EP0347153B1 - Verfahren zur Herstellung von mit einem Polysiloxan behandeltem sanftem Tissuepapier - Google Patents

Verfahren zur Herstellung von mit einem Polysiloxan behandeltem sanftem Tissuepapier Download PDF

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Publication number
EP0347153B1
EP0347153B1 EP89305939A EP89305939A EP0347153B1 EP 0347153 B1 EP0347153 B1 EP 0347153B1 EP 89305939 A EP89305939 A EP 89305939A EP 89305939 A EP89305939 A EP 89305939A EP 0347153 B1 EP0347153 B1 EP 0347153B1
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Prior art keywords
tissue paper
web
polysiloxane
process according
surfactant
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EP89305939A
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French (fr)
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EP0347153A3 (de
EP0347153A2 (de
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Robert Stanley Ampulski
Wolfgang Ulrich Spendel
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/50—Spraying or projecting

Definitions

  • This invention relates, in general, to a process for preparing tissue paper; and more specifically, to a process for preparing high bulk tissue paper having a soft, silky, flannel-like tactile feel; and enhanced tactile perceivable bulk, and physiological surface smoothness.
  • Soft tissue paper is generally preferred for disposable paper towels, and facial and toilet tissues.
  • known methods and means for enhancing softness of tissue paper generally adversely affect tensile strength.
  • Tissue paper product design is, therefore, generally, an exercise in balancing softness against tensile strength.
  • tissue paper which is perceived by users, through their tactile sense, to be soft.
  • Such tactile perceivable softness may be characterized by, but not limited to, resilience, flexibility, and smoothness; and subjective descriptors such as feeling like silk or flannel.
  • the present invention pertains to a process for improving the tactile perceivable softness of tissue paper -- in particular high bulk, creped tissue paper -- through the incorporation of chemical additives: in particular, polysiloxane materials which impart a silky or flannel-like feel to the tissue paper without rendering it greasy or oily to the tactile sense of users of products comprising such tissue paper.
  • surfactant material may be added to further enhance softness and/or surface smoothness and/or to at least partially offset any reduction in wettability caused by the polysiloxane; and binder material such as starch may be added to at least partially offset reductions in strength and or increasing in linting propensity that results from the polysiloxane and, if used, the surfactant additive.
  • tissue paper Other chemical treatments which have been proposed to improve tissue paper include, for example, that disclosed in DE-A-3,420,940, Kenji Hara et al, to wit: to impregnate toilet tissue paper with a combination of a vegetable, animal, or synthetic hydrocarbon oil, and a silicone oil such as dimethylsilicone oil to make it easier to clean and wipe with.
  • tensile strength can be increased without negatively impacting softness; or, alternatively, softness can be improved without negatively impacting tensile strength.
  • US-A-4 028 172 discloses a process for making paper in which a polysiloxane polymer is added to the wet pulp prior to its entrance in the press section of the paper machine. This document relates to wet picking and does not address the problem of making a tissue paper of enhanced softness and of good tensile strength.
  • the present invention encompasses a process for making soft tissue paper.
  • This process includes the steps of wet laying cellulosic fibers to form a web, applying to the web, at a fiber consistency of from about 10% to about 80% (total web weight basis), a sufficient amount of a polysiloxane such that between about 0.004% and about 0.75% of said polysiloxane, dry fiber weight basis, is retained by the tissue paper, and then drying and creping the web.
  • the amount of polysiloxane retained by the tissue paper is between 0.004% to about 0.3%, based on the dry fiber weight of the tissue paper.
  • the resulting tissue paper has a basis weight of from about 10 to about 65 g/m2 and a fiber density of less than about 0.6 g/cc, and has the polysiloxane compond uniformely disposed on its outwardly facing surfaces.
  • the polysiloxane is applied subsequent to formation of the wet web and prior to drying to completion. Surprisingly, it has been found that significant tissue softening benefits can be achieved by much lower levels of polysiloxanes when the polysiloxane is applied to a wet web, as compared to a dry web (e.g., during the converting operation). In fact, an important feature of the process disclosed herein, is that the silicone level is low enough to be economical. Also, tissue paper treated with low levels of polysiloxane retain a high level of wettability, an important feature for a tissue product.
  • Preferred polysiloxanes for use in the process of the present invention include an amino-functional polydimethylpolysiloxane wherein less than about 10 mole percent of the side chains on the polymer contain an amino-functional group. Because molecular weights of polysiloxanes are difficult to ascertain, the viscosity of a polysiloxane is used herein as an objectively ascertainable indicia of molecular weight.
  • substitution has been found to be very effective for polysiloxanes having a viscosity of about 125 ⁇ 10 ⁇ 6m2s ⁇ 1 (125 centistokes); and viscosities of about 5 m2s ⁇ 1 (5,000,000 centistokes) or more are effective with or without substitution.
  • effective substitution may be made with carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, and thiol groups.
  • the family of groups comprising amino, carboxyl, and hydroxyl groups are more preferred than the others; and amino-functional groups are most preferred.
  • Exemplary commercially available polysiloxanes include DOW 8075 and DOW 200 which are available from Dow Corning; and Silwet 720 and Ucarsil EPS which are available from Union Carbide.
  • the process for preparing tissue paper treated with a polysiloxane in accordance with the present invention may further comprise the step of adding an effective amount of a surfactant to enhance the tactile perceivable surface smoothness of the tissue paper and/or to at least partially offset any reduction of wettability of the tissue paper which would otherwise result from the incorporation of the polysiloxane.
  • the effective amount of surfactant is such that, preferably, from about 0.01 to about 2 percent on a dry fiber weight of the tissue paper; and, more preferably, from about 0.05 to about 1.0 percent is retained by the tissue paper.
  • the surfactant is noncationic; and is substantially nonmigratory in situ after the tissue paper has been manufactured in order to substantially obviate post-manufacturing changes in the tissue paper's properties which might otherwise result from the inclusion of surfactant.
  • This may be achieved, for instance, through the use of surfactants having melt temperatures greater than the temperatures commonly encountered during storage, shipping, merchandising, and use of tissue paper product embodiments of the invention: for example, melt temperatures of about 50°C or higher.
  • the process for preparing tissue paper in accordance with the present invention may further comprise the step of adding an effective amount of a binder material such as starch to at least partially offset any reduction of tensile strength and/or increase in linting propensity which would otherwise result from the incorporation of the polysiloxane and, if present, surfactant material.
