US3627787A - Amids- and sulfonamido-substituted fluorans - Google Patents

Amids- and sulfonamido-substituted fluorans Download PDF

Info

Publication number
US3627787A
US3627787A US792435*A US3627787DA US3627787A US 3627787 A US3627787 A US 3627787A US 3627787D A US3627787D A US 3627787DA US 3627787 A US3627787 A US 3627787A
Authority
US
United States
Prior art keywords
diethylamino
fluoran
chromogenic
sheet
mark
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US792435*A
Other languages
English (en)
Inventor
Chao-Han Lin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Appvion LLC
NCR Voyix Corp
National Cash Register Co
Original Assignee
NCR Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NCR Corp filed Critical NCR Corp
Application granted granted Critical
Publication of US3627787A publication Critical patent/US3627787A/en
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.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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

  • R represents a radical having the structural fonnula NHCOY or a radical having the structural formula NHSO -Y wherein Y comprises phenyl, methoxyphenyl, naphthyl, quinolyl, benzyl, alkyl radicals having less than five carbon atoms, and amino-, nitro-, and alkyl-substituted phenyl radicals wherein the alkyl groups have less than five carbon atoms; R comprises hydrogen and alkyl radicals having less than five carbon atoms; and R, comprises alkyl radicals having less than five carbon atoms.
  • Examples include 2'-acetar nido- 6'-diethylaminofluoran; 6-diethylamino-2-(phenylacetamido)fluoran; 6-diethylamino-2'-(p-toluenesulfonamido)fluoran; 2'-acetamido-6diethylamido-3'-methylfluoran; 6'-diethylamino-3 '-methyl-2 '-(p-toluenesulfonamido )fluoran; 6diethylamino-Z(p-nitrobenzenesulfonamido)fluoran; 6'-diethylamino-3 '-methyl-2'-(pnitrobenzenesulfonamido )fluoran; 6 diethylamino-Z 2- naphthalenesulfonamido)fluoran; 6'-diethylamido-2'-( 8-quinolinesulfonamid
  • This invention pertains to novel chromogenic compounds for use in pressure-sensitive record material and to an improved mark-forming manifold system incorporating these novel chromogenic compounds. More specifically, this invention pertains to acetamidoand sulfonamido-substituted diall Pressuresensitive, mark-forming system s of the prior art include that disclosed in application Ser. No. 392,404, filed Aug. 27, 1964 now abandoned in the names of Robert E.
  • R1 ⁇ o I s' Q 1' 2 R a o wherein Rlrepresents a radical having the structural formula --NH--CO--Y or a radical having the structure formula NHSO,Y wherein Y comprises phenyl, methoxyphenyl, naphthyl, quinolyl, benzyl, alkyl having less than five carbon 'atoms, and amino-, nitro-, and alkyl-substituted phenyl wherein the alkyl groups have less than five carbon atoms; R comprises hydrogen and alkyl radicals and R comprises alkyl radicals having less than five carbon atoms. Examples of these novel compounds include 2-acetamido-6'- diethylaminofluoran having the structural formula:
  • 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 1 dark-colored form of the chromogenic compound by the action thereon of said acidic substance.
  • Acid materials employed in this invention can be any compound within the definition of a Lewis acid, i.e., any electron acceptor.
  • acid organic polymers such as phenolic polymers are employed as the acidic material.
  • the novel chromogenic materials exhibit the advantage 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 darkcolored 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.
  • a DRAWING 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 a acid clay or a phenolic polymeric materials 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 two-sheet 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.
  • the capsules can contain the polymeric phenolic materials 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 0 novel substance of the instant invention.
  • the polymeric mark-forming components 5 5 should have a common solubility with the novel chromogenic material in at least one liquid solvent when the acid-reacting 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 U.S. Pat. Nos. 2,7l2,507 issued July 5, I955 on the application of Barrett K. Green; 2,730,457 issued Jan. I0, 1956 on the application of Barrett K. Green and Lowell Schleicher; 2,800,457 issued July 23, i957 on the application of Barrett K. Green and Lowell Schleicher; 2,800,458 issued 5 July 23, 1957 on the application of Barrett K. Green, reissued as Reissue Pat. No. 24.899 on Nov. 29. 1960; and 3,04l,289
  • the microscopic capsules when disposed within or upon a supporting web as a multiplicity in contiguous juxtaposition, are rupturable by pressure, such as normal marking pressure found, for example, in writing or typmg operations.
