US3637757A - Diethylamino fluorans - Google Patents

Diethylamino fluorans Download PDF

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Publication number
US3637757A
US3637757A US792325*A US3637757DA US3637757A US 3637757 A US3637757 A US 3637757A US 3637757D A US3637757D A US 3637757DA US 3637757 A US3637757 A US 3637757A
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United States
Prior art keywords
chromogenic
sheet
mark
diethylamino
solvent
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US792325*A
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English (en)
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Chao-Han Lin
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Appvion LLC
NCR Voyix Corp
National Cash Register Co
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NCR Corp
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Assigned to APPLETON PAPERS INC. reassignment APPLETON PAPERS INC. MERGER (SEE DOCUMENT FOR DETAILS). FILED 12/1781, EFFECTIVE DATE: 01/02/82 STATE OF INCORP. DE Assignors: GERMAINE MONTEIL COSMETIQUES CORPORATION (CHANGED TO APPLETON PAPERS), TUVACHE, INC.
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • 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
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/1455—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring characterised by fluoran compounds

Definitions

  • This invention pertains to chromogenic compounds for use in pressure sensitive record material and to an improved mark-forming manifold system incorporating these chromogenic compounds. More specifically, this invention pertains to acyl-, ether-, and ester-substituted dialkylamino fiuorans which have the form of substantially colorless, i.e., White, or slightly colored solids, or approach being colorless when in liquid solution, but which may be converted to dark-colored forms upon reactive contact with appropriate acidic material.
  • marking in desired areas on support webs or sheets may be accomplished by effecting localized reactive contact between the novel chromogenic material and the acidic material on or in such a web or sheet, such material being brought thereto by transfer, or originally there, in situ--the desired reactive contact forming darkcolored materials in the intended image areas.
  • Pressure-sensitive, mark-forming systems of the prior art include that disclosed in application for Letters Patent No. 392,404 (now abandoned), filed Aug. 27, 1964, in the names of Robert E. Miller and Paul S. Phillips, Jr.
  • the above-mentioned patent application provides a marking system of disposing on and/or Within sheet support material, mutually reactant but unreacted markforming components (at least one component of which is a polymeric material) and a liquid solvent in which each of the mark-forming components is solublesaid liquid solvent being present in such form that is maintained isolated by a pressure-rupturable barrier from at least one of the mark-forming components until an application of pressure causes a breach or rupture of the barrier in the area delineated by the pressure pattern.
  • the mark-forming components thereby are brought into reactive contact, producing a distinctive mark.
  • It is a further object of this invention to provide a new and improved mark-forming system which comprises disposing, within a web or upon the surface of a web or sheet-support-material, unreacted chromogenic material in a location suitable for subsequent reactive contact with an acidic material to produce dark-colored reaction products, thus providing means for making marks of desirable color intensity and hue.
  • a new composition of matter which comprises a dark-colored product of chemical reaction having a r resonant chemical structure and produced by contact of a color-activating material with one of the above-mentioned chromogenic compounds.
  • the color-developing or activating material is an acidic substance useful for converting the chromogenic compounds to colored forms.
  • the method of marking of this invention i.e., the method of developing a dark-colored material from substantially colorless or slightly colored chromogenic compounds, comprises providing a chromogenic compound selected from among the above-mentioned compounds and bringing such chromogenic compound into reactive contact with an acidic color-activating substance, in areas where marking is desired, to produce a dark-colored form of the chromogenic compound by the action thereon of said acidic substance.
  • Acidic materials employed in this invention can be any compound within the definition of a Lewis acid, i.e. any electron acceptor.
  • acidic organic polymers such as phenolic polymers are employed as the acidic material.
  • the novel chromogenic materials exhibit the ad vantage of improved color stability when they are reacted with such phenolic polymers.
