WO1996004424A1 - Soft tissue paper from coarse cellulose fibers - Google Patents

Soft tissue paper from coarse cellulose fibers Download PDF

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Publication number
WO1996004424A1
WO1996004424A1 PCT/US1995/008741 US9508741W WO9604424A1 WO 1996004424 A1 WO1996004424 A1 WO 1996004424A1 US 9508741 W US9508741 W US 9508741W WO 9604424 A1 WO9604424 A1 WO 9604424A1
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WO
WIPO (PCT)
Prior art keywords
fibers
tissue paper
cellulose fibers
length
fiber
Prior art date
Application number
PCT/US1995/008741
Other languages
English (en)
French (fr)
Inventor
Kenneth Douglas Vinson
Howard Thomas Deason
Original Assignee
The Procter & Gamble Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP8506517A priority Critical patent/JPH10503684A/ja
Priority to AU29699/95A priority patent/AU2969995A/en
Priority to EP95925632A priority patent/EP0772716B1/en
Priority to DE69525946T priority patent/DE69525946T2/de
Priority to BR9508461A priority patent/BR9508461A/pt
Priority to CA002194670A priority patent/CA2194670C/en
Publication of WO1996004424A1 publication Critical patent/WO1996004424A1/en

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H27/00Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30Multi-ply
    • D21H27/38Multi-ply at least one of the sheets having a fibrous composition differing from that of other sheets
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21FPAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F11/00Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
    • D21F11/14Making cellulose wadding, filter or blotting paper
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H15/00Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03Non-macromolecular organic compounds
    • D21H17/05Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03Non-macromolecular organic compounds
    • D21H17/05Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07Nitrogen-containing compounds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/59Synthetic 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
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/22Agents rendering paper porous, absorbent or bulky
    • D21H21/24Surfactants
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H11/00Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/02Chemical or chemomechanical or chemothermomechanical pulp
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H11/00Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/02Chemical or chemomechanical or chemothermomechanical pulp
    • D21H11/04Kraft or sulfate pulp

Definitions

  • This invention relates, in general, to tissue paper; and more specifically to sanitary tissue paper made from low grade cellulose pulps characterized as low grade because of their relatively high coarseness.
  • Desirable surface qualities are absent when the lower grade fibers are selected, if the lower grade fibers possess high coarseness.
  • high coarseness is due to the retention of the non-cellulosic components of the original wood substance, such components including lignin and so-called hemicelluloses. This makes each fiber weigh more without increasing its length.
  • Recycled paper can also tend to have a high mechanical pulp content, but, even when all due care is exercised in selecting the wastepaper grade to minimize this, a high coarseness still often occurs. This is thought to be due to the impure mixture of fiber morphologies which naturally occurs when paper from many sources is blended to make a recycled pulp. For example, a certain wastepaper might be selected because it is primarily North American hardwood in nature; however, one will often find extensive contamination from coarser softwood fibers, even of the most deleterious species such as variations of Southern U.S. pine.
  • the present invention is a soft tissue paper comprised of chemically softened cellulose fibers.
  • the chemically softened cellulose fibers comprise a sufficient amount of coarse fibers to raise the composite average coarseness of the tissue paper to greater than about 11.0 mg/100m.
  • the chemically softened cellulose fibers have a depressed coefficient of friction (DCOF, in percentage points) related to its composite average coarseness (C), in mg/100m, by the equation:
  • the soft tissue paper has a specific tensile strength between about
  • the invention provides for a targeted treatment, capable of essentially coating the fibers, in relation to their specific surface, with a substantive chemical softener, preferably in amounts ranging from about 0.05% to about 2.0%, by weight.
  • a substantive chemical softener preferably in amounts ranging from about 0.05% to about 2.0%, by weight.
  • Preferred chemical softeners include quaternary ammonium compounds having the formula:
  • each R is a C14-C22 hydrocarbyl group, preferably tallow
  • R2 is a C1 - C6 alkyl or hydroxyalkyl group, preferably C1-C3 alkyl
  • X is a compatible anion, such as an halide (e.g. chloride or bromide) or methyl sulfate.
  • tallow is a naturally occurring material having a variable composition.
  • Table 6.13 in the above-identified reference edited by Swern indicates that typically 78% or more of the fatty acids of tallow contain 16 or18 carbon atoms. Typically, half of the fatty acids present in tallow are unsaturated, primarily in the form of oleic acid. Synthetic as well as natural "tallows" fall within the scope of the present invention.
  • each Ri is C16-C18 alkyl, most preferably each Ri is straight-chain C18 alkyl.
  • each R2 is methyl and X- is chloride or methyl sulfate.
  • quaternary ammonium compounds suitable for use in the present invention include the well-known dialkyldimethylammonium salts such as ditallowdimethylammonium chloride, ditallowdimethylammonium methyl sulfate, di(hydrogenated) tallow dimethyl ammonium chloride; with di(hydrogenated) tallow dimethyl ammonium methyl sulfate being preferred. This particular material is available commercially from Witco Chemical Company Inc. of Dublin, Ohio under the tradename "Varisoft ®137".
