US3384536A - Process for forming fibrous sheets containing limited penetration of additaments within the sheet and sheets thereof - Google Patents

Process for forming fibrous sheets containing limited penetration of additaments within the sheet and sheets thereof Download PDF

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Publication number
US3384536A
US3384536A US442352A US44235265A US3384536A US 3384536 A US3384536 A US 3384536A US 442352 A US442352 A US 442352A US 44235265 A US44235265 A US 44235265A US 3384536 A US3384536 A US 3384536A
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United States
Prior art keywords
sheet
web
capsules
phase
solution
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US442352A
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English (en)
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Robert W Sandberg
Bruce W Brockett
Donald B Clark
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Appvion LLC
NCR Voyix Corp
National Cash Register Co
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NCR Corp
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Priority to US442352A priority Critical patent/US3384536A/en
Priority to GB7487/66A priority patent/GB1105711A/en
Priority to BR177398/66A priority patent/BR6677398D0/pt
Priority to NO162046A priority patent/NO124273B/no
Priority to AT253766A priority patent/AT269910B/de
Priority to CS1847A priority patent/CS165980B2/cs
Priority to FR54212A priority patent/FR1478652A/fr
Priority to SE3765/66A priority patent/SE301910B/xx
Priority to BE678203D priority patent/BE678203A/xx
Priority to DE19661546271 priority patent/DE1546271C3/de
Priority to DK147866AA priority patent/DK120929C/da
Priority to ES0324631A priority patent/ES324631A1/es
Priority to NL6603889A priority patent/NL6603889A/xx
Priority to CH420766A priority patent/CH453064A/fr
Application granted granted Critical
Publication of US3384536A publication Critical patent/US3384536A/en
Assigned to APPLETON PAPERS INC. reassignment APPLETON PAPERS INC. MERGER (SEE DOCUMENT FOR DETAILS). FILED 12/1781, EFFECTIVE DATE: 01/02/82 STATE OF INCORP. DE Assignors: GERMAINE MONTEIL COSMETIQUES CORPORATION (CHANGED TO APPLETON PAPERS), TUVACHE, INC.
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape
    • D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/025—Applications of microcapsules not provided for in other subclasses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F5/00—Dryer section of machines for making continuous webs of paper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2984—Microcapsule with fluid core [includes liposome]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2984—Microcapsule with fluid core [includes liposome]
    • Y10T428/2985—Solid-walled microcapsule from synthetic polymer
    • Y10T428/2987—Addition polymer from unsaturated monomers only

Definitions

  • ABSTRACT OF THE DISCLOSURE A process for limiting the penetration of particulate material within an embryonic fibrous web by effecting a phase separation of a wall-forming polymeric mater al (coacervate phase) within the web in the presence of the particulate material; the coacervate phase being formed by applying one or more of the components essential to the phase separation to one side of the embryonic web and the products therefrom.
  • This invention rel-ates to a system for limiting the penetration of particulate material through the thickness of a fibrous sheet material, and to the novel product produced thereby.
  • the novel system is capable of limiting the penetration of particulate material into a fibrous sheet, as the sheet is being formed, so that the particles are substantially concentrated adjacent one surface thereof in a firm, well defined stratum of binder material.
  • a liquid slurry of paper fibers, treated with one of the components essential to phase separation is laid down as a soggy web, and a solution of other component(s) essential to the phase separation is applied to said web, all components being present in sufficient amount and under conditions appropriate to the formation of a coacervate, the components thus brought together cause the phase separation and the emergence of the binder material to occur substantially immediately, with the result that the viscous phase is formed within the web in a well defined stratum substantially adjacent the surface of the side of the embryonic web to which the solution was applied.
  • the viscous phase of binder material Wets and adheres to the fibers within its immediate vicinity, and, further, the viscous phase envelops and forms a matrix for any particulate material within the zone of thickness in which the phase separation occurs.
  • the binder stratum is generated in situ in the fiber mat comprising the wet web.
  • at least one essential component is present in the Wet web when the other essential component(s) and particulate material are applied to and penetrate into the wet web.
  • the instant generation of the viscous polymeric material phase (coacervate), which constitutes the binder, causes it to stall for the most part, preventing it and the retained particles from proceeding farther into the web. This occurs with respect to the thickness of the sheet, much before the center line of the sheet is reached, most being retained in the first ten to twenty percent of the sheet thickness.
  • a slurry of paper fibers having present therein a phase-separation-inducing material such as, for example, a polymer of one polarity
  • a phase-separation-inducing material such as, for example, a polymer of one polarity
  • a phase-separation-inducing material such as, for example, a polymer of one polarity
  • the primary aspect of this invention relates to a system (and the product thereof) for limiting the penetration of particulate mark-forming components into markforming sheet record material, during the formation of said record material, to thereby impart a one-sidedness to the sheet material as regards such components; i.e., the sheet material in a cross-section through its thickness has the particulate material essential to the mark formation disposed, for example, substantially to one side of the center-line of said thickness.
  • Pressure-sensitive mark-forming sheet material generally has two forms; namely, the self-contained form, wherein all of the necessary mark-forming components are present in a single sheet in contiguous juxtaposition to each other, and the transfer form, which utilizes two or more sheets wherein one or more of the mark-forming components physically move from one sheet to another sheet.
  • said one sheet is generally considered as the transfer sheet
  • said other sheet is commonly referred to as the receiving sheet
  • said receiving sheet if necessary, containing one or more mark-forming components which cooperate with the transferred markforming components to produce a mark on the receiving sheet.