  • the effective amount of binder material is such that, preferably, from about 0.01 to about 2 percent on a dry fiber weight basis of the tissue paper, is retained by the tissue paper.
  • the present invention provides tissue paper having a silky, flannel-like feel, and enhanced tactile perceivable softness through the addition of a polysiloxane additive to a wet tissue web.
  • a polysiloxane additive to a wet tissue web.
  • Such process may also include the addition of an effective amount of surfactant material and/or a binder material such as starch to the wet web.
  • surfactant may be included to enhance tactile perceivable, physiological surface smoothness and/or to assure sufficient wettability for the intended purposes of the tissue paper (e.g., as toilet tissue); and a binder material such as starch may be included to at least partially offset any reduction of tissue paper tensile strength and/or exacerbation of linting propensity which would otherwise be precipitated by the addition of the polysiloxane and, if used, the surfactant.
  • tissue paper e.g., as toilet tissue
  • a binder material such as starch
  • the present invention is applicable to tissue paper in general, including but not limited to conventionally felt-pressed tissue paper; pattern densified tissue paper such as exemplified by Sanford-Sisson and its progeny; and high bulk, uncompacted tissue paper such as exemplified by Salvucci.
  • the tissue paper may be of a homogenous or multilayered construction; and tissue paper products made therefrom may be of a single-ply or multi-ply construction.
  • the tissue paper has a basis weight of between 10 g/m2 and about 65 g/m2, and density of about 0.60 g/cc or less.
  • basis weight will be below about 35 g/m2 or less; and density will be about 0.30 g/cc or less.
  • density will be between 0.04 g/cc and about 0.20 g/cc.
  • Such paper is typically made by depositing papermaking furnish on a foraminous forming wire.
  • This forming wire is often referred to in the art as a Fourdrinier wire.
  • the furnish is deposited on the forming wire, it is referred to as a web.
  • the web is dewatered by pressing the web and dried at elevated temperature.
  • the particular techniques and typical equipment for making webs according to the process just described are well known to those skilled in the art.
  • a low consistency pulp furnish is provided in a pressurized headbox.
  • the headbox has an opening for delivering a thin deposit of pulp furnish onto the Fourdrinier wire to form a wet web.
  • the web is then typically dewatered to a fiber consistency of between about 7% and about 25% (total web weight basis) by vacuum dewatering and further drying by pressing operations wherein the web is subjected to pressure developed by opposing mechanical members, for example, cylindrical rolls.
  • the dewatered web is then further pressed and dried by a stream drum apparatus known in the art as a Yankee dryer. Pressure can be developed at the Yankee dryer by mechanical means such as an opposing cylindrical drum pressing against the web. Multiple Yankee dryer drums may be employed, whereby additional pressing is optionally incurred between the drums.
  • the tissue paper structures which are formed are referred to hereinafter as conventional, pressed, tissue paper structures. Such sheets are considered to be compacted since the web is subjected to substantial mechanical compressional forces while the fibers are moist and are then dried while in a compressed state.
  • Pattern densified tissue paper is characterized by having a relatively high bulk field of relatively low fiber density and an array of densified zones of relatively high fiber density.
  • the high bulk field is alternatively characterized as a field of pillow regions.
  • the densified zones are alternatively referred to as knuckle regions.
  • the densified zones may be discretely spaced within the high bulk field or may be interconnected, either fully or partially, within the high bulk field.
  • Preferred processes for making pattern densified tissue webs are disclosed in U.S.-A-3,301,746, issued to Sanford and Sisson on January 31, 1967, U.S.-A-3,974,025, issued to Peter G. Ayres on August 10, 1976, and U.S.-A-4,191,609, issued to Paul D. Trokhan on March 4, 1980.
  • pattern densified webs are preferably prepared by depositing a papermaking furnish on a foraminous forming wire such as a Fourdrinier wire to form a wet web and then juxtaposing the web against an array of supports. The web is pressed against the array of supports, thereby resulting in densified zones in the web at the locations geographically corresponding to the points of contact between the array of supports and the wet web. The remainder of the web not compressed during this operation is referred to as the high bulk field. Formation of the densified zones may be accomplished by application of fluid pressure, such as with a vacuum type device or a blow-through dryer, or by mechanically pressing the web against the array of supports.
  • fluid pressure such as with a vacuum type device or a blow-through dryer
  • the web is dewatered, and optionally predried, in such a manner so as to substantially avoid compression of the high bulk field. This is preferably accomplished by fluid pressure, such as with a vacuum type device or blow-through dryer, or alternately by mechanically pressing the web against an array of supports wherein the high bulk field is not compressed.
  • the operations of dewatering, optional predrying and formation of the densified zones may be integrated or partially integrated to reduce the total number of processing steps performed.
  • the web is dried to completion, preferably still avoiding mechanical pressing.
  • from about 8% to about 55% of the tissue paper surface comprises densified knuckles having a relative density of at least 120% of the density of the high bulk field.
  • the array of supports is preferably an imprinting carrier fabric having a patterned displacement of knuckles which operate as the array of supports which facilitate the formation of the densified zones upon application of pressure.
  • the pattern of knuckles constitutes the array of supports previously referred to.
  • Imprinting carrier fabrics are disclosed in U.S.-A-3,301,746, Sanford and Sisson, issued January 31, 1967, U.S.-A-3,821,068, Salvucci, Jr.
  • the furnish is first formed into a wet web on a foraminous forming carrier, such as a Fourdrinier wire.
  • the web is dewatered and transferred to an imprinting fabric.
  • the furnish may alternately be initially deposited on a foraminous supporting carrier which also operates as an imprinting fabric.
  • the wet web is dewatered and, preferably, thermally predried to a selected fiber consistency of between about 40% and about 80%.
  • Dewatering is preferably performed with suction boxes or other vacuum devices or with blow-through dryers.
  • the knuckle imprint of the imprinting fabric is impressed in the web as discussed above, prior to drying the web to completion.
  • One method for accomplishing this is through application of mechanical pressure.
  • nip roll which supports the imprinting fabric against the face of a drying drum, such as a Yankee dryer, wherein the web is disposed between the nip roll and drying drum.