  • Biodegradable mono and di-ester variations of the quaternary ammonium compound can also be used, and are meant to fall within the scope of the present invention.
  • Figure 1 is a schematic flow diagram depicting one method of producing preferred cellulose pulps wherein a length classifying stage is performed first, followed by a centrifuging stage.
  • Figure 2 is a schematic flow diagram depicting an alternate method of producing preferred cellulose pulps wherein a centrifuging stage is performed first, followed by a length classification stage.
  • the present invention is a low extractives tissue paper which has a heretofore unachieved level of softness when the coarseness of its furnish is taken into account.
  • coefficient of friction refers to the coefficient of friction as determined from the force required to drag a fritted glass sled across the smooth surface of a paper specimen which has been prepared by TAPPI standard method T-205. Details of the method used for the measurement are provided hereinafter, however the coefficient of friction could be determined by other methods which produce comparable values.
  • depressed coefficient of friction refers to the percentage amount by which the coefficient of friction is depressed via the addition of the chemical softener.
  • DCOF depressed coefficient of friction
  • DCOF is the depressed coefficient of friction
  • COF ⁇ and COF are the coefficient of friction of the handsheet made from untreated fibers and treated fibers respectively.
  • the term chemical softener refers to a compound capable of increasing the lubricity of papermaking fibers while being essentially substantive to the fibers, i.e. will remain on the fibers even when the fibers are dispersed in water.
  • the present invention preferably contains from about 0.05% to about 2.0% by weight, on a dry fiber basis, of a chemical softener.
  • a most preferred form of chemical softener is 0.05% to 2.0% of a quaternary ammonium compound having the formula:
  • each Ri is C14-C22 hydrocarbyl group, preferably tallow
  • R2 is a C1 - C6 alkyl or hydroxyalkyi group, preferably C1-C3 alkyl
  • X- is a compatible anion, such as an halide (e.g. chloride or bromide) or methyl sulfate.
  • halide e.g. chloride or bromide
  • tallow is a naturally occurring material having a variable composition.
  • Table 6.13 in the above-identified reference edited by Swern indicates that typically 78% or more of the fatty acids of tallow contain 16 or18 carbon atoms.
  • each R is C16-C18 alkyl, most preferably each Ri is straight-chain C18 alkyl.
  • each R2 is methyl and X " is chloride or methyl sulfate.
  • quaternary ammonium compounds suitable for use in the present invention include the well-known dialkyldimethylammonium salts such as ditallowdimethylammonium chloride, ditallowdimethylammonium methyl sulfate, di(hydrogenated) tallow dimethyl ammonium chloride; with di(hydrogenated) tallow dimethyl ammonium methyl sulfate being preferred.
  • This particular material is -7- available commercially from Witco Chemical Company Inc of Dublin, Ohio under the trade ⁇ ame "Va ⁇ soft ® 137"
  • Biodegradable mono and di-ester variations of the quaternary ammonium compound can also be used, and are meant to fall within the scope of the present invention These compounds have the formula
  • each R is an aliphatic C13 - C19 hydrocarbyl group, such as tallow
  • R2 is a C1 - C6 alkyl or hydroxyalkyi group or mixture thereof
  • X" is a compatible anion, such as an halide (e g , chloride or bromide) or methyl sulfate
  • each Ri is C16-C18 alkyl, most preferably each Ri is straight-chain C18 alkyl, and R2 is a methyl
  • Other preferred chemical softeners suitable for use in the tissue papers of the present invention include polysiloxane compounds, preferably amino-functional polydimethylpolysiloxane compounds.
  • substitution may be made with carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, and thiol groups.
  • these effective substituent groups the family of groups comprising amino, carboxyl, and hydroxyl groups are more preferred than the others; and amino-functional groups are most preferred. Suitable types of such polysiloxanes are described in U.S. Patent No. 5,059,282, Ampulksi et al., issued October 22, 1991 , and incorporated herein by reference.
  • Exemplary commercially available polysiloxanes include DOW 8075 and DOW 200 which are available from Dow Corning; and Silwet L720 and Ucarsil EPS which are available from Union Carbide.
  • Still other preferred chemical softener additives suitable for the present invention include nonionic surfactants selected from 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. Patent 4,011 ,389, issued to W. K. Langdon, et al.
  • alkylpolyethoxylated esters such as PegosperseTM 200 ML available from Glyco Chemicals, Inc. (Greenwich, CT); alkylpolyethoxylated ethers and esters such as Neodol® 25-12 available from Shell Chemical Co.; sorbitan esters such as Span 60 from ICI America, Inc., ethoxylated sorbitan esters, propoxylated sorbitan esters, mixed ethoxylated/propoxylated sorbitan esters, and polyethoxylated sorbitan alcohols such as Tween 60 also from ICI America, Inc.
  • composite average coarseness refers to the coarseness determined on the fibrous finished product of tissue, without regard as to whether the product is composed of several furnishes of different coarseness values.
  • the method of determining coarseness of cellulose fibers is described in detail hereinafter.
