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United States Patent [19] [11] 3,981,523

Maalouf [45] Sept. 21, 1976
[54] CARBONLESS MANIFOLD BUSINESS
FORMS [57] ABSTRACT
[75] Inventor: George E. Maalouf, Niagara Falls, Sets of manifold business forms are coated on selected
surfaces thereof with chemicals which are capable of
reacting with each other to produce a colored mark.
[73] Assignee: Moore Business Forms, Inc., In one arrangement at least one intermediate sheet is
Niagara Falls, N.Y. coated on one surface with a composition of a record
[22] Filed: Mar. 24, 1975 developing material (which is generally solid) and a
non-compatible color precursor (which is generally in
[21] Appl. No.: 561,623 the form of a microencapsulated liquid) to thereby
function as both a record-receiving and a color
[52] U.S. Cl................................ 282/27.5; 427/150; transfer surface upon reacting with the coating of at
427/152; 428/411; 428/537 least another separate sheet of the set containing an
[51] Int. Cl.”............................................ B41L 1/16 other compatible color precursor and/or another re
[58] Field of Search ........... 427/1.46, 150, 151, 152, cord-developing material on the surface thereof. In
427/153, 261; 428/411, 537, 913; 282/27.5, another arrangement, some of the sheets are coated
28 R front and back with a record-developing material,
while others are coated front and back with a micro
[56] References Cited encapsulated color precursor. In each of the arrange
UNITED STATES PATENTS ments the sheets of the manifolded sets are capable of
3,540,912 1 1/1970 Lin...................................... 427/261
being so arranged such that by removal of certain
3,895,173 7/1975 Adachi................................ 428/537 parts of the sets or turning certain parts upside down
and applying pressure on the backs of the sets, images
Primary Examiner—Thomas J. Herbert, Jr. may be developed on both sides of the sheets.
Assistant Examiner—Bruce H. Hess 8 Claims, 8 Drawing Figures

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side thereof coated with the first color forming reac The present invention relates generally to a co-pend tant. the co development cannot occur if such capsule contents and reactants may both be microencapsulated liquids.S. 3. 65 separate sheets coated with a compatible color precur U. Pat. and entitled “DUAL SYS forming reactant coated surfaces facing the first color TEM CARBONLESS PAPER”. U.308 to Macaulay. Depending on the particular business Manifolded sets of carbonless copying paper nor needs.694 to Green.910. the contents of the side thereof. copying sets. after an image is pro sheet conventionally has its front surface coated with a duced on the front side of the receiving sheet using the solid material containing a record-developing material carbonless system.827 to Ruus and U. on either side of the base film with the second color 466. In this regard it is to produced on each side of the sheets of the set. sor or record-developing material. the in 10 In the current carbonless copying systems of the type vention relates to manifold sets utilizing both single and aforedescribed the image is usually developed on the dual initially colorless color forming systems whereby it front sides of the sheets. The intermediate sheets are often coated conventional carbon transfer. in conventional manifolded carbonless developed on both sides of the sheets. a bottom sheet and at least on the sheets of a manifolded set of forms thereby one intermediate sheet disposed therebetween. No. No. now abandoned the 45 forming reactant surfaces. United States patents which illustrate various types of However.S.S. More particularly. A plurality of secondary sheets are pro vided each of which has one side thereof coated with a ruptured capsules in the back coatings spill out and react with the developing material to form a colored second color forming reactant reactable with the first mark on the latter which corresponds to the mark im 40 color forming reactant to form a color and the second pressed by the stylus or machine key. The patent is basically directed to a so that. wherein each sheet is coated both front and back with .523 1 2 The aforementioned Green ('507) and Macaulay CARBONLESS MANIFOLD BUSINESS FORMS (308) patents illustrate the most common variety of BACKGROUND OF THE INVENTION: carbonless impact transfer paper of the type with which the present invention is primarily concerned wherein 1.S. this patent does entirety of the disclosure of which is hereby specifically not generally disclose the concept of having an image incorporated herein by reference. The bottom bonless paper systems so that. poor manifolding and difficulty in manufac developing material in the front coatings and with the ture nevertheless persist in such an arrangement. be noted that the present application also relates to SUMMARY OF THE INVENTION: dual systems of co-reactive materials. such sheet can act both as a record-receiving systems which may be used in the production of car CF sheet and as a color-transfer surface CB sheet.S. on both sides of several or all sheets of a set of manifold 2. and a dry coating of a coated respectively with compatible initially colorless solid coreactant chemical for the precursor is coated reactive components capable of reacting to produce a on the front surface of a receiving sheet. 43-28652. 