  • Solution formation of solid particles of the polymeric material in a solvent system with the substantially colorless chromogenic compounds permits penetration of the dark-colored reaction product into a porous support sheet, e.g., paper, so that the colored form of the chromogenic material is absorbed into the body of the sheet and is not merely on the surface of the sheet.
  • the absorption feature provides protection against erasure of recorded data by attrition of the surface of a record sheet made in accordance with the present invention.
  • FIG. 1 is a diagrammatic representation of a two-sheet unit manifold, in perspective.
  • the bottom surface of the overlying sheet is supplied on the surface or near the surface With a multiplicity of minute pressure-rupturable microcapsules containing a solution of the novel, substantially colorless, chromogenic component.
  • An acidic component such as an acid clay or a phenolic polymeric material lies Within the lower web or undersheet or upon the upper surface of the lower web or undersheet.
  • a colored mark is made by the use of a stylus, a type character, or other pressure-exerting means applied to the twosheet unit manifold.
  • FIG. 2 is a sectioned view of the two-sheet unit manifold of FIG. 1.
  • the elements are not to scale and are so-shown in order to more effectively depict their interrelation.
  • the released solution is transferred from the overlying or base-sheet to the receiving surface of'the underlying sheet in conformance with the pressure pattern of the writing operation.
  • the drawing shows that the top of the underlying sheet is coated or impregnated with a material reactant with the chromogenic material, e.g., an acid clay or an acidic phenolic polymer material; and that capsules are present on the overlying or base-sheet which capsules contain a liquid solution of chromogenic material.
  • a material reactant with the chromogenic material e.g., an acid clay or an acidic phenolic polymer material
  • the capsules can contain the polymeric phenolic material in liquid solution and the receiving surface of the underlying sheet can be supplied with the chromogenic material.
  • the improvement in the system resides in the chromogenic material, which chromogenic material is the substance of the instant invention.
  • the chromogenic material located within or upon the sheet; it is possible to incorporate the chromogenic material in a solid, crystalline state in a binder material so that the chromogenic material may be transferred from the overlying sheet, upon the application of pressure, to deposit some of the chromogenic material on the receiving surface of the undersheet, which receiving surface carries a color-activating polymeric material.
  • the chromogenic substance is dissolved in an appropriate solvent and minute droplets of the solution of the chromogenic material are encapsulated in minute, rupturable, capsules.
  • the polymeric mark-forming components should have a common solubility with the chromogenic material in at least one liquid solvent when the acidreacting material is a phenolic or other acidic organic polymer. It is also noted that in a single system several chromogenic materials may be used with the same or different polymeric materials. Several polymeric materials can be reactively contacted with a single chromogenic compound or with a mixture of chromogenic compounds.
  • the solvent can be maintained in physical isolation in minute droplets until such time as it is released by application of pressure. This may be accomplished by several known techniques, but, preferably, isolation is maintained by encapsulation of individual droplets of the solvent in a microcapsule according to the procedures described, for example, in US. Pat. No. 2,712,507, issued July 5, 1955 on the application of Barrett K. Green; 2,730,457 issued Jan. 10, 1956 on the application of Barrett K. Green and Lowell Schleicher; 2,800,457, issued July 25, 1957 on the application of Barrett K. Green and Lowell Schleicher; 2,800,458, issued July 23, 1957 on the application of Barrett K. Green and Lowell Schleicher; 2,800,458, issued July 23, 1957 on the application of Barret K.
  • the material or materials chosen as the wall material for the droplet-containing microcapsules in addition to being pressure rupturable, must be inert or unreactive with respect to the intended contents of the capsules and the other mark-forming components so that the capsule wall material will remain intact under normal storage conditions until such time as it is released by an application of marking pressure.
  • Preferred examples of eligible capsule wall materials include gelatin, gum arabic and many others thoroughly described in the aforementioned patents.
  • the capsule size should not exceed about 50 microns in diameter. Preferably, the capsules should be smaller than about 15 microns in diameter.
