US2548365A - Process for making pressure sensitive record materials - Google Patents

Process for making pressure sensitive record materials Download PDF

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US2548365A
US2548365A US3854848A US2548365A US 2548365 A US2548365 A US 2548365A US 3854848 A US3854848 A US 3854848A US 2548365 A US2548365 A US 2548365A
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substance
film
solid
color
liquid
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Barrett K Green
Robert W Sandberg
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NCR Voyix Corp
National Cash Register Co
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NCR Corp
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Priority to US3854848 priority Critical patent/US2548365A/en
Priority to US3854748 priority patent/US2548364A/en
Priority to US4175648 priority patent/US2548366A/en
Priority to GB1563349A priority patent/GB660502A/en
Priority to GB1615449A priority patent/GB666438A/en
Priority to GB1615349A priority patent/GB666437A/en
Priority to DEP46154A priority patent/DE855998C/en
Priority to BE490053D priority patent/BE490053A/xx
Priority to DEP48197A priority patent/DE851806C/en
Priority to FR994976D priority patent/FR994976A/en
Priority to CH283442D priority patent/CH283442A/en
Priority to NL147566A priority patent/NL72381C/xx
Priority to BE490255D priority patent/BE490255A/xx
Priority to FR995128D priority patent/FR995128A/en
Priority to CH284424D priority patent/CH284424A/en
Priority to CH287576D priority patent/CH287576A/en
Priority to FR995149D priority patent/FR995149A/en
Priority to US183532A priority patent/US2550467A/en
Priority to US18353450 priority patent/US2550469A/en
Priority to US183531A priority patent/US2550466A/en
Priority to US183533A priority patent/US2550468A/en
Priority to US18515150 priority patent/US2550470A/en
Priority to US18515350 priority patent/US2550472A/en
Priority to US18515250 priority patent/US2550471A/en
Priority to US185154A priority patent/US2550473A/en
Application granted granted Critical
Publication of US2548365A publication Critical patent/US2548365A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/025Applications of microcapsules not provided for in other subclasses
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41LAPPARATUS OR DEVICES FOR MANIFOLDING, DUPLICATING OR PRINTING FOR OFFICE OR OTHER COMMERCIAL PURPOSES; ADDRESSING MACHINES OR LIKE SERIES-PRINTING MACHINES
    • B41L1/00Devices for performing operations in connection with manifolding by means of pressure-sensitive layers or intermediaries, e.g. carbons; Accessories for manifolding purposes
    • B41L1/20Manifolding assemblies, e.g. book-like assemblies
    • B41L1/36Manifolding assemblies, e.g. book-like assemblies with pressure-sensitive layers or coating other than carbon
    • 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
    • B41M5/124Duplicating 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
    • 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
    • B41M5/124Duplicating 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
    • B41M5/132Chemical colour-forming components; Additives or binders therefor
    • 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
    • B41M5/124Duplicating 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
    • B41M5/132Chemical colour-forming components; Additives or binders therefor
    • B41M5/155Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
    • B41M5/1555Inorganic mineral developers, e.g. clays
    • 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
    • Y10S101/00Printing
    • Y10S101/29Printing involving a color-forming phenomenon
    • 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
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249994Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
    • Y10T428/249995Constituent is in liquid form