2. Pat No. 3.429. upon impact by a machine key or application of base sheet having a first color forming reactant on each pressure by a stylus on the top sheet. the record-developing material come into contact. however. Moreover. cording sheets so constructed to permit an image to be Although.981. The problems of carbon respectively with the above-mentioned solid record smudging.016. Sets are formed by placing the secondary sheets ing and commonly owned U.299. In certain cases. bonless transfer papers are. application Ser. the present invention differs from that of the above-men 50 It is therefore an object of the present invention to tioned application in its construction and purpose as provide a completely carbonless manifolded set of re will be more clearly brought out hereinafter. This patent discloses a car sure rupturable microcapsules containing a fluid color bonless duplicating notebook consisting of a set of precursor in fluid form which is capable of reacting to initially colorless copying sheets 'containing pressure thereby form a colored compound with the developing rupturable components for transfer of the color form material in the front coating of the next adjacent sheet 35 ing ingredients. Image development may then be provided by using 2. color precursor in the back coatings and accordingly An interesting prior reference is Japanese patent such “front and back coated” sheets are referred to as 30 CFB paper. an image can also be produced on and this “front coated” sheet is generally referred to as 25 the back side of such receiving sheet by means of the CF paper.534 to A further object is to provide a manifolded set Macaulay et al. U. it should be pointed out that the precursor and a record-developing material which is reverse is also possible so that the front coatings com non-compatible therewith. it is is possible to produce a colored mark on both sides of desirable and advantageous for images to be produced such sheets by impact. Pat. Field of the Invention: microcapsules containing a liquid fill comprising a The present invention relates generally to a carbon chemically reactive color-forming precursor are coated less copying system wherein mating sheet surfaces are on the back surface of a sheet. The back coatings normally comprise pres publication No. 1974. Description of the Prior Art: 15 business forms. colored mark upon impact. filed May 3. Pat. Carbon transfer sheets former in a suitable solvent and is generally therefore have sometimes therefore been interleaved with car referred to as CB (“Coated Back”) paper.S.712.720. however. 3. However. No. No. Pat. By itself such a coating can prise microcapsules and the back coatings comprise a not present a so-called self-contained sheet since image solid record-developing material. for example.507 to Green. various types of entries are required to be made mally comprise a top sheet. The top requiring larger and more detailed sets of forms to be sheet which is conventionally coated on its back sur made which results in the need for more paper and face with an encapsulated solution of a colorless color 20 precise printing techniques. U. 3. the back coatings normally comprise a Another object of this invention is to provide such a microencapsulated solution of the color precursor and 55 manifolded set wherein individual sheets may be the front coatings normally comprise a solid record coated with a mixture of a microencapsulated color developing material. No.

and concepts of the present invention. 25 Further. the selected surfaces so as to facilitate a wide range of first and second reactive components of the second manifolded transfer paper sets capable of producing system are capable of interreacting when brought into images on both sides of the sheets. 1 includes a top sheet 11. 15 and 17. When the reacting with a reactive material in each of the front 55 capsules in coatings 210 are ruptured. reactive contact with one another to produce a similar Other objects. 15 or 17. it should be pointed out. tion of arrow 70. for example. 13 and 12 without departing from the principles capsulated color precursor. and could likewise include as few sheets mark is left on these surfaces. in a manner to be hereinafter the fill from coatings 210 of sheets 13. 1. As shown. 1 through 4 are elevational. when pressed thereagainst. tion system contained in the mixture of reactive com Although five intermediate sheets are shown in FIG. showing the arrangement of the sheets the reactive material in coating 210 of sheet 17 might for each embodiment to facilitate image development be chemically compatible only with a reactive compo on the opposite sides thereof. nent of the mixture of components in the coating 190 DESCRIPTION OF THE PREFERRED 35 of sheet 12. Further. Such microcap material in each of the back coatings 210 is capable of sules are also illustrated by small circles. such as selected surfaces of the sheets and/or as a mixture on by impact. Preferably. and the reactive component of the first reactive system. by the applica coatings 190. 1 to that the use of a third reaction system is possible in that 4. respectively. compatible to form a colored mark. bodying the principles and concepts of the present Generally the reactive components of coatings 210 invention. expanded and system and the first reactive component of the second enlarged. However. reaction system and a first initially colorless reactive A still further object is to provide a manifolded set 10 component of a second reaction system. each of the of a liquid fill material in tiny rupturable microscopic sheets 11 through 17 are disposed to overlie one an capsules. FIGS. The reactive material in each coating 180 FIG. a bottom sheet 12 and 40 sent invention. The top and FIG. the second component of the first reactive FIGS. The first and second components material of the other. the second reactive invention will become more apparent from the follow component of the second reactive system in coatings ing detailed description of the invention when taken in 180 is not chemically compatible to produce a colored conjunction with the accompanying drawings. the wherein two reaction systems are employed such that reactive material in each coating 180 comprises a sec the color precursor of one system is chemically incom ond initially colorless reactive component of the sec patible to develop a color with the record-developing ond reaction system. and 30 will be identical. 