  • the one-sidedness is particularly desirable in record material, since it confines the mark or mark-producing material to one side thereof to produce a more commercially acceptable record material.
  • the one-sidedness and retention of the mark-forming material adjacent one surface also mean that, for given marking characteristics, a smaller amount of mark-forming material may be required than when the mark-forming material is incorporated throughout the thickness of the record material, since it is only those marks which are adjacent the surface which can be seen from the outside of the record material, and those marks which are formed deep down in the body of the sheet are not necessary.
  • the one-sidcdness and retention of the mark-forming material adjacent one surface enable a more efiicient transfer of the mark-forming material from that surface than would be possible if the same amount of mark-forming material were distributed throughout the thickness of the record. material.
  • the retention of the mark-forming material adjacent one surface of the record material requires less marleforming material to be used to produce commercially acceptable marking than when the markforming material is dispersed throughout the record material and thus enables a saving to be effected in the manufacture of such record material.
  • At least one of the mark-forming components is present as the potentially mobile internal contents of a minute pressure-rupturable capsule (said capsules being used in large quantities numerically and being the particulate material in one form of this invention), so that, upon application of pressure to the sheet material, the capsule is ruptured and, in the case of self-contained sheet material, the inner contents is released to eoact with the other mark-forming components disposed within said sheet to produce a mark, and, in the case of the transfer system, the inner contents is released to transfer or move from the transfer sheet to the receiving sheet for forming marks on the receiving sheet, in both instances the mark being formed according to the pressure pattern.
  • a minute pressure-rupturable capsule said capsules being used in large quantities numerically and being the particulate material in one form of this invention
  • pressure-sensitive mark-forming sheet material or similar phraseology, is meant that type of material which, upon the application of mark-forming pressure against the sheet material (for example, pressure of a stylus, a type face such as that carried by a typewriter lever, raised type printing plates, or the like) and without any intervening agency such as a ribbon, carbon, ink, or mating impression sheet, or other agency other than the sheet material itself, the configuration of the area receiving the pressure is reproduced on the sheet material as a visible, distinctive mark by mark-forming components in the material itself.
  • mark-forming pressure against the sheet material for example, pressure of a stylus, a type face such as that carried by a typewriter lever, raised type printing plates, or the like
  • intervening agency such as a ribbon, carbon, ink, or mating impression sheet, or other agency other than the sheet material itself
  • Mark-forming sheet materials embodying minute capsules such as those described in US. Letters Patent Nos. 2,730,456 and 2,730,457, issued to Barrett K. Green and Lowell Schleicher on Jan. 10, 1956, and assigned to the assignee herein, have proven commercially successful and have been the practices art in what is often referred to as carbonless carbon-paper systems.
  • pressure-rupturable microcapsules containing one of the mark-forming components are coated onto a sheet material, such as finished paper, to provide, as the case may be, either a self-contained sheet material or a transfer sheet material, said sheet material, in the instance of the self-contained system, also containing at least one other reactive mark-forming component, so that, upon application of marking pressure to the system, a mark is produced either on the sheet bearing the capsules, in the case of the self-contained unit, or on the receiving sheet, in the case of the transfer system.
  • a sheet material such as finished paper
  • the subject invention provides a system for limiting the penetration of capsular material applied to a wet fibrous sheet, or, more broadly, any particulate material so applied, which affords the advantages inherent in having said particulate material disposed within the body of the sheet material and yet accomplishes this end without concomitant intolerable loss of the particulate material, by burying or total escape, to achieve it. Also of considerable significance is that the present invention provides a system and materials that have resulted in particulate material being retained within 10% to 20% of the thickness of the finished sheet as measured from one surface.
  • the subject invention comprises a system (and the product produced ther from) for limiting the penetration of applied particulate material through the thickness of a fibrous sheet material wherein an embryonic web of sheet material is formed on a support member, and the particulate material, preferably in the form of a liquid suspension thereof, is applied to said embryonic web while still wet and draining, and at the same time, or substantially simultaneously, upon appli- Cation of the particulate material, there is caused to emerge or form within the embryonic Web, but adjacent the entering surface, a relatively viscous liquid binder phase stratum capable of wetting the particulate material and the fibers of said web that are in contact proximity to the viscous liquid phase; the viscous liquid enveloping the particulate entities and binding itself and the particulate material to the proximate fibers, yet allowing the residual liquid within the web to drain therefrom.
  • the subject invention provides a conrol or limitation of the penetration of a particulate solid or liquid through a fibrous web by effecting the formation or generation, in a portion of the cross-sectional thickness of the web, of a relatively viscous liquid phase of binder material, which phase wets both the particulate material and the fibers of the web, holding them together.
  • the formed liquid phase is a relatively viscous solution of a film-forming polymeric material which has been induced to separate as such from a solution thereof by introducing into the environment of the fibers one of many known change of condition agents, whether they be of chemical and/or physical nature, to cause said separation.
  • phase separation to produce a relatively viscous liquid solution of a film-forming polymer from a homogeneous liquid solution thereof is referred to as ccacervation
  • tie separated or generated relatively viscous liquid phase consequently is referred to as a coacervate or a coacervate solution
  • various techniques or procedures for effecting it are generally described by H. G. Bungenberg and H. R. Kruyt in Proceedings of the Academy of Sciences of Amsterdam, volume 32, pp. 849 to 856 (1929), and Colloid Science II, by H. R. Kruyt, published by Elsevier Publishing Company, Inc., New York, N.Y., in chapters VIII and XI.
