US3427180A - Pressure-sensitive record system and compositions - Google Patents
Pressure-sensitive record system and compositions Download PDFInfo
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- US3427180A US3427180A US444274A US3427180DA US3427180A US 3427180 A US3427180 A US 3427180A US 444274 A US444274 A US 444274A US 3427180D A US3427180D A US 3427180DA US 3427180 A US3427180 A US 3427180A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/025—Applications of microcapsules not provided for in other subclasses
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2984—Microcapsule with fluid core [includes liposome]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2984—Microcapsule with fluid core [includes liposome]
- Y10T428/2985—Solid-walled microcapsule from synthetic polymer
- Y10T428/2987—Addition polymer from unsaturated monomers only
Definitions
- This invention relates to pressure-sensitive record systems in which a mark is produced according to the pattern of pressure by the chemical reaction of mark-forming components and in particular wherein the mark-forming components comprise a primary chromogenic component, a polymeric material reacting with said chromogenic component, a liquid solvent medium in which the primary chromogenic component and the material are
- This invention relates to improvements in pressuresensitive record systems, and to materials utilized therewith.
- a combination of materials including two types of chromogenic components, one of which, hereinafter called a primary chromogenic material, reacts with a third ingredient to form a mark or color during the application of pressure to the record system, and the second of which, hereinafter termed a secondary chromogenic material, forms a color only upon exposure to light.
- a primary chromogenic material reacts with a third ingredient to form a mark or color during the application of pressure to the record system
- a secondary chromogenic material forms a color only upon exposure to light.
- Another obpect of the invention is to provide a pressure-sensitive record system in which the intensity of the print formed by the application of pressure to the system is maintained at a level easily readable by a sensing organ (e.g., the eye) upon exposure of the print to light.
- a sensing organ e.g., the eye
- Still another object of the invention is to provide a novel mark-forming composition having a combination of chromogenic components which, as when incorporated into a record system sensitive to marking pressures, main- 3,427,180 Patented Feb. 11, 1969 tains the readability of the formed print when it is exposed to light, even when one of the chromogenic materials fails, as by fading.
- Still a further object of the invention is to provide a transfer sheet for use in the aforementioned pressuresensitive record system comprising supporting base or sheet material having disposed thereon and/or therein the above-mentioned mark-forming composition which maintains its reflective intensity by the action of light to which it is exposed.
- this invention comprises combina tions of materials and the pressure-sensitive record systems into which they can be incorporated, either as a single composition or separately.
- These materials which can be disposed on and/or within the supporting sheet or base material of the record systems is contiguous juxtaposition to each other, comprise a first or primary chromogenic component, a polymeric material reactive therewith when both are in solution to form a mark, a liquid solvent medium in which the primary chromogenic component and the polymeric material are soluble, a pressure-rupturable material which isolates the liquid solvent medium from at least either the primary chromogenic components or the polymeric material, and a secondary chromogenic component, which does not react with the primary chromogenie material, the polymeric material, or the liquid solvent, but which upon exposure to light forms a mark itself.
- the application of markforming pressure causes a breach in the pressure-rupturable material, whereupon the formerly isolated liquid solvent, released according to the pressure pattern, dissolves both the primary chromogenic component and the polymeric material, thereby bringing them into contact while each is in solution to permit a primary mark-forming reaction, which results in a distinctive mark.
- the liquid solvent medium also acts as a fluid carrier for the secondary chromogenic material, which can be either dispersed or dissolved in the liquid medium to distribute it throughout the same pattern as the mark produced by the primary mark-forming components.
- the sensitivity of the secondary chromogenic materials to light-induced mark formation is a characteristic personal to each individual chromogenic material.
- the sensitivity should be sufiicient to produce a mark which permits continued manifestation of the mark should the original mark formed by the reaction of the primary chromogenic material and the polymeric material fade considerably or completely.
- a substantially balanced system in which the intensity of the printed mark, as measured by the sensing organ or other sensing means, remains approximately constant. That is, as the original mark fades upon its exposure to light, the intensity of the mark formed by the secondary mark-forming reaction manifestly increases at about the same rate at which the original mark fades.
- Such a balanced system can be obtained by predetermining the rate of fade and the rate of development of the respective marks among eligible chromogenic materials and selecting from them the system appropriate to the expected environment of use.
- the secondary chromogenic mark-forming materials are preferably colorless, though low-intensity hues can be utilized, prior to their exposure to light, and are capable of color change to form an intense, distinctive, easily readable mark upon reactive exposure to light.
- a single compound is utilized, although in some instances, particularly when the aforedescribed substantially balanced systems are employed, combinations 'of two or more secondary chromogenic compounds can be used advantageously for their individual response to light or for their color.
- the secondary chromogenic materials can be insoluble in the liquid solvent used to dissolve the primary chromogenic material and the polymeric material, or, as in the usual case, they also can be dissolved in the same solvent.
- a second solvent utilized specifically to dissolve one of the secondary chromogenic materials also can be present.
- the primary chromogenic mark-forming component generally reacts with the polymeric material through acidic groups to produce a colored material
- the prirnary chromogenic component in its unreacted state is preferably colorless, though low-intensity hues can be tolerated, and is capable of color change to a strong distinctive color upon reactive contact with the polymeric material.