  • the composite average coarseness can also be determined for a product comprised of a blend of different types of cellulose fibers from the coarseness of the individual fibers from which the product is comprised. The exact weight proportions of the different types of fibers needs to be known in order to perform this calculation. To do this, the following formula is used to determine the resultant composite average coarseness C when two fiber types, type 1 and type 2, possessing coarseness C1 and C2, respectively are blended in weight fractions f1 and f2, respectively:
  • tissue papers of the present invention are comprised of cellulose fibers having a composite average coarseness greater than about 11.0mg/m, more preferably, greater than about 12 mg/100m.
  • cellulose fibers refers to naturally- occurring fibrous material derived from wood or other biological material. Wood-derived materials are of particular interest. Cellulose wood fibers from- a variety of sources may be employed to produce products according to the present invention. These include chemical pulps, which are purified to remove substantially all of the lignin originating from the wood substance. These chemical pulps include those made by either the alkaline Kraft (sulfate) or the acid, sulfite processes.
  • Applicable wood fibers can also be derived from mechanical pulps, a term which as used herein, refers to chemi-thermomechanical as well as groundwood, thermomechanical, and semi-chemical pulps, all of which retain a substantial portion of lignin originating from the wood substance. Both hardwood pulps and softwood pulps as well as blends of the two may be employed.
  • the terms hardwood and softwood pulp as used herein refer to fibrous pulp derived from the woody substance of deciduous trees (angiosperms) and coniferous trees (gymnosperms), respectively.
  • fibers derived from recycled paper which may contain any or all of the above categories as well as minor amounts of other fibers, fillers, and adhesives used to facilitate the original papermaking.
  • Fibers derived from recycled paper made with chemical pulp fibers and comprising a blend of hardwood and softwood fibers may also be employed to produce products according to the present invention.
  • recycled paper generally refers to paper which has been collected with the intent of liberating its fibers and reusing them.
  • Ledger paper is usually comprised of chemical pulps and typically has a hardwood to softwood ratio of from about 1 :1 to about 2:1. Examples of ledger papers include bond, book, photocopy paper, and the like.
  • the cellulose fibers used to make the tissue paper of the present invention comprise at least 10%, and more preferably from about
  • coarse cellulose fibers selected from the group consisting of recycled fibers, chemi-thermomechanical fibers and mixtures thereof.
  • Softness refers to the tactile quality of a tissue paper, as judged relatively by expert panel and reported in average panel judging units. Softness is known to be affected by structural artifacts of papermaking other than the fiber morphology as disclosed herein. For example, it is well known to those skilled in the art that softness of sanitary tissue is a function of its weight and tensile strength.
  • the specific tensile useful for the present invention ranges from about 9 g/in/g/m 2 to about 25 g/in/g/m 2 , and, more preferably, from about 11 g/in/g/m 2 to 17 g/in/g/m 2 .
  • Softness is further affected by the bulk resultant from the type of forming and drying performed in papermaking.
  • U.S. Patent 3,301 ,746 issued to Sanford and Sisson in 1967 was pivotal in defining means of preparing exceptionally soft paper useful for sanitary tissues and the like. This art recognized the importance of density in providing softness.
  • density is calculated from the thickness and the weight per unit area, wherein the thickness is determined using any suitably calibrated caliper capable of subjecting the specimen to a uniform compressive load of 95 g/in 2 .
  • the density ranges useful for the present invention range from about .05 g/cc to about 0.2 g/cc, preferably from about .08 g/cc to about 0.15 g/cc.
  • centrifugal screen refers to a pressure screen such as the Model 100 Centrisorter, a tradename of the Bird Machinery Corporation of South Walpole, MA, equipped with a screen basket with hole size capable of separating the fibers in an inlet stream into two fractions having a measurable length difference.
  • tissue papers of the present invention have a composite average fiber length between about 1 mm and about 1.5 mm.-
  • hydraulic cyclone refers to a device such as a 3" Centricleaner, a tradename of the Sprout-Bauer Company of Springfield, OH.
  • the present invention is a soft tissue paper comprised of chemically softened cellulose fibers.
  • the chemically softened cellulose fibers comprise a sufficient amount of coarse fibers to raise the composite average coarseness of the tissue paper to greater than about 11.0 mg/100m.
  • the chemically softened cellulose fibers have a depressed coefficient of friction (DCOF, in percentage points) related to the composite average coarseness (C), in mg/100m, by the equation:
  • the tissue paper has a specific tensile strength between about 9 and about 25 g/in/g/m 2 and a density between about 0.05 and about 0.20 g/cc.
  • the present invention is useful with tissue paper in general, including but not limited to conventionally felt-pressed tissue paper; high bulk pattern densified tissue paper; and high bulk, uncompacted tissue paper.
  • the tissue paper can be of a homogenous or multi-layered construction; and tissue paper products made therefrom can be of a single-ply or multi-ply construction.
  • the tissue paper preferably has a basis weight of between about 10 g/m2 and about 65 g/m 2 , and density of about 0.6 g/cc or less. More preferably, the basis weight will be about 40 g/m 2 or less and the density will be about 0.3 g/cc or less.
  • the density will be between about 0.05 g/cc and about 0.2 g/cc, and most preferably, from about 0.08g/cc to about 0.15g/cc.
  • the tissue papers are of a single ply, multi-layered construction.
