US3020171A

US3020171A - Pressure-sensitive record and transfer sheet material

Info

Publication number: US3020171A
Authority: US
Inventors: Joseph A Bakan; David J Striley; Maierson Theodore
Original assignee: NCR Corp
Current assignee: NCR Voyix Corp; National Cash Register Co
Priority date: 1960-08-26
Filing date: 1960-08-26
Publication date: 1962-02-06
Anticipated expiration: 1979-02-06
Also published as: DE1195335B; US3104980A; BE607355A; CH414698A; GB931885A; NL268635A

Description

Feb. 6, 1962 J. A. BAKAN ETAL PRESSURE-SENSITIVE RECORD AND TRANSFER SHEET MATERIAL Filed Aug. 26, 1960 FlG.l

JOHN DOE ACCOUNT NO. l2

Reacta nt Coating 26 Porous Base Coating With Reactant Coating 23 Receiving Sheet Porous Base Coating With Colorless Phototropic Dye Inclusions Colored Ink lnclusions Receiving Sheet FIG.3

FIG. 6

Porous Base Marked With Colored lnk Coating With Ink Inclusions Conl'aining Colored Dye and Pigment Receiving Sheet Marked With Colored Ink and Pigment INVENTORS JOSEPH A. BAKAN DAVID J. STRILEY a THEODORE MAIERSON THEIR ATTORNEYS 3,92%,171 Patented Feb. d, 1962 tire Filed Aug. 26, 1960, Ser. No. 52,195 14 Claims. (Cl. 11736.2)

This invention relates to pressure-sensitive record and transfer sheet material, and more particularly it relates to such materials which include a web base material, one side of which is coated with a rupturable coating containing minute droplets of a liquid marking material including a dye or coloring material carried in a lowviscosity, volatile vehicle; said marking material being so characterized that, upon being released from said coating by the rupture of the coating upon the application of printing pressure thereto in a desired configuration, it will bleed through, or penetrate, said web material according to the same configuration and thus produce either a latent mark or a visible colored mark on the surface of the web material on the side opposite that of the coated side, and when desired, part of the marking material may simultaneously be transferred to a receiving web in contact with the coating, to produce a similar mark thereon.

Coated pressure-sensitive sheets have been known in the past, but such sheets were so made that the ink would not bleed through, or penetrate, the web material to show printing on the front of such record sheets. The novel sheets of this invention have been so constructed that, by the use of certain materials in combination and by the manner of use of such materials, excellent printing on the top surface of a back-coated pressure transfer sheet has been made possible. At the same time, prints can also be made on a receiving sheet when it is placed in pressure-receiving contact with the coated side of said coated sensitive sheet.

The pressure-sensitive record and transfer sheet of the present invention is particularly useful and adapted for use with printers utilizing letter press or embossed type members. One such use is in printers for making inipressions from embossed identification or charge-authorizing plates. In prior-art printers of this type, the plate was placed in printing position, the sheet to be printed was placed over the plate, and a pressure roller was passed over the sheet, the print being obtained either from ink contained in the pressure roller or from an ink ribbon used in conjunction with the roller. If more than one copy was desired, the above printing would serve only the top sheet, and it would be necessary to intersperse transfer material between other sheets to obtain the additional copies.

in contrast to the use of ink ribbons or inked rollers and interspersed transfer material, as required by priorart printers mentioned above, the ink ribbons or inked rollers and interspersed transfer material are not required when the novel pressure-sensitive record and transfer sheets are used, because the single coating on the back of the recording and transfer sheet produces the print usually obtained from the ink ribbon or inked roller and also produces the transfer print on a second sheet which was usually obtained from the interspersed transfer material. Thus, the single coating enables two distinct prints to be made simultaneously in a single printing operation.

The novel record and transfer sheet consists of a base web of ink-porous material and a rupturable coating on one side thereof, which coatingcontains entrapped liquid droplets of marking material consisting of'coloring material in a quick-drying, low-viscosity vehicle. When printing pressure is applied to the sheet to rupture the coating according to a desired configuration, marking material escapes from the ruptured coating and bleeds through, or penetrates, the porous web material by capillary action and adsorption, or by other phenomena, and so produces a corresponding mark on the surface opposite the surface coated with the entrapped coloring material, without requiring exteriorly-applied ink. At the same time, if the novel coated record element is superimposed over a receiving sheet, rupture of the coating will also provide marking material for deposition and adsorption on and in the web material of a receiving sheet without requiring a separate interleaved sheet of transfer material. Obviously, and of great importance, is the fact that the coated sheet alone maybe used as a record material. However, a preferred form, and the form in which such record materials are advantageously used, consists of the novel sheet as a first sheet superimposed over and in contact with a receiving sheet which serves as a copy'sheet. i

i The coloring materials or dyes which may be included in the coating on the novel sheet record material herein contemplated may be colored or colorless. The one type of colorless dyes, as will be shown hereinafter, produces a distinctive color when adsorbed on an acid clay or like material and, when used, requires that a reactant coating of acid clay or like material be provided on the front of the record and transfer sheet and/or the receiving sheet where printing is desired. Another type of colorless dyes is soluble phototropic colorless compounds which in solution are colorable by subjection to electromagnetic radiation. The colored dyes must be so characterized as to be readily adsorbed aswell as readily absorbed by' the web base material, and any oil-soluble colored dye, or water-soluble dye, with these character istics may be used. It is also within the scope of this invention to combine finely-divided organic or inorganic colored pigment with either the colored or the phototropic dyes mentioned above, and, when such are so used, the resulting color is a blend of the colors individuaily produced by the organic coloring material or dye and that produced by the pigment. Similarly, colored, colorless phototropic, and colorless color-reactant dyes may be combined to produce either the color of the colored dye or the blend of the colors'produced by the colored and the color-forming dyes.