  • the acidic organic polymeric material useful for developrng the color of novel chromogenic compounds in this lnvention include phenolic polymers, phenol acetylene polymers, maleic acid-rosin resins, partially or wholly hydrolyzed styrene-maleic anhydride copolymers and ethylene-maleic anhydride copolymers, carboxy polymethylene and wholly or partially hydrolyzed vinylmethylethermalerc anhydride copolymer and mixtures thereof.
  • phenolic polymers found useful include alkyl-phenol acetylene resins, which are soluble in common organic solvents and possess permanent fusibihty 1n the absence of being treated by cross-linking materials.
  • Another specific group of useful phenolic polymers are members of the type commonly referred to as novolacs (a type of phenolformaldehyde polymeric material) which are characterized by solubility in common organic solvents and which are, in the absence of cross-linking agents, permanently fusible.
  • Resol resins if they are still soluble, may be used, though they are subject to change in properties upon aging.
  • phenolic polymer material found useful in practicing this invention is characterized by the presence of hydroxyl groups and by the absence of groups such as methylol, which tend to promote infusibility or cross-linking of the polymer, and further, by being soluble in organic solvents and relatively insoluble in aqueous media. Again, it should be remembered that mixtures of these organic polymers and other acidic materials can be employed.
  • a laboratory method useful in the selection of suitable phenolic resins is the determination of the infrared absorption pattern. It has been found that phenolic resins which undergo absorption in the 32003 500 cm.-- region (which is indicative of hydroxyl groups) on the resin molecules and which do not absorb in the 1600-1700 cm?" region are eligible. This latter absorption region is indicative of desensitization of hydroxyl groups which densensitization renders such groups unavailable for reaction with the chromogenic materials.
  • the liquid solvent chosen must be capable of dissolving it.
  • the solvent may be volatile or nonvolatile, and a singleor multiple-component solvent may be used which is wholly or partially volatile.
  • volatile solvents useful in practicing the present invention include toluene, petroleum distillate, perchloroethylene, and xylene.
  • nonvolatile solvents include high-boiling-point petroleum fractions and chlorinated biphenyls.
  • the solvent chosen should be capable of dissolving at least about 0.3 percent, by weight, of the chromogenic material, and at least about 3 to 5 percent, by weight, of the acidic polymeric material to yield an effective reaction.
  • the solvent should be capable of dissolving an excess of the polymeric material, so as to provide every opportunity for utilization of the chromogenic material and, thus, to assure maximum coloration at the reaction site.
  • a further criterion for selection of the solvent is that the solvent must not interfere with the mark-forming reaction.
  • the presence of the solvent may be found to interfere with the mark-forming reaction or diminish the intensity of the mark, in which instances the solvent chosen should be sufiiciently volatile to assure its removal from the reaction site soon after having brought the mark-forming components into reactive contact so that the mark-forming reaction can proceed.
  • mark-forming reaction requires that an intimate mixture of the components be brought about through solution of said components, one or more of the markforming components can be dissolved in solvent droplets isolated by encapsulation, the only requirement being that at least one of the components essential to the markforming reaction be maintained isolated until the markforming reaction is desired.
  • the mark-forming components are so chosen as to produce a mark upon application of pressure to a coated system of sheets at room temperature (20 to 25 degrees Centigrade).
  • the present invention also includes a system wherein the solvent component is not liquid at temperatures near room temperature but is liquid and in condition for forming solutions only at elevated temperatures.
  • the support sheet member on which components of the system are disposed may comprise a single or a dual sheet assembly.
  • the record material is referred to as a self-contained or autogenous system.
  • the record material is referred to as a transfer system.
  • a transfer system may also be referred to as a two-fold system, in that at least two sheets are required and each sheet includes a component, or components, essential to the mark-forming reaction.
  • microcapsules are employed, they can be present in the sheet support material either disposed therethroughout or as a coating thereon, or both.