  • the single ply comprises three superposed layers, an inner layer and two outer layers, with the inner layer being located between the two outer layers.
  • the inner layer preferably comprises cellulose fibers with a length- weighted average length of at least about 1 mm, and each of the two outer layers preferably comprises fibers with a length-weighted average length less than about 1 mm. In this preferred embodiment the inner layer comprises from about 15% to about 35% of the total sheet weight.
  • the coarse cellulose fibers are selected from a group consisting of recycled fibers, chemi-thermomechanical fibers and mixtures thereof.
  • the coarse fibers are preferably located in the outer layers where they comprise at least about 10% and more preferably from about 20 to about 60% of the total sheet weight and at least about 12% and, more preferably from about 25 to about 75% by weight, of the outer layers.
  • Such paper is typically made by depositing a papermaking furnish on a foraminous forming wire, often referred to in the art as a Fourdrinier wire. Once the furnish is deposited on the forming wire, it is referred to as a web. The web is dewatered by pressing the web and drying 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 from 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 dried 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 steam 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 can be employed, whereby additional pressing is optionally incurred between the drums.
  • the tissue paper structures that are formed are referred to hereafter as conventional, pressed, tissue paper structures. Such sheets are considered to be compacted since the entire web is subjected to substantial mechanical compressional forces while the fibers are moist and are then dried while in a compressed state.
  • the tissue papers of the present invention are pattern densified.
  • 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 are dispersed within the high bulk zone.
  • the densified zones can be discretely spaced within the high bulk field or can be interconnected, either fully or partially, within the high bulk field.
  • the patterns can be formed in a nonornamental configuration or can be formed so as to provide an ornamental design(s) in the tissue paper. Preferred processes for making pattern densified tissue webs are disclosed in U.S.
  • Patent No. 3,301 ,746 (Sanford et al), issued January 31 , 1967; U.S. Patent No. 3,974,025 (Ayers), issued August 10, 1976; and U.S. Patent No. 4,191 ,609 (Trokhan) issued March 4, 1980; and U.S. Patent 4,637,859 (Trokhan) issued January 20, 1987; all of which are incorporated by reference.
  • 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.
  • This high bulk field can be further dedensified 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.
  • 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 can 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 125% of the density of the high bulk field.
  • the array of supports is preferably an imprinting carrier fabric -15- having a patterned displacement of knuckles that operate as the array of supports that facilitate the formation of the densified zones upon application of pressure.
  • the pattern of knuckles constitutes the array of supports previously referred to.
  • Suitable imprinting carrier fabrics are disclosed in U.S. Patent No. 3,301 ,746 (Sanford et al), issued January 31 , 1967; U.S. Patent No. 3,821 ,068 (Salvucci et al), issued May 21 , 1974; U.S. Patent No. 3,974,025 (Ayers), issued August 10, 1976; U.S. Patent No.
  • 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 can alternately be initially deposited on a foraminous supporting carrier that 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 that 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 can 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 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 about 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.
  • Compacted non-pattem-densified tissue structures are commonly known in the art as conventional tissue structures.
  • compacted, non-pattem-densified tissue paper structures are prepared by depositing a papermaking furnish on a foraminous wire such as a Fourdrinier wire to form a wet web, draining the web and removing additional water with the aid of a uniform mechanical compaction (pressing) until the web has a consistency of 25-50%, transferring the web to a thermal dryer such as a Yankee and creping the web. Overall, water is removed from the web by vacuum, mechanical pressing and thermal means.
  • the resulting structure is strong and generally of singular density, but very low in bulk, absorbency and softness.
  • average fiber length refers to the length weighted average fiber length as determined with a suitable fiber length analysis instrument such as a Kajaani Model FS-200 fiber analyzer available from Kajaani Electronics of Norcross, Georgia.
  • the analyzer is operated according to the manufacturer's recommendations with the report range set at 0 mm to 7.2 mm and the profile set to exclude fibers less than 0.2 mm in length from the calculation of fiber length and coarseness. Particles of this size are excluded from the calculation because it is believed that they consist largely of non-fiber fragments which are not functional for the uses toward which the present invention are directed.
  • coarseness refers to the fiber mass per unit of unweighted fiber length reported in units of milligrams per ten meters of unweighted fiber length (mg/100m) as measured using a suitable fiber coarseness -17- measuring device such as the above mentioned Kajaani FS-200 analyzer.
  • the coarseness C of the pulp is an average of three coarseness measurements of three fiber specimens taken from the pulp.
  • the operation of the analyzer for measuring coarseness is similar to the operation for measuring fiber length. Care must be taken in sample preparation to assure an accurate sample weight is entered into the instrument.
  • An acceptable method is to dry two aluminum weighing dishes for each fiber specimen in a drying oven for thirty minutes at 110° C.
  • the dishes are then placed in a desiccator having a suitable desiccant such as anhydrous calcium sulfate for at least fifteen minutes to cool.
  • the dishes should be handled with tweezers to avoid contaminating them with oil or moisture.
  • the two dishes are taken out of the desiccator and immediately weighed together to the nearest 0.0001 gram. Approximately one gram of a fiber specimen is placed in one of the dishes, and the two dishes (one empty) are placed uncovered in the drying oven for a period of at least sixty minutes at 110° C to obtain a bone dry fiber specimen.
