Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
  • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
  • C07D491/04—Ortho-condensed systems
• • 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
• • 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
  • C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic

Definitions

• each R is hydrogen, an alkyl radical having 1 ABS CT THE DISCLOSURE 10 to 4 carbon atoms, an alkoxy radical having 1 to 4 carbon
• Specific examples of these compounds are represented x X X by the following formula:
• This invention relates to chromogenic compounds. (6) (7) OZHE These colorless, but colorable dyes are employed in pressure-sensitive record material and in mark-forming manifold systems. In another aspect, this invention relates C1116 C2115 to a method of marking on a substrate by developing 40 dark-colored materials from these colorless chromogenic compounds.
• Pressure sensitive recording sheets employing various Ha phthalides, pyromellitides and the like are known in the ⁇ N art. For example, see US. Pats. 3,540,909 through 3,540,914.
• an object of this invention is to provide chromogenic compounds.
• Another object of this invention is to provide pressuresensitive record material and mark-forming manifold systems employing these chromogenic compounds.
• Still another object of this invention is to provide a method of marking on a substrate by developing darkcolored materials from these chromogenic compounds.
• the pyridine and pyrazine compounds of this inven- N tion are represented by the formula Cam Cm 0:0 0:0 0 N W H4311,
• X is one of the following:
• Pressure-sensitive mark-forming systems provide a marking system of disposing on and/ or within sheet support material the unreacted mark-forming components (at least one of which is a polymeric material) and a liquid solvent in which each of the mark-forming components is soluble, said liquid solvent being present in such form that it is maintained isolated by a pressure-rupturable barrier from at least one of the mark-forming components until the 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.
• the acidic materials employed in this invention can be any compound within the definition of a Lewis acid, i.e., an electron acceptor.
• acidic organic polymers such as phenolic polymers are employed as the acidic material.
• the chromogenic compounds exhibit the advantage of improved color stability when reacted with such phenolic polymers.
• the solution formation of the solid particles of polymeric material in the same solvent with the substantially colorless chromogenic compounds allows penetration of the color into the support sheet, if porous, e.g., paper, so that the colored form of the chromogenic compound sinks into the body of the sheet and is not merely on the surface of the sheet. This feature protects against erasure of recorded data by attrition of the surface of the record sheet.
• the polymeric mark-forming components should have a common solubility with the chromogenic compound in at least one liquid solvent when the acid-reacting material is a phenolic or other organic acidic polymer. It is also noted that in a single system several chromogenic compounds can 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 is maintained in physical isolation in minute droplets until such time as it is released by application of pressure. This is accomplished by several known techniques, but preferably isolation is maintained by individual encapsulation of the solvent droplets in a microcapsule according to the procedures described, for example, in US. Pat. No. 2,712,507, issued to Barrett K. Green on July 5, 1955; 2,730,457, issued to Barrett K. Green and Lowell Schleicher on Jan. 10, 1956; 2,800,457, issued to Barrett K. Green and Lowell Schleicher on July 23, 1957; and 2,000,458, issued to Barrett K. Green on July 23, 1957, relssued as Reissue Pat. No. 24,899 on Nov. 29, 1960.
• 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 pressures utilized, for example, in Writing or typing operations.
• the material or materials chosen as the wall material of the microcapsule in addition to being pressure rupturable, must be inert with respect to the contents of the capsule and the other mark-forming components so that the Wall material remains intact under normal storage conditions until such time as it is released by the application of marking pressure.
• Examples of such wall materials are gelatin, gum arabic and many others thoroughly described in the aforementioned patents.
• the capsule size should not exceed 50 microns in diameter. Preferably, the capsules should be smaller than 15 microns in diameter.
• the acidic polymeric material useful in this invention include phenol 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 vinyl methyl ether maleic anhydride copolymer and mixtures thereof.
• phenolic polymers found useful are alkylphenol-acetylene resins, which are soluble in common organic solvents and possess permanent fusibility in the absence of being treated by cross-linking materials.
• a specific group of useful phenolic polymers are members of the type commonly referred to as novolac, (as sold by Union Carbide Corp., New York, N.Y.) which are characterized by solubility in common organic sol- 'vents and which are, in the absence of cross-linking agents, permanently fusible.
• the phonolic polymer material found useful in practicing this invention is characterized by the presence of free hydroxyl groups and the absence of groups such as methylol, which tend to promote infusibility or cross-linking of the polymer, and by their solubility in organic solvents and relative insolubility in aqueous media. Again, obviously, mixtures of these phenol-aldehyde polymers can be employed.