  • the web is molded against the imprinting fabric prior to completion of drying by application of fluid pressure with a vacuum device such as a suction box, or with a blow-through dryer. Fluid pressure may be applied to induce impression of densified zones during initial dewatering, in a separate, subsequent process stage, or a combination thereof.
  • uncompacted, nonpattern-densified tissue paper structures are described in U.S.-A-3,812,000 issued to Joseph L. Salvucci, Jr. and Peter N. Yiannos on May 21, 1974 and U.S.-A-4,208,459, issued to Henry E. Becker, Albert L. McConnell, and Richard Schutte on June 17, 1980.
  • uncompacted, nonpattern-densified tissue paper structures are prepared by depositing a papermaking furnish on a foraminous forming wire such as a Fourdrinier wire to form a wet web, draining the web and removing additional water without mechanical compression until the web has a fiber consistency of at least 80%, and creping the web. Water is removed from the web by vacuum dewatering and thermal drying. The resulting structure is a soft but weak high bulk sheet of relatively uncompacted fibers. Bonding material is preferably applied to portions of the web prior to creping.
  • the papermaking fibers utilized for the present invention will normally include fibers derived from wood pulp.
  • Other cellulosic fibrous pulp fibers such as cotton linters, bagasse, etc., can be utilized and are intended to be within the scope of this invention.
  • Synthetic fibers such as rayon, polyethylene and polypropylene fibers, may also be utilized in combination with natural cellulosic fibers.
  • One exemplary polyethylene fiber which may be utilized is PulpexTM, available from Hercules, Inc. (Wilmington, Delaware).
  • Applicable wood pulps include chemical pulps, such as Kraft, sulfite, and sulfate pulps, as well as mechanical pulps including, for example, groundwood, thermomechanical pulp and chemically modified thermomechanical pulp. Chemical pulps, however, are preferred since they impart a superior tactile sense of softness to tissue sheets made therefrom. Pulps derived from both deciduous trees (hereinafter, also referred to as "hardwood”) and coniferous trees (hereinafter, also referred to as "softwood”) may be utilized.
  • hardwood deciduous trees
  • softwood coniferous trees
  • the papermaking furnish used to make tissue paper structures may have other components or materials added thereto as may be or later become known in the art.
  • the types of additives desirable will be dependent upon the particular end use of the tissue sheet contemplated. For example, in products such as toilet paper, paper towels, facial tissues and other similar products, high wet strength is a desirable attribute. Thus, it is often desirable to add to the papermaking furnish chemical substances known in the art as "wet strength" resins.
  • Polyacrylamide resins have also been found to be of utility as wet strength resins. These resins are described in U.S.-A-3,556,932, issued on January 19, 1971 to Coscia, et al. and US-A-3,556,933, issued on January 19, 1971 to Williams et al.
  • One commercial source of polyacrylamide resins is American Cyanamid Co. of Stanford, Connecticut, which markets one such resin under the mark Parez TM 631 NC.
  • Still other water-soluble cationic resins finding utility in this invention are urea formaldehyde and melamine formaldehyde resins.
  • the more common functional groups of these polyfunctional resins are nitrogen containing groups such as amino groups and methylol groups attached to nitrogen.
  • Polyethylenimine type resins may also find utility in the present invention. It is to be understood that the addition of chemical compounds such as the wet strength resins discussed above to the pulp furnish is optional and is not necessary for the practice of the present development.
  • polysiloxane shall include all of such polymeric, oligomeric, copolymeric and other multiple-monomeric siloxane materials.
  • the polysiloxane can be either a straight chain, a branched chain or have a cyclic structure.
  • Preferred polysiloxane materials include those having monomeric siloxane units of the following structure: wherein, R1 and R2 for each siloxane monomeric unit can independently be any alkyl, aryl, alkenyl, alkaryl, aralkyl, cycloalkyl, halogenated hydrocarbon, or other radical. Any of such radicals can be substituted or unsubstituted. R1 and R2 radicals of any particular monomeric unit may differ from the corresponding functionalities of the next adjoining monomeric unit. Additionally, the radicals can be either a straight chain, a branched chain, or have a cyclic structure.
  • the radicals R1 and R2 can, additionally and independently, be other silicone functionalities such as, but not limited to siloxanes, polysiloxanes, and polysilanes.
  • the radicals R1 and R2 can also contain any of a variety of organic functionalities including, for example, alcohol, carboxylic acid, and amine functionalities.
  • the degree of substitution and the type of substituent have been found to affect the relative degree of soft, silky feeling and hydrophilicity imparted to the tissue paper structure.
  • the degree of soft, silky feeling imparted by the polysiloxane increases as the hydrophilicity of the substituted polysiloxane decreases.
  • Aminofunctional polysiloxanes are especially preferred in the present invention.
  • Preferred polysiloxanes include straight chain organopolysiloxane materials of the following general formula: wherein each R1 - R9 radical can independently be any C1 - C10 unsubstituted alkyl or aryl radical, and R10 is any substituted C1 - C10 alkyl or aryl radical.
  • each R1 - R9 radical is independently any C1 - C4 unsubstituted alkyl group.
  • the mole ratio of b to (a + b) is between 0 and about 20%, more preferably between 0 and about 10%, and most preferably between about 1% and about 5%.
  • R1 - R9 are methyl groups and R10 is a substituted or unsubstituted alkyl, aryl, or alkenyl group.
  • R10 is a substituted or unsubstituted alkyl, aryl, or alkenyl group.
  • Such material shall be generally described herein as polydimethylsiloxane which has a particular functionality as may be appropriate in that particular case.
  • Exemplary polydimethylsiloxanes include, for example, polydimethylsiloxane, polydimethylsiloxane having an alkyl hydrocarbon R10 radical and polydimethylsiloxane having one or more amino, carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, thiol and/or other R10 functionalities including alkyl and alkenyl analogues of such functionalities.
  • an amino functional alkyl group as R10 could be an amino-functional or an aminoalkyl-functional polydimethylsiloxane.
  • the exemplary listing of these polydimethylsiloxanes is not meant to thereby exclude others not specifically listed.
  • Viscosity of polysiloxanes useful for this invention may vary as widely as the viscosity of polysiloxanes in general vary, so long as the polysiloxane is flowable or can be made to be flowable for application to the tissue paper. This includes, but is not limited to, viscosity as low as about 25 ⁇ 10 ⁇ 6m2.s ⁇ 1 (25 centistokes) to about 20 m2.s ⁇ 1 (20,000,000 centistokes) or even higher.