  • the dish with the fiber specimen is then covered with the empty dish prior to removing the dishes from the oven.
  • the dishes and specimen are then removed from the oven and placed in a desiccator for at least 15 minutes to cool.
  • the covered specimen is removed and immediately weighed with the dishes to within 0.0001 gram.
  • the previously obtained weight of the dishes can be subtracted from this weight to obtain the weight of the bone dry fiber specimen. This weight of fiber is referred to as the initial sample weight.
  • An empty 30 liter container is prepared by cleaning it and weighing it on a scale capable of at least 25 kilograms capacity with 0.01 gram accuracy.
  • a standard TAPPI disintegrator such as the British disintegrator referred to in TAPPI method T205, is prepared by cleaning its container to remove all fibers. The initial sample weight of fibers is emptied into the disintegrator container, ensuring that all fibers are transferred to the disintegrator.
  • the fiber sample is diluted in the disintegrator with about 2 liters of water and the disintegrator is run for ten minutes.
  • the contents of the disintegrator are washed into the 30 liter container, ensuring that all fibers are washed into the container.
  • the sample in the 30 liter container is then diluted with water to obtain a water-fiber slurry weighing 20 kilograms, within 0.01 gram.
  • the sample beaker for the Kajaani FS-200 is cleaned and weighed to within 0.01 gram.
  • the slurry in the 30 liter container is stirred with vertical and horizontal strokes, taking care to not set up a circular motion which would tend to centrifuge the fibers in the slurry.
  • a 100.0 gram measure accurate to within 0.1 gram is transferred from the 30 liter container to the Kajaani beaker.
  • the fiber weight in the Kajaani beaker, in milligrams, is obtained by multiplying five (5) times the initial sample weight (as recorded in grams).
  • Kajaani FS-200 profile A minimum fiber length of 0.2 mm is entered into the Kajaani profile so that 0.2 mm is the minimum fiber length considered in the coarseness calculation. A preliminary coarseness is then calculated by the Kajaani FS-200.
  • the coarseness is obtained by multiplying this preliminary coarseness value by a factor corresponding to the weight weighted cumulative distribution of fibers with length greater than 0.2 mm.
  • the FS- 200 instructions provide a method for obtaining this weight weighted distribution. However, the values are reported as a percentage and are accumulated beginning at "0" fiber length.
  • the "weight-weighted cumulative distribution of fibers with length less than 0.2 mm" (which is provided as an output of the instrument) is obtained from the instrument display. This display value is subtracted from 100, and the result is divided by 100 to obtain the factor corresponding to the weight weighted cumulative distribution of fibers with length greater than 0.2 mm.
  • the resulting coarseness is therefore a measure of the coarseness of those fibers in a fiber sample having a fiber length greater than 0.2 mm.
  • the coarseness measurement is repeated, starting with oven drying two weighing dishes and a fiber specimen, to obtain three values of coarseness.
  • the value of coarseness C used herein is obtained by averaging the three coarseness values and converting the units to express the value in mg/100m.
  • the substrate used for the friction evaluation is a laboratory prepared handsheet, prepared according to TAPPI standard
  • T-205 incorporated herein by reference .
  • the friction is measured on the smooth side of the handsheet (the side which is dried against a metal plate according to the method).
  • the substrate is advanced at 1 mm/sec constant rate for the measurement and the friction probe is modified from the standard instrument probe to a two centimeter diameter 40-60 micron glass frit.
  • the coefficient of friction can be calculated by dividing the frictional force by the normal force.
  • the frictional force is the lateral force on the probe during the scanning, an output of the instrument.
  • the average of coefficient of friction obtained by a single scan in the forward direction and a single scan in the reverse direction is reported as the coefficient of friction for the specimen.
  • a standard handsheet is prepared using a sample of the fibers without chemical softener and a standard handsheet is prepared using a sample of the fibers after addition of the chemical softener.
  • the coefficient of friction is measured using each handsheet, and the DCOF is computed using the following formula:
  • DCOF is the depressed coefficient of friction
  • COF ⁇ and COFA are the coefficient of friction of the handsheet made from untreated fibers and those from fibers treated with chemical softener, respectively.
  • tissue paper according to the present invention While many suitable sources of coarse cellulose fibers can be applied to make tissue paper according to the present invention, two embodiments are preferred for its practice.
  • One preferred embodiment employs a chemi-thermomechanical pulp derived from hardwood fibers, such as Aspen CTMP.
  • a second preferred embodiment employs recycled fibers. If recycled fibers are employed in the present invention, it is preferred that they be pre-conditioned according to the following process steps to most favorably dispose them to the product use.
  • Figure 1 is a flow diagram depicting one arrangement which can be used to produce cellulose pulps preferred for use in the tissue papers of the present invention. In this arrangement, the length classifying stage is performed first, followed by the centrifuging stage.
  • an aqueous slurry 21 comprising wood pulp fibers is directed to form the input stream to a length classifying stage 32.