  • 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 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 other thoroughly described in the aforementioned patents.-
  • the capsule size should not exceed about 50 microns in diameter.
  • the capsules should be smaller than about microns in diameter.
  • the acidic organic polymeric material useful for developing the color of novel chromogenic compounds in this invention include phenolic polymers, phenol acetylene polymers, maleic acid-rosin resins, partially or wholly hydrolyzed styrene-maleic anhydride copolymers and ethylenemaleic anhydride copolymers, carboxy polymethylene and wholly or partially hydrolyzed vinylmethylether-maleic anhydride copolymer and mixtures thereof.
  • phenolic polymers found useful include alkyl-phenol acetylene resins, which are soluble in common organic solvents and possess permanent fusibility in 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.
  • phenol.- ic 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 of cross-linking of the polymer. and, further, by
  • a laboratory method useful in the selection of suitable phenolic resins is the determinations of the infrared absorption pattern. It has been found that phenolic resins which undergo absorption in the 3200-3500 cm.”region (which is indicative of hydroxyl groups) on the resin molecules and which do not absorb in the 1600-1700 cm. 'lregion are eligible. This latter absorption region is is indicative of desensitization of hydroxyl groups which desensitization 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 chose 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 sol.- vent must not interfere with the mark-fonning 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 sufficiently 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 mixtureof the components be brought about through solution of said components, one or more of the mark-forming components can be dissolved in solvent droplets isolated by encapsulation, the only requirement being that at least one of the components essential to the mark-forming reaction be maintained isolated until the mark-forming reaction is desired.
  • the mark-forming components are so chose as to produce a mark upon application of pressure to a coated system of sheets at room temperature (20 to 25 C.)
  • 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 solution only at elevated temperatures.
  • 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 C.)
  • 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-containing" or autogenous system.
  • the record material is referred to as a transfer" system.
  • a transfer system
  • uch a system may also be referred to as a twofold" system, in that at least two sheets are required and each sheet includes a component, or components, essential to the mark-forming reaction).
  • a colored mark can be recorded on a second sheet by transfer of the colored reaction product.
  • microcapsules in a preferred case, where microcapsules are employed, they can be present in the sheet support material either disposed there throughout 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 the solution of the acid-reacting 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.
  • the acid-reacting 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 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 markforming 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 mark-forming 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 mark-forming 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 means 500 sheets of 25 inch X38 inch paper, totaling 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 pounds 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. No only 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, U.S. 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 aqueous 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 by wet web of paper or at the size-press station of a papennaking machine.
  • the water-soluble 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. lf desired, an amount of binder material of up to 40 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 fuller 's 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 datarepresenting 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 1 --l 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 the be coated with a solution of another component, the solvent of which is a nonsolvent 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 beused 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 75 percent, by weight, of the phenolic polymeric material in a petroleumbased solvent -the ink being built to a viscosity suitable for printing purposes.