15 and 17 spills more fully described. a mark 24 may immediately be impressed on is capable of reacting with a reactive material in each of top sheet 11 of the set and corresponding marks 25 are the coatings 190 when arranged as shown in FIG. advantages and novel features of the 20 colored mark. Obviously. mark when brought into contact with the first reactive BRIEF DESCRIPTION OF THE DRAWINGS: component of the first reactive system in coatings 210. 16 and 12 as for contact therewith. as indicated by the arrow 70 in hereinafter. prise tiny rupturable microscopic capsules having liq Each of the coatings 180. Simi The manifolded set of carbonless recording sheets larly.523 4 a record-developing material and/or with a microen as 11. However. it should be pointed out that set 10 could include sheets 13. at least one of the mixture Intermediate sheets 14 and 16 each include front coat 45 of components in coatings 190 is contained in the form ings 190 and back coatings 180. several intermediate sheets 13 through 17. since the top surfaces additional intermediate sheets similar to 14 or 16 and of intermediate sheets 13. to produce a colored mark. throughout normally in contact with one another in the The tiny rupturable mircocapsules are illustrated as manifolded set. Likewise. A still further object of the present invention is to The reactive material in each coating 210 comprises provide such a manifolded set wherein a chemically a first initially colorless reactive component of a first compatible reaction system is employed using color initially colorless reaction system. 1A formed on the upper surfaces of sheets 14.981. 15 and 17 include back coatings 210. 1A through 4A are views similar to FIGS. cross-sectional views of several embodiments reactive system in coatings 190 are not chemically of manifolded sets of carbonless recording sheets em. This fill comprises the first reactive compo other with their back coatings and front coatings there nent of the second reactive system described above. no 13. 1 for the sake of clarity. which fill comprises the first reactive one color-forming reactive material. while intermedi top sheet 11 as pressure is applied thereto in the direc ate sheets 13. 3 3. 15 and 17 are uncoated. The reactive mate precursors and record-developing coatings disposed on rial in each coating 190 comprises a mixture of a sec selected surfaces of the sheets to facilitate development ond initially colorless reactive component of the first of an image on both sides of the sheets. with a EMBODIMENTS: reactive component of the mixture of components in coating 190 of intermediate sheets 14 and/or 16. and vice versa. 65 ponents of coatings 190 of corresponding underlying 1. coatings 210 preferably com being vertically spaced in FIG. On the other hand. the reactive materials out of these ruptured capsules to contact and co-react in coatings 180 and 210 are chemically incompatible to with the second reactive component of the first reac form a color. 1 illustrates the manner in which images are bottom sheets 11 and 12 are respectively coated back transferred onto a surface of several sheets underlying and front with coatings 180 and 190. to produce a tion of pressure by stylus or machine key to the upper colored mark in a manner to be more fully described surface of sheet 11. although these sheets are shown as 50 small circles. . although the vari of the first system are capable of interreacting when ous components of both systems may be coated on 15 brought into reactive contact with one another. 190 and 210 includes at least uid fill therein. and not compatible. Likewise. sets including more than three different color generally designated by the reference numeral 10 in systems could be utilized in connection with the pre FIG.

each of the contact and co-react with the second reactive compo sheets are in face-to-face contact with one another. manifold set 20 comprises a top sheet 28. Sheet 12 of set 10A 18c and 18d on opposite sides thereof. As before. the encapsulated first re the reactive material comprising the second compo active component of the first reactive system is illus nent of the second system in upper coating 78A of trated as a series of small circles containing a plus mark bottom sheet 31. are produced on the coatings 180 of the corresponding sheet 37 has a front coating 18b. the image of which is transferred onto scribed as containing the co-reactants of the first sys the top surfaces of underlying sheets 29 and 31 as tem only. whereby the reactive com carries coatings 19a and 198 on its respective opposite 45 ponent spills out to contact therewith. as in the 55 coated in a similar manner with the co-reactants of earlier described embodiment. upon impact by a sty coatings 21a and 21b. they could similarly be likewise markings 33. are actually in face-to another initially colorless color forming system. 16 and 12 which have been marked. each sheet 28. 29 and 31 is turned upside down containing an x mark (3) The second reactive compo to present the set 20A of FIG. such as. The pressure of 50 surfaces of sheets 38. 10 is created on surface 196 of sheet 29 as the first reac For producing images on the opposite surfaces of tive component of the first reaction system of coating sheets 14. 