- the chromogenic material is a base and the complementary polymeric material is acidic; i.e., where the color or change in color is brought about -by the acidic action of the polymer constituent on the primary chromogenic material.
- Suitable basic primary materials having chromogenic groups are diaryl phthalides; leucauramines; acyl auramines; nap-unsaturated aryl ketones; basic mono azo dyes; Rhodamine B Lactams such as N(p-nitrophenyl) Rhodamine B Lactams; polyaryl carbinols; and 8'- methoxy benzoindolinospiropyrans, which may be identified as (8-rnethoxy BIPS).
- Illustrative compounds of each group are diaryl phthalides:-3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (Crystal Violet Lactone, hereinafter referred to as CVL) and 3,3-bis (p-di methylaminophenyl) phthalide (Malachite Green Lactone, hereinafter referred to as MGL); leucauramines:- the N- halophenyl derivatives of leucauramine disclosed in United States Patent No. 2,828,341, issued to Clyde S. Adams, Marjorie J. Cormack, and Mary Lou Frazier on Mar. 25, 1958; and the N-alkylhalophenyl derivatives of leucauramine disclosed in United States Patent No.
- the polymeric mark-forming component(s) chosen must be acidic relativeto the basic primary chromogenic compound and reactive -with the primary chromogenic material to effect distinctive color formation or color change. Moreover, the polymeric mark-forming component(s) shouldhave a common solubility with the primary chromog'enic material in at least one liquid solvent.
- the solvent is maintained in physical isolation in minute droplets until such time as it is released by application of pressure.
- This may be accomplished by any of 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 United States Patents Nos. 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 2,800,458, issued to Barrett K. Green on July 23, 1957, reissued as Reissue Patent No. 24,899 on Nov. 29, 1960.
- the microscopic capsules when disposed in pro fusion within and/or on a support sheet in contiguous juxtaposition, are rupturable by pressure, such as the pressures normally attending writing and printing operations.
- the particular component(s) chosen as the wall material of the microcapsule in addition to being pressurerupturable, must be incompatible with the contents of the capsule and all of the mark-forming components, in the sense that the wall material retains its integrity under normal storage conditions until such time as the contents are released by the application of marking pressure.
- the capsule size generally should not exceed 50 microns; however, the preferable upper limit is 15 microns and most preferably from 5 to 10 microns.
- any polymeric material having the aforementioned characteristics can be used herein.
- certain basic-type primary chromogens as one of the primary mark-forming components, and certain phenol-aldehyde and phenolacetylene polymers, maleic acid-rosin resins, partially or wholly hydrolyzed styrene-maleic anhydride copolymers and ethylene-maleic anhydride copolymers, carboxy polymethylene (Carbopol 934), and wholly or partially hydrolyzed vinyl methyl ether-maleic anhydride copolymer are specified as typical of the reactive acidic polymeric materials.
- phenol-aldehyde polymers found useful are members of the type commonly referred to as novolacs, which are characterized by solubility in common organic solvents and which are, in the absence of cross-linking agents, permanently fusible.
- Another group of useful phenol polymeric materials are alkylphenol-acetylene resins, likewise soluble in common organic solvents and possessing permanent fusibility in the absence of being treated by cross-linking materials.
- the phenolic polymer material is characterized by its solubility in organic solvents and relative insolubility in aqueous media, and 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.
- Resoles if they are still soluble, can be used, though subject to change in properties upon aging.
- a laboratory method useful in the selection of suitable phenolic resins is a determination of the infra-red absorption pattern. It has been found that phenolic resins shown an absorption in the 32003500 cm. region (which is indicative of the free hydroxyl groups) and not having an absorption in the 16001700 cm.- region are suitable. The latter absorption region is indicative of the desensitization of the hydroxyl groups and consequently makes such groups unavailable for reaction with the chromogenic materials.
- maleic anhydride copolymers are 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 pages 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 polymer material can have film-forming properties, with the consequent attainment of high resolution of recorded data that attends the use of a continuous film.
- the polymeric material can be present in the form of a film or finely-divided particles prior to the mark-forming reaction.
- the presence of the polymer in film form provides several advantages; namely, that the zone of marking has a protective film surrounding it, which substantially diminishes removal of the mark by abrasive action.
- the phenolic polymers the water-insolubility of the polymer precludes decoloration by atmospheric moisture attack.
- the polymeric material is disposed originally on the support sheet member as a continuous film, it provides large surface area of reactive material in a form that is readily soluble. Additionally, the presence of the polymer in film form provides for greater ease of adaptability to existing application apparatus, such as, for example, a printing ink applicator. Finally, as compared with prior-art systems, the polymer, because of its great affinity for the substrate, substantially reduces the socalled picking problem associated with coatings of particulate materials such as attapulgite.
- the liquid solvent chosen must be capable of dissolving the primary chromogenic material and the polymeric material. In the majority of cases, it also dissolves at least a portion of the secondary chromogenic material.
- the solvent can be volatile or non-volatile, and a single or multiple component solvent may be used which is wholly or partially volatile. Examples of volatile solvents useful with the aforedescribed components are toluene, petroleum distillate, perchloroethylene, and xylene. Examples of non-volatile solvents are high-boiling-point petroleum fractions and chlorinated diphenyls.