  • the relative amounts of reactive, markforming, 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 bring 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 mark-forming material reacts with the novel chromogenic material to effect distinctive color formation or color change.
  • the acidic mark-forming material reacts with the novel chromogenic material to effect distinctive color formation or color change.
  • it may be desirably to include other materials to supplement the polymer'reactants, For example, kaolin can be added to improve the transfer of the liquid and/or the dissolved materials between the sheets.
  • 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 multisheet to react with a capsule coating on the underside of an overlying sheet is as follows:
  • the mixture is then poured onto about 225 parts, by weight, of ice and made alkaline to a pH of about b by addition of dilute ammonium hydroxide.
  • the alkaline system is extracted by benzene and the benzene is washed with 10 percent, by weight, aqueous sodium hydroxide solution and then with water.
  • the washed benzene extract is then evaporated to dryness and the residue is chromatographically purified over alumina and then recrystallized from benzene-petroleum ether.
  • the purified product is reduced with stannous chloride solution to yield 2- amino-6'-diethylaminofluoran having a melting point of about 2 l4 C.
  • the benzene layer was washed with 10 percent, by weight, aqueous sodium hydroxide solution, then with water, then was concentrated to about 50 milliliters by evaporation.
  • the concentrated benzene extract was chromatographically purified over alumina.
  • a benzene solution of the purified reaction product imparted a red color to paper coated with a mixture of kaolin and phenolic polymer.
  • EXAMPLE 3 Preparation of 6 '-diethylamino-2 p-toluenesulfonamido)fluoran A mixture of 0.4 grams of 2amino'6-diethylaminofluoran (preparation described in example 1, above) 0.2 grams of ptoluenesulfonyl chloride, and 5 milliliters of pyridine was refluxed for 15 minutes and then poured into 100 milliliters of water. The system was then acidified with dilute hydrochloric acid to a pH of about 4 to precipitate the reaction product.
  • the precipitate was extracted with 100 milliliters of benzene and the benzene extract, after a water wash, was concentrated to about 50 milliliters by evaporation.
  • the concentrated extract was treated in an alumina-packed chromatography column to obtain a purified product.
  • a benzene solution of the purified product imparted a red color to paper coated with a mixture of kaolin and phenolic polymer.
  • the fluoran starting material of this example is 2- amino-6'-diethylamino-3'-methylfluoran.
  • a benzene solution of the reaction product imparted a red color to paper coated with a mixture of kaolin and phenolic polymer.
  • benzene solution of the purified reaction product of this example imparted to red color to paper coated with kaolin and phenolic polymer.
  • a benzene solution of the purified reaction product imparted a red color to paper coated with a mixture of kaolin and phenolic polymer.
  • EXAMPLE 7 Preparation of 6'-diethylamino-2-(2-naphthalenesulfonamido)fluoran
  • the reaction of this example was conducted according to the same procedure as that described in example 6, above, with the exception that 2-naphthalenesulfonyl chloride was substituted for the 4-methoxy-benzenesulfonyl chloride of 4example.
  • the purified product exhibited a melting point of l5l-l53 C.
  • a benzene solution of the purified reaction product imparted a red color to p paper coated with a mixture of kaolin and phenolic polymer.
  • EXAMPLE 8 Preparation of 6'-diethylamino-2-( 8-quinolinesulfonamido)fluoran
  • the reaction of this example was conducted according to the same procedure as that described in example 6, above, with the exception that 8-quinolinesulfonyl chloride was substituted for the 4-methoxy-benzenesulfonyl chloride of that example.
  • the purified product exhibited a melting point of 255-256 C.
  • a benzene solution of the purified reaction product imparted a red color to paper coated with a mixture of kaolin and phenolic polymer.
  • a chromogenic compound having the structural formula R represents a chemical radical selected from the group consisting of alkyl groups having less than five carbon atoms.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Color Printing (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
US792435*A 1969-01-21 1969-01-21 Amids- and sulfonamido-substituted fluorans Expired - Lifetime US3627787A (en)