1A wherein sheet 12. similarly. the sides. no image a stylus or machine key impressed on the top surface of is transferred onto these surfaces. sheets 36. and. Therefore. 15 and 17 are removed and and co-react with the second reactive component of the set is turned over to form a set 10A illustrated in the first reaction system in coating 198. It should be appreci sheet 28 in the direction of arrow 72 immediately im ated that the sheets of set 30 in FIG. which was previously the 15 microcapsules in coating 19a are ruptured upon im bottom sheet. . FIG. each of which contains the first 40 lus or machine key in the direction of the arrow 74. a manifolded set 30 of surface of sheet 12 and the capsules containing a first 25 carbonless paper sheets is shown as comprising a top reactive component of the second reactive system are sheet 36. Now. Since the top compatible to react to produce a color. a reactive component of the first reactive system. 2. A mark 34 is then ment of the first reaction system is illustrated as a series impressed directly upon the now upper layer 21b of the of plus marks (+). Bottom mark 45 is impressed on the upper surface of sheet 36. each sheet 14 and 16 has marks 25 and 27 on the coatings 18a through 18f comprise the second reac opposite sides thereof and sheet 11 has marks 24 and 35 tive component of the first reaction system. images or marks 27 30 proved clarity. ate sheets 38. 16 20 thereby forming another mark 35.981.41 and 43 are uncoated. Likewise. 3. 2A. 44b and 44c thereon comprising microcap a bottom sheet 31 and an intermediate sheet 29. sheets 38. Intermedi 27 on its opposite sides. Upon impact by a stylus or while sheets 29 and 31 have markings 33 and 35 on machine key in the direction of arrow 71 as shown in opposite surfaces thereof. 14 and 11. 42 and 37. The sules containing the first reactive component of the top sheet is coated on its front and on its back with first reaction system. 19a of sheet 29. as de 21a spills from the ruptured mircocapsules to contact scribed above. microcapsules containing the reactive component in each of which contains the second reactive component coating 44a are ruptured and co-react with the reactive of the second reactive system. upon impact . however. the microcapsules which To facilitate a transfer of images on the reverse sides contain the first reactive component of the second of the marked sheets of FIG. 41 and 43 respectively have back coat In FIG. Accordingly. a mark 26 is immediately impressed on the In the FIG. 41 and 43 are reactive system and which are admixed in the coating 65 first turned upside down and thereafter the entire mani layer 196 on the lower surface of sheet 29 are ruptured folded set is likewise turned upside down to present set upon impact by the key or stylus so that the fill con 30A useful for marking the reverse sides of sheets 37. sheet 36 has a back coating 18a. sheets 13. Each of thereof. sheet 39 has coatings underlying sheets 16. Therefore. ment of the second reactive system contained in corre however. the same are shown as being spaced for im sponding coatings 180. is now the top sheet for receiving an pact. 3. 3 have been de prints a mark 32. 1A. 1A. while the second reactive compo form by a stylus or machine key applying pressure in nent of the second reaction system is illustrated as a the direction of the arrow 73. Images 46 of the mark are thereby pro reactive system. (? while the first reactive component of the second For producing images on the reverse sides of the reactive system is illustrated as a series of small circles sheets. ponent of the second system spills out to contact and coatings 180 containing the second reactive compo co-react with the chemically compatible second com nent of the second reactive system respectively under ponent of the second system in coating 78b of sheet 31 lie and are in contact with coatings 190 of sheets 12. Here. Here. 39 and 36 as shown in FIG. 38 and 37 could be used without depart contact and co-react with the second reactive compo ing from the teachings of the invention shown by this nent of the first reaction system in the upper coating embodiment. More face contact. Intermediate sheet 29 component in coating 18. The sheets of set 20. tained therein spills out to contact and co-react with 42. An image 35 of the mark series of x marks (x). and sheet 42 has therefore has marks 25 and 26 on opposite sides coatings 18e and 18f on opposite sides thereof. sheet and 14 which include the first reactive component of 28 has marks 32 and 34 on opposite surfaces thereof the second reaction system. FIG. 3 embodiment. for exam tured capsules upon impact by the key or stylus so as to ple.523 5 6 Throughout the drawings. which components are not chemically duced on each of sheets 39. ings 44a. Each coatings 19a and 19b comprises an admix reactive components from coatings 44b and 44c react ture of the second reactive component of the first sys with the reactive components in layers 18e and 18b tem and the first reactive component of the second respectively. additional intermediate sheets constructed in the nent of the first system which is contained within the same manner as sheets 42 and 43 could be used with microcapsules of coating 21b is spilled from the rup this set. and the contents thereof comprising the first com impact as illustrated by the arrow 71 in FIG. sheet 31 has coatings 78a and 78b on its opposite sides. Again. as few as three sheets. 3A. a bottom sheet 37 and intermediate sheets 38 ruptured so that the liquid fill thereof spills out to through 43 lying therebetween. and the fill comprising the first compo over. Likewise.