The common denominator of all the various modifications mentioned above is that, upon rupture of the coating containing the entrapped liquid marking or coloring material coated on the back of the novel pressuresensitive sheet, said marking or coloring material is released to produce a visible or latent mark on the front of said sheets by penetrating and permeating the web structure of said sheets, and a corresponding mark may be obtained on a copy-receiving sheet by transfer of the colorforming materials thereto, said marks having the same configuration on both sheets according to the configuradispersed or dissolved in a volatile vehicle, wherein, upon rupture of the coating, as by a printing element or scribe, a pontion of said marking material will penetrate through the web material and produce a corresponding mark on 'the other side of said novel coated material, and, when the coated side of said novel coated material is placed in direct pressure contact with a copy-receiving sheet, another portion of the marking material will cause a similar mark on the surface of said receiving sheet, thereby providing two marks from a single coating containing marking material.

Another object of the invention is to provide a pressure-sensitive record material on the top surface of which marks of a distinctive color may be produced by the application of localized pressure thereon alone, such as by a printing member, the colored mark having the configuration of such locally-applied pressure, said material consisting of a web material coated on its bottom surface with encapsulated coloring material dispersed in a volatile liquid vehicle, which material is released upon rupture of said capsules so as to penetrate and permeate the web sheet and produce a distinctive colored mark on the top surface of said sheet.

In another form of the invention, the object is to use developable colorless marking material which later is developed to cause the marks to be visible.

Further objects will become apparent from the drawings and the following detailed description of the preferred and several other embodiments of the invention.

The various inventive features of this invention can best be understood by reference to the accompanying drawings, which graphically disclose several embodiments of the invention on an enlarged scale and in diagrammatic form.

FIG. 1 shows a two-sheet form-set embodying the invention, showing printing marks on the top surface of a bottom-coated sheet and corresponding marks on the top surface of a receiving sheet placed in contact with said coated surface.

FIG. 2 shows an enlarged cross-sectional view of one embodiment of a form-set wherein a matrix coating ma terialcontains liquid droplets of a colored dye.

FIG. 3 shows another embodiment similar to that of FIG. 2, except that no receiving sheet is shown used in conjunction with the top sheet, this view showing the mark made by passage of the released liquid colored marking material through the porous web.

FIG. 4 shows yet another embodiment, wherein the coating on the rearv surface contains a colorless dye which coacts with a separate reactant coating on the front surface, or on the surface of a copy-receiving sheet, to produce a colored mark.

FIG. 5 shows an embodiment similar to that of FIG. 4, except that no receiving sheet is used with the top sheet.

FIG. 6 is another embodiment, wherein the droplets of coloring material contain a dye solution and a pigment dispersed therein.

FIG. 7 is an embodiment of the invention in which the droplets of marking material consist of a colorless phototropic material dissolved in a colorless volatile solvent, such leaving a solution mark that can be developed by subjection to electromagnetic radiation, so as to become colored.

Referring to FIG. 1, there is shown therein a plan view of a form-set consisting of a top sheet 10, coated on its underside with a coating 11, containing a profusion of minute droplets of coloring material in a pressurerupturable matrix, which top sheet is superimposed over a copy-receiving sheet 12, with the coating in contact therewith. This combination of a bottom-coated top sheet and a receiving sheet, when pressure is applied by any suitable pressure-printing means, as, for example, when the sheets are pressed against an embossed identification plate or printed on by another embossing element, such as a scribe or ,a stylus, will produce similar sharp distinctively-colored marks, in the event that a colored marking fluid is used, in the shape of the characters made by the printing means, on the top surface of both the top sheet and the bottom copy-receiving sheet, as clearly shown. The matrix may be of continuous nature or discontinuous, such as a coating made of minute capsules.

One embodiment of a form-set consisting of a combination of sheets according to the invention is shown in FIG. 2. In this arrangement, a top sheet 10, of porous material, is provided with a pressure-rupturable matrix coating Jul, containing minute droplets of colored dye material, which coated top sheet is superimposed on a receiving sheet 12. The top sheet is sufficiently opaque to mask the colored coating and is of such a color as to provide a good contrast with the colored dye which is to make the mark thereon. As is clearly shown in FIG. 2, when pressure is applied on the top sheet 16' by an element, such as the stylus 14, the pressure ruptures the matrix material in a defined area 17, thereby releasing the colored ink droplets contained in the said matrix coating, which ink is so constituted and is provided in suflicient quantity that it penetrates, as shown inthe area 16, through the base material of the top sheet 1% to form a colored mark on the opposite surface thereof, as at 15. The ink is also of such a character, as will be described later, that it dries very rapidly and prevents lateral bleed in the base material, so that a clearly-defined colored printed mark appears on the top surface of the top sheet. A portion of the colored ink released by the rupture of the matrix coating in the area 17 is transferred to the surface of the receiving sheet 1.2 to produce a colored mark 13.

The liquid droplets of color-containing, quick-drying, low-viscosity marking material, or ink, which enable the two prints to be obtained, may be applied to the top sheet by any suitable coating means which can entrap and retain the liquid droplets. One such suitable coating arrangement may consist of a continuous polymer film which contains the liquid marking material as droplet inclusions which escape when the matrix is locally ruptured, as disclosed in United States Patent No. 2,374,862, which issued on the application of Barrett K. Green on Mayl, 1945. Another suitable arrangement may consist of minute pressure-rupturable capsules distributed in profusion in a small amount of a binder, as shown in United States Patent No. 2,712,507, which issued on the application of Barrett K. Green on July 5 1955, which capsules entrap and retain the color-containing, quickdrying, low-viscosity marking material and are of such a size and profusion in the coating as to enable the two prints to be made. I

FIG. 3 shows an arrangement similar to that of FIG. 2, without the copy-receiving sheet, the coated sheet being used only as a record member, without any of its transfer features being utilized, the print appearing only i on the top of the coated sheet.