  • the capsules can be applied to the sheet material as a dispersion in the liquid vehicle in which they were manufactured, or, if desired, they can be separated from the vehicle and thereafter dispersed in a solution of the acidreacting polymeric component (for instance, 30 grams of water and 53 grams of a 1 percent, by weight, aqueous solution of polyvinylmethylether-maleic anhydride) to form a sheet-coating composition in which, because of the inertness of the solution and the capsules, both components retain their identity and physical integrity.
  • a solution of the acidreacting polymeric component for instance, 30 grams of water and 53 grams of a 1 percent, by weight, aqueous solution of polyvinylmethylether-maleic anhydride
  • the capsules When this composition is disposed as a film on the support material and dried, the capsules are held therein subject to release of the contained liquid by rupture of the capsule walls.
  • the latter technique relying on the inertness of the microcapsule and the dispersing medium of the film-forming mark-forming polymeric component, provides a method for preparing a sensitive record material coating having the capsules interspersed directly in a dry film of the polymeric material as the film is laid down from solution.
  • a further alternative is to disperse one or more markforming components, and the chromogenic-material-containing microcapsules in a liquid medium not a solvent for either the mark-forming component or the microcapsules, with the result that all components of the markforming system may be disposed on or within the support sheet in the one operation.
  • the several components may be applied individually.
  • the capsules can also be coated onto a sheet as a dispersion in a solution of polymeric material which is not necessarily reactive with the capsule-contained solution of chromogenic materials.
  • Suitable lower amounts include, in the case of the chromogenic material, about 0.005 to 0.075 pound per ream (a ream in this application meaning five hundred (500) sheets of x 38 paper, totalling 3,300 square feet); in the case of the solvent, about 1 to 3 pounds per ream; and in the case of the polymer, about 0.5 pound per ream.
  • the upper limit is primarily a matter of economic consideration.
  • the slurry of capsules can be applied to a wet web of paper, for example, as it exists on the screen of a Fourdrinier paper machine, so as to penetrate the paper web a distance depending on the freeness of the pulp and the water content of the web at the point of application.
  • the capsules can be placed directly in or on a paper or support sheet. Not only capsule structures, but continuous films which contain a multitude of microscopic, unencapsulated, droplets for local release in an area subjected to pressure can be utilized. (See, for example, US. Pat. No. 2,299,694 which issued Oct. 20, 1942, on the application of Barrett K. Green.)
  • a solution thereof in an evaporable solvent can be introduced into an amount of water and the resulting mixture can be agitated while the evaporable solvent is blown off by an air blast.
  • This operation leaves an aque ous colloidal dispersion slurry of the polymeric material, which may be applied to finished paper so as to leave a surface residue or the slurry may be applied to a wet web of paper or at the size-press station of a paper making machine.
  • the water-insoluble polymer can be ground to a desired or required particle size in a ball mill with water, preferably with a dispersing agent, such as a small quantity of sodium silicate.
  • a binder material of hydrophilic properties is ground with the polymeric material, the binder itself may act as a dispersant.
  • an amount of binder material of up to percent, by weight, of the amount of polymeric material can be added to the ball-milled slurry of materials-such binder materials being of the paper coating binder class, including, for example, gum arabic, casein, hydroxyethylcellulose, and latexes (such as styrene-butadiene copolymer).
  • oil absorbents in the form of fullers earths may be combined with the polymeric material particles to assist in retaining, in situ, the liquid droplets of chromogenic material solution to be transferred to it in data-representing configuration, for the purpose of preventing bleeding of the print.
  • Another method for applying the chromogenic or polymeric material individually to a single sheet of paper is by immersing a sheet of paper in 110 percent, by weight, solution of the material in an evaporable solvent.
  • this operation must be conducted individually for each reactant, because if the other reactant material were present, contact of the reactants would result in a premature coloration over the sheet area.
  • a dried sheet with one component can then be coated with a solution of another component, the solvent of which is a non-solvent to the already-supplied component.