Definitions

  • This invention relates to a process for making pressure-sensitive record material, and more particularly pertains to such material having minute particles of two kinds of substances which are color reactive on contact, one of the substances being in liquid form and the other" being in solid form, the particles of the two substances being arranged in proximity in profuse numbers but insulated from contact by material rupturable when pressure is applied, which pressure acts to bring the two kinds of substances together at the points of rupture to produce a distinctively colored localized mark.
  • the record material made by the process of this invention although adapted for response to stylus pressures, is particularly adapted for response to pressures applied in impact printing operations such as by the striking or pressing sensitive to pressures caused by drawing a stylus thereover than to pressures derived from the impact of type.
  • This novel record material also is an;-
  • such material including a rupturable insulating medium in which are interspersed liquid droplets of two kinds which react on contact to form color.
  • the liquid droplets inan ionizing medium, glycerine, which reacted to produce color on contact by interchange of ions.
  • any such liquid ionizing medium available for use in such a system is hygroscopic making the rec-
  • the process of the present invention provides I a record material with exceptional response to impact pressures and one having remarkable stability as no ionizing liquid is required.
  • liquid used to dissolve the active color ingredient 1 in the liquid reactant substance is a non-ionizing inert oily type of material which is non-hygroscopic and is used solely to dissolve the active ingredient and to obtain easier release and greater mobility of the droplets, when the supporting film is ruptured. Because of the mobility of the re leased liquid droplets at points of rupture of the insulating medium the new record material is highly sensitive both to drawing and to impact pressures yet it is resistant to destructive influences encountered in ordinary environment and normal handling operations. Thus, the new rec' 0rd material combines the best characteristics of known pressure responsive record materials by providing a novel liquid-solid reactant structure.
  • the principal object of the invention is to provide process for making a pressure-sensitiveiecord material on which a mark of distinctive color may be produced by the mere application of localized pressure, said material including colorforming substances of two kinds, one being solid and the other being liquid, the two substances normally being held insulated from reaction contact by a rupturable insulating medium until mark,- ing pressures rupture the insulating medium at points of pressure to bring about local contact of the two substances to produce a mark.
  • Another object of the invention is to provide a process for making such a record material in which one of the color reactant substances is dissolved in a non-ionizing oily liquid which may be dispersed as droplets in a rupturable solid insulating film so as to be readily available and mobile locally to make contact with the'other solid reactant'material when. released, by rupture of the film.
  • Another object of the invention is toprovide a process for making such "a record material which is highly sensitive to impact pressures such as are met with in-typewriter or letter press work and for this effectthe two color reactants are arranged in separate overlying layers on-a web so that marking pressures vertical applied to the said layers will cause penetration of the color reactant substance of of the other layer.
  • liquid droplets of color reactant are dispersed in a film-forming substance which is applied as-a coating to a paper web and dried thereon leaving the liquid droplets entrapped therein.
  • the solid color reactant particles, acting as adsorbents, are likewise dispersed in a film-forming substance which is applied as a second overlying coating. Both films are rupturable to force th reactant substances together.
  • the liquid droplets contain an organic substance which is an electron donor aromatic compound having a double bond system which is converted to a more highly polarized conjugated 'form upon taking one layer into that part in an electron donor-acceptor adsorption chemical reaction, giving it a distinctive color
  • the solid particles are of an inorganic substance which is an acid relative to the organic substance so as to be an electron acceptor when in adsorption contact therewith.
  • the solid material is in fine particle formin order to furnish a large reactant surface per unit area of the record material, which enhances the depth of color produced in the record material.
  • the film-forming substances are derived from hydrophilic colloid materials that form pressure-rupturable films.
  • solid reactant particle substance such as Attapulgus clay, or attapulgite
  • the adsorbate substance may include one or more kinds of reactant such as crystal violet lactone, which i 3,3 bis(p-dimethylaminophenyl) -6-dirnethylaminophthalide, and tetrachloro malachite green lactone mixed together and dissolved in the Oily liquid.
  • reactant such as crystal violet lactone, which i 3,3 bis(p-dimethylaminophenyl) -6-dirnethylaminophthalide, and tetrachloro malachite green lactone mixed together and dissolved in the Oily liquid.
  • the web used as a support may be paper or other material suitable as a record base. For instance, either cardboard, glass, metal or wood may be used if desired.
  • the total thickness of the pressure-sensitive film need be no greater than from .001 to .002 of an inch so it may be supported on very thin paper stock.
  • Example 1 constitutes the best mode of applying the principles thereof as contemplated up to the present time and may be considered the preferred embodiment. It comprises a base Web of paper, or the like, on one surface of which two coatings are applied, the first or undercoating being an insulating film in which are entrapped a profuse number of liquid droplets in which a color reactant substance is dissolved. These droplets are,
  • this first coating when dry, is of the order of .001 of an inch.
  • the first coating is made by dissolving one part by Weight of animal gelatin, having an isoelectric point of pH 8 and a jelly strength of 2'75 grams as measured by the Bloom gelometer, with three parts by weight of water heated to 150 Fahrenheit. 7
  • chlorinated diphenyl is 3,3 bis(p dimethylaminophenyl) -6-dimethylamino phthalide, in chlorinated diphenyl is made by dissolving three parts by weight of the crystal violet lactone in ninety-seven parts by weight of the chlorinated diphenyl which has a chlorine content averaging 48 per cent by weight. This chlorinated diphenyl solution is heated to the temperature of the gelatin solution before it is added thereto and emulsified.
  • the emulsion is applied while still hot, or if allowed to 0001 after reheating to and is dried either under normal atmospheric conditions or by artificial means such as a hot air blast or on a heated drying drum such as is commonly used in paper coating machines. It is considered that drying under normal atmospheric environment gives a somewhat better water resistance to the dried film or coating in which the chlorinated diphenyl solution droplets are entrapped.
  • the dried undercoating is next treated to drive the droplets out of the top surface layer and into the interior of the film so as, in effect, to form an impermeable surface skin thereon.
  • This is accomplished by wetting the surface with water at room temperature, that is from 70-80 Fahrenheit, which water has had added thereto 1 per cent by weight of formaldehyde and 0.1 per cent by weight of a wetting agent such as dioctyl ester of sodium sulfosuccinate.
  • the wetting should be allowed to persist for several minutes and thereafter the film is dried in a low humidity atmosphere.
  • the surface wetting may be accomplished by floating the coated paper on the water, coated face down, or by carrying it on a partially submerged drum with the coated surface facing outwardly.