FIG. 4 is an enlarged cross-sectional view of still an- 7 other arrangement embodying the invention; In this arlactone, dissolved in solvent, and has on its top surface a reactive coating 22, such as attapulgite clay particles, which reacts with said coloriess marking material to pro duce a distinctively-colored mark. This double-coated sheet, when superimposed on a receiving sheet 23, which is coated with reactive material 24, is also capable of developing a mark on the receiving sheet when wet with the transferred colorless marking material. As in the case of the embodiment of FIG. 2, pressure applied at the point 26 ruptures the coating at 25, thereby allowing that portion of the therein-contained colorless marking material to penetrate through the web and react with the reactive coating 22 to produce a mark 26 on the surface of the top sheet. A portion of the colorless marking material so released is also deposited on the reactive coating 27 on the receiving sheet 23 to produce a similar mark. In this form of the invention, the base sheet can readily mask the colorless color-forming material in the coating, and greater leeway is possible in the types of base material which may be used for the sheet.

FIG. 5 is a cross-sectional view of an arrangement of sheets similar to that shown in FIG. 4, but the arrangement of FIG. 5 is used only as a record member and is shown without a coated receiving sheet.

FIG. 6 is an enlarged cross-sectional view of still another arrangement embodying the invention. In this arrangement, the top sheet 3% has coated on its bottom surface a coating 31, containing liquid inclusions of coloring material comprising a colored dye and a finely-divided colored pigment. This bottom-coated sheet is superimposed over an uncoated receiving sheet 33. This particular arrangement enables pressure applied to the surface of the top sheet, as at 35, to rupture the coating in the area 34, and thus release the liquid coloring material, so that the colored dye marking material contained therein will penetrate the paper to produce a distinctivelycolored mark at 35 on the top of the sheet, the color of the mark being that of the colored dye, most of the pig ment being ltered out by the web material. A major amount of the colored pigment which was contained in the ink marking material, together with a portion of the colored dye, will be transferred to the receiving sheet 33 and produce a distinctively-colored mark 36 thereon, the color of the mark so produced having a color corresponding to the composite color of the dye and the pigment.

It can be seen that the various arrangements provide means for producing a mark of any desired color on the surface of the top sheet as well as a ditferent-colored or the same-colored mark on the surface of the copy-receiving sheet. For example, it may be desired to have a blue mark on the surface of the top sheet and a corresponding blue-black mark on the surface of the copy-receiving sheet. Such desired result is readily obtained With a top sheet which is bottom-coated with entrapped liquid ink droplets containing blue colored dye and a black pigment. Any other color combination can be obtained by the proper selection and combination of dye and pigment.

In FIG. 7, the droplets 21a enclosed within the coating matrix contain a solution of a phototropic dye such as 1,3,3 trimethyl 6' nitro-spiro(2H-1'-be-nzopyran-2,2- indoline) and others described in a commonly-assigned application for United States Letters Patent, Serial No. 654,578, filed April 23, 1957, by Elliot Berman, now United States Patent No. 2,953,454, issued September 2t), 1966. The crushed coating releases the colorless liquid 25a, which migrates through the porous web 26a to appear as a colorless mark 26a consisting of the oily liquid which has escaped. This oily mark can be converted to a visible colored mark by irradiation with ultraviolet light 27a.

In .order that the various record and transfer systems described in the specification and shown diagrammatically in FIGS. 1 to 7 inclusive perform the functions contemplated in the present invention, it is essential that the base web material, vehicle, coloring materials, and coating or encapsulating materials each comply with certain broad requirements.

In its broad scope, this invention contemplates the use of any specific material within the above genericallydefined materials, which, when used in accordance with the arrangements described herein, will provide a lowviscosity ink comprising a volatile solvent capable of penetrating a web base material coated on one side with said ink in such manner and in such quantity as to produce a visible colored mark or a potentially visible mark on the side opposite the ink-coated side of the base material.

In general, any porous web material may be used as base sheet material. However, the preferred materials are fibrous and generally cellulosic in nature, such as paper, since these materials provide excellent uniformity of fiber structure and thus promote an even and homo geneous penetration of the web material by the coloring material. Equivalent results are obtained by the use of any other porous web materials having the strength, adsorption, and wetability of paper, as well as other characteristics similar to those of paper. For example, such materials may be cellulose, degenerated cellulose, fibrous cellulose acetate, and suitably woven fabric derived from cotton, wool, or similar natural fibers, and equivalents thereof.

Regardless of the particular material used as a porous base member, it must be such as to be sufficiently porous to allow the ink vehicle to readily penetrate and migrate through the thickness of the web structure; yet, it must be dense and compact enough so that the ink vehicle will penetrate the web material in a uniform manner. It must also be sufficiently dense and compact to mask the ink coating, particularly when such coating contains a colored dye or pigment, and be of such a color as to provide a sharp contrast between the colored mark and the web material base.

The thickness of the porous web sheet may vary over a Wide range. As is readily apparent, the thicker the web sheet the more coloring material must be released from the coating to provide enough of said coloring material to penetrate through the sheet and still produce a colored mark with optimum contrast and intensity on the side opposite said coated surface. In general, the amount of coloring material is controlled either by varying the size of the ink-containing droplets or droplet-containing capsules, or by varying the number of coating-ink-containing capsules per unit area, or by the control of both factors. In those instances where thick web base material is desired, it is preferred that the ink material be distributed in a coating consisting of capsules larger than those which would be used for thinner web material.