- the solvent chosen should be capable of dissolving at least 1%, on a weight basis, of the primary chromogenic material, preferably in excess of 2%, and a corresponding amount of polymeric material to form an efficient reaction.
- the solvent should be capable of dissolving an excess of the polymeric material, so as to provide every opportunity for utilization of the primary chromogenic material 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 of either the primary or the secondary chromogenic component.
- the presence of the solvent may interfere with the markforming reaction of the primary chromogenic material or diminish the intensity of the mark, in which case the solvent chosen should be sufficiently vaporizable to assure its removal from the reaction site after having, through solution, brought the primary markforming components into intimate admixture and contact, so that the mark-forming reaction proceeds.
- the primary mark-forming reaction requires an intimate mixture of the primary chromogenic material and the polymeric material to be brought about through their solution
- one or more of these mark-forming components may be dissolved in the isolated solvent droplets, the only requirement being that at least one of the components essential to the primary mark-forming reaction be maintained undissolved by the droplets until they are released by application of pressure.
- the primary mark-forming components are so chosen'as to produce a mark upon application of the pressure at room temperature (20 to 25 degrees centigrade).
- the solvent component is not liquid at temperatures around room temperature but is liquid and in condition for forming solutions only at elevated temperatures.
- microcapsules may be present in the support sheet or base material either disposed therethroughout or as a coating thereon, or both.
- the capsules may 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, for example, 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 incompatibility of the solution and the capsules, both retain their identity and physical integrity.
- the polymeric component for instance, 30 grams of water and 53 grams of a 1% aqueous solution of polyvinyl methyl ether maleic anhydride
- this composition When this composition is disposed as a film on the support material and dried, the capsules are held therein subject to rupture to release the liquid which they contain.
- This latter technique relying on the incompatibility of the microcapsule and the dispersing medium of the film-forming polymeric mark-forming component, allows for a method of preparing a sensitive record coating with the capsules interspersed directly in a dry film of the polymeric material as it is laid down from the solution.
- a further alternative is to disperse in a liquid medium one or more primary mark-forming components, insoluble therein, and disperse in said medium the insoluble 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. Obviously, the several components may be applied individually.
- the application of the secondary chormogenic material(s) to the supporting base material can be accomplished by dispersing them in finely-divided form or in solution, along with the microcapsules, in the solution of the polymeric component or in the liquid medium, as described above.
- the secondary chromogenic component(s) can also be dispersed or dissolved in the liquid solvent contained within the microcapsules.
- a single composition comprising all the ingredients can be produced by encapsulating a solvent solution of one primary mark-forming component and the secondary chormogenic material(s), mixing the capsules with a solution or a dispersion of the other primary mark-forming component, and coating the resultant composition on the supporting base material.
- the several components can also be applied to the supporting base material individually.
- Suitable amounts include, in the case of the secondary chromogenic material, about .01 to about 0.20 pound per ream (a ream in this application means five hundred sheets of 25" x 38" paper, totalling 3,300 square feet), the preferred amount being about .03 and .05 pound per ream; in the case of the primary chromogenic material, about .03 to about .075 pound per rea m, the preferred amount being about .05 pound per ream; in the case of the solvent, about 1 to 3 pounds per ream; and in the case of the polymeric material, about /2 to 3 pounds per ream. In all instances, the upper limit is primarily a matter of economic consideration.
- FIGURE 1 is a diagrammatic perspective view of a preferred embodiment of a pressure-sensitive record system, showing a supporting sheet and a receiving sheet 12 having their adjacent faces coated with pressurerupturable capsules 11 and a polymeric material 13, such as phenolic polymer, respectively.
- FIGURE 2 is a diagrammatic cross-sectional view taken on line 22 of FIGURE 1, showing the results of the application of pressure to the system by a pencil 14, or any stylus, type character, or other pressure-inducing means, producing marks 15 and 16 on the transfer and receiving sheets 10 and 12, respectively.
- the capsules contain a liquid solvent in which are dissolved a basic primary chromogenic component and a secondary chromogenic component.
- a basic primary chromogenic component is usually dissolved in the same solvent as the former, this is not essential.
- the secondary chromogenic material can be dissolved in a second solvent or in some instances merely dispersed in the solution of the primary chromogenic material.
- the solution of the primary and secondary chromogenic components is then released and transferred to the bottom, or receiving, sheet, where the solvent then dissolves the polymeric material; for example, a phenolic polymer, which reacts with the dissolved primary chromogenic material to produce a mark corresponding to the configuration of the pattern formed by the pencil.
- the polymeric material for example, a phenolic polymer, which reacts with the dissolved primary chromogenic material to produce a mark corresponding to the configuration of the pattern formed by the pencil.
- the marking-forming components can be employed in multiple-sheet systems having three or more sheets, it only being necessary to coat the upper and lower surfaces of each contiguous sheet with the components required to produce a mark.
- the lower surface of the sheet 12 can be coated with capsules, and the upper surface of a third sheet (not shown) can be coated with a film of polymeric material.
- a mark is formed on the upper surface of the third sheet in the same manner as the mark produced on the upper surface of the sheet 12.
- the arrangement of the primary color-producing components can be modified in any manner so long as at least of of the components is isolated from the solvent.