  • the formaldehyde may be omitted, if desired.
  • the second, or overcoating then is applied to the dried undercoating.
  • the second coating 20 per cent, by weight, of paper coating starch in water is cooked at 200 Fahrenheit for 15 minutes and cooled to room temperature.
  • 1 part by weight of attapulgite is dispersed in three parts by weight of water by use of a ball mill or equivalent.
  • Four parts, by weight, of the attapulgite dispersion is mixed with one part, by weight, of the starch solution.
  • the resultant mixture is applied, at room temperature, as an overcoating to the prepared paper having the gelatin coating dried thereon.
  • This starch-clay overcoating is applied in any convenient manner, as by a paper coating machine. This overcoating when dry should have a thickness of the order of .0005 of an inch.
  • the thickness of the undercoating and the overcoating may .be varied somewhat without interferring greatly with the sensitivity of the material, such variation range being of the order of 25 per cent in either direction.
  • This record material when finished has a substantially white appearance and produces a dark blue mark which sharply defines the area of pressure or impact.
  • the compound crystal violet lactone has the structure and the process of making it is described in United States Letters Patent No. 2,417,897, issued March 25, 1947, on the application of Clyde S. Adams, filed June 16', 1945, although the compound is incorrectly named in said patent as 3,3 bis(4-dimethylaminophenyl) 6 dimethylaminophenyl phthalide.
  • An application for reissue of said patent is now pending.
  • Example .2.Another embodiment of the invention is the use of malachite green lactone, that is to say 3,3 bis(p-dimethylaminophenyl) phthalide, having the structure in place of the crystal violet lactone of Example 1 and in the same amount. This gives a substantially white record material producing a green mark when the pressure is applied. This green color is not as intense as the blue given by crystal violet lactone.
  • Example 3 is the use of tetrachloro malachite green lactone, that is to say 3,3 bis(p-dimethylaminophenyl) 4,5,6 ⁇ ? tetrachloro phthalide, having the structure in place of the crystal violet lactone of Example 1 and in the same amount. This gives a substantially white record material producing a green mark when pressure is applied.
  • Example 4 is the use of 3,3 bis(p-diethylaminophenyl)-G-dimethylamino phthalide, having the structure in place of the crysta1 violet lactone of Example 1 but using only one-sixth as much by weight.
  • the normal color of this record material is dark yellow and upon pressure being applied it turns to a bluish gray.
  • the attapulgite can be replaced with a synthetic zeolite material of the sodium aluminum silicate type preferably having a maximum particle size of 10 microns and used in essentially the same amount by weight as specified in Example 1 for the attapulgite.
  • a synthetic zeolite material of the sodium aluminum silicate type preferably having a maximum particle size of 10 microns and used in essentially the same amount by weight as specified in Example 1 for the attapulgite.
  • gelatin, methyl cellulose, polyvinyl alcohol, and casein may be substituted for the starch of Example 1 as a binder.
  • Examples 1 to 5 inclusive whether attapulgite or the sodium zeolite is used, there may be substituted for the starch a mixture of starch, casein, and a synthetic latex made of butadienestyrene copolymer material.
  • the amount of starch should be 7 per cent
  • the amount of casein should be 1 per cent
  • the amount of latex should be 7 per cent all by Weight with respect to the weight of the attapulgite or zeolite material.
  • a starch solution is made as described in Example 1 and allowed to cool.
  • one part of casein is dispersed in two parts of cold Water, by weight, and allowed to swell for one-half hour,
  • This binder material is characterized by greater adhesion to the adjacent In such a binder.
  • Attapulgite may be replaced with an equivalent amount of halloysite
  • the attapulgite may be replaced by an equivalent amount of magnesium trisilicate. Mixtures of the adsorbents will do as well as the individual adsorbents.
  • the sodium of the specified sodium aluminum silicate may be replaced with other cations such as nickel, copper, iron, zinc, mercury, barium, lea-d, cadmium and potassium to give zeolites with equivalent or better color reactant qualities.
  • exchangeable calcium cations on natural attapulgite may be replaced by other cations to give workable adsorbents in the same way as noted for the zeolites.
  • hydrogen may be substituted for the calcium exchange cations of attapulgite.
  • the adsorbent material should be accessible to the liquid droplets containing the color reactant material to be adsorbed thereon and the action of the coating binder tends to mask the exterior surface available on such adsorbent particles.
  • the needle-like aggregates of attapulgite and the porous structure of zeolites contain interiorly active surfaces, not masked by the binder, which are left available for adsorbing the color reactant in the liquid droplets and, hence, these types of adsorbent are particularly suited for the novel structure which is the subject of this invention.
  • I-Ialloysite and magnesium trisilicate seem to be of such structure as has available interior adsorbent surfaces and therefore are given as substitute materials to act as the adsorbent material of the system.
  • the method of making a pressure-sensitive record material containing a liquid substance and a solid substance reactive on contact to produce a mark of distinctive color including the steps of first coating a web with an emulsion having as the internal discontinuous phase the liquid reactant substance and having as the external continuous phase a substance dryable to a solid film which entraps the internal phase as liquid droplets; drying said film; treating the surface of the film to form a surface skin; applying a film-like overcoatin to the exposed surface of the first coating said overcoating including a liquid film-forming binder dryable to a solid condition and said overcoating having profusely dispersed therein particles of the solid color-forming reacting substance, the liquid substance including an electron donor aromatic organic compound having a double bond system which is convertible to a more highly polarized conjugated form upon taking part in an electron donor-acceptor adsorption chemical reaction, giving it a distinctive color, and the solid substance being an inorganic material in fine particle form providing a large adsorbent surface area and said in
  • the method of claim 2 is which the dissolved color reactant is 3,3 bis(p-dimethylaminophenyl) 4,5,6 ⁇ ? tetrachloro phthalide having the structure 7.
  • the dissolved color reactant is 2,4 bislp-(p-dimethylaminoazo) ani1ino]-6-,-hydroxy sym. triazine having the structure 8.
  • the oily solvent is a chlorinated diphenyl material.
  • the method of making a pressure-sensitive record material containing liquid droplets and solid particles which react on contact to produce a distinctively colored mark including the steps of dissolving gelatin in water and dispersing therein an oily'substance in which is dissolved a color reactant substance so as to form an emulsion, the continuous gelatin phase of which is dryable to a solid; coating the emulsion in a thin film on a record material web; drying the gelatin film thus entrapping the dispersed phase as liquid droplets; treating the surface of the film to form a surface skin; dispersing the solid color reactant particles in a binder solution dryable to a solid; and coating a film of the binder material dispersion on top of the gelatin film and drying it, the color-reactant in the droplets in cludes an electron donor aromatic organic compound having a double bond system which is convertible to a more highly polarized conjugated form upon taking part in an electron donor-acceptor adsorption chemical reaction, giving it a distinctive color the solid particles being

