US2961334A - Positive printing, pressure-sensitive material and method of making it - Google Patents

Positive printing, pressure-sensitive material and method of making it Download PDF

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Publication number
US2961334A
US2961334A US663415A US66341557A US2961334A US 2961334 A US2961334 A US 2961334A US 663415 A US663415 A US 663415A US 66341557 A US66341557 A US 66341557A US 2961334 A US2961334 A US 2961334A
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Prior art keywords
coating
water
pressure
matrix
agent
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US663415A
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John J Clancy
Alton B Poole
Robert C Wells
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Arthur D Little Inc
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Arthur D Little Inc
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Priority to NL254530D priority Critical patent/NL254530A/xx
Application filed by Arthur D Little Inc filed Critical Arthur D Little Inc
Priority to US663415A priority patent/US2961334A/en
Priority to FR834164A priority patent/FR1289435A/fr
Priority to GB26865/60A priority patent/GB963735A/en
Priority to DE19601421391 priority patent/DE1421391A1/de
Priority to CH884560A priority patent/CH452404A/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0029—Formation of a transparent pattern using a liquid marking fluid
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y10T428/24612—Composite web or sheet
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/253—Cellulosic [e.g., wood, paper, cork, rayon, etc.]

Definitions

  • This invention relates to a coating composition and a resulting coated product. More particularly it relates to a coating which is suitable for application to a flexible backing of a color which is in contrast with the color of the coating, and to acoating which has controllable pressure sensitivity.
  • the coated material thereby becomes a positive pressure-printing sheet which needs only pressure to impart clearly defined marks or characters in the areas and shapes Iwhere the pressure is applied.
  • Carbon paper is the product most widely used in industry ⁇ to make duplicate copies of documents. Although it has been used for many years and in great volume, carbon paper does not provide good copy quality or contrast for easy reading, particularly when more than 3 or 4 copies are required, or where the copy paper -is heavy. lt is not surprising, therefore, that much effort has been spent over the years in an attempt to produce an improved method for making a number of copies simultaneously either by means of writing tools o-r lby mechanical devices.
  • duplicate copies are sometimes made by fusing sheets of paper, the top one of which is treated on the underneath side and the second which is treated on the top side. When these surfaces are contacted and pressure is applied, chemicals contained in the two coatings will be caused to react to give a contrasting colored mark on the top of the second sheet.
  • This system has ythe disadvantage of requiring surface coatings on the two faces of the two sheets which come into contact.
  • this type of duplicating paper can prematurely develop color or can lose the colored marks already made under certain atmospheric conditions.
  • the number of copies which can be made by one application of pressure is limited.
  • marking papers In addition to the requirement for making numerous copies there are also many needs for marking papers Where duplicate copies are not particularly important, but where characteristics, such as resistance to heat., normal pressures of handling, and moisture are required. Normally, such marking papers arel wax-coated with a contrasting color layer beneath the wax. However, when these materials are exposed to elevated temperatures, the waxy often melts and the mark placed upon lthe paper is obliterated.
  • positive pressure-printing material will be used to designate the product of this invention.
  • the application of pressure to the coated backing material causes the color of the backing material to show where the pressure was applied, thus resulting in a positive mark on the material, and giving the product the name applied hereinafter.
  • marks or indicia are used to indicate the configurations, shapes, or areas which are impressed upon the positive pressure-printing material as the result of pressure application. It is desirable that these marks or indicia have good copy quality which may be defined in terms of clearness or sharpness of outline and that they exhibit good copy contrast, ie., contrast in the colors of the background and of the marks or indicia. This contrast does not necessarily have to be between white and black, any color contrast being suitable.
  • backing or support is used to designate the material on whose surface the coating is applied. It will normally be such as paper or a thin plastic film, but it need not be.
  • the positive pressure-printing material of this invention is comprised of a exible backing or Support on one side of which is deposited a cavernulous coating which when pressure is applied is permanently compressed and is believed to make optical contact both between 'the discontinuities of the coating and with the backing material at the points, lines, or areas of pressure application. Such optical contact permits the color of the backing material to show through as contrasting tracings with respect to the color of the coating.
  • the coating composition of this invention comprises:
  • (l) material capable of forming a light scattering opaque matrix hereinafter referred to as the matrix material
  • the transparentizing agent material which itself is transparent or translucent and adequately cohesive to form the necessary permanent optical contact within the coating and with the backing on which the coating is applied, hereinafter called the transparentizing agent;
  • the emulsifying agent may be eliminated under certain circumstances, and the use of the insolubilizing agent is optional and depends on the desired properties of the final coating.
  • a coating composition comprising an emulsion of the above listed components is applied to the surface of the backing material in such a manner as to produce throughout the nal dry coating a multiplicity of airmatrix interfaces, thus causing incident light to be scattered by the coating to give a surface of high relative brightness.
  • These air-matrix interfaces are formed by applying the coating in such a manner that when it is in final dry form, the matrix material is throughout a minutely porous or cavernulous lm which appears to be smooth and homogeneous to the naked eye, but which under a powerful microscope seems to the liquid forming the discontinuous phase.
  • These air spaces are formed by applying the coating in the form of a continuous liquid phase in which is dispersed another liquid forming a discontinuous phase.
  • the transparentizing agenti is believed to form an extremely thin translucent or transparent film or covering at the air-matrix interfaces.
  • the matrix material is at least partially pushed aside and compressed, and that the transparentizing agent permanently welds one air-matrix interface to another and at the same time welds the now-compressed matrix material to the backing material.
  • the optical contact thus made permits the color of the backing material to show through as a sharply defined mark which exhibits good copy quality.
  • a modifying agent may be added according to wellknown procedures to either react with the matrix material to form an insoluble salt or to cause certain crosslinking of the matrix material molecules so as to impart water insensitivity.
  • the coating composition of this invention may then be described as a two-phase liquid emulsion essentially devoid of pigment, comprising an aqueous solution or 'A dispersion of a matrix material as a continuous phase (which may or may not contain an additional modifying agent such as a water-insolubilizing agent), and a liquid having a vapor pressure greater than that of water at f the drying temperature (preferably containing -the transparentizing agent) as a discontinuous phase.