  • a relatively viscous liquid solution phase separates, which, being capable of Wetting the capsules and the fibers, binds the capsules to the fibers so wetted and precludes further penetration into the web by said capsules.
  • any known technique for effecting a phase separation of a viscous liquid phase and wherein the separated viscous liquid phase will form substantially on contact with the fibers of the embryonic web is satisfactory.
  • the separated phase forms instantly upon contact with the fibers of the web so as to maintain substantially all of the applied particulate material within the web as a subsurface stratum or layer adjacent the surface of entry.
  • Other techniques for inducing an emergent coacervate phase of film-forming polymeric material are referred to in the literature cited above, including, without limitation, the following:
  • the necessary concentrations and conditions to bring about the emergence of the enveloping phase may be predetermined and the formation of the em bryonic fibrous sheet material conducted in such a manner that at the time the several components essential to Y causing the emergent phase separation are brought into operational proximity to each other, the appropriate concentrations and conditions will be present within the limits of that portion of the cross-sectional thickness of the fibrous sheet material to which it is desired to restrict the penetration of the particulate material.
  • any particulate material, solid or liquid, dispersable as a separate phase in a liquid medium may be added to the embryonic web of sheet material, for convenience of description, and with the desire to delineate and illustrate various aspects of the invention
  • the specification hereafter will emphasize the application of the invention to a system and product thereof useful in the preparation of pressure-sensitive markforming sheet material employing minute capsules as the particles.
  • the system at the initiation of the particle capture on and among the fibers may be characterized as follows:
  • each phase is an identifiable phase, and further characterized respectively, as follows:
  • drying of the web alone provides a sheet material wherein the particulate material has a limited penetration.
  • the particulate material is wholly liquid, more can be done to retain it in the captured position, such as the hardening by chemical action (or other means) of the viscous emergent wall-forming polymer solution surrounding said liquid particulate material (in effect hardening of embryonic walls), and the drying of the web to provide a finished sheet material having limited penetration of particulate material.
  • a primary objective of the invention is to provide a paper sheet with limited penetration of liquid-containing capsules as the particles that, because of their position in the sheet, when mptured by forces applied to the sheet, release the contained liquid at or near the surface of one side of the sheet only. This objective is accomplished by forming a sheet of paper with the capsules embedded in it only near that one surface, so that liquid released is available at or just beneath that surface only.
  • the amount of capsules applied should be related to the final sheet thickness and the amount of encapsulated liquid necessary or desirable to be provided.
  • Such onesidedness is independent of the presence of one or more other sets of capsules throughout the thickness of the sheet or on the outside of the sheet, and it does not preclude the presence of other material, particulate or other, present in, on the outside of, or otherwise associated with the sheet, to cooperate, or not, with the set of capsules positioned in the sheet by the practice of this invention, cumulatively or countervailing, which produce the one-sidedness, or to serve another purpose.
  • Another objective of this invention is to provide a novel sheet which combines the advantages of one-sidedness and the particle (capsule) physical protection from touch and sight found in sheets where such are distributed throughout the thickness of the sheet.
  • the particles (capsules) may be confined within the sheet, they are of necessity much smaller in their average diameter size than the sheet thickness and preferably are of such size, and present in such quantity, that they are protectively nested in the interstitial spaces between the felted fibers of the paper support sheet, in addition to being adherent to the fiber, even if calendered, without disturbing, from a users viewpoint, the normal physical structure of such a sheet made Without them.
  • the particles are capsules, they are subject to rupture by pressure, indentation of the sheet, or pounding, to release the liquid locally to perform the function, which will be evident only Where the capsules are located.
  • the embedded particles need not be of uniform substance, content, and size.
  • the particles may be a mixture as to size and Wall material, or of difierent content or origin, to serve one or more utilitarian purposes in behavior, or, if capsules, to have walls of varying resistance to rupture or fracture, or to be different in any other aspect of structure or performance (such as resistance to heat or solvents, resistance or non-resistance to electric currents) or different in any organic sense characteristics as to odor or color-or sensitive to magnetic flux in one way or anotheror to be sensitive to heat, light, or other radiation-or to contain chemical reactants, medicines, perfumes, or marking materials which are already colored or which color on release of the contents of the capsule to react with adjacent materials or with materials attached to the capsule walls on the outsideor to contain poisons, food, cosmetics, radiating molecules or atoms, or adsorbents or absorbentsto be different in reflectance or absorption of light, as between the fractured and unfrac
  • Each of the capsules may be self-contained, in that each, upon rupture, creates a color mark, as disclosed in Example II, to follow.
  • the particulate liquid may contain either liquid or solid solute material dissolved therein, or have such materials dispersed therein in any physical state, and may contain materials which may be subject to growth, metamorphosis, or degeneration, all to the purpose of making a paper sheet having utility by being one-sided.
  • capsules if such are used, they may be manufactured in separate batches according to the characteristics of the capsules as to origin, size, contents, or wall material and structure, and thereafter blended in the desired proportions for introduction into the paper as a single applied slurry. This is important where more than one kind of capsule contents (solid or fluid) is to be made use of either by rupture of the capsules or by their characteristics in the unruptured state. It is within the province of this invention to provide capsules having different thicknesses of walls or different strengths of walls, to the end that they may be differentially fractured by variations in pressure, so that some capsules may be ruptured by one pressure and the rupture of other capsules will follow in response to application of a greater pressure.
