Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING 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
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/025—Applications of microcapsules not provided for in other subclasses
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41L—APPARATUS OR DEVICES FOR MANIFOLDING, DUPLICATING OR PRINTING FOR OFFICE OR OTHER COMMERCIAL PURPOSES; ADDRESSING MACHINES OR LIKE SERIES-PRINTING MACHINES
  • B41L1/00—Devices for performing operations in connection with manifolding by means of pressure-sensitive layers or intermediaries, e.g. carbons; Accessories for manifolding purposes
  • B41L1/20—Manifolding assemblies, e.g. book-like assemblies
  • B41L1/36—Manifolding assemblies, e.g. book-like assemblies with pressure-sensitive layers or coating other than carbon
• • 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
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
• • 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
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
  • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
  • B41M5/1555—Inorganic mineral developers, e.g. clays
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S101/00—Printing
  • Y10S101/29—Printing involving a color-forming phenomenon
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
  • Y10T428/249995—Constituent 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)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Inorganic Chemistry (AREA)
• Color Printing (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Paper (AREA)

Priority Applications (25)

Applications Claiming Priority (4)

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Citations (5)

• 1948
  • 1948-07-13 US US3854848 patent/US2548365A/en not_active Expired - Lifetime
  • 1948-07-13 US US3854748 patent/US2548364A/en not_active Expired - Lifetime
  • 1948-07-31 US US4175648 patent/US2548366A/en not_active Expired - Lifetime
• 1949
  • 1949-06-13 GB GB1563349A patent/GB660502A/en not_active Expired
  • 1949-06-17 GB GB1615349A patent/GB666437A/en not_active Expired
  • 1949-06-17 GB GB1615449A patent/GB666438A/en not_active Expired
  • 1949-06-18 DE DEP46154A patent/DE855998C/de not_active Expired
  • 1949-07-02 BE BE490053D patent/BE490053A/xx unknown
  • 1949-07-08 DE DEP48197A patent/DE851806C/de not_active Expired
  • 1949-07-11 FR FR994976D patent/FR994976A/fr not_active Expired
  • 1949-07-12 CH CH283442D patent/CH283442A/fr unknown
  • 1949-07-12 NL NL147566A patent/NL72381C/xx active
  • 1949-07-20 BE BE490255D patent/BE490255A/xx unknown
  • 1949-07-22 FR FR995128D patent/FR995128A/fr not_active Expired
  • 1949-07-26 CH CH287576D patent/CH287576A/fr unknown
  • 1949-07-26 CH CH284424D patent/CH284424A/fr unknown
  • 1949-07-27 FR FR995149D patent/FR995149A/fr not_active Expired
• 1950
  • 1950-09-07 US US18353450 patent/US2550469A/en not_active Expired - Lifetime

Patent Citations (5)

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