- the primary chromogenic material in particulate form can be coated on the upper surface of the receiving sheet 12, and the polymeric material can be dissolved in the solvent contained within the capsules 11.
- other modifications include the arranging of both the polymeric material in either a coating or particulate form,
- each of the aforedescribed primary mark-forming components and capsules can be located throughout the thickness of the sheets of supporting material rather than, or in addition to, being coated on the surface(s) so long as there is a sufficient quantity to provide a clear and distinct mark.
- the secondary chromogenic material need only be exposed to light to produce its mark. Consequently, the arrangement of the latter within the record system is necessarily more limited. Obviously the secondary chromogenic material cannot be located on any surface of the receiving sheet, which is exposed to a light source, since the entire sheet would be colored by the ensuing reaction, leaving no distinctive pattern. Conversely, it usually is located on a surface of the transfer sheet which is not exposed to light. Surface is here meant to include the thickness of the sheet to a depth to which the remaining thickness of the sheet will protect the secondary chromogenic material from premature development when the other surface is exposed to light.
- the secondary chromogenic material is usually arranged in the form of finely-divided discrete particles coated directly on the transfer sheet or, preferably, dispersed in finely-divided form or dissolved in the liquid contained within the capsules positioned thereon.
- the secondary chromogenic material can be distributed throughout the liquid, either as a finely-divided dispersion or as a solution, either prior to or following release of the liquid from the capsules.
- the essential feature is the distribution of this material throughout the liquid, which acts as a carrier to transfer it to the receiving sheet in the configuration of the pattern produced by the pressure-rupture of the capsules.
- All of the components can be arranged on a single transfer sheet as long as sufiicient amounts of solvent are disposed on the bottom surface of or within the thickness of the sheet to effect the transfer to a receiving sheet of an adequate amount of primary and secondary colorforming materials to maintain the mark produced on the receiving sheet at an easily readable level after its exposure to light in the atmosphere.
- the capsules can be applied to the base supporting material in any convenient manner known to the prior art. They can be coated onto the sheets from an aqueous slurry in which they were made, with an amount of aqueous vehicle material added or removed to give the slurry proper coating consistency.
- the slurry can have binder material added, if necessary.
- 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 controlled distance.
- the capsules also can be placed directly in the paper pulp furnish before it is applied to the paper machine screen, and thus appear throughout the thickness of the sheet.
- the remaining components which are not contained within the capsules can be coated on and/ or interspersed throughout the supporting sheets. This also can be accomplished by a variety of methods known to the prior art.
- the component(s) to be interspersed throughout the sheet can be dispersed (or dissolved) in the furnish, which then is passed onto the Fourdrinier wire. While the sheet is in its wet state, or after it is dried, the remaining component(s) can be coated individually or simultaneously onto the support sheet from an aqueous dispersion or a solution, with subsequent removal of the vehicle, in any known manner.
- care must be exercised during the making of the record units to prevent contact of the primary chromogenic component and the polymeric material While both are dissolved. Details of a number of these methods are clearly described in the aforementioned co-pending United States patent application of Robert E.
- the methods disclosed as useful for adding the primary-mark-forming components (e.g., the primary chromogenic material and the polymeric material) to the supporting sheets can also be employed for the application of the secondary chromogenic material; e.g., the N-pivalyl leuco methylene blue, to the supporting members, again care being exercised to dispose the secondary chromogenic material only on one surface of the transfer sheet.
- the primary-mark-forming components e.g., the primary chromogenic material and the polymeric material
- the secondary chromogenic material e.g., the N-pivalyl leuco methylene blue
- the quantities of the aforementioned components which can be added to the supporting material are dependent upon the arrangement of the components and can be tailored to the construction and performance standards desired for each specific record system. Such considerations as the quantity of capsules required to provide sufficient liquid content to make contact with the other components of the system, the position of the components, e.g., on the surface and/or throughout the support sheet, etc., vary with the individual requirements of use of each record system and can be predetermined by one skilled in the art.
- the liquid solvent contained in the aforedescribed capsules also can be isolated from at least one of the primary mark-forming components by other means such as the liquid droplets of a discontinuous emulsion phase in a continuous film of pressure-rupturable material, which, in essence, forms a continuous wall separating the individual droplets.
- Such film-holding of droplets that are released by writing or printing pressure is a well-known expedient, disclosed in United States Patents Nos. 2,299, 694 and 2,374,862, issued to Barrett K. Green on Oct. 20, 1942, and May 1, 1945, respectively, and are made by dispersing the oil droplets in a solution of polymetric film material which is applied to a record sheet and dried.
- liquid solvent in this application, it includes this continuous film structure as a full equivalent of capsules, except that the liquid is more impermeably retained in the capsules, and the latter can be treated as particles for incorporation into the paper-machine furnish.
- the circles shown in the figures represent not only capsule structure but films which hold a multitude of droplets for local release in an area subject to pressure.
- the showing is in an exaggerated form, as the record materials in their manufactured form are hardly distinguishable from ordinary coated-paper printing stock, the normal coloration being that of the base sheet stock, and the sensitizing materials as to particle size, when particles are involved, being small enough to escape observation, but close enough to each other to afford a good recording surface or background surface against which the record can be visually sensed.
