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June 27, 1972 R. E.

MILLER ET AL 3,672,935
Original Filed Aug. 27, 1964 3 Sheets-Sheet l







3}_Q @ G) (?) Q @ G. JR.935 PRESSURE-SENSITIVE RECORD MATERIAL Original Filed Aug. * INVENTORS ROBERT E.June 27. 1972 R. 1964 . E. THEIR AT TORNEYS.672. tax like half-lº *Fººd. ºve .2 (CONTINUED) ºw. MILLER PAUL S. GE . . 27.*::::::#y: EGHGH-OH-6–EG-EG-EG-EG) (. PHILLIPS. 3 Sheets-Sheet 3 () G) O FIG. MILLER ETAL 3.

8'-methoxy BIPS. into mark-forming contact by solution in the re base-acid system. now abandoned. 25. No. and 4-phenylazo-1 mark according to the rupture pattern. the polymeric material mark-forming component.. Crystal Violet car resented a substantial advance over their predecessors. though same applicants on June 17. 2. 1970. 1964. . Jr. and which in turn was a continua terial from any of the known color-producing systems may tion of original application Ser.8-unsaturated aryl ketones.342. tion of the attapulgite particles. Broadly stated. inafter referred to as MGL).S. the invention has particular utility in regard to 27.341. Phillips. both components be aminophenyl) phthalide (Malachite Green Lactone. whereupon the liquid solvent said mark-forming components comprising at least one is released according to the presure pattern and the mark chromogenic material and at least one phenol-aldehyde forming components thereby are brought into reactive con polymeric material soluble in the liquid solvent and re tact. 35 be used. Rhodamine B Lactams: N-(p-nitro tems. and N-acetyl auramine. i. 1972 1 2 3. issued to Clyde S.404. Cormack on Mar. The present invention provides a pressure-sensitive Ser. 4– absorbed by the nearby attapulgite particles to produce a aminoazobenzene (Oil Yellow AAB). pressure-releasable liquid solvent for said mark-forming said liquid solvent being present in such form that it is components arranged in contiguous juxtaposition on said maintained isolated by a pressure-rupturable barrier from sheet material. 744. 55 phenyl derivatives of leucauramine disclosed in U. No. basic mono azo plication of pressure. 744. dibenzylidene acetone. and Mary Lou Frazier on Mar. No. and the the mark-forming components produces a mark or color N-alkylhalophenyl derivatives of leucauramine disclosed in those regions where pressure is brought to bear. 1968. polyaryl carbinols: bis(p-dimethylaminophenyl) While the aforementioned prior units and systems rep methanol. More particularly. and an insoluble yl)-6-dimethylaminophthalide (Crystal Violet Lactone. No. The chromogenic material This is a continuous application for that filed by the in unreacted state preferably should be colorless. said patents being a micro-encapsulated solution of chormogenic material. 27. Ohio. the N-halo upon the application of marking pressure to a capsule. leased portion of said common solvent. basic mono azo dyes: p-dimethyl the solution of chromogenic material migrated to and was aminoazobenzene-o-carboxylic acid (Methyl Red). which may be identified chromogenic component.. called Michler’s Hydrol. No. Miller and Paul S. active with the chromogenic material to produce a mark. there have been provided pressure-sensitive Rhodamine B Lactams.828. leucauramines. Dayton. Dayton.672..3-bis(4-dimethyl form on a supporting sheet material. and ing to the pressure pattern.G. chromogenic material. 25. Upon rupture of a capsule. B41m 5/22 10 atmospheric-sensitive prior systems and which offers ad U. Pat. Marjorie J. upon selective release of minute 40 stituent on the chromogenic material. at least one of the mark-forming compo at least one of the mark-forming components until the ap ments being maintained in isolation from the other mark 20 plication of pressure causes a breach in the barrier accord forming component(s) prior to release of the solvent. 2. solid mark-forming component distributed in particulate hereinafter refered to as CVL) and 3. acyl auramines: N-benzoyl droplets on the under side of a supporting sheet. attapulgite clay) top ketones: dianisylidene acetone. which is a continuation of application Ser. Rhodamine B Lactams such as N(p-nitrophenyl) In the past. Adams. binol. 392. Aug. and consequent Continuation of application Ser. - 392.404. and capable of color change of the Commissioner's Order for Filing Streamlined Con to a strong distinctive color upon reactive contact with tinuation Applications appearing in volume 824 O.United States Patent Office 3. so that. Adams and the most practiced form. and Malachite Green carbinol. the novel mark-forming system of this invention comprises disposing on and/or within sheet support mate ABSTRACT OF THE DISCLOSURE rial the unreacted mark-forming components (at least A pressure-sensitive record unit comprising support 15 one of which is a polymeric material) and a liquid solvent sheet material having mark-forming components and a in which each of the mark-forming components is soluble. In in U.e.3-unsaturated aryl solid particulate material (namely. characterized hereafter.601. believed to be caused by * to National Cash Register Company. 25 The mark-forming components generally comprise a chromogenic material and a polymeric material reactive with the chromogenic material to produce a distinctive mark (through acidic groups).828. Cor chromogenic component. 