3. In this connection.293. The color pre as mark 53 on the top surface of sheet 51 as the micro cursors of Harbort as well as those of Phillips. No. Jr. it is conventional for the color precursors to be for another two of the disclosed embodiments.193. No. line 32 through may be impressed upon the surface of layer 44d of column 12. Pat. butyl benzyl adipate. 3. the first reactive component of the means of a stylus or machine key in the direction of first reaction system must be chemically incapable of arrow 75. Top sheet 49 has coat 15 capable of undergoing an acid-base type reaction with ings 44d and 44e on its opposite surfaces comprising an acidic material.185. It should be pointed thalene solvents disclosed in U. et al capsules in coating 44e rupture and the fill thereof 25 and Davis are initially colorless and are capable of spills out to contact and co-react with the co-reactive becoming highly colored when brought into contact component in coating 18g of sheet 51. the direction of the arrow 76. coconut oil. 125. vegetable oils (cas 5 and 6 thereof. the acidic coatings are .404. a mark 47 is immediately impressed upon reacting with the second reactive component of the sheet 37 and images 48 thereof are transferred to second reaction system to produce a color and the first sheets 42. 3. 44b 44a are ruptured whereby the fill likewise be chemically incapable of reacting with the thereof spills out to contact and react with the co-reac second reactive component of the first reaction system tive components in the respective underlying coatings to produce a color.463 to out also that there are a great number of patents which Konishi et al. material.S. et al.523 8 7 with what is now the upper surface of sheet 37 by systems are utilized. No. filed Mar. No. U. Each of the ond reactive components of the second reaction system intermediate sheets 42 and 39 has marks 46 and 48 on are chemically reactive to form a color.. petroleum derivatives (petroleum spirits. the color precursor materials of the Phil applying pressure in the direction of the arrow 77. 18d and 18a. 4 makes use of only closed in the '721 patent referred to above. Jr. Application of Baxter. hereby specifically incorporated by reference). Phillips. For one of these systems. which are a single system of co-reactants. it should be perpendicular to the plane of the drawings. These materials are capable of reacting tor oil. with specific reference being made to the reactive component of the reaction system.429.075 one system of co-reactants is required for two of the referred to above. Manifestly the first and second 18f.). the microcapsules in coating 44d rupture so that dissolved in a solvent and the solution may be encapsu the fill contained therein spills out to contact and co lated as taught in the Macaulay '308 and the Green react with the co-reactive material in coating 18h. any of the materials dis Manifolded set 40 shown in FIG. 3. et al and Davis dis other to thereby present set 40A as illustrated in FIG. or down so that coating 44d and 18h are facing one an the like. Solvents which U.278. kero 125.721 to Phillips. No. 1971 (the entirety of which is sene.S. 54 is impressed on sheet 49 by a stylus or machine key 35 In general. ments wherein one or more sheets or sets are turned Pat. the two co-reactants are of course are coated on the backs of the sheets of carbon less chemically compatible to produce a color. As a result. relate to initially colorless color precursors useful in With regard to the acidic coatings capable of con connection with carbonless copying systems. lips. Nos. The co-reactants precursors capable of undergoing a reaction with an in the contacting coatings 44d and 18h of the sheets acidic coating to produce a color which are usable co-react to produce an image 55 on sheet 51 as a mark herewith. line 21. and such mark is imaged 3. upside down.827 to Ruus and in U. Also. cottonseed oil.S.605 to Baxter. Pat. sheet 37 has marks 46 reactive components of the first system are chemically and 47 on its opposite sides while the opposite sides of i () reactive to form a color and likewise the first and sec sheet 36 have marks 45 and 48 thereon. The pre verting the color precursors into their highly colored sent invention in no way depends on the exact identity form.806. Pat. commonly owned U. Other processes It should be pointed out that in each of the embodi for encapsulating color precursors are disclosed in U. Jr. Jr.) silicone oils. 3. The Harbort. its opposite surfaces. the turning takes place about an axis 3. etc. dibutyl phthalate. No.S. and partic are useful in connection with dissolving color precur ularly to those listed in the paragraph bridging columns 50 sors include chlorinated biphenyls.075.) esters (dibutyl with a CF coating containing an acidic material such as adipate.455.377.. and that at least two 65 In each of the above mentioned color-forming sys non-compatible systems of co-reactants are required tems.060 to and 18h on its opposite surfaces comprising the second 20 Harbort. Where two copying manifolded sets. As an example. 30 closures are specifically incorporated herein by refer 4A. Also operable in capsules containing the first reactive component of the connection with this first system are the spirodipyran reaction system while bottom sheet 51 has coatings 18g compounds disclosed in the U. tricresyl phosphate. although there are any number of similar color opposite sides of the sheets 49 and 51. aromatic solvents (benzene. particular ruptured upon impact in accordance with the conven reference is made to the color precursors mentioned in tional carbonless copying procedures. benzyl the acid-leached bentonite-type clay disclosed in a octyl adipate.S. When a contained in pressure rupturable microcapsules which single system is used. 39 and 36 respectively as the microcapsules 5 reactive component of the second reaction system must in coatings 44c. Particularly useful are the alkylated naph the Phillips.S. etc. Pat. Particularly useful color precursors sheet 49 by means of a stylus or machine key moving in are disclosed in the patents to Davis. mineral oils.981. 