- the relative amounts of components to be used are the most convenient and economical amounts consistent with 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 efiiciency, and other factors, all of which are things that may be worked out empirically by one familiar with the art.
- EXAMPLE 1 A solution of a primary chromogenic material, Crystal Violet Lactone (CVL), and a second chromogenic material, N-pivalyl leucomethylene blue (PLMB), was encapsulated using the following procedure:
- the resulting mass was then chilled to 10 degrees centigrade or lower and allowed to stand for one hour at this temperature. Subsequently, .5 milliliter of a 25% glutaraldehyde solution was added, and the entire mass was stirred overnight.
- the resulting batch of capsules was chilled to 10 degrees Centigrade or lower, followed by the addition of 7.5 milliliters of glutaraldehyde.
- the resulting batches of capsules and supernatant liquid were then coated on one surface of separate supporting sheets of material and dried to yield a capsule-containing coating of a quantity equal to about 4 /2 pounds per ream of 500 sheets 25 by 38 inches.
- An acidic polymeric material was prepared by the following procedure:
- a sheet of supporting material was impregnated with the polymer by being dipped into a 4% xylene solution of the polymer and dried.
- optical density (O.D.) of the marks produced above was determined and recorded in the following table:
- EXAMPLE 2 Compositions of a primary chromogenic material, Crystal Violet Lactone (CVL), and each of the following secondary chromogenic materials, N-pivalyl leucomethylene blue (PLMB), 2,2 dimethylbutyryl leucomethylene blue (DLMB), and p-anisoyl leuco methylene blue (ALMB), were encapsulated by the following method:
- CVL solution A l /2%, by weight, CVL solution was encapsulated using the same materials and procedures. Only the secondary chromogenic material was removed.
- An acidic polymeric material was prepared by the procedure described in Example 1. The resulting polymer was dried, and 5 grams of the dry polymer was ball-milled with 1% grams of gum'arabic and 43 /2 grams of water,
- a secondary chromogenic material which upon exposure to light forms a mark, selected from the group consisting of N-pivalyl leucomethylene blue, 2,2-dimethylbutyryl leucomethylene blue, and panisoyl leucomethylene blue, and mixtures thereof; each of said primary mark-forming components, said solvent, said pressure-rupturable solvent-isolating means, and said secondary chromogenic material being supported by said base material, said secondary chromogenic material being located only on one surface of said transfer sheet, and said each arranged in contiguous juxtaposition to each other, whereby upon rupture of said solvent-isolating means, the liquid solvent is released therefrom, said primary mark-forming components are brought into reactive contact by the released solvent, said secondary chromogenic material is distributed throughout said solvent, and the said primary mark-forming componets and secondary chromogenic material are transferred to the receiving sheet by the solvent.
- a mark-forming com-position capable of being supported by the transfer sheet of a pressure-sensitive record system comprising:
- primary mark-forming components comprising at least one primary chromogenic material and at least one polymeric material reactive with the primary chromogenic material to produce a mark when both are in solution
- a secondary chromogenic material which upon exposure to light forms a mark, selected from the group consisting of N-pivalyl leucomethylene blue, 2,2-dimethylbutyryl leucomethylene blue, and panisoyl leucomethylene blue, and mixtures thereof.
- composition of claim 9 in which said pressurerupturable means are microcapsules, said microcapsules containing said solvent.
- composition of claim 10 in which said secondary chromogenic material is N-pivalyl leucomethylene blue.
- composition of claim 10 in which said secondary chromogenic material is 2,2-dimet-hylbutyryl leucomethylene blue.
- composition of claim 10 in which said secondary chromogenic material is p-anisoyl leucomethylene blue.
- microcapsules additionally contain said secondary chromogenic material.
- composition of claim 14 in which said secondary chromogenic material is dissolved in said solvent.
- composition of claim 14 in which said primary chromogenic material is basic and said polymeric material is acidic and one of said basic primary chromogenic material and acidic polymeric material is dissolved in said solvent.
- a pressure-sensitive record system comprising:
- a secondary chromogenic material which upon exposure to light forms a mark, selected from the group consisting of N-pivalyl leucomethylene blue, 2,2- dimethylbutyryl leucomethylene blue, and p-anisoyl leucomethylene blue, and mixtures thereof; each of said primary mark-forming components, said sol vent, said pressure-rupturable solvent-isolating means, and said secondary chromogenic material being supported by said base material, said secondary chromogenic material being located on the surface of said transfer sheet adjacent to said receiving sheet; and said each arranged in contiguous juxtaposition to each other whereby upon rupture of said solventisolating means, the liquid solvent is released therefrom, said primary mark-forming components are brought into reactive contact by the released solvent, said secondary chromogenic material is distributed throughout said solvent, and the said primary markforming components which are not located on the receiving sheet and said secondary chromogenic material are transferred to the receiving sheet by the solvent.