1968. coated on an adjacent sheet. or.935 Patented June 27. or. the prior units and systems had 60 Marjorie J. C. the take-up of atmospheric substances at the reactive sites 10 present at the surface of the clay particles. particularly N-(2. and a auramine.935 experience has shown that exposure of the record material PRESSURE-SENSITIVE RECORD MATERIAL to ambient conditions oftentimes resulted in a desensitiza Robert E. and 8' me mark-forming units and systems which comprised a thoxy benzoindolinospiropyrans. 44. here ing arranged in proximate relation to each other. this invention relates is acidic. acyl pristine mark-forming record material prior to the ap 45 auramines.601 and a filing combinations of chromogenic material and polymeric ma date of June 17. and wherein one of Examples of suitable basic materials having chromo the mark-forming components is a polymer present in the genic groups are diaryl phthalides. where the color or change in color is to a novel mark-forming system wherein mark-forming brought about by the acidic action of the polymer con components are brought. The invention will droplets of an isolated common solvent for said compo hereafter be described and illustrated by reference to said ments. loss or diminution of its potential for reaction with the 1968. Illustrative compounds of each in a liquid solvent which is the core or nucleus material 50 group are diaryl phthalides: 3. filed Aug.8 9 Claims ditional advantages. polyaryl carbinols. the color-forming system wherein the chromogenic mate This invention relates to an improved pressure-sensitive rial is a base and the complementary polymeric material record material. This application June 9. and the consequent contact of mack. 1964. under the provisions 30 light tones may be tolerated. dyes. CI.672. issued to Clyde S.S. 117–36. which was given the Ser. Pat.S.5 di such as crystal violet lactone. 1958. In other prior sys naphthylamine. 1958. the capsule ruptures and releases the liquid-carried No.805 mark-forming system which is an improvement over the Int.3-bis(p-dimethylaminophen of a pressure-rupturable microcapsule. producing a distinctive mark. 65 and anisylidene acetone. No. the capsules and the attapulgite were arranged on a phenyl) Rhodamine B Lactam (hereinafter referred to as single sheet. incorporated by reference herein. 70 RBL). generally present as a solute as (8° methoxy BIPS). While page 1. leucauramines. distributed as isolated liquid chlorophenyl) leucauramine. June 17.


as shown in FIG. The liquid of the disposed therethroughout or as a coating thereon. is equivalent to 0. 1a. XIV. then hav In all instances. However. and wherein the remaining components of the system to 3 pounds per ream. (Such a system may also within the scope of the invention. X. or.03 to 0. this architecture to 3 pounds per ream. sheets are required and each sheet includes a component. the remaining necessary com Of the drawings: . and the top surface of the under dispersing medium of the film-forming mark-forming 30 sheet may be supplied with the chromogenic material in component.S. ponent to be interspersed in the support sheet. No. droplet.45 pound per 3000 sq. the surface of the under-sheet is marked with symbols of a 1% aqueous solution of polyvinyl methyl ether maleic (see legend. XI. When this 25 capsules on the rear of the over-sheet are marked with composition is disposed as a film on the support material symbols indicating a contained liquid solution of chromo and dried. if desired. or components. where either the application meaning five hundred sheets of 25” x 38” 50 liquid solvent or one or more of the mark-forming com paper. In the draw component (for instance. and XV). totalling 3. which is sup still dispersed in the liquid vehicle in which they were plied with a material co-reactant with the received liquid manufactured. the of the overlying sheet having a coating of pressure-ruptur several components are interspersed within the support able capsules containing a solution of the basic chromo sheet according to the technique outlined above for views genic component. or near it. in a series of highly dia and thus appear throughout the thickness of a sheet (see grammatic sections through a self-contained record sheet FIG. the bottom surface member. some being set forth in the examples to follow. unit (views V–XIII) or a “couplet” unit of two paper As the liquid content of these capsules of views VIII sheets (views I–IV. Pat. separated and the separated to produce a distinctively-colored mark corresponding to capsules thereafter dispersed in a solution of the polymeric 20 the configuration of the pressure pattern. the capsules may contain the polymeric ma relying on the incompatibility of the microcapsule and the terial in liquid solution. and XV). released droplets is transferred in the pattern of the data The capsules may be applied to the sheet material while configuration to the top of the under-sheet.” depending on the freeness of the pulp and the water con FIG. the following tech Suitable amounts include. on the application material will be further discused hereafter. . X. for instance). 