  • High viscosity polysiloxanes which themselves are resistant to flowing can be effectively deposited upon the tissue paper webs by such methods as, for example, emulsifying the polysiloxane in surfactant or providing the polysiloxane in solution with the aid of a solvent, such as hexane, listed for exemplary purposes only. Particular methods for applying polysiloxanes to tissue paper webs are discussed in more detail below.
  • references disclosing polysiloxanes include U. S.-A-2,826,551, issued March 11, 1958 to Geen; U. S.-A-3,964,500, issued June 22, 1976 to Drakoff; U.S.-A-4,364,837, issued December 21, 1982 to Pader; and GB-A-849,433, published September 28, 1960 to Woolston. Also, Silicon Compounds , pp. 181-217, distributed by Petrarch Systems, Inc., 1984, contains an extensive listing and description of polysiloxanes in general.
  • the polysiloxane is applied subsequent to formation of the wet web and prior to drying to completion. It has been found that addition of the polysiloxane to the wet end of the paper machine (i.e., the paper furnish) is impractical due to low retention levels of the polysiloxane. Therefore, in a typical process, the web is formed and then dewatered prior to application of the polysiloxane in order to reduce the loss of polysiloxane due to drainage of free water.
  • the polysiloxane is applied to the wet web at a fiber consistency level of between 10% and about 80% (based on the weight of the wet web), more preferably at a fiber consistency level between about 15% and about 35%, in the manufacture of conventionally pressed tissue paper; and to a wet web having a fiber consistency of between about 20% and about 35% in the manufacture of tissue paper in papermaking machines wherein the newly formed web is transferred from a fine mesh Fourdrinier to a relatively coarse imprinting/carrier fabric. This is because it is preferable to make such transfers at sufficiently low fiber consistencies that the fibers have substantial mobility during the transfer; and it is preferred to apply the polysiloxane after their mobility has substantially dissipated as water removal progresses through the papermaking machine.
  • addition of the polysiloxane at higher fiber consistencies assures greater retention in and on the paper: i.e., less polysiloxane is lost in the water being drained from the web to increase its fiber consistency. Surprisingly, retention rates in excess of about 90% are expected at the preferred fiber consistencies without the utilization of chemical retention aids.
  • the polysiloxane is preferably applied to the wet web in an aqueous solution, emulsion, or suspension.
  • the polysiloxane can also be applied in a solution containing a suitable, nonaqueous solvent, in which the polysiloxane dissolves or with which the polysiloxane is miscible: for example, hexane.
  • the polysiloxane may be supplied in neat form or, preferably, emulsified with a suitable surfactant emulsifier. Emulsified polysiloxane is preferable for ease of application since a neat polysiloxane aqueous solution must be agitated to inhibit separation into water and polysiloxane phases.
  • the polysiloxane should be applied uniformly to the wet tissue paper web so that substantially the entire sheet benefits from the tactile effect of the polysiloxane. Applying the polysiloxane to the wet tissue paper web in continuous and patterned distributions are both within the scope of the invention and meet the above criteria.
  • Methods of uniformly applying the polysiloxane to the web include spraying and gravure printing. Spraying has been found to be economical, and susceptible to accurate control over quantity and distribution of the polysiloxane, so is most preferred.
  • an aqueous mixture containing an emulsified polysiloxane is sprayed onto the wet tissue web as it courses through the papermaking machine: for example, and not by way of limitation, referring to a papermaking machine of the general configuration disclosed in Sanford-Sisson (referenced hereinbefore), either before the predryer, or after the predryer, depending on the desired fiber consistency level.
  • a less preferred method includes deposition of the polysiloxane onto a forming wire or fabric which is then contacted by the tissue web.
  • Equipment suitable for spraying polysiloxane containing liquids onto wet webs include external mix, air atomizing nozzles, such as the 2 mm nozzle available from V.I.B. Systems, Inc., Tucker, Georgia.
  • Equipment suitable for printing polysiloxane containing liquids onto wet webs includes rotogravure printers.
  • Tissue paper treated with polysiloxane in accordance with the present invention comprises about 0.75% or less polysiloxane. It is an unexpected benefit of this invention that tissue paper treated with about 0.75% or less polysiloxane can have imparted thereto substantial softness and silkiness benefits by such a low level of polysiloxane.
  • tissue paper having less than about 0.3% polysiloxane, preferably less than about 0.2% can provide substantial increases in softness and silkiness and flannel-like quality yet remain sufficiently wettable for use as toilet paper without requiring the addition of surfactant to offset any negative impact on wettability which results from the polysiloxane.
  • the minimum level of polysiloxane to be retained by the tissue paper is at least an effective level for imparting a tactile difference in softness or silkiness or flannel-like quality to the paper.
  • the minimum effective level may vary depending upon the particular type of sheet, the method of application, the particular type of polysiloxane, and whether the polysiloxane is supplemented by starch, surfactant, or other additives or treatments.
  • a sufficient amount of polysiloxane to impart a tactile sense of softness is disposed in both surfaces of the tissue paper: i.e., disposed on the outwardly facing surfaces of the surface-level fibers.
  • polysiloxane When polysiloxane is applied to one surface of the tissue paper, some of it will, generally, at least partially penetrate to the tissue paper interior.
  • sufficient polysiloxane to effect a tactile response penetrates through the entire thickness of the tissue paper such that both surfaces have imparted thereto the benefits of polysiloxane.
  • One method found to be useful for facilitating polysiloxane penetration to the opposing surface when the polysiloxane is applied to one surface of a wet tissue paper web is to vacuum dewater the tissue paper from the other surface of the wet tissue paper at the point of application of the polysiloxane.
  • tissue paper with polysiloxane As described above, it has been found desirable to also treat such tissue paper with surfactant material. This is in addition to any surfactant material that may be present as an emulsifying agent for the polysiloxane.
  • Tissue paper having in excess of about 0.3% polysiloxane is preferably treated with surfactant when contemplated for uses wherein high wettability is desired.
  • a noncationic surfactant is applied to the wet tissue paper web, in order to obtain an additional softness benefit, on a constant tensile basis, as previously discussed.
  • the amount of surfactant required to increase hydrophilicity to a desired level will depend upon the type and level of polysiloxane and the type of surfactant.