  • a satisfactory length classifier is a centrifugal pressure screen such as a Bird "Centrisorter” manufactured by the Bird Escher Wyss Corporation of South Walpole, Massachusetts.
  • the slurry 21 is processed in the length classifying stage 32 to provide an accepts stream 33 of the classifying stage 32 and a rejects stream 34 of the classifying stage 32.
  • the rejects strearrr34 comprises fibers having an average fiber length exceeding that of the fibers in the accepts stream 33.
  • the length classifying stage 32 is configured and operated as described below to provide the accepts stream 33 having an average fiber length which is at least 20%, and preferably at least 30% less than the average fiber length of the rejects stream comprising slurry 34.
  • the fibers in rejects stream 34 are directed to alternative end uses where the characteristics sought as objectives of the present invention are less valued. In this regard they may be blended with other rejects streams, maintained separate or discarded.
  • the fiber weight of the accepts stream 33 of the length classifying stage 32 should be between about 30 to 70 percent of the fiber weight of the input stream to the length classifying stage 32, so that there is about a thirty to seventy percent mass split of the fibers entering the length classifying stage 32 between the accepts stream 33 and the rejects stream 34.
  • a mass split is desirable to ensure that length classifying stage 32 functions to fractionate the input stream by fiber length, rather than just functioning to remove debris such as knots and shives from the input stream.
  • At least a portion of the accepts stream 33 of the length classification stage 32 is directed as shown in Figure 1 to provide an input stream 41 to a second fractionation stage comprising a centrifuging stage 42.
  • a satisfactory centrifuging stage 42 comprises one or more hydraulic cyclones, such as 3 inch "Centricleaner" hydraulic cyclones manufactured by the CE Bauer Company of Springfield, Ohio.
  • a suitable sieve 36 can be positioned intermediate the length classifying stage 32 and the centrifuging stage 42, as illustrated in Figure 1.
  • a suitable sieve 36 comprises a CE Bauer "Micrasieve” equipped with a 100 micron screen.
  • the centrifuging stage 42 processes input stream 41 to provide an accepts stream 43 of the centrifuging stage 42 and a rejects stream 44 of the centrifuging stage 42.
  • the accepts stream 43 exits the overflow side of the hydraulic cyclone and the rejects stream 44 exits the underflow side
  • the normalized coarseness of the fibers in accepts stream 43 is at least 3 percent, and preferably at least 10 percent less than that of the fibers in the rejects stream 44 of the centrifuging stage 42.
  • the process depicted in Figure 1 can be operated to provide an accepts stream 43 comprising the cellulose pulps preferred for the present invention.
  • the accepts stream 43 comprising the cellulose pulps of the present invention includes at least 10 percent softwood fibers, has an incremental surface area less than 0.085 square millimeters, and has a coarseness related to average fiber length by the algebraic expression recited above.
  • the average fiber length of the accepts stream 43 is preferably about 0.70 mm to about 1.1 mm, and more preferably about 0.75 mm to about 0.95 mm to provide this coarseness to fiber length relationship.
  • the fiber weight of the accepts stream 43 of the centrifuging stage 42 should be between about 30 to 70 percent of the fiber weight of the input stream 41 to the centrifuging stage 42, so that there is about a thirty to seventy percent mass split of the fibers entering the centrifuging stage 42 between the accepts stream 43 and the rejects stream 44, respectfully.
  • Such a mass split is desirable to ensure that the centrifuging stage 42 provides an accept stream 43 having a reduced normalized coarseness relative to rejects stream 44, rather than just functioning to remove debris such as knots and shives from the input stream 41.
  • FIG. 2 is a flow diagram depicting another arrangement which can be used to produce cellulose pulps preferred for use in the tissue papers of the present invention.
  • the centrifuging stage is performed first, followed by the length classifying stage.
  • an aqueous slurry 21 comprising wood pulp fibers is first directed to form the input stream to the centrifuging stage 52.
  • the centrifuging stage 52 comprises at least one hydraulic cyclone.
  • the centrifuging stage 52 processes the input stream to provide an accepts stream 53 of the centrifuging stage 52 and a rejects stream 54 of the centrifuging stage 52.
  • the accepts stream 53 exits the overflow side of the hydraulic cyclone, and the rejects stream exits the under flow side (the tip) of the hydraulic cyclone.
  • the normalized coarseness of the fibers in accepts stream 53 is at least 3 percent, and preferably at least 10 percent less than that of the fibers in the rejects stream 54 of the centrifuging stage 52, and the average fiber length of the fibers in the accepts stream 53 is preferably about equal to or greater than that of the slurry 21.
  • At least a portion of the accepts stream 53 of the centrifuging stage 52 is directed to provide an input stream 61 to a length classifying stage
  • the length classifying stage 62 can comprise a screen, such as the centrifugal screen described above. It may be desirable to adjust the consistency of the input stream 61 prior to processing the input stream 61 in the length classifying stage 62. For instance, if it is desirable to remove water from input stream 61 to increase its consistency, a suitable sieve 60 can be positioned intermediate the centrifuging stage 52 and the length classifying stage 62 as illustrated in Figure 2.
  • a suitable sieve 60 comprises a CE Bauer "Micrasieve" equipped with a 100 micron screen.
