EP0347154B1 - Sanftes Tissuepapier - Google Patents

Sanftes Tissuepapier Download PDF

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Publication number
EP0347154B1
EP0347154B1 EP89305940A EP89305940A EP0347154B1 EP 0347154 B1 EP0347154 B1 EP 0347154B1 EP 89305940 A EP89305940 A EP 89305940A EP 89305940 A EP89305940 A EP 89305940A EP 0347154 B1 EP0347154 B1 EP 0347154B1
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EP
European Patent Office
Prior art keywords
tissue paper
polysiloxane
surfactant
paper according
starch
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP89305940A
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English (en)
French (fr)
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EP0347154A3 (de
EP0347154A2 (de
Inventor
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
    • 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
    • D21H21/14—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 function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • D21H21/24—Surfactants
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—Starch
    • 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 tissue paper; and, more specifically, to 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 improving the tactile perceivable softness of tissue paper -- in particular high bulk, creped tissue paper -- through the incorporation of chemical additives: in particular, 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.
  • Exemplary such chemical additives are, for example, polysiloxane materials which are simply referred to hereinafter as polysiloxanes.
  • 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-C-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.
  • DE-C-34 20 940 discloses a tissue paper impregnated with a silicone oil, especially dimethylsilicone.
  • 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.
  • tissue paper having a basis weight of from about 10 to 65 g/m, fiber density of about 0.6 g/cc or less, and which comprises an effective amount of polysiloxane to effect enhanced softness, characterized in that said amount of polysiloxane is from 0.004% to 2% based on the dry fiber weight of said tissue paper and in that said tissue paper is dry and, after aging two weeks after its manufacture, has a wetting time of no more than 2 minutes, the outwardly facing surfaces of the tissue paper having a uniform distribution of polysiloxane, and the polysiloxane being present without the aid of additionnal oils or lotions.
  • the tissue paper has a high degree of tactile softness and smoothness; and a silky and/or flannel-like tactile feel.
  • the tissue paper comprises from about 0.004 to about 0.3 percent of polysiloxane.
  • Preferred polysiloxanes include an amino-functional polydimethylpolysiloxane wherein less than about 10 mole percent of the side chains on the polymer contain an amino-functional group.
  • the degree of substitution is indirectly related to the average molecular weight; and, because molecular weights of polysiloxanes are difficult to ascertain, the viscosity of a polysiloxane is used as an objectively ascertainable indicia of molecular weight.
  • substitution has been found to be very effective for polysiloxanes having a viscosity of about 125 x 10 ⁇ 6ms ⁇ 1 (125 centistokes); and viscosities of about 5 m s ⁇ 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.
  • Chemically treated tissue paper of the present invention may further comprise 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 amount of surfactant is 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 0.5 percent.
  • 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.
  • tissue paper comprising a chemical additive in accordance with the present invention may further comprise an effective amount of a binder material such as starch to at least partially offset any reduction of tensile strength or increase in linting propensity which would otherwise result from the incorporation of the S&S modifier and, if present, surfactant material.
  • the effective amount of binder material is preferably from about 0.01 to about 2 percent on a dry fiber weight basis of the tissue paper.
  • a particularly preferred tissue paper embodiment of the present invention comprises from about 0.004 to about 0.3 percent of a chemical additive such as polysiloxane for imparting a silky, flannel-like tactile feel; from about 0.1 to about 2 percent of surfactant material; and from about 0.1 to about 2 percent of starch, all quantities of these additives being on a dry fiber weight basis of the tissue paper.
  • a chemical additive such as polysiloxane for imparting a silky, flannel-like tactile feel
  • surfactant material from about 0.1 to about 2 percent of starch
  • tissue paper having a silky, flannel-like feel, and enhanced tactile perceivable softness through the incorporation of a chemical additive such as, for example, a polysiloxane.
  • tissue paper may further include an effective amount of surfactant material and/or a binder material such as starch.
  • 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 chemical additive and, if used, the surfactant.
  • tissue paper e.g., as toilet tissue
  • a binder material such as starch