  • the transparentizing agent in the discontinuous phase liquid, it is possible, under certain conditions, -to introduce it in the continuous phase liquid.
  • a solubilizing agent to aid in putting the matrix material into an aqueous solution and to add an emulsifying agent to disperse the discontinuous phase liquid in the aqueous matrix solution or dispersion.
  • the final opaque coating of this invention is to be distinguished from coatings which contain discrete and normally unbroken bubbles.
  • small enveloped liquid particles, or Hakes from blushed coatings, such as are heatand pressure-sensitive; from an ordinary sizing compound which in itself scatters very little light; and from pure wax coatings; or from pressure-resistant coatings which are included in our Serial Number 612,520.
  • Fig. 1 is a greatly enlarged cross-sectional representation of a backing material covered on one side with the coating of this invention after it has been applied, but before any appreciable amount of either liquid has been expelled;
  • Fig. 2 is the same coated background after the matrix solvent or liquid of the continuous phase is driven off, but before the iinal drying is accomplished;
  • Fig. 3 is the same coated background material after drying is completed
  • Fig. 4 is a diagrammatic representation of the coated background material of Fig. 3 showing how an applied pressure forms the required optical contact;
  • Fig. 5 illustrates a manifold of sheets of the positive pressure-printing material of this invention
  • Fig. 6 is a cross-sectional representation of one form of a marking tape made in accordance with this invention.
  • Fig. 7 is a cross-sectional representation of another form of a marking tape made in accordance with this invention.
  • the multitudinous, minute air-matrix interfaces which provide the uniformly cavernulous basic structure of the final coating of this invention are formed by rst expelling or driving off the liquid of the continuous phase to leave the matrix which contains minute pockets of the liquid of the discontinuous phase.
  • the discontinuous phase liquid is then driven off from the minute pockets to form a structure containing the air-matrix interfaces.
  • the transparentizing agent is believed to precipitate or crystallize on at least a portion of the matrix that deiines the discontinuities of the cavernulous film.
  • This coating is in itself transparent or at least translucent and may be of no more than molecular thickness.
  • liquids forming the two phases are immiscible, and that the liquid of the continuous phase is a solvent for the matrix material (in which the term solvent may refer to the continuous phase of a colloidal solution), and is preferably a nonsolvent for the transparentizing agent.
  • the liquid of the discontinuous phase is preferably a solvent for the transparentizing agent and essentially a non-solvent for the matrix material.
  • Photographs made by the electron microscope show little pockets elliptical in cross-section and shape, one to two microns long and about one-half micron wide or high. Most of these pockets appear to be ruptured, presumably as a result of expelling the liquid of the discontinuous phase in proper sequence.
  • coating composition 12 is made up of the continuous phase 14, for example, an aqueous dispersion of casein as the matrix material, and minute globules or pockets 16 of the liquid of the discontinuous phase such as xylene containing paraffin, for example, as the transparentizing agent dissolved therein.
  • the coating comprises the matrix 1S and minute pockets 16 of the liquid of the discontinuous phase. It is believed that after the liquid of the continuous phase is driven off, some shrinking of the coating takes place and the globules 416 probably assume an ellipsoid-like shape. Finally, when the liquid in the globules 1'6 of Fig.
  • air-matrix interfaces 20 which are coated with a translucent or transparent coating 22 of the transparentizing agent, which probably has precipitated or crystallized out ⁇ of ythe discontinuous phase liquid.V
  • These air-matrix interfaces ⁇ serve to scatter incident'light to produce the opaque coating of this invention.
  • These interfaces 20 generally vary inmaximurn dimension from about one-half to one micron high ⁇ or thick and from about one-half to five microns long, depending upon the conditions under which the coating was formed. It is preferable that no appreciable number of air-matrix interfaces have a maximum dimension of more than live microns.
  • Fig. 4 there is a diagrammatic representation of what is believed takes place when pressure is applied by means of a writing tool, or type face, to the coated material of Fig. 3.
  • the indentation made by the marking tool is represented as 24.
  • Pressure applied to the composition 12 pushes ⁇ some of the matrix aside and forces the coating ydown toward the backing material 10, thus laminating multiple thin ⁇ layers of matrix and transparentizing agent until this welded area occupies a very thin section 26 which basically outlines the mark made by the pressing tool and which'forms optical contact at point 28 with backing 10.
  • the components making up the coating composition of this invention may now be ⁇ lfurther described and defined.
  • the matrix-farming materialV The matrix material of the coating of this invention may be any of the Water-soluble or water-dispersible filmforming materials which will adhere tightly to the background area to be covered and which will scatter light at its air interfaces to give a bright, continuous surface.V
  • the materials which are -suitable to form matrices may be defined as those materials which assume colloidal dimensions when peptized.
  • matrix materials are suitable as matrix materials, among which may be listed casein, bentonite (a clay which swells in water), polyvinyl alcohol, methyl cellulose, alpha protein, animal glue, modified starches, sodium silicate, shellac, natural rubber, and the synthetic rubbers such as acrylonitrile-butadiene copolymers and butadiene-styrene copolymers.
  • bentonite a clay which swells in water
  • polyvinyl alcohol methyl cellulose
  • alpha protein alpha protein
  • animal glue modified starches
  • sodium silicate sodium silicate
  • shellac natural rubber
  • synthetic rubbers such as acrylonitrile-butadiene copolymers and butadiene-styrene copolymers.
  • matrix materials which are elastic in nature such as the natural and synthetic rubbers
  • compatible mixtures of any two or more of the above listed matrix materials may be used.
  • casein or alpha protein, or mixtures of these can be put into a Water solution only with the aid of a solubilizing agent which is alkaline in nature and results in the formation of a water-soluble salt of the proteins.
  • solubilizing agents include, but are not limited to, ammonium hydroxide, sodium hydroxide, sodium tetraborate (borax), sodium carbonate and trisodium phosphate. Any of the known solubilizing agents for casein may be used in the process of formulating the coating of this invention.