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Description

Patented Apr. 10, 1951 PROCESS FOR MAKING PRESSURE SENSI- TIVE RECORD MATERIALS Barrett K. Green and Robert W. Sandberg, Dayton, Ohio, assignors to The National Cash Register Company, Dayton, Ohio, a corporation of Maryland No Drawing. Application July 13, 1948, Serial No. 38,548
47 Claims. (01. 117-36) This invention relates to a process for making pressure-sensitive record material, and more particularly pertains to such material having minute particles of two kinds of substances which are color reactive on contact, one of the substances being in liquid form and the other" being in solid form, the particles of the two substances being arranged in proximity in profuse numbers but insulated from contact by material rupturable when pressure is applied, which pressure acts to bring the two kinds of substances together at the points of rupture to produce a distinctively colored localized mark.
The record material made by the process of this invention, although adapted for response to stylus pressures, is particularly adapted for response to pressures applied in impact printing operations such as by the striking or pressing sensitive to pressures caused by drawing a stylus thereover than to pressures derived from the impact of type. This novel record material also is an;-
improvement over that record material disclosed in United States Letters Patent No. 2,229,693, patg ented on October 20, 1942, on the application of Barrett K. Green. That patent discloses pressure-sensitive record material, especially adapted:
for impact work, such material including a rupturable insulating medium in which are interspersed liquid droplets of two kinds which react on contact to form color. The liquid droplets inan ionizing medium, glycerine, which reacted to produce color on contact by interchange of ions.
' Any such liquid ionizing medium available for use in such a system is hygroscopic making the rec- The process of the present invention provides I a record material with exceptional response to impact pressures and one having remarkable stability as no ionizing liquid is required. The
eluded solid color-forming materials dissolved in;
ord material unduly sensitive to moisture. I
liquid used to dissolve the active color ingredient 1 in the liquid reactant substance is a non-ionizing inert oily type of material which is non-hygroscopic and is used solely to dissolve the active ingredient and to obtain easier release and greater mobility of the droplets, when the supporting film is ruptured. Because of the mobility of the re leased liquid droplets at points of rupture of the insulating medium the new record material is highly sensitive both to drawing and to impact pressures yet it is resistant to destructive influences encountered in ordinary environment and normal handling operations. Thus, the new rec' 0rd material combines the best characteristics of known pressure responsive record materials by providing a novel liquid-solid reactant structure.
The principal object of the invention is to provide process for making a pressure-sensitiveiecord material on which a mark of distinctive color may be produced by the mere application of localized pressure, said material including colorforming substances of two kinds, one being solid and the other being liquid, the two substances normally being held insulated from reaction contact by a rupturable insulating medium until mark,- ing pressures rupture the insulating medium at points of pressure to bring about local contact of the two substances to produce a mark.
Another object of the invention is to provide a process for making such a record material in which one of the color reactant substances is dissolved in a non-ionizing oily liquid which may be dispersed as droplets in a rupturable solid insulating film so as to be readily available and mobile locally to make contact with the'other solid reactant'material when. released, by rupture of the film. v
Another object of the invention is toprovide a process for making such "a record material which is highly sensitive to impact pressures such as are met with in-typewriter or letter press work and for this effectthe two color reactants are arranged in separate overlying layers on-a web so that marking pressures vertical applied to the said layers will cause penetration of the color reactant substance of of the other layer. g 1
Further objects and objects relating; to details and economies of the process, will definitely appear from the detailed description to follow.- The objects of this invention have been attainedby the several embodiments thereof described in detail in the following specification. The invention is clearly defined and pointed out in the appended claims.
In the preferred form of this invention the liquid droplets of color reactant are dispersed in a film-forming substance which is applied as-a coating to a paper web and dried thereon leaving the liquid droplets entrapped therein. The solid color reactant particles, acting as adsorbents, are likewise dispersed in a film-forming substance which is applied as a second overlying coating. Both films are rupturable to force th reactant substances together.
Of the reactant materials employed, the liquid droplets contain an organic substance which is an electron donor aromatic compound having a double bond system which is converted to a more highly polarized conjugated 'form upon taking one layer into that part in an electron donor-acceptor adsorption chemical reaction, giving it a distinctive color, and the solid particles are of an inorganic substance which is an acid relative to the organic substance so as to be an electron acceptor when in adsorption contact therewith. The solid material is in fine particle formin order to furnish a large reactant surface per unit area of the record material, which enhances the depth of color produced in the record material.
The film-forming substances are derived from hydrophilic colloid materials that form pressure-rupturable films.
Although in the preferred form of the invention a single kind of solid reactant particle substance is used, such as Attapulgus clay, or attapulgite, it is within the scope of the invention to mix two or more kinds of solid reactants together, such as magnesium trisilicate and attapulgite, or to mix attapulgite with sodium aluminum silicate zeolites, which together act as adsorbents upon which color reactant adsorbates dissolved in the liquid droplets may be adsorbed.
Likewise the adsorbate substance may include one or more kinds of reactant such as crystal violet lactone, which i 3,3 bis(p-dimethylaminophenyl) -6-dirnethylaminophthalide, and tetrachloro malachite green lactone mixed together and dissolved in the Oily liquid.
The web used as a support may be paper or other material suitable as a record base. For instance, either cardboard, glass, metal or wood may be used if desired. The total thickness of the pressure-sensitive film need be no greater than from .001 to .002 of an inch so it may be supported on very thin paper stock. By placing a number of such thin-coated paper sheets in superimposed relation in a typewriter a number of printed copies of typewritten material may be made without the use of a typewriter ink ribbon or carbon manifold paper as is now the common practice.
As it is difficult, if not impossible, to show the exact structure of this coating by use of a drawing none accompanies this specification.
In the following examples, there will be described embodiments of this invention by which the objects of the invention have been successfully attained.
Example 1.--'I'he following embodiment of this invention constitutes the best mode of applying the principles thereof as contemplated up to the present time and may be considered the preferred embodiment. It comprises a base Web of paper, or the like, on one surface of which two coatings are applied, the first or undercoating being an insulating film in which are entrapped a profuse number of liquid droplets in which a color reactant substance is dissolved. These droplets are,
on the average, of the order of from 1 to 5 microns in diameter and are spaced apart, on the average, a distance of the order of /2 micron. The preferred thickness of this first coating, when dry, is of the order of .001 of an inch.
The first coating is made by dissolving one part by Weight of animal gelatin, having an isoelectric point of pH 8 and a jelly strength of 2'75 grams as measured by the Bloom gelometer, with three parts by weight of water heated to 150 Fahrenheit. 7
Into four parts by weight of the gelatin solution there is dispersed, or emulsified, three parts by weight of a solution of crystal violet lactone in chlorinated diphenyl.
4 l is 3,3 bis(p dimethylaminophenyl) -6-dimethylamino phthalide, in chlorinated diphenyl is made by dissolving three parts by weight of the crystal violet lactone in ninety-seven parts by weight of the chlorinated diphenyl which has a chlorine content averaging 48 per cent by weight. This chlorinated diphenyl solution is heated to the temperature of the gelatin solution before it is added thereto and emulsified.