  • tissue paper between about 0.01% and about 2% surfactant retained by the tissue paper, preferably between about 0.05% and about 1.0%, is believed to be sufficient to provide sufficiently high wettability for most applications, including toilet paper, for polysiloxane levels of about 0.75% or less.
  • Surfactants which are preferred for use in the present invention are noncationic; and, more preferably, are nonionic. However, cationic surfactants may be used. Noncationic surfactants include anionic, nonionic, amphoteric, and zwitterionic surfactants. Preferably, as stated hereinbefore, the surfactant is substantially nonmigratory in situ after the tissue paper has been manufactured in order to substantially obviate post-manufacturing changes in the tissue paper's properties which might otherwise result from the inclusion of surfactant.
  • surfactants having melt temperatures greater than the temperatures commonly encountered during storage, shipping, merchandising, and use of tissue paper product embodiments of the invention: for example, melt temperatures of about 50°C or higher.
  • the surfactant is preferably water-soluble when applied to the wet web.
  • the level of noncationic surfactant applied to wet tissue paper webs to provide the aforementioned softness/tensile benefit ranges from the minimum effective level needed for imparting such benefit, on a constant tensile basis for the end product, to about two (2) percent: preferably between about 0.01% and about 1% noncationic surfactant retained by the web; more preferably, between about 0.05% and about 1.0%; and, most preferably, between about 0.05% and about 0.3%.
  • the surfactants preferably have alkyl chains with eight or more carbon atoms.
  • Exemplary anionic surfactants are linear alkyl sulfonates, and alkylbenzene sulfonates.
  • Exemplary nonionic surfactants are alkylglycosides including alkylglycoside esters such as CrodestaTM SL-40 which is available from Croda, Inc. (New York, NY); alkylglycoside ethers as described in U. S.-A-4,011,389, issued to W. K. Langdon, et al. on March 8, 1977; and alkylpolyethoxylated esters such as PegosperseTM 200 ML available from Glyco Chemicals, Inc. (Greenwich, CT). Alkylpolyglycosides are particularly preferred for use in the present invention.
  • the surfactant in addition to any emulsifying surfactant that may be present on the polysiloxane, may be applied by the same methods and apparatuses used to apply polysiloxanes. These methods include spraying and gravure printing. Preferably, an aqueous mixture containing the surfactant is sprayed on to the wet tissue web as it courses through the paper making machine. Other methods include application to a forming wire or fabric prior to contact with the web.
  • Any surfactant other than polysiloxane emulsifying surfactant material is hereinafter referred to as "surfactant,” and any surfactant present as the emulsifying component of emulsified polysiloxane is hereinafter referred to as "emulsifying agent".
  • the surfactant may be applied to the tissue paper simultaneously with, after, or before the polysiloxane.
  • the surfactant is applied subsequent to formation of the wet web and prior to final drying.
  • surfactants are applied to the wet tissue webs at fiber consistency levels of between about 10% and about 80%; and, more preferably, between about 15% and about 35%.
  • retention rates of noncationic surfactant applied to wet webs are high even though the surfactant is applied under conditions wherein it is not ionically substantive to the fibers. Retention rates in excess of about 90% are expected at the preferred fiber consistencies without the utilization of chemical retention aids.
  • binder refers to the various wet and dry strength additives known in the art.
  • the binder may be applied to the tissue paper simultaneously with, after or before the polysiloxane and the surfactant, if used.
  • binders are added to the wet tissue webs at fiber consistency levels of between about 10% and about 80%, and, more preferably, between about 15% and about 35%.
  • Starch has been found to be the preferred binder for use in the present invention.
  • the tissue paper is treated with an aqueous solution of starch and, as mentioned above, the sheet is moist at the time of application.
  • low levels of starch also imparts a modest improvement in the tensile strength of tissue paper without imparting boardiness (i.e., stiffness) which would result from additions of high levels of starch.
  • this provides tissue paper having improved strength/softness relationship compared to tissue paper which has been strengthened by traditional methods of increasing tensile strength: for example, sheets having increased tensile strength due to increased refining of the pulp; or through the addition of other dry strength additives.
  • starch has traditionally been used to build strength at the expense of softness in applications wherein softness is not an important characteristic: for example, paperboard. Additionally, parenthetically, starch has been used as a filler for printing and writing paper to improve surface printability.
  • suitable starch for practicing the present invention is characterized by water solubility, and hydrophilicity.
  • Exemplary starch materials include corn starch and potato starch, albeit it is not intended to thereby limit the scope of suitable starch materials; and waxy corn starch that is known industrially as amioca starch is particularly preferred.
  • Amioca starch differs from common corn starch in that it is entirely amylopectin, whereas common corn starch contains both amplopectin and amylose.
  • Various unique characteristics of amioca starch are further described in "Amioca - The Starch from Waxy Corn", H. H. Schopmeyer, Food Industries, December 1945, pp. 106-108 (Vol. pp. 1476-1478).
  • the starch can be in granular or dispersed form albeit granular form is preferred.
  • the starch is preferably sufficiently cooked to induce swelling of the granules. More preferably, the starch granules are swollen, as by cooking, to a point just prior to dispersion of the starch granule. Such highly swollen starch granules shall be referred to as being "fully cooked.”
  • the conditions for dispersion in general can vary depending upon the size of the starch granules, the degree of crystallinity of the granules, and the amount of amylose present.
  • Fully cooked amioca starch for example, can be prepared by heating an aqueous slurry of about 4% consistency of starch granules at about 190°F (about 88°C) for between about 30 and about 40 minutes.
  • modified starch materials which may be used include modified cationic starches such as those modified to have nitrogen containing groups such as amino groups and methylol groups attached to nitrogen, available from National Starch and Chemical Company, (Bridgewater, New Jersey).
  • modified starch materials have heretofore been used primarily as a pulp furnish additive to increase wet and/or dry strength. However when applied in accordance with this invention by application to a wet tissue paper web they may have reduced effect on wet strength relative to wet-end addition of the same modified starch materials. Considering that such modified starch materials are more expensive than unmodified starches, the latter have generally been preferred.
  • the starch should be applied to the tissue paper while the paper is in a moist condition.
  • the starch based material is added to the wet tissue paper web, preferably when the web has a fiber consistency of about 80% or less.