  • the length classifying stage 62 processes input stream 61 to provide an accepts stream 63 of the length classifying stage and a rejects stream 64 of the length classifying stage.
  • the rejects stream 64 comprises fibers having an average fiber length exceeding that of the fibers in the accepts stream 63.
  • the average fiber length is at least 20 percent less, and preferably at least 30 percent less than the average fiber length of the rejects stream 64 to the length classification stage.
  • the process depicted in Figure 2 can be operated to provide an accepts stream 63 comprising the cellulose pulps preferred for the present invention.
  • the accepts stream 63 comprising the cellulose pulps of the present invention includes at least 10 percent softwood fibers, has an incremental surface area less than 0.085 square millimeters, and has a coarseness related to average fiber length by the algebraic expression recited above.
  • the average fiber length of the accepts stream 63 is preferably about 0.7 mm to about 1.1 mm, and more preferably about 0.75 mm to about 0.95 mm to provide the aforementioned coarseness to fiber length relationship.
  • the operating parameters of the length classification and centrifuging stages can be adjusted for the specific characteristics of the fibers contained in slurry 21 in order to achieve the necessary change in the average fiber length and normalized coarseness respectively required by the present invention.
  • such operating parameters include the consistency of the input and output slurry; the size, shape, and density of perforations in the screen media; the speed at which the screen pulsator rotates; and the flow rates of the inlet and each of the outlet streams. It may also be desirable to use dilution water to aid in the removal of the longer fiber rejects stream from the screen in the sieve 60 if it tends to be excessively thickened by the action of the screen.
  • examples of operating parameters include the consistency of the input stream, the diameter of the cone, the cone angle, the size of the underflow opening, and the pressure drop from the inlet slurry to each leg of the outlet.
  • the present invention requires that the cellulose fibers possess a depressed coefficient of friction achieved via the addition of a chemical softener.
  • the preferred method of adding the chemical softener to the cellulose fibers is to add the softener to an aqueous slurry of papermaking fibers, or furnish, in the wet end of the papermaking machine at some suitable point ahead of the fourdrinier wire or sheet forming stage.
  • the chemical softeners within the scope of this invention are expressly substantive to the fibers, applications of the chemical softeners prior to the papermaking process, for example by adding to aqueous pulp mixtures formed during production of the pulp are also anticipated.
  • chemical softener application subsequent to the formation of the tissue web, including points prior to, during, or after drying can also be designed to meet the requirements of the present invention and are expressly included within its scope.
  • This example illustrates the preparation of a single-ply bath tissue product utilizing a recycled fiber source normally regarded as being inferior for making this type of product.
  • the cellulose fiber types used in the preparation are:
  • NSK Northern Softwood Kraft
  • eucalyptus hardwood Kraft pulp obtained from Ponderosa Fibers' Oshkosh, Wl mill.
  • the virgin Kraft pulps are used as delivered, while the Ponderosa pulp is pre-treated by forming an aqueous slurry and subjecting it to a sequential treatment in a centrifugal screen from which a short fiber fraction is acquired which is then passed through a hydraulic cyclone, from which the accepts or overflow fraction is captured.
  • the screening accepts are about 25% of the feed material and have a fiber length about 50% lower than the starting pulp.
  • a single-pass through the cyclones is taken at about 75 psi pressure drop from inlet to accepts and 0.1 % solids in the feed.
  • the accepts accordingly comprise about 50% of the fiber which is fed to them. This step is known from previous work to result in a fiber with exceptionally low coarseness as a function of its fiber length.
  • the resultant tissue product is formed so that it conforms to the practice of the present invention.
  • the papermaking is done on a pilot scale Fourdrinier papermaking machine. This papermaking machine is operated with enough Whitewater purge to assure that essentially no non-substantive additives will remain in the papermaking web after draining on the forming wire.
  • a 1 % solution of a quaternary salt (dihydrogenated tallow dimethyl ammonium methyl sulfate), obtained from Witco Chemical Company of Dublin, OH is prepared.
  • a quaternary salt dihydrogenated tallow dimethyl ammonium methyl sulfate
  • an equivalent amount of polyethylene glycol of 400 molecular weight is optionally included.
  • the quaternary salt, with the PEG optionally added, are first heated to about 150°F, then added to water at about the same temperature while the water is being agitated.
  • the papermaking headbox is equipped with separator leaves so that long NSK fibers and the shorter eucalyptus or recycled fibers can be laid down in separate layers to deposit each fiber type in its optimum location.
  • This type of forming is common and will be recognized as such by those skilled in the art.
  • Two comparative paper structures are formed.
  • the first is formed by directing 20% of the sheet weight as NSK into the center layer of a three-layered composite wherein the outer layers are comprised exclusively of the eucalyptus pulp.
  • the second is formed by directing 20% of the sheet weight as NSK into the center layer of a three-layered composite wherein the outer layer next to the forming wire is comprised exclusively of the pre-treated recycled pulp, and the other outer layer is comprised of a blend of the pre- treated recycled pulp with eucalyptus in a proportion of 3:5 by weight.
  • the overall content of the recycled pulp is therefore 55%.