It can thus be seen that the coating weight and droplet or capsule size may be varied between wide ranges so long as the quantity of coloring material is so adjusted to the requirements of the particular web base material that a satisfactory print is produced on its top surface by penetration of coloring material through the web from a coating of liquid entities of coloring material on the opposite surface. Coating weights of from 1 to 50 pounds per ream of sheets measuring 24 by 36 inches, containing capsules ranging 'in size from about 5 microns to 500 microns, provide satisfactory results in accordance with this invention. When normal-Weight typewriting sulphite paper, for example, is the web material, coating weights of from 5 to 15 pounds per ream, and preferably 5 to 10 pounds per ream, of compositions containing capsules having a size up to 40 microns, preferably 5 to 30 microns, have been found to yield excellent prints. Any combination or paper thickness, capsule size, and amount of coating which supplies sufficient coloring material to produce a colored mark on the surface of the top sheet of the arrangements disclosed herein will be effective in the practice of this invention.

As previously set forth, this invention provides a web.

material coated on one side with matrix-encased droplets of marking liquid which is so characterized as to volatility, viscosity, and quantity per unit area that, upon release of the liquid by rupture of said matrix material, it will quickly and readily penetrate the web material by capillary and other surface forces to produce a colored mark on the surface of the opposite side. The above desired characteristics are imparted to the ink by including selected solvents therein, preferably high-volatility, low-viscosity solvents. It is generally desirable that such solvents be present in large amounts, preferably in a major amount based on the weight of the liquid ink. Ink formulations so prepared have sufliciently low viscosity to readily penetrate the web materials of this invention. Although no particular viscosity is to be considered as essential, since it may vary depending on the characteristics of the web material, the type of ink, and the concentration thereof, as well as with the amount of solvent, desired results are obtained with an ink viscosity of between .3 and 20 centipoises, and preferably between .4 and 2.5 centipoises. Other liquid formulations which contain low-volatility, high-viscosity solvents are also within the scope of the invention; however, when such solvents are included, it is generally preferred that the liquid contain at least 80%, by weight, of the high-volatility solvent based on the total liquid weight. Marking liquids constituted as above will readily penetrate the porous pressure-sensitive web materials of this invention and, in addition, upon reaching the surface on which a colored mark is to be registered, will quickly dry due to rapid evaporation of said high-volatility solvents.

While it is desired to exclude theoretical considerations, it may be further explained that, as the ink reaches the surface of the record sheet, the volatile ingredients therein immediately evaporate, so that the coloring components are readily absorbed in and/or adsorbed on the web material. This action eifectively prevents the ink from bleeding laterally upon reaching the top surface of the record ortransfer sheet and, thus, results in the formation of characters which are sharply defined and which accurately represent the area and configuration outlined by the printing pressure element which is applied in forming the characters.

Any volatile solvent which meets the requirements outlined above and which, in addition, will dissolve the colored and colorless oil-soluble dyes disclosed herein will (give excellent results. While tetrachloroethylene is the preferred sovent, such solvent and solvent mixtures as the following produce equivalent results when used in accordance with this invention.

(10) Mixture of chlorinated diphenyl with at least a major proportion of any one of the above solvents or mixtures thereof.

While emphasis has been placed on the use of oilsoluble dyes, the invention is not to be deemed limited to such, as water-soluble dyes may be included in coatings such as those disclosed in United States Patent No. 2,299,694, which issued on the application of Barret K. Green on October 20, 1942, and which is concerned with the entrapment in an oil-soluble polymer film of liquid inclusions of, for instance, malachite green or other watersoluble dyes.

As described earlier, the marking material may include colored dyes and pigments and colorless color-forming dyes alone or in combinationwith colored dyes according to the type of recording and transfer sheets desired. Some suitable colored dyes which may be used are Hysol Blue B 200%, Hysol Blue SS, and Oil Black BT, which are used in Examples 1, 4, and 6, respectively, to be given hereinafter; also oil-soluble Nigrosine (Colour Index No. 864); A20 Blue Black (as disclosed in United States latent No. 2,090,938); Azo-OihBlue-Black B; oil brown DN; Sudan II; and Sudan III. Colorless colorforrning dyes which may be used advantageously in accordance with this invention, such as those shown in the arrangements of FIGS. 4 and 5, are organic leuco dye compounds such as Crystal Violet Lactone, Benzoyl Leuco Methylene Blue, and N-(2,5-dichlorophenyl) leucauramine, which color compounds are originally colorless but which become distinctively colored when absorbed on acid clay materials such as attapulgite or like acid complex aluminates, such as natural or artificial metallic zeolite materials; These and other similar suitable dyes are disclosed in United States Patents Nos. 2,646,367; 2,714,074; Re. 23,024; and 2,828,341. Other color-forming compounds which may be used are phototropic (sometimes designated photochromic) colorless dyes that assume a colored form when activated by radiant energy. Some of these are described in commonlyassigned application for United States Letters Patent, Serial No. 827,420, filed by Elliot Berman on July 14, 1959.

If ultra-fine pigments, such as, for example, channel black, a very fine carbon black ranging in particle size from a few rnillimicrons to about forty millimicrons, are

dispersed in the liquid vehicle, or if such pigments are separately encapsulated as liquid-dispersed solids and coated on the web material while closely associated with separately encapsulated liquid coloring materials, rupture of both kinds of said capsules will allow the vehicle so released to penetrate the web material, and, in so doing, the vehicle will further perform the function of carrying a portion of such ultra-fine pigments to the top surface of said sheet. The effect of such pigments on the color of the mark so produced will depend on several variables, the most important being pigment size and color, color and amount of dissolved dye, and characteristics of the paper and the vehicle. All of the above generally-described embodiments and other equivalents apparent to those skilled in the art are deemed to be within the scope of this invention.