Applications Claiming Priority (7)

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

Publications (1)

Publication Number Publication Date
US3627787A true US3627787A (en) 1971-12-14

Family

ID=27568646

Family Applications (6)

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

Country Status (5)

Country Link
US (6) US3627787A (forum.php)
BE (1) BE744705A (forum.php)
CH (1) CH567077A5 (forum.php)
FR (1) FR2028785A1 (forum.php)
GB (1) GB1269601A (forum.php)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3895168A (en) * 1971-03-02 1975-07-15 Ncr Co Pressure-sensitive record sheets employing amido and sulfonamido-substituted fluorans
US3970671A (en) * 1971-08-21 1976-07-20 Kanzaki Paper Manufacturing Co., Ltd. Chromogenic compounds and method for preparation thereof
US3998846A (en) * 1970-07-08 1976-12-21 Yamamoto Kagaku Gosei Kabushiki Kaisha Process for preparing dibenzylamino fluoran compounds
US4410708A (en) * 1973-05-22 1983-10-18 Shin Nisso Kako Co., Ltd. Chromogenic fluoran derivatives and the preparation and use thereof
US5395948A (en) * 1992-03-17 1995-03-07 Ciba-Geigy Corporation Fluoran color formers
EP0688759A1 (en) 1994-06-23 1995-12-27 Fuji Photo Film Co., Ltd. Alpha-resorcylic acid ester derivatives and recording materials incorporating them
EP1211094A2 (en) 2000-12-04 2002-06-05 Fuji Photo Film Co., Ltd. Thermal recording material
EP1275519A1 (en) 2001-06-26 2003-01-15 Fuji Photo Film Co., Ltd. Recording material
EP1297967A2 (en) 2001-09-27 2003-04-02 Fuji Photo Film Co., Ltd. Thermal recording material and production method thereof
EP1331104A2 (en) 2002-01-25 2003-07-30 Fuji Photo Film Co., Ltd. Heat sensitive recording material and recording method
EP1348569A2 (en) 2002-03-26 2003-10-01 Fuji Photo Film Co., Ltd. Heat-sensitive recording material
US20040169071A1 (en) * 2003-02-28 2004-09-02 Appleton Papers Inc. Token array and method employing authentication tokens bearing scent formulation information
US20040214134A1 (en) * 2003-04-22 2004-10-28 Appleton Papers Inc. Dental articulation kit and method
US20040251309A1 (en) * 2003-06-10 2004-12-16 Appleton Papers Inc. Token bearing magnetc image information in registration with visible image information
US20060063125A1 (en) * 2003-04-22 2006-03-23 Hamilton Timothy F Method and device for enhanced dental articulation
US20090087767A1 (en) * 2007-10-01 2009-04-02 Fuji Xerox Co., Ltd. Color toner for flash fusing, method for producing the same, and electrostatic image developer, process cartridge, and image forming apparatus using the same
WO2010090213A1 (ja) 2009-02-04 2010-08-12 富士フイルム株式会社 熱分布表示体及び熱分布確認方法
WO2014124052A1 (en) 2013-02-06 2014-08-14 Fujifilm Hunt Chemicals, Inc. Chemical coating for a laser-markable material
US9409219B2 (en) 2011-02-07 2016-08-09 Valspar Sourcing, Inc. Compositions for containers and other articles and methods of using same
US9475328B2 (en) 2012-08-09 2016-10-25 Valspar Sourcing, Inc. Developer for thermally responsive record materials
US9724276B2 (en) 2012-08-09 2017-08-08 Valspar Sourcing, Inc. Dental materials and method of manufacture
US9944749B2 (en) 2012-08-09 2018-04-17 Swimc, Llc Polycarbonates
US10113027B2 (en) 2014-04-14 2018-10-30 Swimc Llc Methods of preparing compositions for containers and other articles and methods of using same
US10316211B2 (en) 2012-08-09 2019-06-11 Swimc Llc Stabilizer and coating compositions thereof
US10435199B2 (en) 2012-08-09 2019-10-08 Swimc Llc Compositions for containers and other articles and methods of using same
US10526502B2 (en) 2012-08-09 2020-01-07 Swimc Llc Container coating system
US11130835B2 (en) 2015-11-03 2021-09-28 Swimc Llc Liquid epoxy resin composition useful for making polymers
US11130881B2 (en) 2010-04-16 2021-09-28 Swimc Llc Coating compositions for packaging articles and methods of coating