  • tissue paper embodiments of the present invention are generally characterized as being within a tri-parametric domain defined by empirically determined ranges of the following parameters: first, the ratio of their Total Flexibility to their Total Strength; second, their Physiological Surface Smoothness; and third, their Slip-And-Stick Coefficient of Friction.
  • tests conducted in accordance with the following procedures defined by the present invention's tri-parametric domain as: a ratio of Total Flexibility to Total Tensile Strength of about 0.13 or less; Physiological Surface Smoothness of about 0.95 or less; and a Slip-and-Stick Coefficient of Friction of about 0.033 or less for pattern densified tissue papers, and about 0.038 or less for tissue paper embodiments having substantially uniform densities.
  • a ratio of Total Flexibility to Total Tensile Strength of about 0.13 or less
  • Physiological Surface Smoothness of about 0.95 or less
  • a Slip-and-Stick Coefficient of Friction of about 0.033 or less for pattern densified tissue papers, and about 0.038 or less for tissue paper embodiments having substantially uniform densities.
  • Flexibility as used herein is defined as the slope of the secant of the graph-curve derived from force vs. stretch % data which secant passes through the origin (zero % stretch, zero force) and through the point on the graph-curve where the force per centimeter of width is 20 grams.
  • Total Flexibility as used herein means the geometric mean of the machine-direction flexibility and cross-machine-direction flexibility. Mathematically, this is the square root of the product of the machine-direction flexibility and cross-machine-direction flexibility in grams per cm.
  • Total tensile strength as used herein means the geometric mean of the machine and cross-machine breaking strengths in grams per cm of sample width. Mathematically, this is the square root of the product of the machine and cross-machine direction breaking strengths in grams per cm of sample width.
  • the ratio of Total Flexibility to Total Tensile Strength has been determined to be a factor which characterizes embodiments of the invention as being strong yet having high bulk softness. This ratio is hereby dubbed the WABY Factor.
  • WABY Factor Total Flexibility Total Tensile Strength For instance, a sample having a Total Flexibility of 20 g/cm, and a Total Tensile Strength of 154 g/cm has a WABY Factor of 0.13.
  • tactile perceivable softness of tissue paper is inversely related to its WABY Factor; and limited empirical data indicate that tissue paper embodiments of the present invention have WABY Factors of about 0.13 or less. Also, note that the WABY Factor is dimensionless because both Flexibility and Total Tensile Strength as defined above are in g/cm, their ratio is dimensionless.
  • Physiological surface smoothness as used herein is a factor (hereinafter the PSS Factor) derived from scanning machine-direction tissue paper samples with a profilometer (described below) having a diamond stylus, the profilometer being installed in a surface test apparatus such as, for example, Surface Tester KES-FB-4 which is available from KATO TECH CO., LTD., Karato-Cho, Nishikiyo, Minami-Ku, Koyota, Japan.
  • a sample of tissue is mounted on a motorized drum, and a stylus is gravitationally biased towards the drum at the 12 o'clock position. The drum is rotated to provide a sample velocity of one (1) millimeter per second, and moves the sample 2 cm. with respect to the probe.
  • the probe scans a 2 cm length of the sample.
  • the profilometer comprises means for counterbalancing the stylus to provide a normal force of 270 mg.
  • the instrument senses the up and down displacements (in mm) of the stylus as a 2 cm length of sample is scanned under the profilometer probe.
  • the resulting stylus-amplitude vs. stylus-distance-scanned data are digitized, and then converted to a stylus-amplitude vs. frequency spectrum by performing a Fourier Transform using the Proc Spectra standard program available from SAS Institute Inc., Post Office Box 10066, Raleigh, North Carolina 27605.
  • Verrillo This identifies spectral components in the sample's topography; and the frequency spectral data are then adjusted for human tactile responsiveness as quantified and reported by Verrillo (Ronald T. Verrillo, "Effect of Contractor Area on the Vibrotactile Threshold", The Journal of the Accoustical Society of America, 35 , 1962 (1963)).
  • Verrillo's data are in the time domain (i.e., cycles per second)
  • physiological surface smoothness is related to finger-to-sample velocity
  • Verrillo-type data are converted to a spatial domain (i.e., cycles per millimeter) using 65 mm/sec as a standard finger-to-sample velocity factor.
  • PSS Factor is the area under the Verrillo-adjusted frequency (cycles/mm) vs. stylus amplitude curve between zero (0) and ten (10) cycles per millimeter.
  • PSS Factors are average values derived from scanning multiple samples (e.g., ten samples), both forward and backward.
  • the profilometer described above comprises, more specifically, a Gould Surfanalyzer Equipment Controller #21-1330-20428, Probe #21-3100-465, Diamond stylus tip (0.0127 mm radius) #21-0120-00 and stylus tip extender #22-0129-00 all available from Federal Products, Lexington, RI.
  • the profilometer probe assembly is fitted with a counterbalance, and set up as depicted in Figure 22 of US-A-4,300,981 (referenced hereinbefore).
  • S&S COF Slip-and-stick coefficient of friction
  • ⁇ is the ratio of frictional force to probe loading