In practice of this invention, as hereinbefore described, it is necessary that the various coloring materials used be coated on a surface of a porous web material. For this purpose, any conventional coating method, such as brushing, spraying, dipping, rolling, and, preferably, air-knife coating, is'satisfactory. The coating is generally of such a nature that it contains a profuse number of small droplets of liquid coloring material held in a polymeric protective material, such as those disclosed in United States Patents Nos. 2,550,466 to 2,550,469 inclusive, except for the novel volatile low-viscosity vehicle of applicants invention, which enables the ink to penetrate the web material.

A desirable capsular coating composition for usewith the marking liquid of this invention may be made according to the method disclosed in United States Patent No. 2,800,457, which provides a composition containing capsules consisting of a wall of hydrophilic film-forming colloid material deposited around small droplets of waterimmiscible material, said deposits having been caused by coacervate forces.

The following examples will illustrate various methods of encapsulation which are particularly advantageous for encapsulating the above-described coloring materials to be used in accordance with this invention; It is to be understood that these examples are merely illustrative of preferred methods and are not to be deemed as limiting the invention to any particular method of encapsulation or to the use of any particular coloring material, solvent, or capsular wall-forming material.

Example 1 An internal phase, of an intended emulsion, having the following composition is first prepared by making a solution, in parts by weight, of

48.5 parts of xylene 48.5 parts of tetrachloroethylene 3.0 parts of Hysol Blue B 200% [1,4-bis (n-butylamino) anthraquinone dye] A first sol of 11%, by weight, aqueous gelatin with isoelectric point at pH 8.9 is prepared, and the pH of the sol is adjusted to 9 with 10% aqueous NaOH. Then 96 grams of the internal phase is mixed with 109 grams of the gelatin sol and emulsified to a drop size of up to 10 microns. A second sol, consisting of 11%, by weight, aqueous gum arabic, is also prepared. Next, 109 grams of this second sol is dispersed in 786 grams of water, and the pH of the solution is then adjusted to 9 with 10% aqueous NaOH. The temperatures of the emulsion and gum arabic sol are adjusted to 50 degrees centigrade, and the sols are then mixed, with stirring, at that temperature. Complex colloid-rich coacervate material derived from the sol mixture is then formed and caused to deposit around the emulsified droplets of the internal phase by adjusting the pH of the mixture to 4.7 by the slow addition of 10% aqueous acetic acid, with continuous stirring, while the temperature is maintained at 50 degrees centigrade. The resultant liquid coacervate walls deposited around the droplets of the internal phase are gelled by cooling the system to 10 degrees Centigrade. Thereafter, 10 ml. of 25% aqueous glutaraldehyde is slowly added at this temperature to harden the complex colloid capsule wall, the stirring being continued for 20 hours.

A coating of 10 pounds per ream, of sheets 24 by 36 inches, of the composition of this example is applied with a Baker applicator to a sheet, per ream, of 12-pound fibrous sulphite and dried. The coating applied is shown as coating 11 in the arrangements of FIGS. 2 and 3.

Example 2 Example 1 was repeated with the following internal phase, in parts by weight:

2.5 parts of benzoyl leuco methylene blue 2.5 parts of crystal violet lactone 95 parts of xylene A coating consisting of capsules containing this internal phase was used to make a system according to FIGS. 4 and 5.

Example 3 Example 1 was repeated with the following internal phase, in parts by weight:

3 parts of 2,5-dichlorophenyleucauramine 97 parts of xylene A coating consisting of capsules containing this internal phase was used to make a system according to FIGS. 4 and 5.

10 Example 4 An internal phase of an intended emulsion is first prepared by dissolving a dye in a mixed solvent, the final composition consisting of:

3% Hysol Blue SS (a :50 by weight mixture of 1,4- bis (n-butylarnino) anthraquinone o N-OH CHziCHqCHa and l N methylamino-4-N-isopropylamino anthraquinone) i NOH:

u 0 ripen H CH5 15% Arochlor 1221 (21% chlorinated diphenyl); and 82% tetrachloroethylene.

A mixture of the following is prepared:

The temperature of the mixture is adjusted to 40 de grees centigrade, and the pH is then adjusted to 9 by the addition of 10% aqueous NaOH.

Then, 1120 grams of the internal phase is emulsified to a drop size ranging from about 5 microns to about 20 microns in 1260 grams of an 11%, by weight, aqueous gelatin (iso-electric point pH 8.9) solution while maintained at 40 degrees centigrade, the pH of which has previously been adjusted to 9 with 10% NaOH. The emulsion then is added to the aqueous gum-arabic-polyethylene-maleic-anhydride polymer solution, the pH being reduced to 7.5 with 10% aqueous acetic acid, and with stirring, after which the system is cooled to 10 degrees centigrade in an ice bath, forming gelled capsules. To harden the capsule wall material which has gelled around each of the internal phase droplets upon cooling the system, 69.3 mls. of 25 by weight, aqueous glutaraldehyde is added while the dispersion is stirred. Stirring is continued for about 20 hours while the temperature is allowed to rise slowly to room temperature, at which time the dispersion of hardened capsules is coated on suitable we'b material in the manner of Example 1.