  • the matrix material components of the coating is a mixture of casein or alpha protein and a water-soluble synthetic matrix material
  • the synthetic materials are put into solution by any appropriate procedure.
  • polyvinyl alcohol may be mixed by sifting the powder into water which is being stirred very rapidly, preferably rapidly enough to form a vortex.
  • the polyvinyl alcohol powder is introduced into the vortex and stirring is continued (usually for about 10 minutes) until the powder is completely wetted and dispersed.
  • the dispersion is then heated to a temperature of 195 F. until the polyvinyl alcohol has all gone into solution.
  • the polyvinyl alcohol solution may be mixed with a casein or an alpha protein solution.
  • a modified starch e.g., a hydroxyethyl ether derivative of corn starch
  • the matrix material is sensitive to water, as casein is known to be, it may be rendered insensitive by converting it to a water insoluble condition in the nal coating by the addition of any suitable Water-insolubilizing agent known in the art.
  • any suitable Water-insolubilizing agent known in the art.
  • this may be conveniently done by addng to the casein solution an inorganic metal salt which is appreciably soluble in water and which forms an insoluble derivative with casein.
  • Such an inorganic metal salt is zinc sulphate.
  • the resulting coating then comprises the water-insoluble zinc salt of casein making the iinal coating practically water insoluble.
  • Casein, alpha protein, glue or the matrix mixtures containing one or a combination of these may also be modified by reacting with other metallic ions such ⁇ as copper, aluminum or chromium to form waterinsoluble products.
  • the amount of modifying agent to be added is based upon the assumption that a reaction takes place between the modifier and casein (or alpha protein) as indicated below, using zinc sulphate and ammonium caseinate as examples of the reaction.
  • the ammonium caseinate was, of course, formed when ammonium ions were introduced to aid in solubilizing the casein.
  • the ratio of matrix material to the liquid of the discontinuous phase will range from about 1:5 to 1:25.
  • the actual ratio will depend upon the characteristics of the nal coating desired. As a rule the more liquid used with respect to the matrix material, the higher the brightness in the final coating and the more sensitive the coating will be to pressure.
  • stearic acid emulsifying agent
  • xylene discontinuous-phase liquid
  • parain a parain havng a melting point of about 128 F. as the transparentizing agent.
  • the xylene was heated to about 160 F. and maintained at that temperature until the stearic acid and the parafinic were completely in solution.
  • This solution of stearic acid and paraffin in xylene was added to the warmed casein solution (120 F.) while the latter was being stirred rapidly. Stirring was continued until the emulsion had been formed.
  • the paraffin i.e., the transparentizing agent, was present in a concentration equivalent ⁇ to labout 71% of the weight of the matrix material (solid asis).
  • This coating composition had a viscosity of approximately 2900 centipoises. It was applied at a temperature of approximately F. by means of a coating roller to a number of samples of 10-pound tissue paper, the tissue being black or brightly colored such as red, blue, green, etc. The coated paper was then dried in a stream of air heated to F. to form the multitudinous aircasein interfaces required in the coating. The nal coated tissue was pure white on the coated side and was relatively smooth.
  • a sheet of uncoated tissue and l5 sheets of the material coated as described above were placed contiguously in an electric typewriter and the top uncoated tissue was typed upon.
  • the resulting l5 copies were all legible, the last copy having better definition and contrast than normally associated with the sixth or seventh carbon copy when conventional one-use carbon paper and tissue paper of the same basis weight are used.
  • the resulting emulsion had a viscosity of about 1000 cente'poises and was applied to 10-pound tissue paper by means of a paper-coating roller.
  • the drying of this coating was accomplished in the same manner as that described for ⁇ Example I and the iinal coating created a bright white surface which was not overly waxy-like.
  • a hand-held instrument such as a pen or pencil, or by type face to the white surface, there resulted a clear, well defined tracing in the color of the tissue paper backing on the coated sheet.
  • the final coating of this example exhibited good Water and heat resistance.
  • EXAMPLE III A dispersion of matrix material was made up by wetting 1.75 pounds of methyl cellulose in 17.5 pounds of hot water. When the methyl cellulose had been completely wetted, an additional 21.9 pounds of cold water was added along with 17.5 pounds of ammonia (28% NH4OH). In a separate vessel the transparentizing agent and the emulsifying agent were put into solution with the discontinuous phase liquid by adding 2.65 pounds of stearic acid and 1.1 pounds of paraffin (melting point 128 F.) to 15.7 pounds of Stoddard solvent (mineral spirits having a boiling fraction ranging from 310 to 375 F.). The matrix dispersion was then stirred rapidly and into it was added the discontinuous phase liquid solution until a good emulsion had been formed.
  • T he transparentizing agent should be a material which in itself is transparent or at least translucent when deposited in the form of a thin iilm. It should possess certain characteristics which enable it to provide the necessary optical contact believed to be required in the mechanism described above. It is preferable, moreover, that it be of such a nature that it can be added with the discontinuous phase of the emulsion.
  • the transparentizing agent may be a liquid, paste or solid so long as it provides the necessary optical contact.
  • the transparentizing agent should be cohesive, i.e., it should be capable of uniting layers or particles of itself as well as layers or particles of the matrix material with itself. The requirement for cohesion is illustrated in Fig. 4 in which the laminated layer 26 of transparentizing agent and matrix material is shown.
  • the transparentizing agent should also be capable of wetting the matrix material, a property which contributes to its cohesiveness.
  • the transparentizing agent In order to form the necessary 'indentation v24 (see Fig. 4) which apparently requires some local vdisplacement of the matrix material and the transparentizing agent, the transparentizing agent should be plastically deformable or flowable to a degree to permitsuch localized displacement. Moreover, to achieve the maximum effect in contrasts and good clear copy, the transparentizing agent should be at least translucent when ⁇ deposited in a thin tilm and it should have a refractive index of the same order as the matrix material to prevent the formation of scattering interfaces in the final copy. It appears from the mechanism which has been postulated for the action Y of the transparentizing agent that it should possess all,
  • the transparentizing agent is preferably one which will not migrate either into the backing material, the matrix material, or to the surface of the coating. Although migration does not at first materially reduce the performance of the final product (i.e., the positive pressure-printing material) it can shorten its useful life if migration is excessive.