  • ⁇ ⁇ is the average value of ⁇
  • X is 2 cm.
  • tissue paper having enhanced tactile responsiveness includes but is 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 preferably has a basis weight of between about 10 g/m and about 65 g/m, and density of about 0.60 g/cc or less.
  • basis weight will be below about 35 g/m or less; and density will be about 0.30 g/cc or less.
  • density will be between about 0.08 g/cc and about 0.20 g/cc.
  • Papermaking fibers which may be utilized for the present invention 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 made by the Kraft, sulfite, and sulfate processes; and mechanical pulps including, for example, groundwood, thermomechanical pulp and chemically modified thermomechanical pulp. Chemical pulps, however, are preferred since they impart a superior tactile perceivable softness to tissue sheets made therefrom. Pulps may be utilized which are derived from both deciduous trees which are sometimes referred to as "hardwood”; and coniferous trees which are sometimes referred to as "softwood”.
  • the papermaking furnish used to make tissue paper structures may have other components or materials added thereto: for example, wet-strength and temporary wet-strength resins.
  • Suitable polysiloxane materials which are useful as S&S modifiers in accordance with the present invention include polymeric, oligomeric, copolymeric, and other multiple-monomeric siloxane materials.
  • 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 x 10 ⁇ 6 m . s ⁇ 1 (25 centistokes) to about 20 m . 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 can be applied to tissue paper as it is being made on a papermaking machine or thereafter: either while it is wet (i.e., prior to final drying) or dry (i.e., after final drying).
  • an aqueous mixture containing the polysiloxane is sprayed onto the tissue paper 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, or even after the Yankee dryer/creping station although the web is preferably creped after the polysiloxane is applied.
  • 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 is preferably applied after web formation has been effected.
  • the web is formed and then dewatered prior to polysiloxane application in order to reduce the loss of polysiloxane due to drainage of free water.
  • the polysiloxane is preferably applied to the wet web at a fiber consistency of greater than about 15% 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.
  • Methods of 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 polysiloxane, so is most preferred. Other methods which are less preferred include deposition of the polysiloxane onto a forming wire or fabric which is then contacted by the tissue web; and incorporation of the polysiloxane into the furnish prior to web formation.
  • 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.
  • the polysiloxane should be applied uniformly to the tissue paper web. A uniform distribution is desirable so that substantially the entire sheet benefits from the tactile effect of polysiloxane. Continuous and patterned distributions are both within the scope of the invention and meet the above criteria.
  • Polysiloxane can be applied to dry paper webs by the same methods previously discussed with respect to wet paper web polysiloxane treatments.
  • Tissue paper treated with polysiloxane in accordance with the present invention comprises about 2% or less polysiloxane. It is an unexpected benefit of this invention that tissue paper treated with about 2% 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 non-cationic 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 0.5%, is believed to be sufficient to provide sufficiently high wettability for most applications, including toilet paper, for polysiloxane levels of about 2% 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 0.01% and about 0.5%; 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.
  • 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. 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”
  • emulsifying agent any surfactant present as the emulsifying component of emulsified polysiloxane
  • 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.
  • noncationic surfactants are applied at fiber consistency levels of between about 10% and about 75%; 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.
  • tissue paper is treated with a relatively low level of a binder such as starch for lint control.
  • a binder such as starch
  • the tissue paper is treated with an aqueous solution of starch and, also preferably, 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.
  • 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.
  • This result is especially surprising since 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 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 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 15% and about 80%.
  • 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 starch to provide lint control and concomitant strength increase upon drying relative to a non-starch treated but otherwise identical sheet is preferably applied to the sheet.
  • 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 x 4-3/4 inch (about 11.1 cm x 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/in (15.5 g/cm).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Sanitary Thin Papers (AREA)
  • Materials For Medical Uses (AREA)