Example 5 The procedure and materials of the previous example were used except for the substitution of the following internal phase for that shown therein, in parts, by weight:

2% parts of benzoyl leuco methylene blue 2 /4 parts of crystal violet lactone 15 parts of Arochlor 1221 (21% chlorinated diphenyl) 80.5 parts of tetrachloroethylene Example 6 160 mls. of an internal phase consisting of, in parts by weight:

3 parts of Oil Black BT (Colour Index No. 26150) 97 parts of tetrachloroethylene is emulsified at 40 degrees centigrade to a drop size of about 10 microns in 180 grams of an 11%, by weight, aqueous gelatin (iso-electric point at pH 8.9) solution which has been adjusted to pH 9 with 10% aqueous NaOI-I. Next, a solution consisting of the following is made up:

After adjusting the temperature of the solution to 50 degrees centigrade and the pH to 9 with 10% aqueous NaOH, it is added to the emulsion with continuous stirring. To this mixture, which is constantly stirred, 10% aqueous acetic acid is added to adjust the system to a pH of 4.6 to form capsules with liquid walls, the system then being cooled with continued stirring to a temperature of 10 degrees centigrade to gel the capsule walls. Finally, the system is allowed to stand overnight, with continuous stirring, after first adding 10 mls. of aqueous glutaraldehyde to harden the capsules. The encapsulated dye composition is coated on porous web material as in Example 1.

. Example 7 Example 1 is repeated except for the substitution of the following internal phase, in parts by weight, for the internal phase shown therein:

3 parts of 1,3,3-trimethyl-6-nitro-spiro(2H-1-benzopyran-2,2-indoline) [1,3,3 trimethylindolino-6-nitrobenzopyrylospiran] (a phototropic dye disclosed in application for United States Letters Patent, Serial No. 654,578, filed by Elliot Berman on April 23, 1957, now United States Patent No. 2,953,454, issued September 1 20, 1960); and I 97 parts of o-diethylbenzene.

The encapsulated ink composition of this example is coated as in Example 1 to provide the ink coating 21a as shown in FIG. 7. Localized rupture of the dye-containing capsules by the application of pressure with an Example 4 was repeated except for the substitution of the following internal phase, in parts by Weight, for the internal phase shown therein:

3 parts of Oil Black BT (Colour Index No. 261.50) 20 parts'of carbon black (particle size 1 to 3 microns) 77 parts of xylene 12 This composition was used to provide the ink coating in the arrangement shown in FIG. 6.

Example 9 An internal phase of an intended emulsion consisting of a solution of the following, in parts by weight:

52.5 parts of Aroclor 1242 (42% chlorinated diphenyl);

52.5 parts of Cosol No. 2 (White refined aromatic solvent obtained from coal tar distillation having a distillation range of degrees to 270 degrees centrigrade;

3.03 ports of Crystal Violet Lactone; and

2.52 parts of 'benzoyl leuco methylene blue.

is added to a solution consisting of the following, in parts by weight:

164 parts of 11% aqueous gelatin (iso-electric point at pH 8.9) solution previously adjusted to pH 6.5 with 20% NaOH and thereafter maintained at- 55 degrees centigrade V 25 part of 2% aqueous solution of polyethylene-maleicanhydride copolymer as defined in Example 4, above 2 parts of 5% aqueous solution of Armac HT, a dispers ing agent consisting of a mixture of 25% hexadecyl amine acetate, 70% octadecyl amine acetate, and 5% octadecenyl amine acetate.

The m xture is agitated in suitable apparatus, such as a Waring Biendor, until the immiscible dye containing droplets of the internal phase are reduced to a size of about 10 microns or less. The emulsion so formed is blended with a mixture of 124.6 grams of an 11% aqueous gum arabic solution maintained at 55 degrees centigrade, the pH of which has previously been adjusted to 9 with 20% NaOH, and 700 grams of Water. While being stirred, the pH of the resulting mixture is first adjusted to 9 and then slowly reduced to 4.5 by the dropwise addition of 14% acetic acid. Thereafter 9 mls. of glutaraldehyde is added to the mixture after it has first been chilled to 10 degrees centrigrade. One hour later, 14 mls. of 5% aqueous methyl vinyl ether-maleic anhydride copolymer solution, previously adjusted to pH 9, is added to this mixture. The specific viscosity of the copolymer ranges from .8 to 1.2 when measured in methyl ethyl ketone at 25 degrees centigrade with a modified Ostwald viscosimeter (ASTM-D445-46T).

One hour after the copolymer addition, 20% NaOH is slowly added to the mixture, while stirred, until a pH of 9 is attained, the stirring being continued overnight. The small hardened ink-containing capsules 'so produced are concentrated to a dispersion containing 25 solids.

A coating of 15 pounds per ream (25 inches by 38 inches) of this compositionwas applied with a Gardner bar to the bottom side of a 9-pound manifold paper, the top side of which was coated with reactive clay; e.g., attapulgite. When this sheet was placed with the ink coating in contact registry with the clay coating on another sheet of paper, rupture of the ink-containing capsules by the application of localized pressure to the sheets so arranged produced sharp and distinct bluecolored marks on the top surfaces of both sheets, the arrangement corresponding to that of FIG. 4.

If the capsules contain more than enough ink to form the print on the top surface of the ink-coated sheet, a further similar mark may be formed on an oversheet placed on the top of the ink-coated sheet, the excess ink being transferred from the top surface. of said inkcoated sheet to said oversheet.

While the various embodiments, ingredients, and

methods described above are well adapted to fulfill the stated objects of the invention, it is to be understood that those enumerated are merely illustrative, and that the invention is not to be deemed limited thereto, for numerous changes may be made in the operation, arrangements, and'materials above disclosed without departingfrom the spirit of the invention, as defined in the following claims.

What is claimed is:

1. A combined record and transfer material consisting of a porous base member and a rupturable coating on one side of the member, said coating containing a profusion of entrapped liquid droplets of ink, which ink is made up of coloring material in a vehicle capable of readily penetrating the pores of the base member, the droplets being of such a size and present in such profusion as to supply suificient ink upon rupture of the coating according to a desired configuration to enable a portion of said ink to penetrate through the porous base member to produce a mark of the same configuration on the side of the base member opposite the coated side, and to enable a further portion of the released ink to be deposited in the same configuration to produce another mark on another surface in contact with the coated surface of the member.