• Resoles if they are still soluble, are used, though subject to change in properties upon aging.
• 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 showing an absorption in the 3200-6500 cm.” region (which is indicative of the free hydroxyl groups) and not having an absorption in the 1600-1700 cm. region are suitable. The latter absorption region i indicative of the desensitization of the hydroxyl groups and, consequently, makes such groups unavailable for reaction with the chromogenic materials.
• maleic anhydride copolymer is described in the literature, such as, for example, one of the maleic anhydride vinyl copolymers, as disclosed in the publication, Vinyl and Related Polymers, by Calvin E. Schildknecht, second printing, published April 1959, by John Wiley & Sons, Incorporated, See pp. 65 to 68 (styrene-maleic anhydride copolymer), 628 to 630 (vinyl methyl) ether-maleic anhydride copolymer, and 530 to 531 (ethylene-maleic anhydride copolymer).
• the liquid solvent chosen must be capable of dissolving the mark-forming components.
• solvent can be volatile or non-volatile, and a single or multiple component solvent may be used which is wholly or partially volatile.
• volatile solvents useful in the aforedescribed basic chromogen-acidic polymer are toluene, petroleum, distillate, perchloroethylene, and xylene.
• non-volatile solvents are high-boiling point petroleum fractions and chlorinated biphenyls.
• the solvent chosen should be capable of dissolving at least 0.3%, on a weight basis, of the chromogenic compound and about a 3-5 on a weight basis, of the polymeric material to form an eflicient 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 compound and, thus, to assure the maximum coloration at a reaction site.
• a further criterion of the solvent is that it must not interfere with the mark-forming reaction.
• the presence of the solvent can interfere with the mark-forming reaction or diminish the intensity of the mark, in which case the solvent chosen should be suf ficiently vaporizable to assure its removal from the reaction site after having, through solution, brought the markforming components into intimate admixture, so that the mark-forming contact proceeds.
• the mark-forming reaction requires an intimate mixture of the components to be brought about through solution of said components, one or more of the markforming components can be dissolved in the isolated solvent droplets, the only requirement being that at least one of the components essential to the mark-forming reaction be maintained isolated until reactively contacted with the other.
• the mark-forming components are so chosen as to produce a mark upon application of pressure at room temperature (20 to 25 degrees centigrade).
• the present invention includes a system in which the solvent component is not liquid at temperatures around room temperature but is liquid and in condition for forming solutions only at elevated temperatures.
• the support member on which the components of the system are disposed may comprise a single or dual sheet assembly.
• the record material is referred to as a self-contained system.
• the record material is referred to as a transfer system.
• uch a system can 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.
• a copious amount of the colored reaction product in liquid form is produced on a surface of one sheet, it can produce a mark by transfer to a second sheet as a colored mark.
• microcapsules are employed, they can be present in the support material either disposed therethroughout or as a coating thereon, or both.
• the capsules can be applied to the sheet material while still dispersed in the liquid vehicle in which they were manufactured, or, if desired, separated and the separated capsules thereafter dispersed in a solution of the polymeric component (for instance, 30 grams of water and 53 grams of a 1% aqueous solution of polyvinyl methyl ether maleic anhydride) to form a coating composition in which, because of the inertness of the solution and the capsules, both retain their identity and physical integrity.
• a solution of the polymeric component for instance, 30 grams of water and 53 grams of a 1% aqueous solution of polyvinyl methyl ether maleic anhydride
• the respective amounts of the several components vary, depending primarily upon the nature of the materials and the architecture of the record material unit. Suitable lower amounts include, in the case of the chromogenic material, about .005 to .075 pound per ream (a ream in this application meaning five hundred (500) sheets of 25" x 38" 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 /2 pound per ream. In all instances, the upper limit is primarily a matter of economic consideration.
• the slurry of capsules can be applied to a wet web of paper as it exists on the screen of a Fourdrinier paper machine, so as to sink into 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 the paper or in a support sheet. Not only capsule structures, but films which hold a multitude of droplets for local release in an area subject to pressure may be utilized. (See U.S. Pat. No. 2,299,694, which issued Oct. 20, 1942, to B. K. Green.)
• the acidic organic polymeric component With respect to the acidic organic polymeric component, a solution thereof in an evaporable solvent is introduced into twice as much water and agitated while the evaporable solvent is blown ofi by an air blast. This leaves an aqueous colloidal dispersion slurry of the polymeric material, which can be applied to the paper so as to leave a surface residue, or the slurry can be applied to paper at the size-press station of a paper-making machine by roller.