  • the transparentizing agent will normally be water insoluble but soluble or dispersible in the discontinuous phase liquid. It is therefore preferably introduced by dissolving or dispersing it in the discontinuous phase liquid. Those transparentizing agents which are insoluble in water appear to contribute to making the final coating more water insensitive.
  • a large number of transparentizing agents have been used in the practice of this invention. This can be seen in the following example which contains a tabulation of the results from a large number of different coating formulations prepared in accordance with the practice of this invention. Each coating composition was made up in the manner described in Example IV. A basic casein dispersion was used to form the continuous phase of the emulsion. Xylene was used as the discontinuous phase liquid and different transparentizing agents were used in the formulation.
  • EXAMPLE IV A basic casein dispersion in water was made by slowly adding 3.8 pounds of casein to 10 pounds of water with stirring. The resulting mixture was permitted to stand for about 20 minutes .until the casein particles were wetted and swollen by the water. An additional 9.2 pounds of water was added and the mixture was heated to about 160 F. To this heated mixture was added 1.52 pounds of ammonium hydroxide (28% NH4OH) and the batch was stirred continuously until the casein was completely peptized. Care was exercised not to overheat the casein solution, and as soon as all the casein had been peptized the solution was allowed to cool to room temperature.
  • the amount of transparentizing agent will be determined by the degree of sharpness or definition required in the final tracing on the positive pressure-printing material of this invention. Because of the role of the transparentizing agent ⁇ as a coating for thematrix interfaces, the amount of transparentizing agent will depend primarily on the amount and type of matrix material present in the iinal coating. v
  • a preferred range is from about ⁇ to 75% -of the weight of Athe matrix material.
  • lf too little transparentizing agent is presentgthe ⁇ desired etiectobtainable fromthe transparentizing agentis not fully realized while if too much of the transparentizing agent is used, the iinal coatiugitakes onV the characteristics of a wax rather than a coating suitable for apositive pressure-printing material.
  • VFor example in the case of the bentonite it was desirable lto u'semore transparentizing agent since it also served in therole of a water-insensitizing agent.
  • Example I The range of-the transparentizing agent is shown below in' ExamplesfVwand ⁇ VI in which hydrocarbon wax with a melting point of about 128 F. was usedtinta tissue paper were coated with this composition, dried as described in Example I, and tested for good copy quality. Although pressure applied by means of a pen, pencil, or the face of a typewriter key gave good copy, it was not as satisfactory as far as optical contact achieved as was the composition of Example I, in ⁇ which the parafn was present in about 71% of the Weight of the solid casein.
  • EXAMPLE Vl A matrix dispersion was prepared as described in Example I and a xylene rsolution of stearic acid and paraffin was prepared as given also in Example l, except that 3.3 pounds of parain was substituted for the 2.7 pounds. This parain was equivalent to about 87% of the solid weight of the casein.
  • the coating composition was prepared, applied, and dried in the same manner as described in Example l. The iinal dried surface gave good copy quality, excellent water and heat resistance without showing any strong tendency towards being waxy. i i
  • the emulsifying agent if present, can also serve as: a transparentizing. agent.
  • the quantity of emulsifying agent thus serving in an alternate role is in addition to the quantity Aof the transparentizing agent specified.
  • Emulsz'fyng agent has a dual role in the coating composition of this invention. It acts both as an aid in forming the desired ⁇ emulsion and also as a transparentizing agent.
  • Incthe mixingof the coating composition of this in ventionfzailthorougli dispersingof .one liquid ⁇ in another is required to form the necessary emulsion and it is desirable under some conditions ⁇ to add an emulsifying agent such as those commonly used to prepare emulsions.
  • emulsifying agents may be one of the appropriate soaps which may be defined as salts of a strong base such as ammonium hydroxide, or sodium hydroxide, and o-f a fatty acid such as stearic, palmi'tic, or lauric.
  • the soap used as an emulsifying agent should be one which is a solid at room temperature in the final form which appears in the coating.
  • the emulsifying agent can be omitted provided it is not essential to the making of the emulsion, but it is preferable to have one, inasmuch as it serves also as a transparentizing agent.
  • the emulsifying agent may be formed in situ by reaction between the fatty acid and an alkali metal ion furnished for example from an excess of a solubilizing agent used in connection with the matrix material.
  • a solubilizing agent used in connection with the matrix material.
  • the amount of emnlsifying agent used will be determined fii'st by the quantity required to produce a good emulsion of the continuous phase and discontinuous phase liquids, and secondly by the amount desirable to contribute to the effect of the transparentizing agent. Thus, if no emulsifying agent is required to form the necessary emulsion and no additional transparentizing effect is required, no emulsifying agent need be added. However, if an emulsifying agent is required to lform the emulsion and/ or is required in the role of a transparentizing agent, then the amount of emulsifying agent may be as high as about four times the weight of the matrix material solids present in the continuous phase portion of the emulsion.
  • the incorporation of large quantities of emulsifying agent into the formulation may require an increase in the amount of discontinuous phase liquid.
  • the desired amount of emulsifying agent used will vary from about 3 to 10 -percent of the weight of the discontinuous phase liquid containing the emulsifying agent in solution.
  • EXAMPLE VII A casein dispersion was first formed by mixing 14.1 pounds of casein, 73.2 pounds of water, and 5.7 pounds of ammonia (28% NH4OH). After the casein had been solubilized, 1.4 pounds of ZnSO4, ⁇ dissolved in 5.6 pounds of water, was added to the casein dispersion. The dispersion was otherwise made up in the manner described in Example I. To twenty-five parts by weight of this dispersion was added 10 parts by weight of water to dilute it to the proper consistency. In a separate vessel 5.4 pounds of stearic acid, and 2.5 pounds of paraffin (melting point 128 F.) were dissolved in 54 pounds of warm xylene and the mixture was stirred until complete solution had been obtained.
  • Example 14 EXAMPLE vnr A coating composition was made up exactly as described in Example VII except that an equal weight of palmitic acid was substituted for the stearic acid of Example VII.