  • the preferred system comprises laying down a wet web of fibrous material on a supporting member to form an embryonic sheet, said web having disposed therein a suitable agent to effect phase separation or emergence of a relatively viscous liquid solution of film-forming polymeric material from a less viscous homogeneous solution of applied polymeric material, and applying to said web the less viscous solution of the said film-forming polymeric material having dispersed in it the aforementioned minute capsules, the contents of which capsules comprise a mark-forming component material, whereupon on contact of the agent and the less viscous solution the viscous liquid binder phase emerges and binds the capsules to the proximate fibers.
  • the applied solution is of low viscosity and is easily flowed uniformly onto the wet sheet.
  • the viscous separated phase in part, by reason of its viscosity, does not penetrate through the sheet, and, because of its exceptional wetting characteristics, clings to the proximate fibers to become bound thereto.
  • Suitable fibrous sheet material can be readily formed from a liquid slurry, generally an aqueous slurry, or wet stock of any paper-forming fibers which forms a substantially unified fibrous web, the most common fibers being cellulose rag and wood pulp fibers, which are ordinarily used to form papers.
  • Other discontinuous randomly or otherwise oriented fibers including what are commonly referred to as fibrils, mica and synthetic mica platelets, or other filament-forming solids (e.g. fibers of polyacrylonitriles, polyesters, and polyamids, that can be deposited from a slurry on a paper-making machine to form a unified paper or paper-like web having interstitial voids on a paper-making machine) can be used.
  • Suitable capsular material containing at least one of the mark-forming components are described in the aforementioned United States Patents Nos. 2,730,456 and 2,730,457.
  • FIGS. 1 and 2 are schematic diagrams showing the various components of the Fourdrinier paper machine, and apparatus for introducing the materials used in the practice of this invention.
  • the headbox contains the aqueous slurry of paper pulp, which is passed onto the Fourdrinier wire 11, table rolls 12 and suction boxes 13 being shown.
  • Particulate material the penetration of which is to be limited, is added to an embryonic web being formed on the Fourdrinier wire 11, as at a dandy roll 14.
  • the web W After leaving the wire 11 at the couch roll 15, the web W passes through a series of presses 16, 17, and 18 and from there through a series of drying drums 19 (shown in fragmented section) to a wind-up roll 20.
  • FIG. 2 represents a more detailed schematic view showing storage of sheet-forming materials, and distribution to and recirculation from the Fourdrinier wire section to the storing vessels of such materials, and application of the liquid slurry to the dandy roll.
  • the stock and the size are introduced into a mixer 20 and then to a machine chest 21, wherein they are blended with white water from the couch pit 22 through the conduit 23.
  • the resulting slurry may be diluted further by introduction of water through a conduit 24, after which the mass is passed through at Jones refiner 25 and conveyed through a pump 26 and then a conduit 27 to the inlet storage vessel 28, whereat a material that takes part in the subsequently occuring phase separation, such as a cationic starch sol, is added.
  • the resulting slurry is metered through a Bird screen 29 via a conduit 30 to the headbox 31 and thence to the Fourdrinier Wire 32, thus forming an embryonic web (W).
  • the embryonic web moves toward the dandy roll 33, the screen of which in turn is being supplied by a slurry comprising the particular matter dispersed in an aqueous sol of, for example, Karaya gum.
  • FIGS. 1 and 2 are merely illustrative. It is within the scope of this invention to add the capsules or other particulate material by means other than the dandy roll and at any point in the web formation, provided that the web at the time of addition of the particulate material is sufficiently wet and penetrable, either by reason of undrained liquid or because the particulate material was added as a liquid slurry, to permit emergence of a relatively viscous liquid solution of polymeric material and its fixation on the fibers.
  • the preferred procedure as shown in FIGS.
  • EXAMPLE I The following is a description of the preferred embodiment of the invention as carried out using the process steps and apparatus shown in FIGS. 1 and 2, wherein minute capsules were added to a wet web of fibrous paper on a Fourdrinier paper-making machine.
  • Karaya gum was present in the capsular slurry, and cationic starch was present in the pulp, these materials, Karaya gum and cationic starch, acting in concert to cause the emergence, within the sheet of wet fibers, of a relatively viscous liquid phase, which in its emergent form is present as a plurality of entities.
  • the emergent liquid phase becomes less in volume and, in contracting from the original volume occupied by the solution, breaks up into entities carrying with them the associated capsules, which are thus enveloped.
  • the entities themselves when formed among the topmost fibers, wet them and entangle with them and clothe them, thus in eii'ect securing and binding the capsules against migration through the sheet, thereby forming a strat
  • the Karaya gum solution and the cationic starch solution were prepared in the following manner:
  • Cationic starch s0lnti0n.--The cationic starch (Q-TAC 3891, manufactured by Corn Products, Inc., and described in Corn Products Technical Bulletin No. QT-27-002 as a cationic derivative of corn starch produced by the reaction of starch with a quaternary amine) solution was prepared by heating a surry of the starch at degrees Fahrenheit for a minimum of fifteen minutes to provide a 1%, by weight, starch-in-water solution.
  • Acid slnrry.-Benzoyl leuco methylene blue (BLMB) and crystal violet actone (CVL) were dissolved in chlorinated diphenyl and kerosene.
  • the resulting oil was dispersed as a liquid phase in an aqueous gelatin sol.
  • gum arabic and polyvinyl methyl maleic anhydride (PVM/MA) which, upon lowering of pH with acetic acid at the proper dilution, effects the formation of a coacervate solution of the gelatin, said coacervate forming embryonic capsule walls of coacervate solution about the dispersed oil droplets.