  • the polymeric material can also be dissolved in ink composition vehicles to form a printing ink of colorless character and, thus, may be used to spot-print a proposed record-sheet-unit sensitized for recording, in a reactionproduced color in those spot-printed areas, by application of a solution of the chromogenic material.
  • a printing ink may be made of up to percent, by weight, of the phenolic polymeric material in a petroleum-based solventthe ink being built to a viscosity suitable for printing purposes.
  • the relative amounts of reactive, mark-forming, components to be used in practice of this invention are those most convenient and economical amounts consistent with adequate, desired or required visibility of the recorded data.
  • the resolution of the recorded data is dependent on, among other things, particle or capsule size, distribution and amount of particles or capsules, liquid solvent migration, chemical reaction efficiency, and other factors, all of which can be optimized empirically by one skilled in the art. Such factors do not determine the principle of the present invention, which invention, in part, relates to means for enabling the bringing into solution contact, by marking pressure, two normally solid, chemically reactive, components dissolved in a common liquid solvent component held isolated as liquid droplets.
  • the isolated liquid droplets are preferably in marking-pressure-rupturable capsules having polymeric-film walls, or are isolated, as a discontinuous phase, in a continuous marking-pressure-rupturable film.
  • the acidic markforming material reacts with the chromogenic material to effect distinctive color formation or color change.
  • the chromogenic material may be desirable to include other materials to supplement the polymer reactants.
  • kaolin can be added to improve the transfer of the liquid and/ or the dissolved materials between the sheets.
  • other materials such as bentonite, attapulgite, talc, feldspar, halloysite, magnesium trisilicate, silica gel, pyrophyllite, zinc sulfate, calcium sulfate, calcium citrate, calcium phosphate, calcium fluoride, barium sulfate and tannic acid can be included.
  • compositions useful for coating mark-forming materials into supporting sheets can be employed in compositions useful for coating mark-forming materials into supporting sheets.
  • An example of the compositions which can be coated onto the receiving surface of an underlying sheet of a multi-sheet to react with a capsule coating on the underside of an overlying sheet is as follows:
  • Percent Coating composition by weight Phenolic polymer mixture 17 Paper coating kaolin (white) 57 Calcium carbonate l2 Styrene butadiene latex 4 Ethylated starch 8 Gum arabic 2 Having disclosed, generally, the novel chromogenic materials of this invention and preferred methods for utilizing the novel chromogenic materials, in combination with other materials, as reactive components in mark-forming record material; examples will now be disclosed wherein preparation of several of the novel chromogenic materials is described.
  • the benzene extract was washed 3 times with SO-rnilliliter volumes of 10 percent, by weight, aqueous sodium followed by a wash with Water.
  • the Water-Washed benzene extract was evaporated to dryness to obtain 0.45 gram of crude reaction product.
  • the crude product was chromotographically purified over activated alumina.
  • a benzene solution of the purified reaction product imparted a reddish-purple color to paper coated with a mixture of kaolin and phenolic resin.
  • EXAMPLE 2 Preparation of 2'-formyl-6-diethylaminofluoran A reaction mixture of 3.1 grams of 2-carboxy-4-diethyl-amino-2-hydroxybenzophenone, 1.2 grams of p-hydroxybenzaldehyde, and milliliters of 90 percent, by weight, aqueous sulfuric acid solution was heated for about 1 hour at 140-145 degrees centigrade. The reaction mixture was then poured into about 0 milliliters of water and made alkaline to a pH of above about 8 by addition of dilute, aqueous, ammonium hydroxide solution. The reaction mixture was extracted by 250 milliliters of benzene and the benzene extract was Washed with sodium hydroxide solution and then with water. The reaction product was chromatographically purified over alumina. A benzene solution of the purified reaction product imparted an orange color to paper coated with a mixture of kaolin and phenolic resin.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
US792325*A 1969-01-21 1969-01-21 Diethylamino fluorans Expired - Lifetime US3637757A (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US79232469A 1969-01-21 1969-01-21
US79227969A 1969-01-21 1969-01-21
US79243569A 1969-01-21 1969-01-21
US79227769A 1969-01-21 1969-01-21
US79240169A 1969-01-21 1969-01-21
US79232569A 1969-01-21 1969-01-21
US10560071A 1971-01-11 1971-01-11