  • the performance of the coating when applied to tissue paper was similar to that achieved by the coating composition containing stearic acid as an emulsifying agent.
  • Example VII The stearic acid in the coating composition of Example VII was replaced by an equal Weight of lauric acid and the coating composition treated and handled in the same manner as in Example VII. The resulting coating composition was not as satisfactory as lthatobtained in Example VII in that the whiteness of the coating produced was inferior.
  • Example VII The stearic acid in Example VII was replaced with an equal weight of oleic acid.
  • the resulting coating composition which was mixed, applied and dried as in Example VII, was not found to be as satisfactory because the oleic acid present as an emulsifier was not a solid at room temperatures. This, in turn, caused the oleic acid to migrate into the pores of the tissue paper.
  • Continuous-phase [liquid Liquids suitable for the continuous phase of Ithe emulsion forming the coating of this invention should be solvents for the matrix material and preferably nonsolvent for the transparentizing agent. Liquids other than water may be used to form the continous phase, but Water Vis preferred for practical and economical reasons; It should be noted that the use of a water-soluble matrix material, and hence of an aqueous solution as a continuous phase, means that the cost of ythe coating composition of this invention can be materially reduced below the cost of an oil-base paint or a coating using an organic vehicle to form the continuousV phase.
  • Dlscontnuous-phase liquid The liquid forming the discontinuous phase mus-t have a vapor pressure less than that of the liquid forming the continuous phase, i.e., usually less than that of water at the drying temperature, but for practical purposes it should have a boiling point not above 325 F.
  • Such liquids include, but are not limited to, xylene, kerosene, mineral spirits, high-flash naphthas, ketones (such as butyl methyl Iketone and amyl ethyl ketone), paraffin hydrocarbons such as octane, and the higher boiling acetates such as butyl acetate or amyl acetate.
  • the choice of the liquid forming the discontinuous phase will have some influence on the pressure sensitivity of the final coating.
  • a liquid is used for the discontinuous phase which has a relatively high vapor pressure, i.e., fairly close but somewhat below that of water
  • some of the discontinuous phase liquid I will pass off from the coating simultaneously with the water leaving less of the discontinuous phase liquid Within the matrix thus forming smaller globules of the liquid which in turn means less distortion of the matrix to form the air-matrix interfaces.
  • the final result of using a high vapor phase liquid means a strong matrix and hence a more pressure-resistant final coating.
  • the final choice of theV liquid for the discontinuous phase may also require the consideration of such points as that which will give the brightest coating for a given weight per unit area of surface for a specific film-forming material; that which will prove to be the most compatible with other components such as the binder, the emulsifying agent, and any dye or dyes added; and that which will meet certain other requirements such as toxicity, inflammability, adaptability to production procedures, cost, and the like.
  • the amount of discontinuous p hase liquid with relation to the amount of continuous phase liquid may vary within the limits which may be used to form ⁇ the type of emulsion required, normally an oil-in-water emulsion.
  • the limits on such liquid ratios are well known or can easily be determined.
  • the amount of discontinuous phase liquid may be varied in accordance with the amount of emulsifying agent added.
  • it may ⁇ be desirable to use more discontinuous'phase liquid when the larger quantities of emulsifying agent are used.
  • the amount of discontinuous phase liquid may also be expressed in terms of the weight ratio of discontinuous liquidto matrix material in the coating composition, i.e., in the emulsion. As noted above in connection with the matrix material, this Weight ratio may vary from about :1 to 25:1. Generally, the less discontinuous liquid present with respect to the amount o f matrix material, the more prsure it willrequire to markthe iinal positive, pressure-printing material. This is due to relatively large amounts of casein solids in thecoating which make the coating hard and hence diiicult to break down the porous, cavernulous structure. Where relatively large quantities of discontinuous phase liquid, with respect to matrix material, are used, the final structure of the coating is very porous and requires relatively little pressure to mark.
  • i i f v Of the discontinuous phase liquids listed'.4 above, the preferred liquid is xylene, a liquid which has been ⁇ illustrated in Examples Iyand II, and Examples III through X.
  • Example A XI The xylene of Example I was replaced with a petroleum fraction boiling between 153 and 200 C., i.e., normally called kerosene. The formulation otherwise was the same as that described for Example I and the resulting coating was equally satisfactory.
  • the essentially non-pigmented coating of this invention may be made in any desired color by adding one or more dyes to the coating composition.
  • the dyes may be either of the oil-soluble or water-soluble type added to the appropriate phase of the coating composition depending upon the effects desired.
  • the examples given above have illustrated in detail the steps in the process of mixing the coating composition of this invention.
  • the process may be described generally as comprising the steps of forming a solution or dispersion of the matrix material in the continuous phase liquid, adding a portion of a strong base if it is to bensed to form the emulsifying agent in Vsitu, adding additional continuous phase liquid, preparing a solution of the transparentizing agent and the emulsifying agent (or the fatty acid portion of the emulsifying agent) in the discontinuous phase liquid, adding about one-half of the solution to the dispersion of the matrix material in the continuous phase liquid with very rapid stirring, and finally adding the remaining portion of the strong base and the solution of the emulsifying agent and transparentizing agent in the discontinuous phase liquid.
  • additional continuous phase liquid may be added at the end of the mixing to adjust the viscosity.
  • the viscosityof the coating composition just prior to application can be controlled by the amount of continuons phase and discontinuous phase liquid used and, aS noted above, the viscosity may be iinallyreduced if necessary by adding the necessary quantity of continuous phase liquid.
  • Viscosities of a-wide range have been successfully used, the practical upper limit being about 2960 centipoises while thepractical lower limit is about 400 to 600 centipoises.
  • the optimum viscosity will be determined by such factors fas (1) the method used to coat or apply the coating composition, (2') the mobility of the matrix material, and (3) the type of backing used to which the coating is applied. ⁇ ,For example, it would be desirable 3when using aknife coater to employ a coating of relatively high viscosity, while when a reverse-roll is' used, coating compositions of lower ⁇ viscositieswould be desirable.