2. The combined record and transfer material of claim 1 wherein the porous base member is paper.

3. A pressure-sensitive record and transfer system consisting of a porous base member and a coating on one side of the member, said coating containing a profusion of entrapped liquid droplets of ink, which ink contains coloring material in a low-viscosity quick-drying vehicle capable of readily penetrating the pores of the base member, the coating containing the droplets being pressure-rupturable and the droplets being of a size and profusion to supply sufficient ink upon rupture of the coating in a particular configuration to enable a portion of said ink to penerate through the porous base member to produce a visible mark of the same configuration on the side of the base member opposite the coated side, and to enable a further portion of the released ink to be deposited in the same configuration on another surface in contact with the coated surface of the member.

4. A pressure-sensitive record material consisting of a porous base member and a coating on one side of the member, said coating containing a pro-fusion of entrapped liquid droplets of ink, which ink is made up of coloring material in a low-viscosity quick-drying vehicle capable of readily penetrating the pores of the base member, the coating containing the droplets being pressure-rupturable and the droplets being of a size to supply sufficient ink upon rupture of the coating in a particular configuration to enable said ink to penetrate through the porous base member to produce a visible mark of the same configuration on the side of the base member opposite the coated side.

5. A pressure-sensitive record and transfer material consisting of a porous base member and a coating on one side of the member, said coating containing a profusion of encapsulated liquid droplets of ink, which ink contains coloring material in a vehicle capable of readily penetrating the pores of the base member, the capsules containing the droplets being pressure-rupturable and of a size and profusion to supply sufiicient ink upon rupture of the capsules by pressure applied according to a desired configuration to enable a portion of said ink to penetrate through the porous base member to produce a visible mark of the same configuration on the side of the base member opposite the coated side, and to enable a further portion of the released ink to be deposited in the same configuration on another surface in contact with the coated surface of the member.

6. A pressure-sensitive record material consisting of a porous base member and a coating on one side of the member, said coating containing a profusion of encapsulated liquid droplets of ink, which ink contains coloring material in a vehicle capable of readily penetrating the pores of the base member, the capsules containing the droplets being pressure rupturable and the droplets being of a size and profusion to supply suflicient ink upon rupton of the coating by pressure applied according to a desired configuration to enable said ink to penetrate through the porous base member to produce a visible mark of said configuration on the side of the base member opposite the coated side.

7. A pressure-sensitive record and transfer material consisting of a porous base sheet and a coating on one side of the sheet, said coating containing a profusion of entrapped liquid droplets of ink, which ink is made up of at least one colored dye in a vehicle capable of readily penetrating the pores of the base sheet, the porous base sheet being opaque and masking the colored coating and being of a color which contrasts with the color of the dye, the coating containing the droplets being pressure-rupturable and the droplets being of a size and profusion to supply sufficient ink upon rupture by applied pressure according to a desired configuration to enable a portion of said ink to penerate through the porous base sheet to produce a visible mark of the color of the dye and of said configuration on the side of the base sheet opposite the coated side, and to enable a further portion of the released ink to be deposited on a surface of another sheet in contact with the coated surface of the base sheet to produce thereon a mark of the color of said dye and of said configuration.

8. A pressurre-sensitive record and transfer material consisting of a porous base sheet and a coating on one side of the sheet, said coating containing a profusion of encapsulated liquid droplets of ink, which ink is made up of at least one colored dye in a quick-drying lowviscosity vehicle capable of readily penetrating the pores of the base sheet, the porous base sheet being opaque and masking the colored coating and being of a color which contrasts with the color of the dye, the capsules containing the droplets being pressure-rupturable and of a size and profusion to supply suificient ink upon rupture by applied pressure according to a desired configuration to enable a portion of said ink to penetrate through the porous base sheet to produce a visible mark of the color of the dye and of said configuration on the side of the base sheet opposite the coated side, and to enable a further portion of the released ink to be deposited on a surface of another sheet in contact with the coated surface of the base sheet to produce thereon a mark of the color of said dye and of said configuration.

9. A pressure-sensitive record and transfer material consisting of a porous base sheet having a coating of a first reactant material on one side of the sheet "and having a rupturable coating on the other side of the sheet, said rupturable coating containing a profusion of entrapped liquid droplets of ink, which ink includes a. colorless color-reactant material dissolved in a vehicle capable of readily penetrating the pores of the base sheet, said colorless color-reactant material forming a color when reacting with said first reactant material, the droplets being of such a size and in such profusion as to supply sufficient ink upon rupture of the coating by pressure applied according to a desired configuration to enable a portion of said ink to penetrate through the porous base sheet "and react with said first reactant material to produce a visible colored mark of said desired configuration on said one side of the base sheet, and to enable a further portion of the released ink to be deposited on a surface of a further sheet, which is coated with said first reactant material and which is in contact with the inkcarrying coating of the double-coated sheet to produce a similar mark on the further sheet.

10. A pressure-sensitive record and transfer material consisting of a porous base sheet having a coating of a first reactant material on one side of the sheet and having a rupturable coating on the other side of the sheet, said rupturable coating containing a profusion of entrapped liquid droplets of ink, which ink includes a dye of one color and a colorless color-reactant dye dissolved in a quick-drying low-viscosity vehicle capable of readily penetrating the pores of the base sheet, said colorless colorreactant dye forming a second color when reacting with said first reactant material, the droplets being of such a size and in such profusion as to supply sufficient ink upon rupture of the coating by pressure applied according to a desired configuration to enable a portion of said ink to penetrate through the porous base sheet and carry the colored dye and the color-reactant dye to said first reactant material to produce a visible mark of the combined colors and of said desired configuration on said one side of the base sheet, and to enable a further portion of the released ink to deposit the colored dye on a surface of a further sheet, which is in contact with the inkcarrying coating of the double-coated sheet to enable the colored dye to produce a similar mark of said one color on the further sheet, whereby two-color printing is obtained from the same ink-bearing coating.