The emulsion is applied while still hot, or if allowed to 0001 after reheating to and is dried either under normal atmospheric conditions or by artificial means such as a hot air blast or on a heated drying drum such as is commonly used in paper coating machines. It is considered that drying under normal atmospheric environment gives a somewhat better water resistance to the dried film or coating in which the chlorinated diphenyl solution droplets are entrapped.
The dried undercoating is next treated to drive the droplets out of the top surface layer and into the interior of the film so as, in effect, to form an impermeable surface skin thereon. This is accomplished by wetting the surface with water at room temperature, that is from 70-80 Fahrenheit, which water has had added thereto 1 per cent by weight of formaldehyde and 0.1 per cent by weight of a wetting agent such as dioctyl ester of sodium sulfosuccinate. The wetting should be allowed to persist for several minutes and thereafter the film is dried in a low humidity atmosphere. The surface wetting may be accomplished by floating the coated paper on the water, coated face down, or by carrying it on a partially submerged drum with the coated surface facing outwardly. The formaldehyde may be omitted, if desired.
The second, or overcoating, then is applied to the dried undercoating. In making the second coating 20 per cent, by weight, of paper coating starch in water is cooked at 200 Fahrenheit for 15 minutes and cooled to room temperature. Separately, 1 part by weight of attapulgite is dispersed in three parts by weight of water by use of a ball mill or equivalent. Four parts, by weight, of the attapulgite dispersion is mixed with one part, by weight, of the starch solution. The resultant mixture is applied, at room temperature, as an overcoating to the prepared paper having the gelatin coating dried thereon. This starch-clay overcoating is applied in any convenient manner, as by a paper coating machine. This overcoating when dry should have a thickness of the order of .0005 of an inch.
The thickness of the undercoating and the overcoating may .be varied somewhat without interferring greatly with the sensitivity of the material, such variation range being of the order of 25 per cent in either direction.
This record material when finished has a substantially white appearance and produces a dark blue mark which sharply defines the area of pressure or impact.
The impact of a marking instrument on the surface of this record material locally releases the oily droplets from the gelatin film and forces them into contact with the overlying attapulgite particles. The needle-like crystal aggregate structure of attapulgite prevents any substantial masking of it by the starch binder, thus leaving the attapulgite available to adsorb the color reactant crystal violet lactone from the released oil. Therefore, in this coating system the attapulgite solid particles are held in a non- This solution of crystal violet lactone. Whisk; 3:15 mas g on-insu at n binder Whereas the oil carried other reactant is protected as entrapped droplets in the gelatin insulating film.
The compound crystal violet lactone has the structure and the process of making it is described in United States Letters Patent No. 2,417,897, issued March 25, 1947, on the application of Clyde S. Adams, filed June 16', 1945, although the compound is incorrectly named in said patent as 3,3 bis(4-dimethylaminophenyl) 6 dimethylaminophenyl phthalide. An application for reissue of said patent is now pending.
While not nearly as good as the arrangement of the layers or films just described, it is within the broad aspects of the invention to apply the adsorbent-bearing film or coating first on the paper and next to apply the crystal violet lactone-bearing film as an overcoating.
Example .2.Another embodiment of the invention is the use of malachite green lactone, that is to say 3,3 bis(p-dimethylaminophenyl) phthalide, having the structure in place of the crystal violet lactone of Example 1 and in the same amount. This gives a substantially white record material producing a green mark when the pressure is applied. This green color is not as intense as the blue given by crystal violet lactone.
Example 3.Another embodiment of the invention is the use of tetrachloro malachite green lactone, that is to say 3,3 bis(p-dimethylaminophenyl) 4,5,6}? tetrachloro phthalide, having the structure in place of the crystal violet lactone of Example 1 and in the same amount. This gives a substantially white record material producing a green mark when pressure is applied.
Example 4.Another embodiment of the invention is the use of 3,3 bis(p-diethylaminophenyl)-G-dimethylamino phthalide, having the structure in place of the crysta1 violet lactone of Example 1 but using only one-sixth as much by weight. The normal color of this record material is dark yellow and upon pressure being applied it turns to a bluish gray.
In Examples 1 to 4 inclusive the attapulgite can be replaced with a synthetic zeolite material of the sodium aluminum silicate type preferably having a maximum particle size of 10 microns and used in essentially the same amount by weight as specified in Example 1 for the attapulgite. For use with the zeolite type of adsorbent, gelatin, methyl cellulose, polyvinyl alcohol, and casein may be substituted for the starch of Example 1 as a binder.
In Examples 1 to 5 inclusive, whether attapulgite or the sodium zeolite is used, there may be substituted for the starch a mixture of starch, casein, and a synthetic latex made of butadienestyrene copolymer material. when dried with the attapulgite or zeolite material therein, the amount of starch should be 7 per cent, the amount of casein should be 1 per cent, and the amount of latex should be 7 per cent all by Weight with respect to the weight of the attapulgite or zeolite material. In making such a binder a starch solution is made as described in Example 1 and allowed to cool. Next one part of casein is dispersed in two parts of cold Water, by weight, and allowed to swell for one-half hour,
. after which seven more parts of cold water and water contains 0.2% of sodium pyrophosphate.
To 10 parts by weight of the dispersed adsorbent, eliminating the weight of the water, is added 3.5 parts by weight of the starch solution, 1.6 parts by weight of the latex, and 1 part by Weight of the casein solution. This binder material is characterized by greater adhesion to the adjacent In such a binder.
coating and by excellent properties as far as the access of the adsorbent material to the action of the liquid color reactant droplets is concerned.
In Examples 1 to 5 the attapulgite may be replaced with an equivalent amount of halloysite,
and in Examples lto 4 the attapulgite may be replaced by an equivalent amount of magnesium trisilicate. Mixtures of the adsorbents will do as well as the individual adsorbents.
With respect to the zeolite material the sodium of the specified sodium aluminum silicate may be replaced with other cations such as nickel, copper, iron, zinc, mercury, barium, lea-d, cadmium and potassium to give zeolites with equivalent or better color reactant qualities.
The exchangeable calcium cations on natural attapulgite may be replaced by other cations to give workable adsorbents in the same way as noted for the zeolites. In addition hydrogen may be substituted for the calcium exchange cations of attapulgite.
The adsorbent material should be accessible to the liquid droplets containing the color reactant material to be adsorbed thereon and the action of the coating binder tends to mask the exterior surface available on such adsorbent particles. The needle-like aggregates of attapulgite and the porous structure of zeolites, contain interiorly active surfaces, not masked by the binder, which are left available for adsorbing the color reactant in the liquid droplets and, hence, these types of adsorbent are particularly suited for the novel structure which is the subject of this invention. I-Ialloysite and magnesium trisilicate seem to be of such structure as has available interior adsorbent surfaces and therefore are given as substitute materials to act as the adsorbent material of the system.
The pressure-sensitive record material made by the process as disclosed herein is disclosed and claimed in the copending application of Barrett K, Green and Robert W. Sandberg, Serial No. 38,547, filed July 13, 1948.
It is understood that the processe for making pressure-sensitive record material described herein are susceptible of considerable variations without departing from the spirit of the invention.
What is claimed is:
l. The method of making a pressure-sensitive record material containing a liquid substance and a solid substance reactive on contact to produce a mark of distinctive color, including the steps of first coating a web with an emulsion having as the internal discontinuous phase the liquid reactant substance and having as the external continuous phase a substance dryable to a solid film which entraps the internal phase as liquid droplets; drying said film; treating the surface of the film to form a surface skin; applying a film-like overcoatin to the exposed surface of the first coating said overcoating including a liquid film-forming binder dryable to a solid condition and said overcoating having profusely dispersed therein particles of the solid color-forming reacting substance, the liquid substance including an electron donor aromatic organic compound having a double bond system which is convertible to a more highly polarized conjugated form upon taking part in an electron donor-acceptor adsorption chemical reaction, giving it a distinctive color, and the solid substance being an inorganic material in fine particle form providing a large adsorbent surface area and said inorganic material being an acid relative to the organic compound and acting as an adsorbent therefor 4. The method of claim 2 in which the dissolved color reactant is 33 bis(p-diethylaminophenyl)-fi-dimethylamino phthalide having the structure (C2115) zN- (C2 5) 2 5. The method of claim 2 in which the dissolved color reactant is 3,3 bis(p-dimethylaminophenyl) phthalide having the structure 6. The method of claim 2 is which the dissolved color reactant is 3,3 bis(p-dimethylaminophenyl) 4,5,6}? tetrachloro phthalide having the structure 7. The method of claim 2 in which the dissolved color reactant is 2,4 bislp-(p-dimethylaminoazo) ani1ino]-6-,-hydroxy sym. triazine having the structure 8. The method of claim 2 in which the oily solvent is a chlorinated diphenyl material.
9. The method of claim 8 in which the chlorinated diphenyl material has a chlorine content of approximately 48 per cent by weight.
10. The method of claim 1 in which the continuous phase of the emulsion is gelatin.
11. The method of claim 1 in which the web is paper. 7
12. The method of claim 1 in which the solid color reactant substance is attapulgite.
13. The method of claim 12 in which the solid color reactant substance attapulgite is held in a starch binding film.
14. The method of claim 1 in which the solid color reactant substance is dispersed in fine particle form in a starch binder material in a dryable liquid and coated over the film containing the liquid droplets.
15. The method of making a pressure-sensitive record material containing a liquid substance and a solid substance reactive on contact to produce a mark of distinctive color including the steps of preparing an emulsion having a continuous gelatin phase and a discontinuous phase of an inert oily substance in which is dissolved a color reactant substance to form the liquid color reactant 10 is starch and the color reactant solid is atta= pulgite. k
23. The method of claim 15 in which the color reactant solid is attapulgite.
24. The method of claim 15 in which the color reactant substance in the liquid droplets is 3,3- bis(p-dimethylaminophenyl) 6 dimethylamino phthalide having the structure (CHmN more):
( 2 5) 2 N a a) 2 substance; the step of coating the emulsion on a web and drying the coating so the gelatin will form a solid film in which the discontinuous phase of the emlusion persists as liquid droplets; treating the surface of the film to form a surface skin; the step of preparing a dispersion of particles of the solid color reactant in a dryable a distinctive color, and the solid substance being an inorganic material in fine particle form providing a large adsorbent surface area and said inorganic material being an acid relative to the organic compound and acting as an adsorbent therefor so as to be an electron acceptor when the organic compound is in adsorption contact therewith.
16. The method of claim 15 in which the web is paper.
17. The method of claim 15 in which the inert oily substance is a chlorinated diphenyl material.
18-. The method of claim 17 in which the chlorinated diphenyl material has a chlorine content of approximately 48 per cent.
19. The method of claim 15 in which the dried gelatin film is wet on the surface with water and quickly dried.
20. The method of claim 19 in which the water contains a slight amount of formaldehyde.
21. The method of claim 15 in which the binder is starch.
22. The method of claim 15 in which the binder N(C a)2 26. The method of claim 15 in which the color reactant substance in the liquid droplets is 3,3 bis(p-dimethylaminophenyl) phthalide having the structure 27. The method of claim 15 in which the dissolved color reactant is 3,3 bis(p-dimethylaminophenyl) 4,5,6}? tetrachloro phthalide having the structure 28. The method of claim 15 in which the dissolved color reactant is 2,4 bis[p(p-dimethylii aminoazo) anilinol -6-hydroxy sym. triazine havmg the structure 29. The method of making a pressure-sensitive record material containing liquid droplets and solid particles which react on contact to produce a distinctively colored mark, including the steps of dissolving gelatin in water and dispersing therein an oily'substance in which is dissolved a color reactant substance so as to form an emulsion, the continuous gelatin phase of which is dryable to a solid; coating the emulsion in a thin film on a record material web; drying the gelatin film thus entrapping the dispersed phase as liquid droplets; treating the surface of the film to form a surface skin; dispersing the solid color reactant particles in a binder solution dryable to a solid; and coating a film of the binder material dispersion on top of the gelatin film and drying it, the color-reactant in the droplets in cludes an electron donor aromatic organic compound having a double bond system which is convertible to a more highly polarized conjugated form upon taking part in an electron donor-acceptor adsorption chemical reaction, giving it a distinctive color the solid particles being an inorganic substance of such fineness as to provide a large adsorbent surface area, and said inorganic substance being an acid relative to the organic compound so as to be an electron acceptor when in adsorption contact with said organic compound.
30. The method of claim 29 in which the surface of the dried gelatin film is treated with water and quickly dried, to drive the liquid droplets out of the top layer before the binder material dispersion is applied thereover.
31. The method of claim 29 in which the droplets average between-l and 5 microns in diameter.
32. The method of claim 29 in which the droplets are spaced apart on the average, a distance of A; micron.
33. The method of claim 29 in which the droplets average between 1 and 5 microns in diameter and are spaced apart, on the average, a distance of micron.
34. The method of claim 29 in which the thickness of the dried gelatin film is of the order of one thousandth of an inch.
35. The method of claim 29 in which the gelatin has an isoelectric point of approximately pH 8 and a jelly strength of approximately 275 grams as measured by the Bloom gelometer.
36. The method of claim 29 in which one part by weight of the gelatin is dissolved in three parts by weight of water.
37. The method of claim 36 in which four parts by weight of the gelatin-water solution are used with three parts by weight of a solution of three parts by weight of 3,3 bis'(p-dimethylaminophenyl) -6-dimethylamino phthalide in ninetyseven parts by weight chlorinated diphenyl of approximately 48 per cent chlorine by weight.
38. The method of claim 37 in which the material dissolved in the chlorinated diphenyl is 3,3 bis (p-diethylaminophenyl) -6-dimethylamino phthalide.
39. The method of claim 37 in which the material dissolved in the chlorinated diphenyl is 3,3 bis(p-dimethylaminophenyl) phthalide.
40. The method of claim 37 in which the material dissolved in the chlorinated diphenyl is 3,3 bis(p-dimethylaminophenyl) 4,5,6,7 tetrachloro phthalide.
41. The method of claim 37 in which the material dissolved in the chlorinated diphenyl is 2,4 bis [p-(p-dimethylaminoazo) an'ilinol-G- hydroxy sym. triazine.
42. The method of claim 29 in which the surface of the gelatin film after being dried to a solid is wet with water of -80 Fahrenheit and containing approximately 1 per cent of formaldehyde.
43. The method of claim 42 in which the water with which the surface of the gelatin is treated contains approximately V10 of a per cent of dioctyl ester of sodium sulfo'su'ccinate or its equivalent as a wetting agent.
44. The method of claim 29 in which the average size of the solid color reactant particles in the binder is of the order of 10 microns in diameter.
45. The method of claim 29 in which the binder solution for the solid particles comprises approximately 20 per cent by weight of paper coating starch in water cooked at 200 Fahrenheit for 15 minutes.
46. The method of claim 29 in which four parts by weight of a dispersion of one part by weight of the solid reactant material in three parts by weight of water is mixed with one part by weight of the starch binder solution.
47. The method of claim 29in which the coating containing the solid color reactant when dried, has a thickness of the order of .0005 of an inch.
- BARRETT K. GREEN.
ROBERT W. SANDBERG.
REFERENCES CITED The following references are of record in the file of this patent:
UNI'IED STATES PATENTS OTHER REFERENCES ,Hau ser et 2.1., Color Reactions Between Clays and Amines, July19 10, pgs. 1811-14.