  • the embryonic walls were set, by cooling, and hardened with glutaraldchyde.
  • the weight ratio of oil to gelatin was on the order of 10:1, and average diameter of the resulting aggregate of individual droplets was on the order of 8 to 12 microns.
  • the embryonic Walls were set by cooling and g; svlgr g throw cougidrmin g thfingddirf the hardened with glutaraldehyde, and the coacervate solution gg Gvm zolutiojatfhe dand tank g was treated wtih colloidal silica (United States Letters T112; ul used in etc'ri of the uns re orted in Table I Pamnt issued to Bruce Brockett on p p p April 20, 1965, and assigned to the assignee herein). The was 75% bleached kraft and bleached sulfite, re-
  • weight ratio of 011 to gelatin was on the order of 3.5 to 1, fined to a nominal Jordan freeness of 250 cc. Canadian so and the average diameter of the resulting aggregate of Standard at degrees cenmgrade'
  • the pulp was Sued individual droplets was on the order of 8 to 12 microns with 1.2% rosin and 2.4% alum based on the pulp. No pH adjustment was made.
  • EXAMPLE 11 The following is a description of a series of runs wherein minute capsules and other particulate matter were added to a wet web of fibrous paper on a Fourdrinier papermaking machine to make a self-contained record material.
  • Karaya gum, colloidal silica, and kaolin clay were present in a modified capsular slurry, and the cationic starch was present in the pulp, the Karaya gum and the cationic starch acting in concert to cause the emergence, Within the sheet of wet fibers, of a relatievly viscous liquid phase, as in Example I.
  • the Karaya-clay-modified capsular slurry was added at the dandy roll, as shown in FIG. 1.
  • the Karaya gum and cationic starch solutions were prepared in the following manner:
  • the above modified capsular slurry was prepared by first mixing the kaolin clay and the capsular slurry, and then passing this mixture through a colloid mill. Then the oxidized potato starch, the colloidal silica, and the ZnCl were stirred in. The Karaya gum solution was added last, just prior to use.
  • Cationic starch solution The cationic starch (Q-TAC 3891 Corn Products) solution was prepared by heating a slurry of the starch at 195 degrees Fahrenheit for a mini mum of fifteen minutes to provide a 1%, by weight, starch-in-water solution.
  • the pulp used was bleached kraft and 25% bleached sulfite, refined to a nominal Jordan freeness of 420 cc. Canadian Standard at 30 degrees Centigrade.
  • the pulp was sized with 1.2% rosin and 2.4% alum based on the pulp.
  • Concentrated sulfuric acid was added to the 1 3 machine chest to control pH. The operating data and results for these runs are set forth in Table H.
  • the embryonic sheet has the particles fixed in it in a stratum, or layer, predominately just beneath one surface, from which position they cannot migrate, subsequent operations may be performed on the web. Any other applications of materials may be made to the web, while wet, either while being pressed, while being dried, or in off-the-machine conversion of the finished sheet, as may be desired in view of the ultimate use for it.
  • one or more coatings of mate-rial may subsequently be placed on either surface or on both surfaces .as may be desired.
  • coatings containing minute capsules or particles which are applied to the side opposite said one surface, making the sheet useful as one of a stack of such sheets for making multiple copies by pressure.
  • Other coatings may be applied to make the sheet sensitive to light, heat, or other energy application, or to give it magnetic or radiation properties, coloration, luminescence, or to make it photoelectrically or photoconductively responsive or non-responsive, or modified as may be desired in any pattern or mode of response not inconsistent with the presence of the novel stratum of particles.
  • EXAMPLE III Other combinations of materials useful to effect a phase separation within a fibrous sheet material are shown in Table III. In each case, an embryonic hand sheet was formed, and the indicated materials were .applied in the manner described hereafter.
  • Table 111 gives a tabulation of the modifying agents used and .an indication of the response characteristics of the sheets.
  • the embryonic Walls were set "by cooling and hardened with glutaraldehyde.
  • the capsule-making process is described in the Katchen et a1. United States Patent No. 3,041,289, of which mention has been made.
  • the weight ratio of oil to gelatin was on the order of 10:1, and average diameter of the resulting aggregate of individual droplets was on the order of 8 to r12 microns.
  • aqueous capsular slurry Additions to aqueous capsular slurry.
  • the aqueous slurry of capsules described above had the various agents indicated in Table III below added thereto.
  • the agents were added as an aqueous sol (solution) to give a modified slurry which contained capsules in an amount of 8% by Weight of the total slurry.
  • puIp The pulp, consisting of kraft and 25% bleached sulfite, was beaten to a Canadian Standard 'Freeness of approximately 250 cc. at 30 degrees centigrade.
  • the pulp was sized with 1.2% rosin .and 2.4% papermakers alum, both 'by weight on the dry fiber. The sized pulp was used at 0.5% solids.
  • Modification of sized pulp.-T0 600 cc. of the sized pulp described above were added the agents in the amounts indicated in Table III, based on the dry fiber weight.
  • the agents were added as a sol (solution) or, in the case where the agent is insoluble in water, as an aqueous dispersion.
  • Table III shows various agents and amounts thereof that were added to the capsular slurry and the pulp, respectively, and also shows the dry capsule weight per ream (DOW/R), ream size being 25" x 38"/500 sheets, and the typewriter intensity (TI) (more fully described below).