  • casein is the matrix material
  • the viscosity should be adjusted with relation ⁇ to the porosity of the paper and the absorbing rate of the paper. Papers which do not absorb easily can toleratecoating compositions of 'lower viscosity.
  • the coating composition may be applied to the supporting material by any well-known technique such as rolling, brushing, spraying, printing, and the like.
  • the coating may be dried by atmospheric action only, it is more practical to dry it by passing a warm stream of air atabout F. over the coating or over the uncoated side. of the backing material.
  • Other Vsuitable drying techniques may of course be used.
  • the thicknessof the coating when first applied will rangerfrom about 8-10 mils. When drying has been completed, the final coating thickness will range from between about 0.2 and 0.5 mil.
  • the coating composition of this invention may be deposited on a variety of backing or supporting materials.
  • the purpose is to produce a positive ⁇ pressure-printing material and achieve production of a number of copies without the use of any carbon paper or carbon backing, it is necessary to deposit the coating on relatively thin backing material; If the final copies are to becolor'ed tracings on a white background, a white coating will be used over a dark colored backing, e.g., black, red, green, blue, ⁇ etc. To obtain good clear copy itis ⁇ desirable to use a backing which is fairly highly colored.
  • the backing is, of course, not limited to tissue paper but may be any material or surface on which it is desired to make tracings, etc. Where marking tape for example, is to bemade it would be advantageous to use a material which has an adhesive on one side.
  • the coating composition of this invention when appliedto a colored tissue gives good clear copy even whenit is theitwenty-tifth copy, it has been-found that the quality ⁇ and clarity of the copy may be improved by exposing the sheet after pressure application to a very brief heating up 'to temperatures at or below which the wax and the coatingcomposition will melt and flow appreciably. Once paper, to which pressure had been applied and the tracing has been made, has been heated the coating becomes practically completely water-insensitive and heat-insensitive.
  • the amount of transparentizing agent and/ or emulsifying agent which may serve as a transparentizing agent the greater the ratio of transparentizing agent and emulsifying agent to the amount of matrix material the more pressure sensitive is the final coating;
  • the pressure sensitivity of the final coating may vary over a wide range.
  • the actual pressure sensitivity of the final coating will be, of course, dictated by the application to which it is put. For example if the coating is for a positive pressure-printing duplicating paper which is to be used in multiple sheets for making many duplicate copies the coating should be relatively sensitive to pressure. Likewise, if the pressure is to be applied by hand tools such as pencils or pens, the coating should be more pressure sensitive than if pressure is to be applied by mechanical devices using type. On the other hand, where the coating is to be applied to marking tapes where duplicates are not required, a lesser degree of pressure sensitivity is required because more handling, etc., may be involved.
  • This invention contemplates the binding of a number of sheets of forms, pads, or stacks of sheets suitable for making multiple copies by means of applying pressure to the top sheet without the use of any carbon backing or interleaving carbon paper. It has been shown for example that it is possible when pressure is applied by means of a typewriter to make up to 25 duplicate copies with this type of paper.
  • Sheets of positive pressure-printing material 30 are bound to an uncoated upper sheet 32 at one edge 34 by means of any suitable device such as staples 36.
  • the sheet may have perforations 38 for easy separation.
  • the sheets 30 may, of course, be white coating on different colored backgrounds so that copies can be made with tracings in different colors. This is often useful in business forms where it is necessary to sort out copies for various uses.
  • coated sheets which give a. variety of colored tracings, it is also possible to selectively coat portions of these sheets so that when pressure is applied to the top sheet, selective marking on the subsequent sheets is achieved.
  • This invention also contemplates the making of marking tapes by depositing the coating composition of this invention on a suitable exible backing which is coated with an adhesive on the side not containing the coating composition.
  • Two such marking tapes are illustrated in Figs. 6 and 7.
  • the coating composition of this invention 40 is applied to backing 42 which has a layer of adhesive 44 on the other side.
  • backing 42 is of a color which exhibits sufiicient contrast to coating 40 to give a good mark.
  • backing 42. is not highly colored or is transparent, then it will be desirable to interpose a colored layer 46 (Fig. 7) to give well defined marks.
  • a coating composition capable of forming a thin, opaque, essentially non-pigmented film on a surface, said composition consisting essentially of an oil-in-water emulsion, the continuous phase of said emulsion being water containing a hlm-forming matrix material which acquires colloidal dimensions when peptized, and the discontinuous phase of said emulsion being an organic liquid which is a non-solvent for said matrix material, immiscible with water and having a boiling point above water and containing dissolved therein a plastically deformable transparentizing agent which is a cohesive, highly viscous to solid material, the weight ratio of said matrix material to said discontinuous liquid ranging from about 1:5 to about 1:25, and said transparentizing agent being present in an amount equivalent to from about l0 to 300% or' the weight of said matrix material.
  • a coating composition capable of forming a thin, opaque, essentially non-pigmented film on a surface, said composition consisting essentially of an oil-in-water emulsion, the continu-ous phase of said emulsion being water 'containing a film-forming matrix material which acquires colloidal dimensions when peptized, and the discontinuous phase of said emulsion being an organic liquid which is a non-solvent for said matrix material, immiscible with water and having a boiling point above water and containing dissolved therein an emulsifying agent and a plastically deformable transparentizing agent which is a cohesive, highly viscous to solid material, said emulsifying agent being one which is solid when said coating composition forms said film and which is present in an amount ranging from about 3 to 10% by weight of said discontinuous phase liquid, the weight ratio of said matrix material to said discontinuous liquid ranging from about 1:5 to about 1:25, and said transparentizing agent being present in an amount equivalent to from about 10 to 300% of the weight of said matrix material.
  • a coating composition capable o-f forming a thin, opaque, essentially non-pigmented film on a surface, said composition consisting essentially on an oil-in-water emulsion, the continuous phase of said emulsion being water containing a film-forming matrix material which acquires colloidal dimensions when peptized, and an insolubilizing agent for said matrix material whereby said matrix material becomes substantially water insoluble upon formation of said film, and the discontinuous phase of said emulsion being an organic liquid which is a nonsolvent for said matrix material, immiscible with Water and having a boiling point above water and containing dissolved therein a plastically deformable transparentizing agent which is a cohesive, highly viscous to solid material; the weight ratio of said matrix material to said discontinuous liquid ranging from about 1:5 to about 1:25, and said transparentizing agent being present in an amount equivalent to from about to 300% of the weight of said matrix material.