  • Non-cationic starch materials are sufficiently retained in the web to provide an observable effect on softness at a particular strength level relative to increased refining; and, are preferably applied to wet tissue webs having fiber consistencies between about 10% and about 80%, more preferably, between about 15% and 35%.
  • Starch is preferably applied to tissue paper webs in an aqueous solution. Methods of application include, the same previously described with reference to application of polysiloxane: preferably by spraying; and, less preferably, by printing. The starch may be applied to the tissue paper web simultaneously with, prior to, or subsequent to the addition of polysiloxane and/or surfactant.
  • At least an effective amount of a binder, preferably starch, to provide lint control and concomitant strength increase upon drying relative to a non-binder treated but otherwise identical sheet is preferably applied to the sheet.
  • a binder preferably starch
  • the level of polysiloxane retained by the tissue paper can be determined by solvent extraction of the polysiloxane with an organic solvent followed by atomic absorption spectroscopy to determine the level of silicon in the extract;
  • the level of nonionic surfactants, such as alkylglycosides can be determined by extraction in an organic solvent followed by gas chromatography to determine the level of surfactant in the extract;
  • the level of anionic surfactants, such as linear alkyl sulfonates can be determined by water extraction followed by colorimetry analysis of the extract;
  • the level of starch can be determined by amylase digestion of the starch to glucose followed by colorimetry analysis to determine glucose level.
  • Hydrophilicity of tissue paper refers, in general, to the propensity of the tissue paper to be wetted with water. Hydrophilicity of tissue paper may be somewhat quantified by determining the period of time required for dry tissue paper to become completely wetted with water. This period of time is referred to as "wetting time.”
  • wetting time the following procedure may be used for wetting time determinations: first, a dry (greater than 90% fiber consistency level) sample unit sheet, approximately 4-3/8 inch ⁇ 4-3/4 inch (about 11.1 cm ⁇ 12 cm) of tissue paper structure is provided; second, the sheet is folded into four (4) juxtaposed quarters, and then crumpled into a ball approximately 0.75 inches (about 1.9 cm) to about 1 inch (about 2.5 cm) in diameter; third, the balled sheet is placed on the surface of a body of distilled water at 72°F (about 22°C), and a timer is simultaneously started; fourth, the timer is stopped and read when wetting of the balled
  • tissue paper used in a variety of applications, e.g., toilet paper, to completely wet in a relatively short period of time to prevent clogging once the toilet is flushed.
  • wetting time is 2 minutes or less. More preferably, wetting time is 30 seconds or less. Most preferably, wetting time is 10 seconds or less.
  • Hydrophilicity characters of tissue paper embodiments of the present invention may, of course, be determined immediately after manufacture. However, substantial increases in hydrophobicity may occur during the first two weeks after the tissue paper is made: i.e., after the paper has aged two (2) weeks following its manufacture. Thus, the above stated wetting times are preferably measured at the end of such two week period. Accordingly, wetting times measured at the end of a two week aging period at room temperature are referred to as "two week wetting times.”
  • the density of tissue paper is the average density calculated as the basis weight of that paper divided by the caliper, with the appropriate unit conversions incorporated therein.
  • Caliper of the tissue paper is the thickness of the paper when subjected to a compressive load of 95 g/in2 (15.5 g/cm2).
  • the purpose of this example is to illustrate one method that can be used to make soft tissue paper sheets treated with a polysiloxane in accordance with the present invention.
  • a pilot scale Fourdrinier papermaking machine is used in the practice of the present invention.
  • the paper machine has a layered headbox having a top chamber, a center chamber, and a bottom chamber. Where applicable as indicated in the following examples, the procedure described below also applies to such later examples. Briefly, a first fibrous slurry comprised primarily of short papermaking fibers is pumped through the top and bottom headbox chambers and, simultaneously, a second fibrous slurry comprised primarily of long papermaking fibers is pumped through the center headbox chamber and delivered in superposed relation onto the Fourdrinier wire to form thereon a three-layer embryonic web.
  • the first slurry has a fiber consistency of about 0.11% and its fibrous content is Eucalyptus Hardwood Kraft.
  • the second slurry has a fiber consistency of about 0.15% and its fibrous content is Northern Softwood Kraft.
  • Dewatering occurs through the Fourdrinier wire and is assisted by a deflector and vacuum boxes.
  • the Fourdrinier wire is of a 5-shed, satin weave configuration having 35 (87) machine-direction and 30 (76) cross-machine-direction monofilaments per cm (inch), respectively.
  • the embryonic wet web is transferred from the Foudrinier wire, at a fiber consistency of about 22% at the point of transfer, to a carrier fabric having a 5-shed satin weave, 14 (35) machine-direction and 13 (33) cross-machine-direction monofilaments per cm (inch), respectively.
  • the non-fabric side of the web is sprayed with an aqueous solution containing an emulsified polysiloxane composition, further described below, by a 2 mm spray nozzle located directly opposite a vacuum dewatering box.
  • the wet web has a fiber consistency of about 22% (total web weight basis) when sprayed by the aqueous solution.
  • the sprayed web is carried on the carrier fabric past the vacuum dewatering box, through blow-through predryers after which the web is transferred onto a Yankee dryer.
  • the other process and machine conditions are listed below.
  • the fiber consistency is about 27% after the vacuum dewatering box and, by the action of the predryers, about 65% prior to transfer onto the Yankee dryer; creping adhesive comprising a 0.25% aqueous solution of polyvinyl alcohol is spray applied by applicators; the fiber consistency is increased to an estimated 99% before dry creping the web with a doctor blade.
  • the doctor blade has a bevel angle of about 24 degrees and is positioned with respect to the Yankee dryer to provide an impact angle of about 83 degrees; the Yankee dryer is operated at about 350°F (177°C); the Yankee dryer is operated at about 800 fpm (feet per minute) (about 244 meters per minute).
  • the dry creped web is then passed between two calender rolls.
  • the two calender rolls are biased together at roll weight and operated at surface speeds of 660 fpm (about 201 meters per minute).
  • the aqueous solution sprayed through the spray nozzle onto the wet web contains 0.71% by weight of Dow Corning Q2-7224 (a 35% nonionic emulsion of an amino-functional polydimethylpolysiloxane marketed by Dow Corning Corp.).
  • the volumetric flow rate of the aqueous solution through the nozzle is about 3 gal./hr.-cross -direction ft (about 37 liters/hr-meter).