2. showing the physical 75 and XI. it the surface. a type character. fore.05 pound per ream. phenolic polymeric material coating on the upper Sur The slurry of capsules may be applied to a “wet” web face of the lower sheet. XI. and in the case of the polymer. where microcapsules are em Sules in data-representing configuration in printing or ployed. are disposed within the support member. for instance). Green. with a profusion of minute pres may produce a mark by transfer to a second sheet as a Sure-rupturable microcapsules each containing a liquid colored mark. ream. are shown in U. depending primarily upon the nature of the mate are interspersed throughout a single support sheet ma rials and the architecture of the record material unit. in the case of the solvent. One half pound per ream of 3300 may be achieved by supplying in the furnish the com sq. Where there must be a migra accompanying them. 3. in that at least two coming within the principle of the invention are possible. ft. IX. º/. Obviously. and the both retain their identity and physical integrity. which issued July 5. The respective amounts of the several components will 45 In the instance where the mark-forming components vary. 0. in the case of the chromogenic niques or procedures have been found useful: material. with or without mark-forming compo of the mark-forming components in symbol form to il nent. or both. terial (so-called self-contained unit). and specific of Barrett K. the preferred amount ponents are disposed on the surface of the support mem being 0. FIG. so as to sink into the paper web a distance writing means applied to the “couplet. the record material is referred to as a fied by characters translatable according to the legend “self-contained” system. 1a is a highly diagrammatic cross-section of a tent of the web at the point of application. 2. and the The arrangement and the physical state of the compo method of making them. these capsules may be ap medium one or more mark-forming components. having an acid-reacting OH group. 1955. views VIII. 2.712. if desired. and disperse in said medium the insoluble micro they were made. the several if considered necessary. the solution.) FIG. the various components are “couplet” system with adjacent faces of the sheets sensi 60 coated individually or simultaneously onto the support tized with mark-forming components. In the case where all components are disposed arrangement of the various components which are identi on a single sheet. with the result that all components of the mark terial added or removed to give the slurry proper coating forming system may be disposed on or within the sup consistency. views I to XV. and which has been mentioned be arrangements are shown in the drawings. After the economic consideration. there to make a colored mark as of paper as it exists on the screen of a Fourdrinier paper by the use of a stylus. from one sheet to another.672. ponent or components may be coated thereon. the record material is re lustrate some constructions of record material coming ferred to as a “transfer” system. XII. be material (a novolac type of phenolic polymer material cause of incompatibility of the solution and the capsules. Other constructions be referred to as a “couplet” system. The droplets are released on rupture of the cap . The slurry may have binder material added. and the acidic component being a Vb through Vä. allows for a method of preparing a sensitive particulate form. In the preferred case. FIG. This latter technique. they may be present in the support material either writing operations.075 pound per ream (a ream in this In FIG. 1 ber. essential to the mark-forming reaction. 2. portion of a transfer system being subjected to a stylus 70 The capsules may be placed directly in the paper pulp impression. 1 generally shown a two-sheet unit in perspective Where a copious amount of the colored reaction product 10 in which the under side of the over-sheet is supplied on in liquid form is produced on a surface of one sheet. insoluble 35 plied to a support sheet from an aqueous slurry in which therein. A representative number of architectural record coating with the capsules interspered directly in a arrangements of the several components with respect to dry film of the polymeric material as it is laid down from support material are shown in FIG. ft. These views show the disposition tion of the solvent. with an amount of aqueous vehicle ma capsules. 2) indicating a polymeric reactant film anhydride) to form a coating composition in which. FIG. 40 microscopic size and containing printing fluid. formed sheet is dried. In FIG.935 5 6 assembly. the capsules are held therein subject to rup genic material (CVL or MGL. port sheet in the one operation. and XIII.507.300 square feet). furnish before it is applied to the paper machine screen. must make contact with the dry . A further alternative is to disperse in a liquid As noted generally above. 2 is a representation. ture to release the liquid contained. or other pressure machine. In FIG. the upper limit is primarily a matter of ing the furnish pass onto the Fourdrinier wire. 1 is a highly diagrammatic representation of a views VII. nents of the mark-forming system in relation to support 2. 30 grams of water and 53 grams ing. and XV. views VIII. 2. views Vb through Val. for instance. Paper coated with capsules of components may be applied individually.

