
US3287154A (en) * 1963-04-24 1966-11-22 Polaroid Corp Pressure responsive record materials
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
US2588572A (en) * 1947-09-23 1952-03-11 Potteiger Roy Victor Method of making mechanical negatives for photocopies
US2810661A (en) * 1954-05-20 1957-10-22 Columbia Ribbon Carbon Mfg Transfer sheet
US2872863A (en) * 1954-12-02 1959-02-10 Columbia Ribbon & Carbon Hectograph duplicating
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
US3241996A (en) * 1962-10-10 1966-03-22 Polaroid Corp Heat-sensitive copy sheet system and process of copying
US3287154A (en) * 1963-04-24 1966-11-22 Polaroid Corp Pressure responsive record materials
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 (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4882211A (en) * 1988-08-03 1989-11-21 Moore Business Forms, Inc. Paper products with receptive coating for repositionable adhesive and methods of making the products

Also Published As

Publication number Publication date
JPS5123201B2 (fr) 1976-07-15
FR2194158A5 (fr) 1974-02-22
JPS4952012A (fr) 1974-05-21
GB1378268A (en) 1974-12-27
CA1007266A (en) 1977-03-22
DE2337360A1 (de) 1974-02-14
IT998168B (it) 1976-01-20

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