Claims (15)

  1. Tissue-Papier mit einem Flächengewicht von 10 bis 65 Gramm pro Quadratmeter und einer Dichte von nicht mehr als 0,6 Gramm/ml, wobei dieses Papier Fasern auf Zellulosebasis und eine Menge eines Polysiloxanmaterials umfaßt, dadurch gekennzeichnet, daß die genannte Polysiloxanmenge von 0,004 % bis 2 %, bezogen auf das Trockenfasergewicht des genannten Tissue-Papiers, beträgt und daß das genannte Tissue-Papier trocken ist und nach einer zweiwöchigen Alterung nach seiner Herstellung eine Benetzungszeit von nicht mehr als 2 Minuten aufweist, wobei die nach außen gerichteten Oberflächen des Tissue-Papiers eine gleichmäßige Verteilung des Polysiloxans aufweisen und das Polysiloxan ohne die Hilfe zusätzlicher Öle oder Lotionen vorliegt.
  2. Tissue-Papier nach Anspruch 1, worin die Polysiloxanmenge von 0,004 % bis 0,3 % Polysiloxan, bezogen auf das Trockenfasergewicht des genannten Tissue-Papiers, beträgt.
  3. Tissue-Papier nach einem der Ansprüche 1 und 2, worin das genannte Polysiloxan Polydimethylpolysiloxan ist, das eine funktionelle Wasserstoffbindungsgruppe, ausgewählt aus Amino-, Carboxyl-, Hydroxyl-, Ether-, Polyether-, Aldehyd-, Keton-, Amid-, Ester- und Thiolgruppen, aufweist, wobei die genannte funktionelle Wasserstoffbindungsgruppe in einem molaren Prozentsatz der Substitution von 20 % oder weniger vorliegt.
  4. Tissue-Papier nach Anspruch 3, worin das genannte Polysiloxan einen molaren Prozentsatz der Substitution von 10 % oder weniger und eine Viskosität von 25 x 10⁻⁶ms⁻¹ oder mehr aufweist.
  5. Tissue-Papier nach einem der Ansprüche 3 und 4, worin das genannte Polysiloxan einen molaren Prozentsatz der Substitution von 1,0 bis 5 % und eine Viskosität von 25 x 10⁻⁶ms⁻¹ bis 20 ms⁻¹ aufweist.
  6. Tissue-Papier nach einem der Ansprüche 3 bis 5, worin der genannte molare Prozentsatz der Substitution bei etwa 2 % liegt und die genannte Viskosität etwa 125 x 10⁻⁶ms⁻¹ beträgt.
  7. Tissue-Papier nach einem der vorhergehenden Ansprüche, das weiters ein oberflächenaktives Material (Surfactant) umfaßt.
  8. Tissue-Papier nach Anspruch 7, das eine ausreichende Menge eines oberflächenaktiven Materials umfaßt um zu gewährleisten, daß das genannte Tissue-Papier nach zweiwöchiger Alterung nach seiner Herstellung eine Benetzungszeit von nicht mehr als 30 Sekunden aufweist.
  9. Tissue-Papier nach einem der Ansprüche 7 und 8, worin das genannte oberflächenaktive Material in einer Menge von 0,01 % bis 2 %, bezogen auf das Trockenfasergewicht des genannten Tissue-Papiers, vorliegt.
  10. Tissue-Papier nach Anspruch 9, worin das genannte oberflächenaktive Material in einer Menge von 0,05 % bis 0,5 %, bezogen auf das Trockenfasergewicht des genannten Tissue-Papiers, vorliegt.
  11. Tissue-Papier nach einem der Ansprüche 7 bis 10, worin das genannte oberflächenaktive Material nicht-kationisch ist.
  12. Tissue-Papier nach einem der Ansprüche 7 bis 11, worin das genannte Surfactant einen Schmelzpunkt von mindestens 50°C hat.
  13. Tissue-Papier nach einem der vorhergehenden Ansprüche, das weiters eine wirksame Menge an Bindermaterial umfaßt, um mindestens teilweise jede Herabsetzung der Zugfestigkeit oder Steigerung der Neigung zur Fusselbildung des genannten Tissue-Papiers wettzumachen, die sonst aus dem Einbau des genannten Polysiloxans und, sofern anwesend, des genannten Surfactants entstehen würden.
  14. Tissue-Papier nach Anspruch 13, worin das genannte Bindermaterial Stärke ist.
  15. Tissue-Papier nach Anspruch 14, worin die genannte wirksame Menge der genannten Stärke zwischen 0,01 % und 2 %, bezogen auf das Trockenfasergewicht des genannten Tissue-Papiers, liegt.
EP89305940A 1988-06-14 1989-06-13 Sanftes Tissuepapier Revoked EP0347154B1 (de)