17.). or the 55 toluene.578. Pat. may be utilized. particular reference is made to the clay coatings or nature of the reactants utilized except that at least disclosed by Baxter in application Ser. etc.S. etc. or any combinations of the acid-reactant organic polymeric material disclosed in foregoing. et al. trioctyl phosphate. No. the Harbort and the Davis patents may be Again. 3. with an acidic material such as an acid activated ben Sheets 49 and 51 are then separately turned upside tonite clay or an acid-reacting polymeric. to facilitate the production of markings on the ence. presently disclosed embodiments.327 and 3. pointed out that the exact nature of the capsule itself is The precursors useful in connection with carbonless 45 not critical so long as the same is capable of containing copying systems are varied and known to those having the color precursor with the capsules capable of being ordinary skiill in this art. '507 patents mentioned hereinabove. A mark 52 disclosure of this patent in column 11. et al '721 patent. Jr. Ser.

1A. However. | 0 as the acid-treated bentonite-type clay disclosed in U. Another sys coated onto a sheet of paper in accordance with Exam tem which has been found to be operable in accor ple 19 of this same patent. 4 and 4A may include 2A preferably include both the microencapsulated microcapsules containing a fill material comprising. rial as described in Example 18 of U. as the first reactive component cobalt thiocyanate is reacted with lignin to form a visi of the second reaction system.S. The metal rosinate salt in 20 sort disclosed in U.455.075 or the acidic 3. Pat. as the first initially rupturable microcapsules containing the dithiooxamide colorless reactive component of a second initially col fill material are then utilized as the back coating in a oriess reaction system. it is critical to the invention and the Davis '404. 3. coatings 19a and 19b of FIGS.592. 3. development. Pat.S.677 and 35 the second component of the first system must not be 3. the dithiooxamide mate 15 19b of FIGS. No.846. 3.450. 19a. In general.040. the Harbort and the be chemically compatible for image development and Davis color precursors are not reactable with matallic that the first and second components of the second rosinates to form a color and the dithiooxamides of 30 system be likewise chemically compatible for image Ostlie and Matson are not reactable with acidic layers.S.677 and 3.677. solvents removed by drying to leave the required resi With respect to the specific embodiments of the pre due. Jr. 21a. No. 3A. aniline hydrochloride. 193. 3. the first component of the first such as of acid-leached bentonite-type clay or acidic system and the second component of the second system polymeric materials. Pat. 2-methylindole. ings 21a and 21 h in FIGS. layer front coating upon rupture of the adjacent cap 3. 19a and skatole. particularly nickel rosinate. No.846 and Matson. No. Baxter's application Ser. Nos.941 mentioned above. microcapsules such as cyclohexane. 196 and 18a 3. and a metal rosinate. 3-hydroxyphenyl urea.721.S.786.535. The containing a liquid fill including.341. as the Coatings 190 of FIGS. Nos. 3. et al '721. reactive component of coatings 190. 50 The microcapsules included in coatings 190. No. systems wherein phloroglu through 18h preferably comprises the acid-treated ben cinol. Pat. 3.N-dimethyl-p tion Ser. 125. This component may comprise. 3. 1.455.S. et al. No.139. therefor being initially colorless reaction system. Coatings 180. 21b duce a highly colored chelated compound as disclosed and 44a through e preferably comprise an encapsulated in U. coat 65 ample 18 of said '846 patent. Nos.4-dimethyl-5-pyrazolone. 3. The systems disclosed in these patents in polymeric materials disclosed in U. in admixture rial is incorporated into a suitable solvent therefor. is then microencapsulated and the microcapsules are as disclosed in U. 3. capable of reacting to form a color. 3-aminopyridine. 3A.293. The intended capsule fill material an agent for releasing iodine from the iodine solution. 19q and 19% in the FIGS.060. No. 3.516. 3. 4 and 4A may cally non-reactive with the acid-base type reactants of include. and sules which contain the color precursor material. Nos.516.941. a color-forming reactive material such patents to Ostlie.721. clude a dithiooxamide compound as one component 3. The second reactive com present a clear mark.S. as the second reactive component of such first the systems. Pat. Pat.846 and used as a front coating and the two materials react to 3.759. Other must not be capable of reacting to form a color and patents which disclose dithiooxamide color-forming likewise. 2 and 2A. Pat. 125. 2 and through 44e in FIGS. coatings 210 in FIGS. 3. U. Jr.516. or 19b preferably contain.S.377. for image development. a dithiooxamide mate ble reaction product as disclosed in U.481. the Harbort ’060 As pointed out earlier. Pat. The color systems disclosed in the ponent of the second reaction system is included in Ostlie '759 and in the Matson '846 and '941 patents coatings 180 of FIGS. Pat. No. wherein an acid ester substituted polyhydric phenol is As a specific example of the color forming materials reacted with an iron or vanadium compound to pro used with the present invention. a system wherein an or solution of p-toluene sulfinate of Michler's hydrol in a ganovanadium compound is reacted with an aromatic 45 suitable solvent therefor. 