11. A pressure-sensitive record and transfer material consisting of a porous base sheet having a rupturable coating on side side thereof, said rupturable coating containing a profusion of entrapped liquid droplets of ink, which ink includes a colored dye dissolved in a quickdrying low-viscosity vehicle capable of readily penetrating the pores of the base sheet and also includes finely-divided colored pigment dispersed in the vehicle, the droplets being of such a size and in such profusion as to supply sufiicient ink upon rupture of the coating by pressure applied according to a desired configuration to enable a portion of said ink to penetrate through the porous base sheet and carry the colored dye alone to make a visible mark of the color of the dye and of said desired configuration on the other side of the base sheet, and' to enable a further portion of the released ink'to deposit the colored dye and colored pigment on a surface of a further sheet, which is in contact with the ink-carrying coating of the double-coated sheet to enable the pigment to produce a mark having the said desired configuration and the combined color of the dye and pigment on the further sheet.

12. A pressure-sensitive record and transfer material consisting of a porous base sheet having a rupturable coating on one side thereof, said rupturable coating containing a profusion of entrapped liquid droplets of ink, which ink includes a phototropic dye dissolved in an evaporable vehicle capable of readily penetrating the pores of the base sheet, said dye being colorable to a distinctive color when subjected to electromagnetic radiation, the droplets being of such a size and in such profusion as to supply sufficient ink upon rupture of the coating by pressure applied according to a desired configuration to enable a portion of said ink to penetrate through the porous base sheet to produce a latent image having said configuration on the other side of the base sheet, and to enable a further portion of the released ink to be deposited as a latent image in the same configuration on another surface in contact with the coated surface of the base sheet, and whereby said latent image is transformed to a distinctive color when subjected to electromagnetic radiation.

13. A pressure-rupturabie record and transfer material consisting of a porous base sheet having a rupturable coating on one side thereof, said rupturable coating containing a profusion of entrapped liquid droplets of ink, which ink includes a phototropic dye dissolved in a quickdrying low-viscosity vehicle capable of readily penetrating the pores of the base sheet, and also includes finely-divided colored pigment dispersed in the vehicle, said dye being colorable to a distinctive color when subiected to electromagnetic radiation, the droplets being of such a size and in such profusion as to supply sufiicient ink upon rupture of the coating by pressure applied according to a desired configuration to enable a portion of said ink to penetrate through the porous base sheet, thus allowing the phototropic dye alone to produce a latent image of said desired configuration on the other side of the base sheet, the latent image becoming colored when subjected to electromagnetic radiation, and to enable a further portion of the released ink to deposit the colored pigment and also produce a latent image on a surface of a further sheet, which is in contact with the ink-carrying coating of the double-coated sheet to enable the pigment to produce a mark of the desired configuration on the further sheet having the combined color of said pigment and of the color produced by electromagnetic irradiation of said latent image.

14. A sheet of record material thatnot only is responsive to marking pressures to produce a mark thereon but also by the same pressures will make a corresponding mark on a copy-receiving sheet, consisting of a base web of ink porous material having a front surface adapted to be marked by ink conducted through the pores of the base web from a pressure-ruptured coating on the rear surface of the sheet; and an ink-supplying coating on said rear surface of the sheet, said coating including a profusion of droplets of liquid ink protected in pressurerupturable matrix material, whereby marking pressures applied in selective configurations to the sheet will run ture the matrix material locally, releasing the ink for passage through the pores to make a mark on the front surface of the sheet according to the selected configuration, with sufiicient ink released also to make a transfer mark of the same configuration on a copy sheet placed in contact with the ruptured matrix material.

References Cited in the file of this patent UNITED STATES PATENTS UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,020, 171 February 6, 1962 Joseph A. Bakan et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 7, line 49, for "so'vent" read solvent line 53 for "centrigrade" read centigrade line 71, for "Barret" read Barrett column 13, line Z30 for "penerate" read penetrate line 73, for "rupton" read rupture column 14, line 15, for "penerate" read penetrate line 23, for "pressurpe" read pressure column l5 line 17, for "side" first occurrence read one Signed and sealed this 19th day of June 1962.

(SEAL) Attest:

ERNEST w. SWIDER DAVID LADD Atteating Officer Commissioner of Patents

Claims

1. A COMBINED RECORD AND TRANSFER MATERIAL CONSISTING OF A POROUS BASE MEMBER AND A RUPTURABLE COATING ON ONE SIDE OF THE MEMBER, SAID COATING CONTAINING A PROFUSION OF ENTRAPPED LIQUID DROPLETS OF INK, WHICH INK IS MADE UP OF COLORING MATERIAL IN A VEHICLE CAPABLE OF READILY PENETRATING THE PORES OF THE BASE MEMBER, THE DROPLETS BEING OF SUCH A SIZE AND PRESENT IN SUCH PROFUSION AS TO SUPPLY SUFFICIENT INK UPON RUPTURE OF THE COATING ACCORDING TO A DESIRED CONFIGURATION TO ENABLE A PORTION OF SAID INK TO PENETRATE THROUGH THE POROUS BASE MEMBER TO PRODUCE A MARK OF THE SAME CONFIGURATION ON THE SIDE OF THE BASE MEMBER OPPOSITE THE COATED SIDE, AND TO ENABLE A FURTHER PORTION OF THE RELEASED INK TO BE DEPOSITESD IN THE SAME CONFIGURATION TO PRODUCE ANOTHER MARK ON ANOTHER SURFACE IN CONTACT WITH THE COATED SURFACT OF THE MEMBER.