- a pressure sensitive record unit comprising sheet material supporting mark-forming components in contiguous juxtaposition but isolated from each other and a pressure releasable liquid solvent for at least one of the materials characterized in that the sheet material supports as mark-forming components, a primary system comprising a primary chromogenic material and a chromogenicmaterial-reactive polymeric material, said primary chromogenic material and polymeric material being both soluble in the solvent, and a secondary light-sensitive chromogenic material which is selected from the group consisting of N-pivalyl leucomethylene blue, 2,2-dimethyl- 1 5 butyryl leucomethylene ⁇ blue, and p-anisoyl leucomethylene blue, and mixtures thereof, said secondary chromogenic material being so disposed as to be transferred to a surface of an underlying receiving sheet in a pattern produced by the released liquid.
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Color Printing (AREA)
- Stacking Of Articles And Auxiliary Devices (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US44427465A | 1965-03-31 | 1965-03-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3427180A true US3427180A (en) | 1969-02-11 |
Family
ID=23764216
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US444274A Expired - Lifetime US3427180A (en) | 1965-03-31 | 1965-03-31 | Pressure-sensitive record system and compositions |
Country Status (8)
Country | Link |
---|---|
US (1) | US3427180A (de) |
AT (1) | AT268333B (de) |
BE (1) | BE678526A (de) |
CH (1) | CH451972A (de) |
DE (1) | DE1571855B1 (de) |
DK (1) | DK115854B (de) |
GB (1) | GB1090866A (de) |
NO (1) | NO122109B (de) |
Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3501331A (en) * | 1967-01-27 | 1970-03-17 | Fuji Photo Film Co Ltd | Pressure sensitive fluoran derivative containing copying paper |
US3506471A (en) * | 1966-11-14 | 1970-04-14 | Fuji Photo Film Co Ltd | Pressure-sensitive fluorane derivative containing copying paper |
US3514310A (en) * | 1966-11-18 | 1970-05-26 | Fuji Photo Film Co Ltd | Pressure sensitive fluoran derivative copying paper |
US3514311A (en) * | 1967-10-31 | 1970-05-26 | Fuji Photo Film Co Ltd | Pressure sensitive 3-substituted amino - 6 chlorofluoran containing copying paper |
US3516845A (en) * | 1967-01-24 | 1970-06-23 | Ncr Co | Record sheet sensitized with salt modified kaolin-phenolic material |
US3525630A (en) * | 1967-12-06 | 1970-08-25 | Ncr Co | Colorless ink to give black print |
DE2116258A1 (de) * | 1970-04-02 | 1971-11-04 | Fuji Photo Film Co Ltd | Verfahren zur Herstellung von Kap sein aufweisenden Bahnen |
US3634121A (en) * | 1969-03-17 | 1972-01-11 | Ncr Co | Acid-sensitized record sheet |
US3649357A (en) * | 1967-01-23 | 1972-03-14 | Mead Corp | Production of colored images on paper bases |
US3663256A (en) * | 1964-08-27 | 1972-05-16 | Ncr Co | Mark-forming record material |
US3793075A (en) * | 1971-12-20 | 1974-02-19 | Moore Business Forms Inc | Dialkyl tartrate-heteropolyacid developing system for dye precursor compounds |
US3836382A (en) * | 1971-09-21 | 1974-09-17 | Ciba Geigy Ag | Pressure-sensitive copying material |
US3859112A (en) * | 1972-07-20 | 1975-01-07 | Mitsubishi Paper Mills Ltd | Water resistant heatsensitive recording composition containing an ethyleneimine hardener |
US3873340A (en) * | 1972-07-27 | 1975-03-25 | Hodogaya Chemical Co Ltd | Pressure-sensitive copying paper containing phenoxazine compounds |
US3874895A (en) * | 1971-11-01 | 1975-04-01 | Fuji Photo Film Co Ltd | Recording sheet |
US3895173A (en) * | 1972-02-17 | 1975-07-15 | Matsushita Electric Ind Co Ltd | Dichromatic thermo-sensitive recording paper |
US3900217A (en) * | 1970-06-13 | 1975-08-19 | Fuji Photo Film Co Ltd | Pressure-sensitive copying paper |
US3955026A (en) * | 1973-10-02 | 1976-05-04 | Fuji Photo Film Co., Ltd. | Pressure-sensitive recording sheet |
US3955025A (en) * | 1973-10-02 | 1976-05-04 | Fuji Photo Film Co., Ltd. | Pressure-sensitive copying sheet |
US3963853A (en) * | 1971-12-30 | 1976-06-15 | Wiggins Teape Limited | Pressure sensitive transfer sheet |
US3995088A (en) * | 1974-02-01 | 1976-11-30 | Ciba-Geigy Corporation | Coated pressure-sensitive recording material |
US4012554A (en) * | 1972-12-15 | 1977-03-15 | Ncr Corporation | Single coating record system-solvent loss produces color |
US4093278A (en) * | 1976-12-27 | 1978-06-06 | Monsanto Company | Dye solvents for pressure-sensitive copying systems |
US4132436A (en) * | 1976-02-04 | 1979-01-02 | Fuji Photo Film Co., Ltd. | Recording material |