Claims (1)

1. THE METHOD OF MAKING A PRESSURE-SENSITIVE RECORD MATERIAL CONTAINING A LIQUID SUBSTANCE AND A SOLID SUBSTANCE REACTIVE ON CONTACT TO PRODUCE A MARK OF DISTINCTIVE COLOR, INCLUDING THE STEPS OF FIRST COATING A WEB WITH AN EMULSION HAVING AS THE INTERNAL DISCONTINUOUS PHASE THE LIQUID REACTANT SUBSTANCE AND HAVING AS THE EXTERNAL CONTINUOUS PHASE A SUBSTANCE DRYABLE TO A SOLID FILM WHICH ENTRAPS THE INTERNAL PHASE AS LIQUID DROPLETS; DRYING SAID FILM; TREATING THE SURFACE OF THE FILM TO FORM A SURFACE SKIN; APPLYING A FILM-LIKE OVERCOATING TO THE EXPOSED SURFACE OF THE FIRST COATING SAID OVERCOATING INCLUDING A LIQUID FILM-FORMING BINDER DRYABLE TO A SOLID CONDITION AND SAID OVERCOATING HAVING PROFUSELY DISPERSED THEREIN PARTICLES OF THE SOLID COLOR-FORMING REACTING SUBSTANCE, THE LIQUID SUBSTANCE INCLUDING AN ELECTRON DONOR AROMATIC ORGANIC COMPOUND HAVING A DOUBLE BOND SYSTEM WHICH IS CONVERTIBLE TO A MORE HIGHLY POLARIZED CONJUGATED FORM UPON TAKING PART IN AN ELECTRON DONOR-ACCEPTOR ADSORPTION CHEMICAL REACTION, GIVING IT A DISTINCTIVE COLOR, AND THE SOLID SUBSTANCE BEING AN INORGANIC MATERIAL IN FINE PARTICLE FORM PROVIDING A LARGE ADSORBENT SURFACE AREA AND SAID INORGANIC MATERIAL BEING AN ACID RELATIVE TO THE ORGANIC COMPOUND AND ACTING AS AN ADSORBENT THEREFOR SO AS TO BE AN ELECTRON ACCEPTOR WHEN THE ORGANIC COMPOUND IS IN ADSORPTION CONTACT THEREWITH.
US3854848 1948-07-13 1948-07-13 Process for making pressure sensitive record materials Expired - Lifetime US2548365A (en)

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US3854848 US2548365A (en) 1948-07-13 1948-07-13 Process for making pressure sensitive record materials
US3854748 US2548364A (en) 1948-07-13 1948-07-13 Pressure sensitive record materials
US4175648 US2548366A (en) 1948-07-13 1948-07-31 Manifold record material and process for making it
GB1563349A GB660502A (en) 1948-07-13 1949-06-13 Record material for producing visible marks under pressure and method of manufacture thereof
GB1615449A GB666438A (en) 1948-07-13 1949-06-17 Manifold record material system
GB1615349A GB666437A (en) 1948-07-13 1949-06-17 Record material for use in a manifold assembly
DEP46154A DE855998C (en) 1948-07-13 1949-06-18 Process for the production of pressure-sensitive recording material
BE490053D BE490053A (en) 1948-07-13 1949-07-02
DEP48197A DE851806C (en) 1948-07-13 1949-07-08 Copying sheets
FR994976D FR994976A (en) 1948-07-13 1949-07-11 A method of manufacturing a pressure sensitive recording material and a product obtained by this method
NL147566A NL72381C (en) 1948-07-13 1949-07-12
CH283442D CH283442A (en) 1948-07-13 1949-07-12 Recording equipment showing colored marks in places where it is subjected to pressure, and method of making such equipment.
BE490255D BE490255A (en) 1948-07-13 1949-07-20
FR995128D FR995128A (en) 1948-07-13 1949-07-22 Multiple inscription material and its manufacturing process
CH284424D CH284424A (en) 1948-07-13 1949-07-26 Set of superimposed sheets, for obtaining inscriptions in several copies.
CH287576D CH287576A (en) 1948-07-13 1949-07-26 Registration and transfer material.
FR995149D FR995149A (en) 1948-07-13 1949-07-27 Multiple listing set
US18353450 US2550469A (en) 1948-07-13 1950-09-07 Manifold record material and process for making it
US183531A US2550466A (en) 1948-07-13 1950-09-07 Manifold record material and process for making it
US183533A US2550468A (en) 1948-07-13 1950-09-07 Manifold record material and process for making it
US183532A US2550467A (en) 1948-07-13 1950-09-07 Manifold record material and process for making it
US18515150 US2550470A (en) 1948-07-13 1950-09-15 Pressure sensitive record material
US18515350 US2550472A (en) 1948-07-13 1950-09-15 Pressure sensitive record material
US18515250 US2550471A (en) 1948-07-13 1950-09-15 Pressure sensitive record material
US185154A US2550473A (en) 1948-07-13 1950-09-15 Pressure sensitive record material

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US3854748 US2548364A (en) 1948-07-13 1948-07-13 Pressure sensitive record materials
US4175648 US2548366A (en) 1948-07-13 1948-07-31 Manifold record material and process for making it
US18353450 US2550469A (en) 1948-07-13 1950-09-07 Manifold record material and process for making it

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US4175648 Expired - Lifetime US2548366A (en) 1948-07-13 1948-07-31 Manifold record material and process for making it
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927802A (en) * 1988-12-09 1990-05-22 Ppg Industries, Inc. Pressure-sensitive multi-part record unit