. which. The relative amounts of components to be used are retained in the capsules. The resolution furnish. . . disclosed gerated form.S. . may be used to spot-print a proposed with the dry particles are details that must be tailored to record sheet unit sensitized for recording in a reaction the desired construction and performance standards de produced color in those areas by application of a solution sired. which does not reside solely in meric material in a petroleum solvent to a viscosity suit the isolation of them in capsules. 2 shows the relative relation of mark empirically by one familiar with the art... Green on Oct. . if the other re 70 Preparation of sheet having the chromogenic material actant material were type. of two normally solid com ble. an amount of components materials. 20 each other to afford a good recording surface or back it includes this continuous film structure as a full equivalent ground surface against which the record can be visually of capsules. but close enough to made to the isolation of liquid droplets in this application. except that the liquid is more impermeably sensed. there. or an intentionally-made difference binder material of up to 40%. it is to be understood.935 7 8 polymeric material component of the record unit of this The polymeric material may be dissolved in ink. The same criteria must be met wherever the liquid of the chromogenic material. . If a binder material of hydrophilic prop under-sheet. . Such construction examples without naming specific color re film-holding of droplets that are released by writing or actants. which in themselves constitute specific in a continuous film of pressure-rupturable material. for the purpose of preventing “bleeding” of the wherein a basic chromogenic material is dissolved in a print. 3. and the desired particle size in a ball mill with water. . among other things. by weight. . is situated or whatever it contains. Thus. . . the water-insoluble polymer is ground to action with the top surface of a second under-sheet. the normal coloration being 1945. wherein 30 not determine the principle of the invention. If desired. and are made by dispersing the oil that of the base sheet stock.672. In the case of phenolic polymer. . example pertains to that form of droplets to be transferred to it in data-representing con the invention termed the “transfer” or “couplet” system. the chromogenic material was one component then may be coated with a solution of the CVL.. of the phenolic poly essence of the invention. when particles are involved. of the employed in the physical arrangement of the components between amount of the polymeric material may be added to the the back of the second sheet and the top of the third sheet ball-milled slurry of materials. and the sensitizing materials droplets in a solution of polymeric film material which is as to particle size. as the record materials in their manufac in U.299. and one part by to the already-supplied component. respectively. involves means for enabling the bringing into solu particles of both components. such binder materials be according to the various species of the invention shown ing of the paper-coating binder class including gum arabic. it could transfer the released solvent for sensitized sheet.. hydroxyethylcellulose. the binder of an intentionally-made difference in the selection of itself may act as a dispersant. in situ. view I. Thus. 20. . it would result in a pre mature coloration over the sheet area. . and latex (such as styrene The invention is further illustrated in the following butadiene copolymer).862.. . tured form are hardly distinguishable from ordinary issued to Barrett K. be done alone for each reactant because. Wherever reference is small enough to escape observation. this must to the sheet supporting the capsules. In the arrangement of material components of a multi To make a dispersion of water-insoluble particulate 40 ple-sheet unit which requires one or more components to polymeric material. - Another way of applying the chromogenic or polymeric 65 Solvent. and other droplets for local release in an area subject to pressure. supplied on the otherwise uncoated back surface of the This leaves an aqueous colloidal dispersion slurry of the under-sheet. by marking pressure. No. .S. in the sheet that receives the droplets has buried in it solid part. . which may be applied to the paper so of three or more sheets to furnish another rendition of as to leave a surface residue. preferably in marking-pressure the over-sheet as droplets in sufficient amount to penetrate 35 rupturable capsules having film walls. The isolated solvent is applied to the under side of lated as liquid droplets. all of which are things that may be worked out View Ia of FIG. the quantity of capsules. such as a small quantity of 50 middle sheet and the sensitizing material of the second sodium silicate. A dried sheet with In this example as made. or else held isolated among the paper fibers of the under-sheet to mutually dis in a continuous marking-pressure-rupturable film as a solve the particulate color-forming components disposed discontinuous phase. . 2. . which. . the action between the back of the ably with a dispersing agent. If desired. Pat. Pat. and which do forming components disposed in a two-sheet unit. dependent on the droplets on or in a support sheet. In another method of making a polymer taining capsules. .374. and the availability of the liquid to make contact character and. 2 show circles as 25 of the recorded data is. in the drawings and disclosed in the specification. and wherein an acidic polymeric material is disposed on mersing a sheet of paper in a 1% to 10% solution of the a second support sheet placed in contigous juxtaposition material in an evaporable solvent. and they may be treated as the most convenient and economical amounts consistent particles for incorporation into the paper-machine with proper visibility of the recorded data. the preferred. liquid capsule structures but films which hold a multitude of solvent migration. the under to paper at the size-press station of a paper-making ma sheet were coated on its back surface with solvent-con chine by roller. 2. . . casein. by weight. it could serve as the middle sheet of a stack polymeric material. prefer so on. 1942. said solvent and dissolved chromogenic material material individually to a single sheet of paper is by im being microencapsulated and disposed on a support sheet. coated-paper printing stock. being applied to a record sheet and dried. oil adsorbents in the examples: form of fuller's earths may be added to the polymeric 60 EXAMPLE I materal particles to assist in retaining. 75 Weight of petroleum solvent having a boiling range of .” may be retained as a discontinuous emulsion droplet phase In all the views. . In this respect. or the slurry may be applied 45 the recorded data. the showing is in exag printing pressures is a well-known expedient. . figuation. a printing ink may The presence of droplets of isolated liquid is of the be made of up to 75%. the liquid This.694 and in U. distribution and amount of particles. . . it means not only particle size. and the solvent comprised two parts by weight of other component. a solution thereof in an evaporable be on the back of an overlying sheet such as that shown solvent is introduced into twice as much water and agitated in FIG. where the views of FIG. being water-insolu tion. it could serve as the middle sheet of a stack erties is ground with the phenolic material. the quantity of retained position vehicles to form a printing “ink” of colorless liquid. if in FIG. as the liquid droplets able for printing purposes. the solvent of which is a non-solvent chlorinated diphenyl (Aroclor 1242). 2. No. Obviously. 2. views I to IV. may be incorporated in a paper sheet as it is being ponents in a common liquid solvent component held iso made. factors. chemical reaction efficiency. if the co-reactant material were while the evaporable solvent is blown off by an air blast. and May 1. thus. . .