• the water-insoluble polymer is ground to the desired 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 phenolic material, the binder itself may act as a dispersant.
• an amount of binder material of up to 40%, by weight of the employed amount of the polymeric material can be added to the ball-milled slurry of materials, such binder materials being of the paper coating binder class, including gum arabic, casein, hydroxyethylcellulose, and latex (such as styrene-butadiene copolymer).
• oil adsorbents in the form of fullers earths may be added to the polymeric material particles to assist in retaining, in situ, the liquid droplets to be transferred to it in data-representing configuration, for the purpose of preventing bleeding of the print.
• Another way of applying the chromogenic or polymeric material individually to a single sheet of paper is by immersing a sheet of paper in a 1% to solution of the material in an evaporable solvent. Obviously, this must be done alone for each reactant, because if the other reactant material were present, it would result in a premature coloration over the sheet area.
• a dried sheet with one component then can be coated with a solution of the other component, the solvent of which is a non-solvent to the already supplied component.
• the polymeric material can be dissolved in ink composition vehicles to form a printing ink of colorless character and, thus, can be used to spot-print a proposed record sheet unit sensitized for recording in a reactionproduced color in those areas by application of a solution of the chromogenic material.
• a printing ink can be made of up to 75% weight, of the phenolic polymeric material in a petroleum solvent to a viscosity suitable for printing purposes.
• the relative amounts of components to be used are the most convenient and economical amounts consistent with the proper visibility of the recorded data.
• the resolution of the recorded data is, among other things, dependent on particle size, distribution and amount of particles, liquid solvent migration, chemical reaction efficiency, and other factors, all of which are things that can be worked out empirically by one familiar with the art, and which do not determine the principle of the invention, which, in part, involves means for enabling the bringing into solution, by marking pressure, of two normally solid components in a common liquid solvent component held isolated as liquid droplets, preferably in marking-pressure rupturable capsules having film Walls, or else held isolated in a continuous marking-pressure-rupturable film as a discontinuous phase.
• the acidic mark-forming component(s) reacts with the basic chromogenic material( s) to effect distinctive color formation or color change.
• the basic chromogenic material( s) In a multi-sheet system in which an acid organic polymer is employed, it is desirable to include other materials to supplement the reactants. For example, kaolin can be added to improve the transfer of the liquid and/ or the dissolved materials between the sheets.
• compositions of the mark-forming materials into their supporting sheets.
• An example of the compositions which can be coated onto the surface of an underlying sheet of a two-sheet system to react with the capsule coating on the underside of any overlying sheet is as follows:
• the benzene was dried (Na SO and evaporated to a small volume and chromatographed on alumina, eluting with benzene, then benzenezether and then ether and then ethyl acetate.
• the concentrates were dissolved in benzene and pet ether added and seeds were added. After standing overnight, filtering and drying, 2.3 g. of nicely crystalline material was obtained.
• the material has a nondescript M.P. but can be characterized by its T.L.C. characteristics which are on silica gel very bright green aging to a brownish-black. Its color (benzene soln.) on resin sheets are bright green and on Silton a dark green.
• resin unless otherwise stated, is 80 parts by weight para-tertiary butylphenol and 20 parts by weight para-chlor0phenol and clay, unless otherwise stated, is Silton.
• keto-acid was allowed to react with an indole, pyrrole or substituted aniline by heating a few mgs. of each with a few drops of acetic anhydride, diluting with water, ammonia and extracting the reaction mixture with benzene.
• the benzene layer was washed with water and applied to paper coated with resin or clay.
• the colors are tabulated below:
• EXAMPLE X Prints were made on sensitized sheets with 3 compounds. The following table consists of the reflective intensities obtained on a variety of prints. R is defined as:

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• 0
  • BE BE791793D patent/BE791793A/fr not_active IP Right Cessation
• 1971
  • 1971-12-06 US US00205325A patent/US3775424A/en not_active Expired - Lifetime
• 1972
  • 1972-09-28 CA CA152,803A patent/CA971172A/en not_active Expired
  • 1972-11-13 GB GB5230672A patent/GB1367569A/en not_active Expired
  • 1972-11-29 JP JP47119724A patent/JPS5116807B2/ja not_active Expired
  • 1972-12-04 FR FR7242985A patent/FR2169803B3/fr not_active Expired
• 1973
  • 1973-04-19 US US00352832A patent/US3853869A/en not_active Expired - Lifetime

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