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1416867A (en) * 1971-12-30 1975-12-10 Wiggins Teape Ltd Colour formers
CA944151A (en) * 1970-06-08 1974-03-26 Hiroharu Matsukawa Light-resistant-color developing sheet for pressure-sensitive copying paper
JPS4917490B1 (forum.php) * 1970-07-23 1974-05-01
BE794459A (fr) * 1972-01-24 1973-05-16 Fuji Photo Film Co Ltd Feuille d'enregistrement
JPS5122413B2 (forum.php) * 1972-06-24 1976-07-09
US3940275A (en) * 1973-01-24 1976-02-24 Ncr Corporation Record material and marking liquid
US3821010A (en) * 1973-02-05 1974-06-28 Champion Int Corp Bisfluoran chromogenic compounds,preparation thereof,and pressure-sensitive copy systems employing same
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
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
US4343885A (en) 1978-05-09 1982-08-10 Dynachem Corporation Phototropic photosensitive compositions containing fluoran colorformer
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
US5331097A (en) * 1991-08-13 1994-07-19 Milliken Research Corporation Poly(oxyalkylene) substituted xanthene colorant and method for making the same
US5250708A (en) * 1991-08-13 1993-10-05 Milliken Research Corporation Poly(oxyalkylene) substituted aminophenol intermediate and xanthene colorant
EP0591106B1 (de) * 1992-09-30 1998-01-14 Ciba SC Holding AG Konzentrierte, wässrige Flüssigformulierungen von Farbbildnern
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
JP2003094827A (ja) 2001-09-27 2003-04-03 Fuji Photo Film Co Ltd 感熱記録材料
US20040043314A1 (en) * 2002-08-30 2004-03-04 Nusrallah Jubran Organophotoreceptors with a fluoran-based compound
US6995784B2 (en) 2002-11-12 2006-02-07 Appleton Papers Inc. Secure point of sale imageable substrate
US7910754B2 (en) * 2007-02-06 2011-03-22 Xerox Corporation Colorant compounds
CN106349091A (zh) * 2016-08-30 2017-01-25 沈阳化工大学 一种熔融态合成2‑（4‑二乙氨基‑2‑羟基苯甲酰基）苯甲酸的方法
CN118812555A (zh) * 2024-07-30 2024-10-22 上海瑞年精细化工有限公司 一种红色热敏成色剂及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3514310A (en) * 1966-11-18 1970-05-26 Fuji Photo Film Co Ltd Pressure sensitive fluoran derivative copying paper

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1553291A (forum.php) * 1967-01-27 1969-01-10

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3514310A (en) * 1966-11-18 1970-05-26 Fuji Photo Film Co Ltd Pressure sensitive fluoran derivative copying paper

Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998846A (en) * 1970-07-08 1976-12-21 Yamamoto Kagaku Gosei Kabushiki Kaisha Process for preparing dibenzylamino fluoran compounds
US3895168A (en) * 1971-03-02 1975-07-15 Ncr Co Pressure-sensitive record sheets employing amido and sulfonamido-substituted fluorans
US3970671A (en) * 1971-08-21 1976-07-20 Kanzaki Paper Manufacturing Co., Ltd. Chromogenic compounds and method for preparation thereof
US4410708A (en) * 1973-05-22 1983-10-18 Shin Nisso Kako Co., Ltd. Chromogenic fluoran derivatives and the preparation and use thereof
US4677203A (en) * 1973-05-22 1987-06-30 Shin Nisso Kako Co., Ltd. Chromogenic fluoran derivatives
US5395948A (en) * 1992-03-17 1995-03-07 Ciba-Geigy Corporation Fluoran color formers
EP0688759A1 (en) 1994-06-23 1995-12-27 Fuji Photo Film Co., Ltd. Alpha-resorcylic acid ester derivatives and recording materials incorporating them
EP1211094A2 (en) 2000-12-04 2002-06-05 Fuji Photo Film Co., Ltd. Thermal recording material
EP1275519A1 (en) 2001-06-26 2003-01-15 Fuji Photo Film Co., Ltd. Recording material
EP1297967A2 (en) 2001-09-27 2003-04-02 Fuji Photo Film Co., Ltd. Thermal recording material and production method thereof
EP1331104A2 (en) 2002-01-25 2003-07-30 Fuji Photo Film Co., Ltd. Heat sensitive recording material and recording method
EP1348569A2 (en) 2002-03-26 2003-10-01 Fuji Photo Film Co., Ltd. Heat-sensitive recording material
US20040169071A1 (en) * 2003-02-28 2004-09-02 Appleton Papers Inc. Token array and method employing authentication tokens bearing scent formulation information
US7108190B2 (en) 2003-02-28 2006-09-19 Appleton Papers Inc. Token array and method employing authentication tokens bearing scent formulation information
US20040214134A1 (en) * 2003-04-22 2004-10-28 Appleton Papers Inc. Dental articulation kit and method
US6932602B2 (en) 2003-04-22 2005-08-23 Appleton Papers Inc. Dental articulation kit and method
US20060063125A1 (en) * 2003-04-22 2006-03-23 Hamilton Timothy F Method and device for enhanced dental articulation
US20040251309A1 (en) * 2003-06-10 2004-12-16 Appleton Papers Inc. Token bearing magnetc image information in registration with visible image information
US8097389B2 (en) 2007-10-01 2012-01-17 Fuji Xerox Co., Ltd. Color toner for flash fusing, method for producing the same, and electrostatic image developer, process cartridge, and image forming apparatus using the same
US20090087767A1 (en) * 2007-10-01 2009-04-02 Fuji Xerox Co., Ltd. Color toner for flash fusing, method for producing the same, and electrostatic image developer, process cartridge, and image forming apparatus using the same
WO2010090213A1 (ja) 2009-02-04 2010-08-12 富士フイルム株式会社 熱分布表示体及び熱分布確認方法
US12234371B2 (en) 2010-04-16 2025-02-25 Swimc Llc Coating compositions for packaging articles and methods of coating
US11130881B2 (en) 2010-04-16 2021-09-28 Swimc Llc Coating compositions for packaging articles and methods of coating
US10294388B2 (en) 2011-02-07 2019-05-21 Swimc Llc Compositions for containers and other articles and methods of using same
US9409219B2 (en) 2011-02-07 2016-08-09 Valspar Sourcing, Inc. Compositions for containers and other articles and methods of using same
US11634607B2 (en) 2011-02-07 2023-04-25 Swimc Llc Compositions for containers and other articles and methods of using same
US11053409B2 (en) 2011-02-07 2021-07-06 Jeffrey Niederst Compositions for containers and other articles and methods of using same
US11628974B2 (en) 2012-08-09 2023-04-18 Swimc Llc Compositions for containers and other articles and methods of using same
US10316211B2 (en) 2012-08-09 2019-06-11 Swimc Llc Stabilizer and coating compositions thereof
US10435199B2 (en) 2012-08-09 2019-10-08 Swimc Llc Compositions for containers and other articles and methods of using same
US10526502B2 (en) 2012-08-09 2020-01-07 Swimc Llc Container coating system
US9724276B2 (en) 2012-08-09 2017-08-08 Valspar Sourcing, Inc. Dental materials and method of manufacture
US10894632B2 (en) 2012-08-09 2021-01-19 Swimc Llc Compositions for containers and other articles and methods of using same
US9475328B2 (en) 2012-08-09 2016-10-25 Valspar Sourcing, Inc. Developer for thermally responsive record materials
US12043448B2 (en) 2012-08-09 2024-07-23 Swimc Llc Compositions for containers and other articles and methods of using same
US11306218B2 (en) 2012-08-09 2022-04-19 Swimc Llc Container coating system
US9944749B2 (en) 2012-08-09 2018-04-17 Swimc, Llc Polycarbonates
WO2014124052A1 (en) 2013-02-06 2014-08-14 Fujifilm Hunt Chemicals, Inc. Chemical coating for a laser-markable material
US10745514B2 (en) 2014-04-14 2020-08-18 Swimc Llc Methods of preparing compositions for containers and other articles and methods of using same
US11525018B2 (en) 2014-04-14 2022-12-13 Swimc Llc Methods of preparing compositions for containers and other articles and methods of using same
US10113027B2 (en) 2014-04-14 2018-10-30 Swimc Llc Methods of preparing compositions for containers and other articles and methods of using same
US11130835B2 (en) 2015-11-03 2021-09-28 Swimc Llc Liquid epoxy resin composition useful for making polymers
US12351677B2 (en) 2015-11-03 2025-07-08 Swimc Llc Liquid epoxy resin composition useful for making polymers