US4138522A (en) * | 1974-09-17 | 1979-02-06 | Fuji Photo Film Co., Ltd. | Color image forming system including a layer formed from a dried residue of a developing ink containing a polyester resin binder |
DE2915928A1 (de) * | 1978-04-24 | 1979-10-25 | Ciba Geigy Ag | Carbazolylmethanverbindungen, ihre herstellung und verwendung als farbbildner in druckempfindlichen oder waermeempfindlichen aufzeichnungsmaterialien |
US4180656A (en) * | 1976-04-27 | 1979-12-25 | Ciba-Geigy Corporation | Azomethine compounds |
US4303719A (en) * | 1980-07-29 | 1981-12-01 | Vassiliades Anthony E | Chromogenic copy system |
US4360548A (en) * | 1980-10-24 | 1982-11-23 | The Standard Register Company | Self-contained covert image |
US4366188A (en) * | 1973-07-09 | 1982-12-28 | Moore Business Forms, Inc. | Method of employing encapsulated material |
US4372583A (en) * | 1980-07-29 | 1983-02-08 | Vassiliades Anthony E | Chromogenic copy system and method |
US4648699A (en) * | 1985-10-31 | 1987-03-10 | The Mead Corporation | Point contact development of imaging sheets employing photosensitive microcapsules |
US4940738A (en) * | 1988-01-07 | 1990-07-10 | The Standard Register Company | High solids CB printing ink containing a protective colloid blend |
US5178949A (en) * | 1989-03-27 | 1993-01-12 | Jujo Paper Co., Ltd. | Color-former |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0036117B1 (de) | 1980-03-14 | 1986-02-05 | Spezial-Papiermaschinenfabrik August Alfred Krupp GmbH & Co | Druckempfindliches Aufzeichnungsmaterial |
US4375492A (en) * | 1981-05-22 | 1983-03-01 | Appleton Papers Inc. | Dielectric record material |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1814314A (en) * | 1929-11-11 | 1931-07-14 | John C Kane | Radiator ornament |
US2374862A (en) * | 1942-06-19 | 1945-05-01 | Ncr Co | Coating for paper |
US2783228A (en) * | 1955-06-27 | 1957-02-26 | Ncr Co | Nitro derivatives of benzoyl leuco methylene blue |
US2929736A (en) * | 1957-07-25 | 1960-03-22 | Ncr Co | Heat and pressure responsive record material |
US2972547A (en) * | 1957-08-05 | 1961-02-21 | Antioch College | Acyl hydrazine compositions and methods of producing color therewith |
US3020171A (en) * | 1960-08-26 | 1962-02-06 | Ncr Co | Pressure-sensitive record and transfer sheet material |
US3168864A (en) * | 1960-09-28 | 1965-02-09 | Minnesota Mining & Mfg | Lithographic printing plate and method of producing an image thereon |
US3223546A (en) * | 1962-01-17 | 1965-12-14 | Minerals & Chem Philipp Corp | Color-reactable inorganic adsorbent pigment and coating composition containing the same |
US3287154A (en) * | 1963-04-24 | 1966-11-22 | Polaroid Corp | Pressure responsive record materials |
-
1965
- 1965-03-31 US US444274A patent/US3427180A/en not_active Expired - Lifetime
-
1966
- 1966-03-02 GB GB9147/66A patent/GB1090866A/en not_active Expired
- 1966-03-19 NO NO162196A patent/NO122109B/no unknown
- 1966-03-26 DE DE19661571855 patent/DE1571855B1/de active Pending
- 1966-03-28 BE BE678526D patent/BE678526A/xx unknown
- 1966-03-29 AT AT294566A patent/AT268333B/de active
- 1966-03-30 DK DK165266AA patent/DK115854B/da unknown
- 1966-03-30 CH CH474966A patent/CH451972A/fr unknown
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1814314A (en) * | 1929-11-11 | 1931-07-14 | John C Kane | Radiator ornament |
US2374862A (en) * | 1942-06-19 | 1945-05-01 | Ncr Co | Coating for paper |
US2783228A (en) * | 1955-06-27 | 1957-02-26 | Ncr Co | Nitro derivatives of benzoyl leuco methylene blue |
US2929736A (en) * | 1957-07-25 | 1960-03-22 | Ncr Co | Heat and pressure responsive record material |
US2972547A (en) * | 1957-08-05 | 1961-02-21 | Antioch College | Acyl hydrazine compositions and methods of producing color therewith |
US3020171A (en) * | 1960-08-26 | 1962-02-06 | Ncr Co | Pressure-sensitive record and transfer sheet material |
US3168864A (en) * | 1960-09-28 | 1965-02-09 | Minnesota Mining & Mfg | Lithographic printing plate and method of producing an image thereon |
US3223546A (en) * | 1962-01-17 | 1965-12-14 | Minerals & Chem Philipp Corp | Color-reactable inorganic adsorbent pigment and coating composition containing the same |
US3287154A (en) * | 1963-04-24 | 1966-11-22 | Polaroid Corp | Pressure responsive record materials |
Cited By (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3663256A (en) * | 1964-08-27 | 1972-05-16 | Ncr Co | Mark-forming record material |
US3506471A (en) * | 1966-11-14 | 1970-04-14 | Fuji Photo Film Co Ltd | Pressure-sensitive fluorane derivative containing copying paper |