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US3637757A true US3637757A (en) 1972-01-25

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ID=27568646

Family Applications (6)

Application Number Title Priority Date Filing Date
US792325*A Expired - Lifetime US3637757A (en) 1969-01-21 1969-01-21 Diethylamino fluorans
US792277*A Expired - Lifetime US3641011A (en) 1969-01-21 1969-01-21 5- and 6-dialkylaminobenzylidene-aminofluorans
US792279*A Expired - Lifetime US3624107A (en) 1969-01-21 1969-01-21 Nitro- and amino-substituted fluorans
US00792324A Expired - Lifetime US3769302A (en) 1969-01-21 1969-01-21 Aliphatic amino-substituted flourans
US792435*A Expired - Lifetime US3627787A (en) 1969-01-21 1969-01-21 Amids- and sulfonamido-substituted fluorans
US00105600A Expired - Lifetime US3713863A (en) 1969-01-21 1971-01-11 Mark-forming record materials and process

Family Applications After (5)

Application Number Title Priority Date Filing Date
US792277*A Expired - Lifetime US3641011A (en) 1969-01-21 1969-01-21 5- and 6-dialkylaminobenzylidene-aminofluorans
US792279*A Expired - Lifetime US3624107A (en) 1969-01-21 1969-01-21 Nitro- and amino-substituted fluorans
US00792324A Expired - Lifetime US3769302A (en) 1969-01-21 1969-01-21 Aliphatic amino-substituted flourans
US792435*A Expired - Lifetime US3627787A (en) 1969-01-21 1969-01-21 Amids- and sulfonamido-substituted fluorans
US00105600A Expired - Lifetime US3713863A (en) 1969-01-21 1971-01-11 Mark-forming record materials and process

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US (6) US3637757A (OSRAM)
BE (1) BE744705A (OSRAM)
CH (1) CH567077A5 (OSRAM)
FR (1) FR2028785A1 (OSRAM)
GB (1) GB1269601A (OSRAM)

Cited By (3)

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Publication number Priority date Publication date Assignee Title
US3963853A (en) * 1971-12-30 1976-06-15 Wiggins Teape Limited Pressure sensitive transfer sheet
US4110343A (en) * 1973-02-05 1978-08-29 Champion International Corporation Bisfluoran chromogenic compounds, preparation thereof, and pressure-sensitive copy systems employing same
US5395948A (en) * 1992-03-17 1995-03-07 Ciba-Geigy Corporation Fluoran color formers