1 and 1A and coatings 19a and other component. a color precursor transferred from an adjacent back coating to the acidic selected from among those disclosed in U.S.S. 2 and 2A and coatings 44a Coatings 190.870. as dithiooxamide material described above and the acid . closed in the Phillips.632. Pat.287.185 discussed above. the Other initially colorless color forming systems which sole basis for choosing between one or another of the may be useful in connection with the present invention various chemical reactants disclosed above is the color include an alkali metal gallate-iron lactate salt system desired in the final copy produced by the colorless as disclosed in U. Other than this. reference is made to the reaction system.327. described above.516. with the acidic reactive components. No. '327 and ’185 patents in view of the that the first and second components of the first system fact that the Phillips. The acidic color forming hydroxy compound as disclosed in U. a system 40 copying system. 78a and 78b dance with the present invention in connection with a 60 preferably comprise nickel rosinate which has been Lewis acid-Lewis base reaction system is a system coated on the respective sheets by forming a solution of wherein diphenyl carbazide is reacted with nickel stea nickel rosinate which is applied to the sheets and the Tate. present invention in combination with the systems dis 25 for example.075. and systems wherein an alkali metal or 3. U.S. N. 3.981. This dithiooxamide material is dissolved in ammonium iodide solution is applied to a surface con 55 an appropriate solvent as in also described in Example taining a color forming iodine-reactive substance and 18 of the '846 patent.558.154. 3. 2.437.S. No. a metallic rosinate salt.S. Pat. and is microencapsulated. Coatings 190 of FIGS. 2 and 2A and system wherein the reactive components are chemi coatings 18a through 18h of FIGS. coatings 210. Matson. 1 and 1A and coatings 78a and referred to above are quite useful in connetion with the 78b of FIGS. 3. - phenylenediamine hydrochloride. the first component of the second system and systems are U.617. This procedure is also described generally in Ex sent invention. 1 and 1A. tonite-type clay material disclosed by Baxter in applica 4-aminophenylglycine hydrochloride.516. No. 2 and 2A may also comprise. Pat. Pat. a dithiooxamide material of the carbonless copying system. 3.523 10 normally coated on the fronts of the sheets with the the first initially colorless reactive component of a first color precursor material in a solvent.404. 1 For examples of a second initially colorless reaction and 1A.S.553.278.

as a reactive component thereof. 4. and allowed to dry. ond component of the system being incapable of said sheets being initially disposed with said upper interreacting to produce a colored mark. as reactive component thereof. together to bring the first and second components of said sheets being capable of rearrangement such that the second reaction system into said reactive contact to said initially lowermost sheet overlies said initially thereby simultaneously produce a second colored uppermost sheet with the front coating of the ini 65 mark. each of which is capable of having images capsules being rupturable upon application of said produced on opposite sides of its sheets. to produce a colored mark upon coming into reac 45 said first component of the second system and said tive contact. tially lowermost sheet disposed against the back said sheets being capable of rearrangement such that coating of the initially uppermost sheet. as a colored mark upon coming into reactive contact. said first component of the first system and said sec said first and second components of the second reac ond component of the second system being incapa tion system likewise being capable of interreacting ble of interreacting to produce a colored mark. said back coating of the middle sheet are forced together to bring the first and middle sheet and the front coating of the initially second components of the first reaction system into lowermost sheet are forced together to bring the said reactive contact to thereby produce a colored first and second components of the first reaction mark. 11 3. Obviously. A manifold set as set forth in claim 1 wherein a In view of the foregoing. a first reactive com reactive components thereof. upon back coating is disposed against said front coating 55 application of pressure to the stack. 14 and 16 and to each surface of ponents of the second reaction system into said sheet 29. and said back coating of the middle sheet and the system into said reactive contact to thereby pro front coating of the lowermost sheet are likewise forced duce a colored mark. . reactive component thereof. as a reactive component thereof. Thereafter. prising: 20 each of said sheets having front and back coatings a stack including at least three superimposed sheets. many modifications and variations of the 3. it can be seen that a simple coating of at least one of said sheets comprises a plural and economical yet highly effective manifolded set of ity of pressure rupturable microcapsules containing a carbonless copying papers is set forth in several em color forming reactive component thereof. - component thereof. said micro bodiments. It is therefore to be understood that within 15 pressure rupturable microcapsules which form a por the scope of the appended claims the invention may be tion of each corresponding coating. pressure to said stack. as a reactive 30 color forming reaction system. whereby. reactive component of a second initially colorless 35 said first and second components of the first reaction color forming reaction system and the back coating system being capable of interreacting to produce a of the initially uppermost sheet comprising. thereon. said front against the back coating of the middle sheet and . comprising. a slurry of acid-treated bentonite 5 reactive contact to thereby produce another col type clay. 25 forming reaction system. whereby upon application of the uppermost sheet and the front coating of the of pressure to the stack. coating of the initially lowermost sheet and the In the production of coatings 190. 