US3514310A (en) * | 1966-11-18 | 1970-05-26 | Fuji Photo Film Co Ltd | Pressure sensitive fluoran derivative copying paper |
US3649357A (en) * | 1967-01-23 | 1972-03-14 | Mead Corp | Production of colored images on paper bases |
US3653945A (en) * | 1967-01-23 | 1972-04-04 | Mead Corp | Production of reactant sheets for developing colorless dye images |
US3516845A (en) * | 1967-01-24 | 1970-06-23 | Ncr Co | Record sheet sensitized with salt modified kaolin-phenolic material |
US3501331A (en) * | 1967-01-27 | 1970-03-17 | Fuji Photo Film Co Ltd | Pressure sensitive fluoran derivative containing copying paper |
US3514311A (en) * | 1967-10-31 | 1970-05-26 | Fuji Photo Film Co Ltd | Pressure sensitive 3-substituted amino - 6 chlorofluoran containing copying paper |
US3525630A (en) * | 1967-12-06 | 1970-08-25 | Ncr Co | Colorless ink to give black print |
US3634121A (en) * | 1969-03-17 | 1972-01-11 | Ncr Co | Acid-sensitized record sheet |
DE2116258A1 (de) * | 1970-04-02 | 1971-11-04 | Fuji Photo Film Co Ltd | Verfahren zur Herstellung von Kap sein aufweisenden Bahnen |
US3900217A (en) * | 1970-06-13 | 1975-08-19 | Fuji Photo Film Co Ltd | Pressure-sensitive copying paper |
US3836382A (en) * | 1971-09-21 | 1974-09-17 | Ciba Geigy Ag | Pressure-sensitive copying material |
US3874895A (en) * | 1971-11-01 | 1975-04-01 | Fuji Photo Film Co Ltd | Recording sheet |
US3793075A (en) * | 1971-12-20 | 1974-02-19 | Moore Business Forms Inc | Dialkyl tartrate-heteropolyacid developing system for dye precursor compounds |
US3963853A (en) * | 1971-12-30 | 1976-06-15 | Wiggins Teape Limited | Pressure sensitive transfer sheet |
US3895173A (en) * | 1972-02-17 | 1975-07-15 | Matsushita Electric Ind Co Ltd | Dichromatic thermo-sensitive recording paper |
US3859112A (en) * | 1972-07-20 | 1975-01-07 | Mitsubishi Paper Mills Ltd | Water resistant heatsensitive recording composition containing an ethyleneimine hardener |
US3873340A (en) * | 1972-07-27 | 1975-03-25 | Hodogaya Chemical Co Ltd | Pressure-sensitive copying paper containing phenoxazine compounds |
US4012554A (en) * | 1972-12-15 | 1977-03-15 | Ncr Corporation | Single coating record system-solvent loss produces color |
US4366188A (en) * | 1973-07-09 | 1982-12-28 | Moore Business Forms, Inc. | Method of employing encapsulated material |
US3955026A (en) * | 1973-10-02 | 1976-05-04 | Fuji Photo Film Co., Ltd. | Pressure-sensitive recording sheet |
US3955025A (en) * | 1973-10-02 | 1976-05-04 | Fuji Photo Film Co., Ltd. | Pressure-sensitive copying sheet |
US3995088A (en) * | 1974-02-01 | 1976-11-30 | Ciba-Geigy Corporation | Coated pressure-sensitive recording material |
US4138522A (en) * | 1974-09-17 | 1979-02-06 | Fuji Photo Film Co., Ltd. | Color image forming system including a layer formed from a dried residue of a developing ink containing a polyester resin binder |
US4132436A (en) * | 1976-02-04 | 1979-01-02 | Fuji Photo Film Co., Ltd. | Recording material |
US4180656A (en) * | 1976-04-27 | 1979-12-25 | Ciba-Geigy Corporation | Azomethine compounds |
US4093278A (en) * | 1976-12-27 | 1978-06-06 | Monsanto Company | Dye solvents for pressure-sensitive copying systems |
DE2915928A1 (de) * | 1978-04-24 | 1979-10-25 | Ciba Geigy Ag | Carbazolylmethanverbindungen, ihre herstellung und verwendung als farbbildner in druckempfindlichen oder waermeempfindlichen aufzeichnungsmaterialien |
US4303719A (en) * | 1980-07-29 | 1981-12-01 | Vassiliades Anthony E | Chromogenic copy system |
US4372583A (en) * | 1980-07-29 | 1983-02-08 | Vassiliades Anthony E | Chromogenic copy system and method |
US4360548A (en) * | 1980-10-24 | 1982-11-23 | The Standard Register Company | Self-contained covert image |
US4648699A (en) * | 1985-10-31 | 1987-03-10 | The Mead Corporation | Point contact development of imaging sheets employing photosensitive microcapsules |
US4940738A (en) * | 1988-01-07 | 1990-07-10 | The Standard Register Company | High solids CB printing ink containing a protective colloid blend |
US5178949A (en) * | 1989-03-27 | 1993-01-12 | Jujo Paper Co., Ltd. | Color-former |
Also Published As
Publication number | Publication date |
---|---|
DK115854B (da) | 1969-11-17 |
GB1090866A (en) | 1967-11-15 |
DE1571855B1 (de) | 1970-08-06 |
AT268333B (de) | 1969-02-10 |
BE678526A (de) | 1966-09-01 |
CH451972A (fr) | 1968-05-15 |
NO122109B (de) | 1971-05-18 |
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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 |