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DE2128518B2 (de) * 1970-06-08 1973-09-13 Fuji Photo Film Co. Ltd., Ashigara, Kanagawa (Japan) Farbentwicklungsblatt fur druck empfindliche Kopierpapiere
US3998846A (en) * 1970-07-08 1976-12-21 Yamamoto Kagaku Gosei Kabushiki Kaisha Process for preparing dibenzylamino fluoran compounds
JPS4917490B1 (OSRAM) * 1970-07-23 1974-05-01
US3895168A (en) * 1971-03-02 1975-07-15 Ncr Co Pressure-sensitive record sheets employing amido and sulfonamido-substituted fluorans
JPS5348124B2 (OSRAM) * 1971-08-21 1978-12-27
BE794459A (fr) * 1972-01-24 1973-05-16 Fuji Photo Film Co Ltd Feuille d'enregistrement
JPS5122413B2 (OSRAM) * 1972-06-24 1976-07-09
US3940275A (en) * 1973-01-24 1976-02-24 Ncr Corporation Record material and marking liquid
JPS5138245B2 (OSRAM) * 1973-05-22 1976-10-20
US3929825A (en) * 1974-04-18 1975-12-30 Mead Corp Pyrazoloxanthene compounds and process for producing same
US3930108A (en) * 1974-11-21 1975-12-30 Moore Business Forms Inc 9-(4-Aminophenyl polymethine)-9-xanthenol compounds and pressure sensitive system therewith
US3928685A (en) * 1974-11-21 1975-12-23 Moore Business Forms Inc 1-Hydroxy-1-(4-aminophenyl polymethine) naphthalan compounds and pressure-sensitive recording system therewith
US4343885A (en) 1978-05-09 1982-08-10 Dynachem Corporation Phototropic photosensitive compositions containing fluoran colorformer
CA1164710A (en) * 1978-05-09 1984-04-03 Edward J. Reardon, Jr. Phototropic photosensitive compositions containing fluoran colorformer
US4552830A (en) * 1978-05-09 1985-11-12 Dynachem Corporation Carbonylic halides as activators for phototropic compositions
CA1153610A (en) * 1978-05-09 1983-09-13 Edward J. Reardon, Jr. Carbonylic halides as activators for phototropic compositions
US4515971A (en) * 1980-03-31 1985-05-07 Hilton-Davis Chemical Co. 5'/6'-Carboxyfluorans and derivatives thereof
US4524373A (en) * 1982-02-24 1985-06-18 Kanzaki Paper Manufacturing Co., Ltd. Fluoran derivatives as new compounds, process for preparing the same and recording system utilizing the same as colorless chromogenic material
DE3337387A1 (de) * 1983-10-14 1985-04-25 Basf Ag, 6700 Ludwigshafen Neue fluorane und deren verwendung
US5250708A (en) * 1991-08-13 1993-10-05 Milliken Research Corporation Poly(oxyalkylene) substituted aminophenol intermediate and xanthene colorant
US5331097A (en) * 1991-08-13 1994-07-19 Milliken Research Corporation Poly(oxyalkylene) substituted xanthene colorant and method for making the same
DE59307983D1 (de) * 1992-09-30 1998-02-19 Ciba Geigy Ag Konzentrierte, wässrige Flüssigformulierungen von Farbbildnern
US5693374A (en) 1994-06-23 1997-12-02 Fuji Photo Film Co., Ltd. Alpha-resorcyclic acid ester derivatives and recording materials using the same
GB9414637D0 (en) 1994-07-20 1994-09-07 Wiggins Teape Group The Limite Presure-sensitive copying material
JPH10129021A (ja) * 1996-10-25 1998-05-19 Fuji Photo Film Co Ltd 感熱記録システム
US5955398A (en) * 1997-04-25 1999-09-21 Appleton Papers Inc. Thermally-responsive record material
US6294502B1 (en) 1998-05-22 2001-09-25 Bayer Aktiengesellschaft Thermally-responsive record material
EP1211094B8 (en) 2000-12-04 2007-06-13 FUJIFILM Corporation Thermal recording material
EP1275519B1 (en) 2001-06-26 2005-08-31 Fuji Photo Film Co., Ltd. Recording material
JP2003094827A (ja) 2001-09-27 2003-04-03 Fuji Photo Film Co Ltd 感熱記録材料
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JP3776810B2 (ja) 2002-01-25 2006-05-17 富士写真フイルム株式会社 感熱記録材料及び感熱記録方法
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US4110343A (en) * 1973-02-05 1978-08-29 Champion International Corporation Bisfluoran chromogenic compounds, preparation thereof, and pressure-sensitive copy systems employing same
US5395948A (en) * 1992-03-17 1995-03-07 Ciba-Geigy Corporation Fluoran color formers

Also Published As

Publication number Publication date
GB1269601A (en) 1972-04-06
FR2028785A1 (OSRAM) 1970-10-16
US3624107A (en) 1971-11-30
BE744705A (fr) 1970-07-01
DE2001864A1 (de) 1970-07-30
US3769302A (en) 1973-10-30
US3713863A (en) 1973-01-30
CH567077A5 (OSRAM) 1975-09-30
DE2065643B2 (de) 1977-03-31
US3627787A (en) 1971-12-14
DE2065643A1 (de) 1974-11-14
US3641011A (en) 1972-02-08
DE2001864B2 (de) 1977-05-26

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