the present example illus A receiving sheet was prepared according to the method trates the invention wherein the polymer is present on the described in Example I. - minutes. The capsules so produced were then coated on CVL was the chromogenic material used.8 mole of formalde approximately eighty hours to a particle size of under five hyde.935 9. was diluted by the addition of 600 grams of water at a tem subsequently passed onto a Fourdrinier wire in order to perature of 55 degrees centigrade. 3. The preparation of the microcapsules. 1 gram of oxalic acid hours. - grams of water. after which the reaction 40 until the flask temperature reached 120 to 130 degrees mass was allowed to cool. and 6. Said polymer was prepared 5 grams of the polymer of Example I.5 grams of according to the method of Example II. 75 receiving sheet. having had added thereto arabic sol was slowly added. 10 cubic centimeters Imlanner: of concentrated hydrochloric acid (37%). using one mole of gum arabic. set out in Example on the receiving sheet. ceiving sheet in the following manner: (b) Coacervation: 75. a blue mark was formed by the addition of 14% aqueous acetic acid until a pH of 20 on the polymer-bearing sheet. with stirring. The pH was then ad form a sheet. Likewise. and the coating of the capsules EXAMPLE IIb on the transfer sheet were the same as in Example I.8 grams of 11% aqueous gum The dispersion of Example Ia. Upon bringing the capsule-coated surface of the associ 50 EXAMPLE IIa ated support sheets into contiguous relation to the poly meric-impregnated sheet and applying a pressure stroke The transfer sheet was prepared as in Example I. the resin canted. five-to-one ratio of pulp to polymer solids. the support 30 sheet was coated with the microcapsules as in Example I. Following the A receiving sheet was treated as in Example I with a vacuum distillation. the solution of the chromogenic material. and 40 cubic 170 grams (1 mole) of paraphenylphenol. With the blendor running at slow speed. a pressure as in Example IIa produced a blue mark on the vivid blue mark was produced on the receiving sheet. the preparation of the polymer. the preparation blendor was operated until the particle size of the dis of the polymer. using one mole 55 EXAMPLE Ia of the p-tertiary-amyl phenol compound to 8 mole of formaldehyde.5 milliliters of 25% glutaralde 25 the polymer is the p-cyclohexyl phenol-formaldehyde con hyde solution was added and allowed to stir for ninety densation product. a vivid blue mark was produced on the polymer aldehyde condensation product. with the capsule side of the microcapsule-coated sheet. solution of poly port sheet but is substantially evenly distributed through vinylmethylether maleic anhydride copolymer in water. the system was chilled to 10 degrees centigrade to gel the The following example illustrates the invention wherein coacervate walls. and 40 cubic centimeters of water were added and the water layer was decanted. Following the vacuum distillation. and 113. Preparation of sheet having the polymeric material The polymer was prepared as follows: 176 grams of p-cyclohexyl phenol.672. 30 out the body of the sheet. 10 cubic centimeters of con fluxed at the boiling point of the water for eight to twelve centrated hydrochloric acid (37%).6 was reached. Said polymer was prepared bearing support sheet. using the phenol-formaldehyde receiving sheet in particulate form and as a coating on 60 polymer of this example. and the water layer was de centigrade. 1.1 pH unit per minute and. like wise. dihydrate. Were the same as in Example I. 4. The resulting aqueous dispersion was then coated The receiving sheet was prepared as in Example I. and the prep a support sheet (transfer sheet) to yield a dried coating of aration of the CVL solution and its microencapsulation 4 pounds per ream of 500 sheets 25 by 38 inches. was coated with the polymeric material in the following The polymer used was the p-nonyl-phenol-formalde Inaniºlet: hyde condensation product. i(c) Hardening: After the encapsulation was completed. to the uncoated side of the sheet containing the micro The polymer used was the p-tertiary-amylphenol-form capsules. In distinction to Example I. and the was carried out as in Example I. 200 grams chromogenic material. Upon contacting the the p-nonyl-phenol-formaldehyde polymer. and the coating on a transfer sheet of the CVL solution (internal phase) was added. The resin mass was to a resin kettle and refluxed at the boiling point of the then distilled under reduced pressure (bench aspirator) water for eight to twelve hours.5%. and. 65 grams of 37% The polymeric material was prepared in the following aqueous solution of formaldehyde. and dried. After thorough stirring. microns. as opposed to the impreg untreated side of the transfer sheet produced a blue mark nation. and 43. after bringing the surfaces stainless steel tray and allowed to cool. according to the method of Example II. A 3% EXAMPLE Ib solution of CVL was then microencapsulated in the fol lowing manner: This example illustrates the invention wherein the poly (a) Emulsification: Into a Waring Blendor were meric material is present in particulate form in the sup weighed 53 grams of 1%. The sheet so formed was placed in contact justed to about 9. The pH was lowered at the rate of 0.7 grams of 11% aqueous gelatin The preparation of the microcapsules.5 grams of water were bail-milled for 70 the p-nonyl-phenol compound and . I. to thereby cause a liquid coacervate wall EXAMPLE II to separate and deposit about the dispersed internal phase.0 by the addition of sodium hydroxide. to the internal a sufficient quantity of a pulp dispersion to produce a phase-gelatin-sol emulsion (a). The polymer was incorporated in the re persed internal phase was about 5 microns or less. . a blue mark was by being dipped into a 4% xylene solution of the resin formed on the polymer-bearing sheet. the solution of sol. using onto one side of a receiving sheet. Application of sheet surfaces as in Example I and applying pressure. 