  • DOW/R dry capsule weight per ream
  • TI typewriter intensity
  • Weight/Ream A (None) (None) 3 44 44 B (%onc) (None) 3 78 78 1.
  • 5%Q-TAC quaternary amine derivative 0.5% Karaya gum 3.1 49 50 cationic starch 2 0.2% Karaya gum, 2.0% Q-TAC do 3.
  • 4 52 54 3. 0.5% Polymin P (polyetliylenimine). do i. 3.0 44 44 4. 0.8% Polymin P do 3. 4 40 42 5.
  • 5% Colloidal Alumina do 2. 7 52 50 6. 0.2% Karaya, 1.0% Colloidal Alumina do 2.
  • Polymin P is manufactured by Badischc Anilin-E' Soda-Fabrik AG and is described in their bulletin No. MlllSe, 80950 (610) FKi, dated July 1961, as an aqueous solution of 'polyethyleniminc (50% solids), molecular weight 2030,000.
  • Arquad 18-50 is manufactured by Armour Chemical Company, described in their technical bulletin on Fatty Acid Derivatives, and Industrial Oils, dated 1957, is a quaternary ammonium chloride salt.
  • PVA 72-60 is manufactured by Du Font and described in their technical bulletin entitled Elvanol, polyvinyl alcohol, third edition, 1961, as a completely hydrolyzed, high viscosity grade of polyvinyl alcohol.
  • Separan NP-1O is manufactured by Dow Chemical Company and is described in Dows technical booklet No. 125-28442, entitled Separan, dated 1961, as .a high molecular weight polyacrylamide.
  • Separan AP-30 manufactured by Dow Chemical Company, is described as a high molecular weight polyacrylamide in their technical booklet No.125-284-62, entitled Soparan, dated 1961.
  • CATO-8 is manufactured by National Starch & Chemical Corporation and is described in their Technical Service Bulletin No. 20S rev., and further described in US. Patent No. 2,917,506.
  • Pen'ford Gum 250 Starch is manufactured by Penick & Ford, Ltd. and is described in the Corn Refining Divisions technical letter No. 87, dated February 2, 19611, as a hydroxy ethyl ether derivative of corn starch.
  • CMC-7L manufactured by Hercules is described in their technical bulletin Sodium Carb'oxymethylcellulose, dated 1963, as a sodium carboxymethyl cellulose gum having a degree of substitution range of 0.65 to 0.85 and a low viscosity in the range of 30 to 50 cps. for a 2% solution.
  • a standard mark is prepared by taking a sheet having the dye-containing capsules coated on its outer surface, and placing said surface against the surface of a coated second sheet having the other mark-forming component, whereupon a pressure is brought to bear on the two sheets over an area of the sheet to produce a marked area, by transfer of the ruptured capsule contents to the second sheet.
  • the reflectances of incident light from the unmarked area and the marked area after a period of time (twenty minutes) are then measured and compared.
  • the typewriter intensity is the ratio of the reflectance of the marked area to the unmarked areaxlOO, the lower said ratio value the more intense the mark.
  • the values of reflectance given are relative numbers only, but show the variance from the values obtained from standard coated sheets and from sheets in which the capsules were distributed through the body of fibers (the control sheet).
  • the typewriter intensity value was similar to or compared favorably with that of the present standard commercial paper coated with capsules.
  • the smudge resistance is a measure of the frictional smudge properties of a sheet material and is determined in general by disposing a sheet containing a complementary mark-forming reactant which completes the markforming reaction onto the sample sheet, so that the colorreactant-bearing surfaces of the two sheets are in contact, placing on said pair of sheets a standard weight, and drawing the top sheet across the under (sample) sheet for a fixed distance, both in a machine direction and in a cross-machine direction of the paper. Thereafter, the reflectance of the area of the top sheet which was under the weight is measured. Smudge resistance, as reported, is the ratio of the reflectance of the weighted area to the background area l00.
  • sheet material more particularly a microcapsule-containing paper
  • sheet material more particularly a microcapsule-containing paper
  • the sample sheet is split in a plane through its thickness.
  • a sample sheet prepared according to Run No. 3 of Table I was successively split as described above to yield sliver sections corresponding to the top /2, A, and A; of the thicknesses of the sample sheet.
  • the overall thickness of the sample was about 4 mils and the particle size of the capsules was about 4 to microns, it was beyond reasonable expectation and highly gratifying to find that the major portion of the capsules resided in the upper quarter of the paper. This was particularly surprising when considera- 18 tion is given to the pull through" forces that exist on a paper-making machine due to gravity, liquid entrainment, and suction.
  • the particulate matter whose penetration into a wet fibrous web is to be limited, is an oilsoluble dye, Azo Blue Black B.
  • aqueous particulate slurry Preparation of aqueous particulate slurry.-Microfine titanium dioxide was dispersed in water, using sodium silicate and Triton N- as the dispersing agents. To this dispersion was added the solid Azo Blue Black B in powdered form, and the entire mixture was blended in a Waring Blendor. After blending and just prior to use, dilute (0.1%) Karaya gum was stirred in. Octauol was added as a foam killer. The formulation for this slurry is as follows:
  • Emergence of the expected relatively viscous liquid phase occurred when the aqueous particulate slurry was drawn across the top of the cationic-starch-treated web. The web was then pressed and dried.
  • a further aspect of the subject invention concerns the nature of the fibrous sheet material resulting from carrying out the process of this invention.
  • the sheet of the invention differs from earlier fibrous sheets in that the penetration of the particulate material is substantially uniform.
  • the penetration of the particulate material is substantially uniform.