Also Published As

Publication number Publication date
DE2065643B2 (de) 1977-03-31
CH567077A5 (forum.php) 1975-09-30
US3641011A (en) 1972-02-08
US3637757A (en) 1972-01-25
BE744705A (fr) 1970-07-01
DE2065643A1 (de) 1974-11-14
DE2001864B2 (de) 1977-05-26
DE2001864A1 (de) 1970-07-30
FR2028785A1 (forum.php) 1970-10-16
GB1269601A (en) 1972-04-06
US3624107A (en) 1971-11-30
US3713863A (en) 1973-01-30
US3769302A (en) 1973-10-30

Similar Documents

Publication Publication Date Title
US3627787A (en) Amids- and sulfonamido-substituted fluorans
US3540909A (en) Pressure sensitive recording sheets employing 3,3-bis(phenylindol - 3-yl) phthalide
US3491111A (en) Indole- and carbazole-substituted phthalides
US3681390A (en) Dialkylamino fluoran chromogenic compounds
US3775424A (en) Furo(3,4-b)pyridine-7(5h)-ones
US3672935A (en) Pressure-sensitive record material
US3455721A (en) Color sensitized record material comprising phenolic resin and acid type mineral
US3736337A (en) Tetrahalogenated chromogenic compounds and their use
US3427180A (en) Pressure-sensitive record system and compositions
US3642828A (en) Alkyl or halo substituted tetrahalofluorans
US3769057A (en) Pressure-sensitive record sheets employing amido- and sulfonamido-substituted fluorans
US3540914A (en) Pressure sensitive record sheets employing indole substituted pyromellitides
US3594369A (en) 3,5(6)-disubstituted-3-(para-diloweralkyl-aminophenyl) phthalides
US3746562A (en) Mark forming record materials
US3849164A (en) Pressure-sensitive record unit comprising a mixture of two chromogenic compounds
US3654314A (en) Tetrachlorinated chromogenic compounds
US3764369A (en) Pressure sensitive recording unit
US3804855A (en) Naphthalide compounds
US3715226A (en) Mark-forming record materials
US3730755A (en) Pressure-sensitive record materials
US3787325A (en) Alkylamino spiro {8 12-h{8 1{9 benzopyran {8 3,2f{9 {14 quinoline-12,1{40 phthalide
US3721576A (en) Mark forming record materials and process for their use
US3730754A (en) Pressure sensitive recording sheet
US3857675A (en) Mixtures of two chromogenic compounds
US3694461A (en) Chromogenic compounds

Legal Events

Date Code Title Description
AS Assignment

Owner name: APPLETON PAPERS INC.

Free format text: MERGER;ASSIGNORS:TUVACHE, INC.;GERMAINE MONTEIL COSMETIQUES CORPORATION (CHANGED TO APPLETON PAPERS);REEL/FRAME:004108/0262

Effective date: 19811215