65 grams of centimeters of water were added to a resin kettle and re 37% aqueous formaldehyde. 10 390 to 496 degrees Fahrenheit (Shell Dispersol). reached 120 to 130 degrees centigrade. resulting from the dipping step. Application of pressure to the the surface of the support sheet. upon application of pressure. and then hav the contents of the blendor was passed into a vessel and 15 ing been diluted to a final solids content of 0. the resin mass was poured into a 45 solution of said polymer. after which the reaction mass was allowed to cool. A second support of the support sheets into contiguous juxtaposition rela sheet (receiving sheet) was impregnated with the polymer tion and applying pressure thereto. likewise. The resin mass then was distilled under reduced mass was poured onto a stainless steel tray and allowed pressure (bench aspirator) until the flask temperature to cool. The receiving sheet The transfer sheet was prepared as in Example I. by weight.

75 preSSure. and 44. . Subsequently. the Ethocel (Hercules Powder Company. . s . where the particular phenol ample IV except that the chromogenic material was p is disclosed as being reacted with acetylene at elevated diphenyl aminostyrylquinoline. issued July 23. EXAMPLE IIIa EXAMPLE VII All materials and procedures were the same as in Ex As an alternative to the impregnation procedure of EX ample IV except that the chromogenic material was a 3%. record unit system containing N-benzoyl auramine as the The phenol used for the preparation of the phenol chromogenic material gave a green-blue mark upon appli acetylene resin was para-tertiary-butyl phenol. which material was dissolved in 2/1 ratio by volume of The preparation of the CVL solution and its microen chlorinated diphenyl (Aroclor 1242) and petroleum dis capsulation were the same as in Example I. and 50 30 degrees Fahrenheit) Again. The pH of the mass was then slowly lowered by N-(2. The materials and procedures of this example were In Examples IV to VIII which follow. that the chromogenic material was. A record unit comprising timeters of 11% aqueous gum arabic sol. likewise. mark upon the application of pressure in the usual man her. and a receiving sheet equal parts by volume of chlorinated diphenyl and petro was impregnated therewith by being dipped into the solu leum distillate (boiling range 316 to 358 degrees Fahren tion. The dispersion was prepared as follows: phenyl in petroleum distillate (boiling range 385 to 496 20 grams of resin.5-dichlorophenyl) leucauramine gave a blue mark the addition of 10% acetic acid until the visual test of upon application of pressure. solution being made by dissolving 4 grams of the BIPS Type N 14. a blue mark was formed mogenic material in this example yielded a red-brown on the polymer-bearing sheet. a record unit containing the grams of water were ball-milled for eighty-four hours. and the entire mass was stirred overnight before use. the emul 60 A record unit comprising the receiving sheet of Ex sion was diluted by the addition of water to make one ample IX and a transfer sheet bearing microcapsules of liter. vinylmethylether-maleic anhydride co manner: polymer. Two grams of the chro temperature and pressure.. The poly upon application of pressure in the usual manner. 80 cubic cen as reactive.5. A record unit comprising the receiving sheet of Ex (c) Hardening step: The mass was then chilled to 10 ample IX and a transfer sheet bearing microcapsules of degrees centigrade and allowed to stand for one hour CVL gave a blue mark upon application of pressure. 14. Upon ample IX and a transfer sheet bearing microcapsules of application of pressure to contiguously-disposed transfer Michler's Hydrol gave a blue mark upon application of and receiving sheets.672.” procedure of Example I.5 grams 8'-methoxy BIPS was the chromogenic material. the polymer mixture of chlorinated diphenyl and petroleum distillat and the receiving sheet were prepared according to the 40 (boiling range 385 to 496 degrees Fahrenheit). pro EXAMPLE VIII duced a colored mark upon application of marking pres 35 sure to the transfer sheet. A 4% solution of the para-tertiary-butyl phenol-ace mogenic material was dissolved in a sufficient amount of tylene resin in benzene was prepared. . a support sheet was coated on one side with an by weight. . solution of N-(2. to give a 1% N-benzoyl auramine solution. N-benzoyl auramine. . and the blendor was operated until the 55 microcapsules of benzoyl auramine gave a green-blue BIPS internal phase droplet size was 5 microns or less. preparation of the resin was according to the procedure ExAMPLE VI outline on page 73 of the publication “Industrial and En All materials and procedures were the same as in Ex gineering Chemistry. Styrene-maleic anhy The BIPS solution was encapsulated in the following dried copolymer.458. ample III. . - The dispersion was coated onto the surface of a sup timeters of 11% aqueous gelatin sol. 2.5-dichloro phenyl) leucaur aqueous dispersion of said para-tertiary-butyl phenol-ace amine in a 2/1 weight ratio mixture of chlorinated di tylene resin. thereby emulsify the BIPS solution in the gelatin-gum arabic sols. 1. 