  • the subject invention it has been found that the particulate matter penetrates over the area applied, to a substantially uniform degree through a limited thickness of the web.
  • a process for limiting the penetration of particulate material within an embryonic fibrous sheet comprising forming a wet web of the fibrous material on a suitable support member, said wet web being sufficiently free to allow drainage of associated liquid and micro-size particulate material therethrough; While the web is in said state of freeness, applying particulate material to one surface of said web, and then substantially simultaneously with the application of said particulate material, forming a coacervate solution of a film-forming polymeric material within a limited thickness of the sheet, said coacervate solution enveloping the particulate material and wetting the fiber(s) in proximate relation thereto to thereby bind the particulate material to the fiber(s).
  • a process for limiting the penetration of particulate material within a fibrous sheet comprising and forming a wet web of fibrous material having a coacervate phaseenducing agent present therein on a suitable support member, said web being sufficiently free to allow drainage of liquid and particulate material therethrough, and then applying particulate material in the form of a liquid suspension to said wet web, said suspension containing in solution a film-forming polymeric coacervatable material to form a coacervate solution of film-forming polymeric material within a limited thickness of the sheet which envelopes the particulate material and simultaneously adheres to the proximate fibers thereby to atfix the particulate material to the fibers.
  • the particulate material is pressure-rupturable microcapsules each having a mark-forming component therein
  • the coacervate-phaseinducing agent is a cationic starch
  • the film-forming polymeric material is ammonia-treated Karaya gum.
  • wet web comprises paper fibers and associated aqueous liquid and wherein the particulate material is applied when the wet web comprises from 92% to 98% water.
  • the particulate material is pressure-rupturable microcapsules each having a mark-forming component therein
  • the coacervate-phaseinducing agent is a cationic starch
  • the film-forming polymeric material is ammonia-treated Karaya gum.
  • phase-inducing agent and the film-forming polymeric material are of opposite polarity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
US442352A 1965-03-24 1965-03-24 Process for forming fibrous sheets containing limited penetration of additaments within the sheet and sheets thereof Expired - Lifetime US3384536A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US442352A US3384536A (en) 1965-03-24 1965-03-24 Process for forming fibrous sheets containing limited penetration of additaments within the sheet and sheets thereof
GB7487/66A GB1105711A (en) 1965-03-24 1966-02-21 Method of limiting the depth of penetration of particulate material into a fibrous sheet material
BR177398/66A BR6677398D0 (pt) 1965-03-24 1966-02-28 Processo para formar uma folha fibrosa
NO162046A NO124273B (es) 1965-03-24 1966-03-10
AT253766A AT269910B (de) 1965-03-24 1966-03-17 Verfahren zum Begrenzen der Eindringtiefe eines feinteiligen, in einer Flüssigkeit dispergierten Stoffes in ein faseriges Blattmaterial
CS1847A CS165980B2 (es) 1965-03-24 1966-03-18
FR54212A FR1478652A (fr) 1965-03-24 1966-03-21 Procédé destiné à limiter la profondeur de pénétration d'une substance finement divisée dans une feuille de matière fibreuse
BE678203D BE678203A (es) 1965-03-24 1966-03-22
SE3765/66A SE301910B (es) 1965-03-24 1966-03-22
DE19661546271 DE1546271C3 (de) 1965-03-24 1966-03-22 Verfahren zum Begrenzen der Eindringtiefe eines in Form sehr kleiner Teilchen vorhandenen Stoffes in ein faseriges Blattmaterial
DK147866AA DK120929C (da) 1965-03-24 1966-03-22 Fremgangsmåde til fremstilling af en bane af fiberformet materiale.
ES0324631A ES324631A1 (es) 1965-03-24 1966-03-24 Metodo para limitar la profundidad de penetracion de material particulado en una red humeda de material fibroso, y el resultado de la operacion.
NL6603889A NL6603889A (es) 1965-03-24 1966-03-24
CH420766A CH453064A (fr) 1965-03-24 1966-03-24 Procédé de fabrication d'une feuille de matière fibreuse ayant incorporée une substance finement divisée

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CH (1) CH453064A (es)
CS (1) CS165980B2 (es)
DK (1) DK120929C (es)
ES (1) ES324631A1 (es)
GB (1) GB1105711A (es)
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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3472675A (en) * 1966-01-27 1969-10-14 Ncr Co Pressure-sensitive capsule-containing foraminated sheet material
FR2041112A1 (es) * 1969-04-01 1971-01-29 Ncr Co
DE2116258A1 (de) * 1970-04-02 1971-11-04 Fuji Photo Film Co Ltd Verfahren zur Herstellung von Kap sein aufweisenden Bahnen
US3620801A (en) * 1968-06-07 1971-11-16 Wiggins Teape Res Dev Sized transfer sheet
US3630835A (en) * 1968-02-13 1971-12-28 Appleton Coated Paper Co Method for coating paper with pressure rupturable fluid containing capsules