  • a positive, pressure-printing material comprising a iexible ⁇ backing having deposited on one side thereof a coating characterized by being a matrix of a ilmforming material having uniformly distributed throughout its entire volume, multitudinous, minute air-matrix interfaces varying in maximum dimensions from about one-half to one micron with no appreciable number exceeding ve microns providing a uniform cavernulous structure and containing a plastically deformable transparentizing agent present in an amount equivalent to from about 10 to about 300% of the weight of said matrix, said agent being further characterized as a cohesive, highly viscous to solid material, said film-forming ma terial being a water swellable material which acquires colloidal dimensions when peptized.
  • a manifold of exible sheets joined in superimposed arrangement and suitable for simultaneously making a number of copies by application of pressure alone to the top sheet of said manifold comprising a plurality of sheets of a flexible material, each sheet under the top sheet consisting essentially of a exible colored backing having deposited on the top side thereof a coating characterized by being of a color which contrasts with the color of said backing, said coating being a matrix of a film-forming material having distributed throughout its entire volume, multitudinous, minute airmatrix interfaces varying in maximum dimensions from about one-half to one micron with no appreciable number exceeding ve microns providing a uniform cavernulous structure and containing a plastically deformable transparentizing agent present in an amount equivalent to from about 10 to about 300% of the weight of said matrix and being further characterized asia cohesive, highly viscous to solid material, said ilmform ing material being a water swellable material which acquires colloidal dimensions when peptized.
  • Process for coating a substrate area with a coating composition to form a pressure-sensitive positive printing marking surface comprising the steps of preparing a dispersion of a matrix material in water, preparing a solution of a transparentizing agent in an organic liquid .immiscible with water and having a boiling point above that of water but below about 350 F., rapidly stirring said dispersion and simultaneously adding said solution to form an oil-in-water emulsion, ⁇ depositing said coating composition on said tiexible backing material, expelling first a majorportion of said water and forming in the resulting film of said matrix material a multiplicity of small pockets of said Organic liquid, and then expelling saidorganic liquid thereby to form multitudinous airrnatrixinterfaces while simultaneously precipitating out said transparentizing agent in said air-matrix interfaces uniformly distributed throughout the volume of said film and which range in maximum dimensions from about one-half to one micron with no appreciable number exceeding tive microns, whereby said lm becomes opaque and light scattering; said transparent thermo
  • Process in accordance with claim 14 further characterized by the step of introducing an emulsifying agent into said discontinuous phase liquid.

Landscapes

  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Color Printing (AREA)
US663415A 1957-06-04 1957-06-04 Positive printing, pressure-sensitive material and method of making it Expired - Lifetime US2961334A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL254530D NL254530A (enrdf_load_stackoverflow) 1957-06-04
US663415A US2961334A (en) 1957-06-04 1957-06-04 Positive printing, pressure-sensitive material and method of making it
FR834164A FR1289435A (fr) 1957-06-04 1960-07-27 Articles pourvus d'un revêtement
GB26865/60A GB963735A (en) 1957-06-04 1960-08-03 Coated articles including coated-sheet manifolds
DE19601421391 DE1421391A1 (de) 1957-06-04 1960-08-04 Verfahren zum Beschichten von biegsamem Material
CH884560A CH452404A (de) 1957-06-04 1960-08-04 Verfahren zur Herstellung eines mit einem Ueberzug versehenen Gegenstandes

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US (1) US2961334A (enrdf_load_stackoverflow)
CH (1) CH452404A (enrdf_load_stackoverflow)
DE (1) DE1421391A1 (enrdf_load_stackoverflow)
GB (1) GB963735A (enrdf_load_stackoverflow)
NL (1) NL254530A (enrdf_load_stackoverflow)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3086873A (en) * 1960-08-25 1963-04-23 Alexander H Steinbrunner Silk screen printing ink
US3108009A (en) * 1960-10-04 1963-10-22 Little Inc A Process coating a substrate with an opaque coating and resultant article
US3149967A (en) * 1954-12-03 1964-09-22 Du Pont Process for preparing printing element stencils from clarifiable polymeric materials
US3157533A (en) * 1963-07-17 1964-11-17 Little Inc A Starch stabilized casein coating emulsions
US3290149A (en) * 1962-03-01 1966-12-06 Du Pont Process for increasing optical densities
US3309224A (en) * 1963-03-07 1967-03-14 Kimberly Clark Co Method of coating paper with pigmented protein containing oil-in-water emulsions having epoxy resin dispersed in oil phase
US3320089A (en) * 1964-03-09 1967-05-16 Judson Bigelow Inc Method of making blush coated recording sheet, coated sheet and coating composition
US3324762A (en) * 1965-08-02 1967-06-13 Sperry Rand Corp Marking method and apparatus
US3328184A (en) * 1963-07-02 1967-06-27 Kimberly Clark Co Printing paper having opaque cellular coating and method and composition for forming the same
US3372050A (en) * 1966-02-07 1968-03-05 Robert E. Weber Paper coating composition and method of coating
US3411925A (en) * 1966-03-24 1968-11-19 Kimberly Clark Co Oxidized starch-protein composition and methods for producing and using the same