  • the retention rate of the polysiloxane applied to the web in general, is about 90%.
  • the resulting tissue paper has a basis weight of 30g/m2, a density of 0.10g/cc, and contains 0.025% by weight, of the amino-functional polydimethylpolysiloxane compound.
  • the resulting tissue paper has a silky, flannel-like feel, and enhanced tactile softness.
  • the purpose of this example is to illustrate one method that can be used to make soft tissue paper sheets wherein the tissue paper is treated with polysiloxane, surfactant and starch.
  • a 3-layer paper sheet is produced in accordance with the hereinbefore described process of Example I.
  • the tissue web is, in addition to being treated with a polysiloxane compound as described above, also treated with CrodestaTM SL-40 (an alkyl glycoside polyester nonionic surfactant marketed by Croda Inc.) and with a fully cooked amioca starch prepared as described in the specification.
  • CrodestaTM SL-40 an alkyl glycoside polyester nonionic surfactant marketed by Croda Inc.
  • the surfactant and starch are applied simultaneously with the emulsified polysiloxane composition as part of the aqueous solution sprayed through the papermachine spray nozzle.
  • Concentration of the CrodestaTM SL-40 nonionic surfactant in the aqueous solution is adjusted so that the level of surfactant retained is about 0.15%, based upon the weight of the dry fibers.
  • concentration of the starch in the aqueous solution is adjusted so that the level of amioca starch retained is about 0.2%, based upon the weight of the dry fibers.
  • the resulting tissue paper has a basis weight of 30g/m2, a density of 0.10g/cc, and contains 0.025% by weight of the Dow Q2-7224 polydimethypolysiloxane, 0.15% by weight of CrodestaTMSL-40 nonionic surfactant and 0.2% by weight of the cooked amioca starch.
  • the resulting tissue paper has a silky flannel-like feel, enhanced tactile softness and has higher wettability and lower propensity for lint than tissue paper treated only with the polysiloxane composition.

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Claims (16)

  1. Ein Verfahren zur Herstellung von weichem Tissue-Papier, welches an seinen nach außen gerichteten Oberflächen eine Polysiloxanverbindung gleichmäßig angeordnet aufweist, wobei das genannte Verfahren folgende Schritte umfaßt:
    a) Naßlegen von Fasern auf Zellulose-Basis zur Bildung einer Bahn;
    b) Aufbringen der genannten Polysiloxanverbindung auf die genannte Bahn;
    c) Trocknen der genannten Bahn;
    wobei
    - das genannte Verfahren zur Herstellung von weichem Tissue-Papier mit einem Flächengewicht von 10 bis 65 g/m² und einer Dichte von weniger als 0,60 g/cm³ bestimmt ist;
    - im genannten Schritt b) die Polysiloxanverbindung auf die Bahn bei einer Faserkonsistenz von 10 % bis 80 %, bezogen auf das Gesamtgewicht der Bahn, aufgebracht wird und die Menge der auf die Bahn aufgebrachten Polysiloxanverbindung derart ist, daß 0,004 % bis 0,75 % genanntes Polysiloxan, bewogen auf das Fasertrockengewicht des genannten Tissue-Papiers, von dem genannten Tissue-Papier zurückgehalten wird; und
    - der genannte Schritt c) außerdem einen Schritt der Kreppung der Bahn umfaßt.
  2. Ein verfahren nach Anspruch 1, bei welchem 0,004 % bis 0,3 % genanntes Polysiloxan von dem genannten Tissue-Papier zurückgehalten werden.
  3. Ein Verfahren nach einem der Ansprüche 1 und 2, bei welchem das genannte Polysiloxan ein Polydimethylpolysiloxan mit einer funktionellen Wasserstoffbindungsgruppe, ausgewählt aus Amino-, Carboxyl-, Hydroxyl-, Ether-, Polyether-, Aldehyd-, Keton-, Amid-, Ester- und Thiolgruppen, ist, wobei die genannte funktionelle Wasserstoffbindungsgruppe in einem molaren Prozentsatz der Substitution von 20 % oder weniger vorliegt.
  4. Ein Verfahren nach Anspruch 3, bei welchem das genannte Polysiloxan einen molaren Prozentsatz der Substitution von 10 % oder weniger und eine Viskosität von 25 x 10⁻⁶m²s⁻¹ oder mehr aufweist.
  5. Ein Verfahren nach einem der Ansprüche 3 und 4, bei welchem das genannte Polysiloxan einen molaren Prozentsatz der Substitution von 1,0 % bis 5 % und eine Viskosität von 25 x 10⁻⁶ m²s⁻¹ bis 20 m²s⁻¹ aufweist.
  6. Ein Verfahren nach Anspruch 5, bei welchem das genannte Polysiloxan einen molaren Prozentsatz der Substitution von etwa 2 % und eine Viskosität von etwa 125 x 10⁻⁶ m²s⁻¹ aufweist.
  7. Ein Verfahren nach einem der vorhergehenden Ansprüche, bei welchem das genannte Polysiloxan auf die genannte Bahn aufgebracht wird, wenn die genannte Bahn eine Faserkonsistenz von 15 % bis 35 % aufweist.
  8. Ein Verfahren nach einem der vorhergehenden Ansprüche, das weiters den Schritt der Aufbringung eines wasserlöslichen Surfactants auf die genannte Bahn bei einer Faserkonsistenz von 10 % bis 80 %, bezogen auf das Gesamtgewicht der Bahn, in einer ausreichenden Menge umfaßt, sodaß 0,01 % bis 2,0 % genanntes Surfactant, bezogen auf das Fasertrockengewicht des genannten Tissue-Papiers, von dem genannten Tissue-Papier zurückgehalten werden.
  9. Ein Verfahren nach Anspruch 8, bei welchem die auf die genannte Bahn aufgebrachte Menge Surfactant derart ist, daß 0,05 % bis 1,0 % Surfactant, bezogen auf das Fasertrockengewicht des genannten Tissue-Papiers, von dem Tissue-Papier zurückgehalten werden.
  10. Ein verfahren nach einem der Ansprüche 8 und 9, bei welchem das Surfactant nichtkationisch ist.
  11. Ein Verfahren nach Anspruch 10, bei welchem das nichtkationische Surfactant ein nichtionisches Surfactant ist.
  12. Ein verfahren nach einem der Ansprüche 8 bis 11, bei welchem das genannte Surfactant einen Schmelzpunkt von mindestens 50°C hat.