US3775172A (en) * 1972-01-07 1973-11-27 Ncr Process for film-coating articles
US3978204A (en) * 1969-02-04 1976-08-31 L'oreal Cosmetic composition containing microencapsulated solvents for nail enamel
US4282275A (en) * 1980-01-14 1981-08-04 The Mead Corporation Coating method apparatus for capsular coatings
US4710270A (en) * 1980-09-19 1987-12-01 Olof Sunden Paper making process utilizing fillers with hardened envelopes of cationic starch
US4995944A (en) * 1988-09-16 1991-02-26 Dearborn Chemical Company Ltd. Controlling deposits on paper machine felts using cationic polymer and cationic surfactant mixture
US5104487A (en) * 1988-09-02 1992-04-14 Betz Paper Chem., Inc. Papermaking using cationic starch and naturally anionic polysacchride gums
US5223097A (en) * 1986-01-09 1993-06-29 W. R. Grace Ab Method for controlling pitch on a paper-making machine
US5626720A (en) * 1986-01-09 1997-05-06 W.R. Grace & Co.-Conn. Method for controlling pitch on a papermaking machine
US5820937A (en) * 1992-06-15 1998-10-13 The Mead Corporation Process for making high abrasion overlays
US6723204B2 (en) * 2002-04-08 2004-04-20 Hercules Incorporated Process for increasing the dry strength of paper
US20140231036A1 (en) * 2011-06-24 2014-08-21 Smurfit Kappa hoya Papier and Karton GmbH Fibre Product for Packaging

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2730457A (en) * 1953-06-30 1956-01-10 Ncr Co Pressure responsive record materials
US2730456A (en) * 1953-06-30 1956-01-10 Ncr Co Manifold record material
US3041288A (en) * 1958-12-22 1962-06-26 Ncr Co Method of manufacturing microscopic capsules having walls of alcohol-fractionated gelatin
US3137631A (en) * 1959-12-01 1964-06-16 Faberge Inc Encapsulation in natural products
US3257267A (en) * 1965-05-19 1966-06-21 Harold R Hay Retarding liberation of an additament in forming a fibrous web by embedding the additament in a gel matrix prior to addition to the fibers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2730457A (en) * 1953-06-30 1956-01-10 Ncr Co Pressure responsive record materials
US2730456A (en) * 1953-06-30 1956-01-10 Ncr Co Manifold record material
US3041288A (en) * 1958-12-22 1962-06-26 Ncr Co Method of manufacturing microscopic capsules having walls of alcohol-fractionated gelatin
US3137631A (en) * 1959-12-01 1964-06-16 Faberge Inc Encapsulation in natural products
US3257267A (en) * 1965-05-19 1966-06-21 Harold R Hay Retarding liberation of an additament in forming a fibrous web by embedding the additament in a gel matrix prior to addition to the fibers

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3472675A (en) * 1966-01-27 1969-10-14 Ncr Co Pressure-sensitive capsule-containing foraminated sheet material
US3630835A (en) * 1968-02-13 1971-12-28 Appleton Coated Paper Co Method for coating paper with pressure rupturable fluid containing capsules
US3620801A (en) * 1968-06-07 1971-11-16 Wiggins Teape Res Dev Sized transfer sheet
US3978204A (en) * 1969-02-04 1976-08-31 L'oreal Cosmetic composition containing microencapsulated solvents for nail enamel
FR2041112A1 (es) * 1969-04-01 1971-01-29 Ncr Co
DE2116258A1 (de) * 1970-04-02 1971-11-04 Fuji Photo Film Co Ltd Verfahren zur Herstellung von Kap sein aufweisenden Bahnen
US3775172A (en) * 1972-01-07 1973-11-27 Ncr Process for film-coating articles
US4282275A (en) * 1980-01-14 1981-08-04 The Mead Corporation Coating method apparatus for capsular coatings
US4710270A (en) * 1980-09-19 1987-12-01 Olof Sunden Paper making process utilizing fillers with hardened envelopes of cationic starch
US5223097A (en) * 1986-01-09 1993-06-29 W. R. Grace Ab Method for controlling pitch on a paper-making machine
US5626720A (en) * 1986-01-09 1997-05-06 W.R. Grace & Co.-Conn. Method for controlling pitch on a papermaking machine
US5104487A (en) * 1988-09-02 1992-04-14 Betz Paper Chem., Inc. Papermaking using cationic starch and naturally anionic polysacchride gums
US4995944A (en) * 1988-09-16 1991-02-26 Dearborn Chemical Company Ltd. Controlling deposits on paper machine felts using cationic polymer and cationic surfactant mixture
US5820937A (en) * 1992-06-15 1998-10-13 The Mead Corporation Process for making high abrasion overlays
US6723204B2 (en) * 2002-04-08 2004-04-20 Hercules Incorporated Process for increasing the dry strength of paper
US20140231036A1 (en) * 2011-06-24 2014-08-21 Smurfit Kappa hoya Papier and Karton GmbH Fibre Product for Packaging
US9051115B2 (en) * 2011-06-24 2015-06-09 Smurfit Kappa Hoya Papier Und Karton Gmbh Fibre product for packaging
EP3175985B1 (de) 2011-06-24 2017-11-29 Smurfit Kappa Hoya Papier und Karton GmbH Fasererzeugnis für verpackungen
EP2723564B1 (de) 2011-06-24 2020-02-26 Smurfit Kappa Hoya Papier und Karton GmbH Fasererzeugnis für verpackungen

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AT269910B (de) 1969-04-10
DE1546271A1 (de) 1970-07-02
GB1105711A (en) 1968-03-13
BR6677398D0 (pt) 1973-06-14
NL6603889A (es) 1966-09-26
SE301910B (es) 1968-06-24
DK120929B (es) 1971-08-02
CH453064A (fr) 1968-05-31
ES324631A1 (es) 1967-05-01
CS165980B2 (es) 1975-12-22
DK120929C (da) 1971-12-20
NO124273B (es) 1972-03-27
BE678203A (es) 1966-09-01

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