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US20662188A 1988-06-14 1988-06-14
US206621 1988-06-14

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EP0347154A2 EP0347154A2 (de) 1989-12-20
EP0347154A3 EP0347154A3 (de) 1991-05-02
EP0347154B1 true EP0347154B1 (de) 1996-01-03

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EP (1) EP0347154B1 (de)
JP (1) JP2806974B2 (de)
KR (1) KR0140223B1 (de)
AT (1) ATE132556T1 (de)
AU (1) AU634963B2 (de)
BR (1) BR8902848A (de)
CA (1) CA1330382C (de)
DE (1) DE68925309T2 (de)
ES (1) ES2081303T3 (de)
GR (1) GR3018609T3 (de)
MX (2) MX170318B (de)
NZ (1) NZ229550A (de)

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US7497925B2 (en) 2002-11-27 2009-03-03 Kimberly-Clark Worldwide, Inc. Shear-calendering processes for making rolled tissue products having high bulk, softness and firmness

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US6080686A (en) * 1993-01-19 2000-06-27 Th. Goldschmidt Ag Soft cellulosic nonwovens and a method for softening nonwovens
US5449551A (en) * 1993-06-03 1995-09-12 Kawano Paper Co., Ltd. Highly water absorbent fibrous web and a process for producing the same
JP3297340B2 (ja) * 1997-02-13 2002-07-02 河野製紙株式会社 紙製品
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
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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
JP3456956B2 (ja) * 2000-08-10 2003-10-14 株式会社飾一 繊維コート素材およびそれに使用するコート液
US6860967B2 (en) 2001-01-19 2005-03-01 Sca Hygiene Products Gmbh Tissue paper penetrated with softening lotion
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JP3950400B2 (ja) 2001-10-24 2007-08-01 河野製紙株式会社 繊維ウェブ製品、及びその製造方法
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US6887348B2 (en) 2002-11-27 2005-05-03 Kimberly-Clark Worldwide, Inc. Rolled single ply tissue product having high bulk, softness, and firmness
US6893535B2 (en) 2002-11-27 2005-05-17 Kimberly-Clark Worldwide, Inc. Rolled tissue products having high bulk, softness, and firmness
US7497925B2 (en) 2002-11-27 2009-03-03 Kimberly-Clark Worldwide, Inc. Shear-calendering processes for making rolled tissue products having high bulk, softness and firmness
US7497926B2 (en) 2002-11-27 2009-03-03 Kimberly-Clark Worldwide, Inc. Shear-calendering process for producing tissue webs

Also Published As

Publication number Publication date
GR3018609T3 (en) 1996-04-30
MX170318B (es) 1993-08-16
CA1330382C (en) 1994-06-28
KR0140223B1 (ko) 1998-07-01
AU634963B2 (en) 1993-03-11
JPH02224626A (ja) 1990-09-06
BR8902848A (pt) 1990-03-20
ATE132556T1 (de) 1996-01-15
AU3636389A (en) 1989-12-21
KR910001168A (ko) 1991-01-30
MX167009B (es) 1993-02-22
EP0347154A3 (de) 1991-05-02
ES2081303T3 (es) 1996-03-01
DE68925309T2 (de) 1996-05-23
EP0347154A2 (de) 1989-12-20
JP2806974B2 (ja) 1998-09-30
DE68925309D1 (de) 1996-02-15
NZ229550A (en) 1992-01-29

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