US3478716A (en) * 1963-03-07 1969-11-18 Kimberly Clark Co Printable paper product having a cellular coating containing pigment and a reaction product of protein and an epoxy resin defining the cell walls
US3520757A (en) * 1967-06-22 1970-07-14 Richard Heaney Pressure printing card
US3637431A (en) * 1968-09-30 1972-01-25 Little Inc A Coating composition and article coated with same
US3819398A (en) * 1970-07-17 1974-06-25 Champion Int Corp Process for production of pressure-sensitive copy sheet
JPS5014567B1 (enrdf_load_stackoverflow) * 1970-07-17 1975-05-29
US3928702A (en) * 1968-09-16 1975-12-23 Fuji Photo Film Co Ltd Process for manufacturing an activated clay-coated paper for use as a pressure-sensitive copying paper
US3951899A (en) * 1970-06-22 1976-04-20 Ppg Industries, Inc. Opaque, microcellular films from latex compositions, process and composition for preparing the same
US4977070A (en) * 1986-05-20 1990-12-11 Minnesota Mining And Manufacturing Company Transparentizable antihalation layers
JP2019206666A (ja) * 2018-05-30 2019-12-05 トヨタ自動車株式会社 水溶性高分子の多孔質体の製造方法

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US1783442A (en) * 1928-02-04 1930-12-02 Charles W Mayer Recording paper
US2299694A (en) * 1940-03-09 1942-10-20 Ncr Co Manifolding material
US2299991A (en) * 1941-01-18 1942-10-27 Mc Laurin Jones Co Chart paper
US2306525A (en) * 1938-01-06 1942-12-29 Interchem Corp Method of preparing multitone coated articles
US2310795A (en) * 1939-08-31 1943-02-09 Stein Hall & Co Inc Emulsion for treating textiles
US2374862A (en) * 1942-06-19 1945-05-01 Ncr Co Coating for paper
US2519660A (en) * 1947-09-06 1950-08-22 Little Inc A Recording material
US2648924A (en) * 1949-12-16 1953-08-18 Brewster Ernest Billings Label structure
US2655453A (en) * 1952-04-23 1953-10-13 Ncr Co Manifold sheet having a crushresistant transfer film
US2710263A (en) * 1951-02-02 1955-06-07 Minnesota Mining & Mfg Heat-sensitive copying-paper
US2739909A (en) * 1950-06-29 1956-03-27 Nashua Corp Coated paper suitable for stylus inscription and method of making the same

Patent Citations (11)

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Publication number Priority date Publication date Assignee Title
US1783442A (en) * 1928-02-04 1930-12-02 Charles W Mayer Recording paper
US2306525A (en) * 1938-01-06 1942-12-29 Interchem Corp Method of preparing multitone coated articles
US2310795A (en) * 1939-08-31 1943-02-09 Stein Hall & Co Inc Emulsion for treating textiles
US2299694A (en) * 1940-03-09 1942-10-20 Ncr Co Manifolding material
US2299991A (en) * 1941-01-18 1942-10-27 Mc Laurin Jones Co Chart paper
US2374862A (en) * 1942-06-19 1945-05-01 Ncr Co Coating for paper
US2519660A (en) * 1947-09-06 1950-08-22 Little Inc A Recording material
US2648924A (en) * 1949-12-16 1953-08-18 Brewster Ernest Billings Label structure
US2739909A (en) * 1950-06-29 1956-03-27 Nashua Corp Coated paper suitable for stylus inscription and method of making the same
US2710263A (en) * 1951-02-02 1955-06-07 Minnesota Mining & Mfg Heat-sensitive copying-paper
US2655453A (en) * 1952-04-23 1953-10-13 Ncr Co Manifold sheet having a crushresistant transfer film

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3149967A (en) * 1954-12-03 1964-09-22 Du Pont Process for preparing printing element stencils from clarifiable polymeric materials
US3086873A (en) * 1960-08-25 1963-04-23 Alexander H Steinbrunner Silk screen printing ink
US3108009A (en) * 1960-10-04 1963-10-22 Little Inc A Process coating a substrate with an opaque coating and resultant article
US3290149A (en) * 1962-03-01 1966-12-06 Du Pont Process for increasing optical densities
US3478716A (en) * 1963-03-07 1969-11-18 Kimberly Clark Co Printable paper product having a cellular coating containing pigment and a reaction product of protein and an epoxy resin defining the cell walls
US3309224A (en) * 1963-03-07 1967-03-14 Kimberly Clark Co Method of coating paper with pigmented protein containing oil-in-water emulsions having epoxy resin dispersed in oil phase
US3328184A (en) * 1963-07-02 1967-06-27 Kimberly Clark Co Printing paper having opaque cellular coating and method and composition for forming the same
US3157533A (en) * 1963-07-17 1964-11-17 Little Inc A Starch stabilized casein coating emulsions
US3320089A (en) * 1964-03-09 1967-05-16 Judson Bigelow Inc Method of making blush coated recording sheet, coated sheet and coating composition
US3324762A (en) * 1965-08-02 1967-06-13 Sperry Rand Corp Marking method and apparatus
US3372050A (en) * 1966-02-07 1968-03-05 Robert E. Weber Paper coating composition and method of coating
US3411925A (en) * 1966-03-24 1968-11-19 Kimberly Clark Co Oxidized starch-protein composition and methods for producing and using the same
US3520757A (en) * 1967-06-22 1970-07-14 Richard Heaney Pressure printing card
US3928702A (en) * 1968-09-16 1975-12-23 Fuji Photo Film Co Ltd Process for manufacturing an activated clay-coated paper for use as a pressure-sensitive copying paper
US3637431A (en) * 1968-09-30 1972-01-25 Little Inc A Coating composition and article coated with same
US3951899A (en) * 1970-06-22 1976-04-20 Ppg Industries, Inc. Opaque, microcellular films from latex compositions, process and composition for preparing the same
US3819398A (en) * 1970-07-17 1974-06-25 Champion Int Corp Process for production of pressure-sensitive copy sheet
JPS5014567B1 (enrdf_load_stackoverflow) * 1970-07-17 1975-05-29
US4977070A (en) * 1986-05-20 1990-12-11 Minnesota Mining And Manufacturing Company Transparentizable antihalation layers
JP2019206666A (ja) * 2018-05-30 2019-12-05 トヨタ自動車株式会社 水溶性高分子の多孔質体の製造方法

Also Published As

Publication number Publication date
DE1421391A1 (de) 1968-10-17
GB963735A (en) 1964-07-15
NL254530A (enrdf_load_stackoverflow)
CH452404A (de) 1968-05-31

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