  13. Ein Verfahren nach einem der vorhergehenden Ansprüche, das weiters den Schritt der Aufbringung eines Bindemittels auf die genannte Bahn bei einer Faserkonsistenz von 10 % bis 80 %, bezogen auf das Gesamtgewicht der Bahn, in einer ausreichenden Menge umfaßt, sodaß 0,01 % bis 2,0 % genanntes Bindemittel, bezogen auf das Fasertrockengewicht des genannten Tissue-Papiers, von dem genannten Tissue-Papier zurückgehalten werden.
  14. Ein Verfahren nach Anspruch 13, bei welchem die auf die Bahn aufgebrachte Menge Bindemittel derart ist, daß 0,1 % bis 1,0 % genanntes Bindemittel, bezogen auf das Fasertrockengewicht des genannten Tissue-Papiers, von dem genannten Tissue-Papier zurückgehalten werden.
  15. Ein Verfahren nach Anspruch 11, bei welchem das genannte Bindemittel Stärke ist.
  16. Ein Verfahren nach Anspruch 15, bei welchem das genannte Bindemittel Amioka-Stärke ist.
EP89305939A 1988-06-14 1989-06-13 Verfahren zur Herstellung von mit einem Polysiloxan behandeltem sanftem Tissuepapier Expired - Lifetime EP0347153B1 (de)

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Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4950545A (en) * 1989-02-24 1990-08-21 Kimberly-Clark Corporation Multifunctional facial tissue
US5215626A (en) * 1991-07-19 1993-06-01 The Procter & Gamble Company Process for applying a polysiloxane to tissue paper
NZ255839A (en) * 1992-08-27 1997-02-24 Procter & Gamble Process for applying chemical papermaking additives from a thin film to dry tissue paper
US5246545A (en) * 1992-08-27 1993-09-21 Procter & Gamble Company Process for applying chemical papermaking additives from a thin film to tissue paper
US5246546A (en) * 1992-08-27 1993-09-21 Procter & Gamble Company Process for applying a thin film containing polysiloxane to tissue paper
US5679218A (en) * 1994-07-29 1997-10-21 The Procter & Gamble Company Tissue paper containing chemically softened coarse cellulose fibers
CN1200780A (zh) * 1994-07-29 1998-12-02 普罗克特和甘保尔公司 由粗纤维素纤维制成的软薄页纸
US5529665A (en) * 1994-08-08 1996-06-25 Kimberly-Clark Corporation Method for making soft tissue using cationic silicones
CN1039506C (zh) * 1994-09-12 1998-08-12 宝山钢铁(集团)公司 室内空间静电防治和泄漏方法
ES2136307T3 (es) * 1994-09-16 1999-11-16 Sca Hygiene Prod Gmbh Procedimiento de fabricacion de papel tissue por medio de un agente de tratamiento.
US5573637A (en) * 1994-12-19 1996-11-12 The Procter & Gamble Company Tissue paper product comprising a quaternary ammonium compound, a polysiloxane compound and binder materials
US5624532A (en) * 1995-02-15 1997-04-29 The Procter & Gamble Company Method for enhancing the bulk softness of tissue paper and product therefrom
ZA965679B (en) * 1995-07-21 1997-01-24 Kimberly Clark Co Method for making soft tissue with improved bulk softness and surface softness
DE19711452A1 (de) 1997-03-19 1998-09-24 Sca Hygiene Paper Gmbh Feuchtigkeitsregulatoren enthaltende Zusammensetzung für Tissueprodukte, Verfahren zur Herstellung dieser Produkte, Verwendung der Zusammensetzung für die Behandlung von Tissueprodukten sowie Tissueprodukte in Form von wetlaid einschließlich TAD oder Airlaid (non-woven) auf Basis überwiegend Cellulosefasern enthaltender flächiger Trägermaterialien
JP4255167B2 (ja) 1999-05-24 2009-04-15 東レ・ダウコーニング株式会社 拭き取り紙用水系処理剤および拭き取り紙の処理方法
DE19963828A1 (de) * 1999-12-30 2001-07-19 Sca Hygiene Prod Gmbh Verfahren zur schichtweisen Applikation von Behandlungschemikalien auf flächige Erzeugnisse auf Faserbasis und damit hergestellte Produkte
DE19963835C2 (de) * 1999-12-30 2002-03-28 Sca Hygiene Prod Gmbh Verfahren zur Applikation von Behandlungschemikalien auf flächige Erzeugnisse auf Faserbasis, insbesondere Tissue, und damit hergestellte Produkte
DE19963834C2 (de) * 1999-12-30 2002-03-28 Sca Hygiene Prod Gmbh Verfahren zur Applikation von Behandlungschemikalien auf ein flächiges Erzeugnis auf Faserbasis und damit hergestellte Produkte
US6860967B2 (en) 2001-01-19 2005-03-01 Sca Hygiene Products Gmbh Tissue paper penetrated with softening lotion
US6905697B2 (en) 2001-01-19 2005-06-14 Sca Hygiene Products Gmbh Lotioned fibrous web having a short water absorption time
US20040084162A1 (en) 2002-11-06 2004-05-06 Shannon Thomas Gerard Low slough tissue products and method for making same
DE102005036075A1 (de) * 2005-08-01 2007-02-15 Voith Patent Gmbh Verfahren zur Herstellung von Tissuepapier
DE102005049502A1 (de) 2005-10-13 2007-04-19 Voith Patent Gmbh Verfahren zur Herstellung von Tissuepapier
EP3231939A1 (de) 2016-04-11 2017-10-18 Fuhrmann, Uwe Mehrlagiges papiertaschentuch zur reduzierung der übertragung von krankheitserregern
JP7384117B2 (ja) * 2020-06-15 2023-11-21 王子ホールディングス株式会社 書籍用紙およびその製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4028172A (en) * 1974-04-15 1977-06-07 National Starch And Chemical Corporation Process of making paper

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EP0347153A3 (de) 1991-05-02
ES2070174T3 (es) 1995-06-01
DE68922024D1 (de) 1995-05-11
DE68922024T2 (de) 1995-09-28
EP0347153A2 (de) 1989-12-20
ATE120820T1 (de) 1995-04-15

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