3. . indi 65 EXAMPLE XI cated that coacervation was complete. . 70 ExAMPLE XII The capsules so produced were then coated on a trans A record unit comprising the receiving sheet of Ex fer sheet according to the technique of Example I. cloudiness. and 80 cubic cen port sheet (receiving sheet). boiling range 316 to 358 degrees Fahrenheit (Shell transfer sheet bearing said microcapsules was prepared 360). as outline in Green and Schleicher United States Patent No. > -.935 11 12 EXAMPLE III EXAMPLE V This example illustrates the invention wherein a phenol All components were the same as in Example IV except acetylene polymer condensation product was used. 3. . the pH was ad the said receiving sheet and a transfer sheet coated with justed to 6–6. a brown mark was produced. Upon the application of pressure on the support 20 heit) to yield a 2% solution.1% Ethoxyl). and the cation of pressure. . and. 1957. 5 cubic centimeters of 25% glutaraldehyde solution was added. different chro the same as in Example IV except that the chromogenic mogenic material was used in conjunction with p-phenyl material was 3% of Michler's Hydrol in 2/1 weight ratio phenol-formaldehyde polymer. to mark upon application of pressure. at this temperature.” 1949.800.5 grams of gum arabic.25 grams of carbon compound in 100 cubic centimeters of chlorinated di tetrachloride were admixed to give a dispersion of the co phenyl (Aroclor 1242). CVL was the chromogenic material used. the tillate. mer-coated sheet. and carboxy polymethylene are useful substitutes (a) Emulsification: Into a Waring Blendor were placed for the ethylene-maleic anhydried copolymer but are not 80 cubic centimeters of the BIPS solution. The according to Example I. EXAMPLE Ix EXAMPLE IV Five grams of a partially-hydrolyzed ethylene-maleic anhydride copolymer (Monsanto DX—843–81). . upon contact with the transfer sheet having the microencapsulated chromogenic material. with constant stirring. A record unit using the chro sheets held in contact position. and indicated chromogenic material produced a blue mark the dispersion was coated on a sheet and dried. EXAMPLE X (b) Coacervation: The emulsion of step (a) was trans ferred to a beaker. Ethyl Cellulose. polymer in the carbon tetrachloride. In all cases.

2. the phenolic polymers—the scribed in Example IV.935 13 14 ExAMPLE XIII Generally. 30 It also may be desirable to mix polymeric components and a paraphenylphenol formaldehyde condensation prod for economic reasons or reaction characteristics. 2. tion product. For instance. the pressure pattern. as com pared with prior-art systems. pounds. a polymer in solution form provides for greater ease of mark was produced on the coated surface according to 15 adaptability to existing application apparatus. was then coated on the support sheet material and dried. produced according to the pressure pattern. on the support sheet member as a continuous film. Additionally. Vc. a mark was component(s). The chro the zone of marking has a protective film surrounding mogenic material was 3% CVL in chlorinated diphenyl it. a printing ink applicator. diphenyl (Aroclor 1242). 3. wherein the several components are in film form provides several advantages. with the consequent attainment of high in the phenolic polymeric material is a condensate of a resolution of recorded data that attends the use of a phenol having a hydrocarbon substituent in the para continuous film. CVL was used as the chromogenic material. of the sheet. wherein the aldehyde capsular product was dispersed therein. The record unit of claim 1. Upon application of pressure to the coated sheet. 3.672. such as. the solvent was able liquid organic solvent for both said mark-form chlorinated diphenyl (Aroclor 1221). it pro The dispersions of capsules and polymer as a mixture vides large surface area of reactive material in a form were then coated upon a support sheet and dried. in the case of the pre solution was encapsulated according to the technique de ferred material—namely. - The polymer was made into a dispersion according to 10 Where the polymeric material is disposed originally Example I. 75 position and an aldehyde. views X. and the same method is color would visually combine to a dark purple approach used in introducing the polymeric material into the body ing blackness. as shown in FIG. a mark 70 in the phenolic polymeric material is a condensate of a was produced in accordance with the pressure pattern. 2. pressure release of the liquid organic solvent. on sules were spray-dried to produce a free-flowing powder. XI. namely. it is applied as a part of the aqueous furnish of compound yielding a blue color and one yielding a red fiber to the Fourdrinier wire. The dispersion is formaldehyde. The 60 cross-linking agents and being further characterized chromogenic material was CVL. said phenolic polymeric material also ponents are distributed within a continuous film of the being permanently fusible in the absence of added polymeric material. and Vd of FIG. The presence of the polymer in FIG. the polymeric material at the marking sites will be present as a film subsequent to the production of This example depicts a self-contained sheet as shown the mark-forming reaction. 