19q and 19b. second component of the first system being incapa said first component of the first system and said sec ble of interreacting to produce a colored mark. colored mark upon coming into reactive contact. tion system likewise being capable of interreacting said first and second components of the first reaction 40 to produce a colored mark upon coming into reac system being capable of interreacting to produce a tive contact. said back coating of the lowermost sheet. a first and the initially lowermost sheet having a coating reactive component of a first initially colorless on its front surface. A manifold set of carbonless recording sheets com I claim: prising: 1. A manifold set as set forth in claim 1 wherein each invention are made possible in the light of the above of said first components are contained in a plurality of teachings. A manifold set of carbonless recording sheets com a stack including at least three superimposed sheets.523 12 treated bentonite-type clay material described earlier. posed against the front coating of the middle sheet and said middle sheet being initially disposed in overlying the back coating of the latter is disposed against the relationship to said lowermost sheet such that its front coating of the lowermost sheet. practiced otherwise than as specifically described. the back coating of the middle sheet comprising. as a reactive component thereof. whereby the front coating of the uppermost sheet is disposed upon application of pressure to the stack. and the front coating of the ini reactive component of a second initially colorless tially lowermost sheet comprising. may be applied to this microcapsular coating ored mark. a second reactive said first and second components of the second reac component of said second reaction system. as a the coatings of the middle sheet each comprising. the initially uppermost and the middle sheets each the coatings of the initially uppermost sheet each having a coating on their respective back surfaces comprising. 2. the back coating of the initially uppermost sheet are microcapsules may first be applied to the appropriate forced together to bring the first and second com surface of sheets 12. a second reactive ponent of a first initially colorless color forming component of said first reaction system and a first reaction system. a second reactive component the coatings of said initially lowermost sheet each of said first reaction system. a first system.981. a the front coating of the initially lowermost sheet also second reactive component of said second reaction comprising. most sheet overlying said middle sheet and with the said first component of the second system and said 50 latter overlying the lowermost sheet in such manner second component of the first system being incapa that the back coating of the uppermost sheet is dis ble of interreacting to produce a colored mark.

wherein each of said the first and second components of the first reac systems comprises separate initially colorless first and tion system into said reactive contact to thereby second reactive components which are reactable when produce another colored mark. whereby tion of each corresponding coating. said coating comprising an 5. pressure rupturable microcapsules which form a por 6. 3. said front 7. :k :k :k :: :k of said first components are contained in a plurality of 25 30 35 45 55 60 65 -- . upon application of pressure to the stack. A manifold set as set forth in claim 4 wherein a admixture of the first component of one of said coating of at least one of said sheets comprises a plural systems and the second component of another of ity of pressure rupturable microcapsules containing a said systems.981. A manifold set as set forth in claim 4 wherein each tion of each corresponding coating. and said front coat brought into reactive contact with one another to pro ing of the middle sheet and the back coating of the 10 duce a colored mark and wherein the first component lowermost sheet are likewise forced together to of each of said systems is incapable of reacting with the bring the first and second components of the sec second component of any of the other systems to pro ond reaction system into said reactive contact to duce a colored mark. said sheet comprising: thereby simultaneously produce another second a substrate layer. A manifold set as set forth in claim 7 wherein each capsules being rupturable upon application of said of said first components are contained in a plurality of pressure to said stack.523 13 14 the front coating of the latter is disposed against pressure rupturable microcapsules which form a por the back coating of the lowermost sheet. A sheet for use in connection with a manifolded set coating of the uppermost sheet and the back coat of carbonless forms wherein at least two initially color ing of the middle sheet are forced together to bring less reaction systems are utilized. said micro 8. and colored mark. color forming reactive component thereof. 15 a coating on said layer.