Families Citing this family (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR999064A (en) * 1948-11-16 1952-01-25
US2672396A (en) * 1951-06-23 1954-03-16 Ncr Co Eradication of marks from reactant record material
NL81776C (en) * 1951-06-23
US2646367A (en) * 1951-06-28 1953-07-21 Ncr Co Transfer paper
US2712507A (en) * 1953-06-30 1955-07-05 Ncr Co Pressure sensitive record material
DE1122495B (en) * 1953-06-30 1962-01-25 Ncr Co Process for the production of microscopic capsules containing oil
NL95043C (en) * 1953-06-30
US2730456A (en) * 1953-06-30 1956-01-10 Ncr Co Manifold record material
US2755203A (en) * 1954-02-03 1956-07-17 Du Pont Process of converting a polyamino-triarylmethane dye coating on a base from a stabilized leuco form to a colored form
GB788087A (en) * 1955-01-26 1957-12-23 Oxford Paper Co Improvements in pressure-sensitive, heat-resistant, recording material and method ofmaking same
US2939009A (en) * 1956-02-01 1960-05-31 Jack M Tien Thermotransfer duplicating process
US2977320A (en) * 1957-01-07 1961-03-28 Lloyd T Jenkins Luminous writing
BE566360A (en) * 1957-02-22
US2977689A (en) * 1958-10-30 1961-04-04 Gerhard T Rugland Multiple choice response device
NL131538C (en) * 1962-01-13
US3389007A (en) * 1962-07-20 1968-06-18 Oda Ryohei Record transfer sheet material, method of making and composition
DE1210902B (en) * 1963-01-24 1966-02-17 Schleipen & Erkens Ag Paper for reproduction
NL292921A (en) * 1963-05-17 1900-01-01
US3330691A (en) * 1963-09-16 1967-07-11 Mead Corp Process of coating paper with attapulgite clay
US3305382A (en) * 1964-01-02 1967-02-21 Ibm Pressure sensitive transfer sheet
US3314814A (en) * 1964-03-02 1967-04-18 Columbia Ribbon & Carbon Method of preparing transfer elements
US3272533A (en) * 1964-10-05 1966-09-13 Milton Frank Allen Publication Detection treatment of paper money and other negotiable paper
US3363558A (en) * 1965-03-02 1968-01-16 Everett A. Johnson Tabulatable recording and duplicating master
US3383121A (en) * 1965-06-22 1968-05-14 Avery Products Corp Self-adhesive copy label
US3373682A (en) * 1966-01-17 1968-03-19 Arthur M. Angel Transaction recorder for printing on pressure-sensitive journal tape
US3411976A (en) * 1966-03-21 1968-11-19 Minnesota Mining & Mfg Self-marking record material
US3486752A (en) * 1967-08-28 1969-12-30 Minnesota Mining & Mfg Target toy device
BE794617A (en) * 1972-01-28 1973-05-16 Mizusawa Industrial Chem AQUEOUS COMPOSITION CONTAINING A COLOR FORMER FOR PRESSURE RECORDING PAPER, AND PROCESS FOR ITS MANUFACTURING
US3968299A (en) * 1975-02-21 1976-07-06 Angleman John D Two-way, selective directional, image-transfer sheet
DE2703811A1 (en) * 1977-01-29 1978-08-10 Basf Ag PRESSURE SENSITIVE RECORDING MATERIAL
JPS5538826A (en) * 1978-09-11 1980-03-18 Fuji Photo Film Co Ltd Color-developing ink
FR2461593A1 (en) * 1979-07-20 1981-02-06 Nashua Corp Low viscosity, high solids pressure-sensitive recording compsn. - contg. polymer latex partly replacing carboxymethyl cellulose
DE3014621B1 (en) * 1980-04-16 1981-04-23 MD Papierfabriken Heinrich Nicolaus GmbH, 8060 Dachau Response carbon paper
ZA813913B (en) * 1980-06-12 1982-06-30 Wiggins Teape Group Ltd Record material carrying a colour developer composition
US4391850A (en) 1980-06-13 1983-07-05 The Wiggins Teape Group Limited Record material carrying a color developer composition
FR2498525A1 (en) * 1981-01-27 1982-07-30 Raymond Bernard Duplicating paper coating and stacking - uses coupled pairs of sheets in double stack with neutral backs and alternately coated top faces
US4509065A (en) * 1981-12-04 1985-04-02 The Wiggins Teape Group Limited Record material
ZA828473B (en) * 1981-12-04 1983-10-26 Wiggins Teape Group Ltd Record material
JPS59120654A (en) * 1982-12-27 1984-07-12 Shin Nisso Kako Co Ltd Fluoran compound
JPS59197463A (en) * 1983-04-26 1984-11-09 Shin Nisso Kako Co Ltd Fluoran compound
US4740015A (en) * 1986-07-01 1988-04-26 Moore Business Forms, Inc. Security document and method of testing same
JP2566628B2 (en) * 1988-08-24 1996-12-25 保土谷化学工業株式会社 Fluorane compound and recording material
US5127879A (en) * 1989-04-06 1992-07-07 Schubert Keith E Apparatus for recordkeeping
US5135437A (en) * 1989-11-13 1992-08-04 Schubert Keith E Form for making two-sided carbonless copies of information entered on both sides of an original sheet and methods of making and using same
US5248279A (en) * 1989-04-06 1993-09-28 Linden Gerald E Two-sided, self-replicating forms
US5137494A (en) * 1989-11-13 1992-08-11 Schubert Keith E Two-sided forms and methods of laying out, printing and filling out same
US5154668A (en) * 1989-04-06 1992-10-13 Schubert Keith E Single paper sheet forming a two-sided copy of information entered on both sides thereof
US5395288A (en) * 1989-04-06 1995-03-07 Linden; Gerald E. Two-way-write type, single sheet, self-replicating forms
US5224897A (en) * 1989-04-06 1993-07-06 Linden Gerald E Self-replicating duplex forms
US6280322B1 (en) 1989-11-13 2001-08-28 Gerald E. Linden Single sheet of paper for duplicating information entered on both surfaces thereof
US5209947A (en) * 1989-12-16 1993-05-11 The Wiggins Teape Group Limited Process for the production of record material
JPH04338758A (en) * 1991-05-15 1992-11-26 Brother Ind Ltd Image recording method
GB9110608D0 (en) * 1991-05-16 1991-07-03 Wiggins Teape Group Ltd Colour developer composition
JPH0592674A (en) * 1991-10-02 1993-04-16 Brother Ind Ltd Image-receiving sheet
GB9300555D0 (en) * 1993-01-13 1993-03-03 Carrs Paper Ltd Carbonless copy paper
JPH06324511A (en) * 1993-05-14 1994-11-25 Brother Ind Ltd Photosensitive microcapsule type toner
JP3362745B2 (en) * 1993-07-28 2003-01-07 ブラザー工業株式会社 Photosensitive microcapsule type toner
US6544926B1 (en) 2001-10-11 2003-04-08 Appleton Papers Inc. Microcapsules having improved printing and efficiency
CN101522433B (en) 2006-09-29 2011-08-17 日本制纸株式会社 Heat-sensitive recording material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1781902A (en) * 1929-01-15 1930-11-18 Jr Edwin R Gill Manifolding
US2168098A (en) * 1938-02-03 1939-08-01 Groak Josef Transfer copying material
US2299693A (en) * 1940-02-23 1942-10-20 Ncr Co Coating for paper
US2299694A (en) * 1940-03-09 1942-10-20 Ncr Co Manifolding material
US2374862A (en) * 1942-06-19 1945-05-01 Ncr Co Coating for paper

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1781902A (en) * 1929-01-15 1930-11-18 Jr Edwin R Gill Manifolding
US2168098A (en) * 1938-02-03 1939-08-01 Groak Josef Transfer copying material
US2299693A (en) * 1940-02-23 1942-10-20 Ncr Co Coating for paper
US2299694A (en) * 1940-03-09 1942-10-20 Ncr Co Manifolding material
US2374862A (en) * 1942-06-19 1945-05-01 Ncr Co Coating for paper

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927802A (en) * 1988-12-09 1990-05-22 Ppg Industries, Inc. Pressure-sensitive multi-part record unit

Also Published As

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CH283442A (en) 1952-06-15
CH287576A (en) 1952-12-15
GB666438A (en) 1952-02-13
FR994976A (en) 1951-11-26
CH284424A (en) 1952-07-31
BE490255A (en) 1949-08-16
FR995149A (en) 1951-11-28
DE855998C (en) 1952-11-17
US2550469A (en) 1951-04-24
GB660502A (en) 1951-11-07
DE851806C (en) 1952-10-09
BE490053A (en) 1949-07-30
US2548366A (en) 1951-04-10
US2548364A (en) 1951-04-10
FR995128A (en) 1951-11-28
GB666437A (en) 1952-02-13
NL72381C (en) 1952-12-15

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