25 polymeric material. The polymeric material was encapsulated (c) at least one of the mark-forming components be according to the procedure of Example IV. A pressure-sensitive record unit comprising: throughout the support sheet (FIG. and that one sheet may have data marked there on in one color and the next underlying sheet may yield 40 the same mark configurations in same or different colors. more of the components of the system are interspersed Under some circumstances. substantially reduces the 20 so-called “picking” problem associated with coatings of This example specifies an architecture wherein one or particulate materials such as attapulgite. for example. acid-reactive chlorinated diphenyl (Aroclor 1221) and encapsulated groups and solubility of at least 2% by weight in according to Example I. the presence of the Upon application of pressure to the support sheet. such hues blending to produce a If the chromogenic material is in the body of the compound visual effect. The solvent was chlorinated duce a desired end product. zation by atmospheric moisture attack. This example demonstrates an architecture wherein What is claimed is: the several components of the system are interspersed 1. . Upon the ing maintained in isolation from other mark-forming application of pressure to the finished sheet. to provide a chromogenic solution. because of its EXAMPLE XIV great affinity for the substrate. polymeric material was prepared. The polymeric material was para water-insolubility of the polymer will preclude decolori phenylphenol formaldehyde. The pressure-sensitive record unit of claim 1 where.” phenolic polymeric material which is acidic relative EXAMPLE XVI to the basic chromogenic material and reactive with 55 the basic chromogenic material to effect distinctive This example demonstrates a self-contained unit where color formation or color change. Upon the application of pres 35 It becomes apparent that the invention described is sure to the support sheet. para-substituted phenol and an aldehyde. a mixture of a sheet. are The polymeric material was a paraphenylphenol form 65 brought into reactive contact by mutual solution in aldehyde condensation product. XII). which substantially diminishes removal of the mark (Aroclor 1221). which was dissolved in by the presence of free-hydroxyl. that is readily soluble. 2. and the polymeric 45 ing components arranged in contiguous juxtaposi material was paraphenylphenol formaldehyde condensa tion and supported by said sheet material. This by abrasive action. view Va. the polymer. with the exception that the cap said liquid organic solvent. and the dry powdered 2. (b) mark-forming components. and a pressure-releas The chromogenic material was CVL. Additionally. A xylene solution of the the released liquid organic solvent. The pressure-sensitive record unit of claim 1 where ing properties. it may be desirable to have throughout the support member and the remaining com the chromogenic material present as a mixture of com ponents are coated on the surface as depicted in views pounds which yield different hues on reaction with the Vb. and (a) support sheet material. Thus a uct was used as the acidic polymer. or even in regard to single and double sheet EXAMPLE XV systems. which components. Finally. The top coatings are mixture of the phenolic polymers specified may be used applied from aqueous dispersions of the particles or cap with one or more of the chromogenic materials to pro sules in the usual manner. The chosen polymeric material may have film-form 4. that disposed on the surface of the support sheet. 50 (d) said mark-forming components comprising at least The several components were dispersed in water and one basic chromogenic material and at least one supplied to the Fourdrinier wire with the “furnish. a mark was produced accord not limited in the use of single pairs of reactant com ing to the pressure pattern. said phenolic poly in the several components of the system are coated onto meric material being a condensate of a phenol and the support member and further wherein the several com an aldehyde. view VII.

171 2/1962. . 11/1966 Haas -------------.2 8. .S. 6.1 wherein the liquid.547 2/1961 Tien -------------. . -----. . The pressure-sensitive record unit of claim 1 where in the phenolic polymeric material is a condensate of References Cited para-phenylphenol and formaldehyde. 117–36's polymeric material is present in the sheet material in an amount of about 0. Primary Examiner polymeric material is present in the sheet material in an U. CI. 155 UA . 2. The record material of claim 1 wherein the phenolic * 3.935 15 16 5.374.929.8 in said liquid organic solvent prior to pressure-release.9 and further wherein the chromogenic material is dissolved 3.862 5/1945 Green ------------. amount of about 0. . The record unit of claim. . material unit of claim 5 wherein the 3. UNITED STATES PATENTs . 9. . . 15 117–36.020. or 2.117–36. .184..287. -------.972.672. x. III. . . The record material of claim 2 wherein the phenolic MURRAY KATZ. . Bakam et al.117–36.168.154.. .2.117–36.117–36.736 3/1960 Miller et al.466. 9/1969 Bowler et al. -------. The record. 36. . . 3. .5 to 3 pounds per ream.9.117–36.117–36.864.5 to 3 pounds per ream. 3. .R.2 7. 2/1965 Brandle et al.2 chromogenic material is crystal violet lactone. .8 ganic solvent is present as the nucleus of a microcapsule * 2.