  • the forming is completed similarly on the two furnishes.
  • the quaternary salt is added to the stocks during approach flow when their consistencies are about 3%.
  • the quaternary salt is proportioned so that the ratio added to the wire-side furnish is twice that of the felt side furnish.
  • No quaternary salt is added to the NSK.
  • the amount of quaternary salt added is sufficient to retain 0.105% in the finished product.
  • the only other change necessary in the process when using the recycled fiber, is a slight refining of the NSK to compensate for some strength losses.
  • This example illustrates the preparation of a single-ply bath tissue product utilizing a chemi-thermomechanical fiber source normally regarded as being inferior for making this type of product.
  • the cellulose fiber types used in the preparation are:
  • NSK Northern Softwood Kraft
  • eucalyptus hardwood Kraft pulp eucalyptus hardwood Kraft pulp
  • CTMP pulp a market hardwood CTMP pulp
  • the pulps are all used as delivered and the resultant tissue product is formed so that it conforms to the practice of the present invention.
  • the papermaking is done on a pilot scale Fourdrinier papermaking machine. This papermaking machine is operated with enough water purge so that essentially no non-substantive additives will remain in the papermaking web after draining on the forming wire.
  • a 1 % solution of a quaternary salt (diester dihydrogenated tallow dimethyl ammonium chloride), obtained from Witco Chemical Company of Dublin, OH is prepared.
  • a quaternary salt diester dihydrogenated tallow dimethyl ammonium chloride
  • an equivalent amount of polyethylene glycol of 400 molecular weight is optionally included.
  • the quaternary salt, with the PEG optionally added, are first heated to about 185°F, then added to water at about the same temperature while the water is being agitated.
  • the papermaking headbox is equipped with separator leaves so that long NSK fibers and the shorter eucalyptus or recycled fibers can be laid down in separate layers to deposit each fiber type in its optimum location. This type of forming is common and will be recognized as such by those skilled in the art. Two comparative paper structures are formed.
  • the first is formed by directing 20% of the sheet weight as NSK into the center layer of a three-layered composite wherein the outer layers are comprised exclusively of the eucalyptus pulp.
  • the second is formed by directing 20% of the sheet weight as NSK into the center layer of a three-layered composite wherein the outer layers are supplied by a furnish comprising a blend of eucalyptus and CTMP in proportions of 7:4.
  • the overall content of the CTMP pulp is therefore 28%.
  • the quaternary salt is added to the stocks during approach flow when their consistencies are about 3%.
  • the quaternary salt is proportioned so that the ratio added to the wire-side furnish is half that of the felt side furnish.
  • No quaternary salt is added to the NSK.
  • the amount of quaternary salt added is sufficient to retain 0.325% in the finished product.
  • DCOF coefficient of friction

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Sanitary Thin Papers (AREA)
  • Nonwoven Fabrics (AREA)
PCT/US1995/008741 1994-07-29 1995-07-12 Soft tissue paper from coarse cellulose fibers WO1996004424A1 (en)

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JP8506517A JPH10503684A (ja) 1994-07-29 1995-07-12 粗質なセルロース繊維からの柔軟なティッシュペーパー
AU29699/95A AU2969995A (en) 1994-07-29 1995-07-12 Soft tissue paper from coarse cellulose fibers
EP95925632A EP0772716B1 (en) 1994-07-29 1995-07-12 Soft tissue paper from coarse cellulose fibers
DE69525946T DE69525946T2 (de) 1994-07-29 1995-07-12 Aus rauhen zellstofffasern hergestelltes sanftes tissuepapier
BR9508461A BR9508461A (pt) 1994-07-29 1995-07-12 Papel de seda macio
CA002194670A CA2194670C (en) 1994-07-29 1995-07-12 Soft tissue paper from coarse cellulose fibers

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US08/282,331 1994-07-29

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CA (1) CA2194670C (ja)
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WO1997034047A1 (en) * 1996-03-13 1997-09-18 The Procter & Gamble Company Tissue paper containing chemically softened coarse cellulose fibers
WO1998023813A1 (en) * 1996-11-26 1998-06-04 Kimberly-Clark Worldwide, Inc. Method of making sanitary paper products from recycled newspapers
WO1998027278A1 (en) * 1996-12-17 1998-06-25 Kimberly-Clark Worldwide, Inc. Fractionation process for cellulosic fibers
US5882743A (en) * 1997-04-21 1999-03-16 Kimberly-Clark Worldwide, Inc. Absorbent folded hand towel
WO2000019005A1 (en) * 1998-09-30 2000-04-06 Kimberly-Clark Worldwide, Inc. A sanitary paper product made by modifying coarse fibers and process thereof
US6146494A (en) * 1997-06-12 2000-11-14 The Procter & Gamble Company Modified cellulosic fibers and fibrous webs containing these fibers
WO2002081819A1 (en) * 2001-04-09 2002-10-17 Scott Paper Limited Tissue products containing softness
WO2019152969A1 (en) * 2018-02-05 2019-08-08 Pande Harshad Paper products and pulps with surface enhanced pulp fibers and increased absorbency, and methods of making same
US10563356B2 (en) 2014-02-21 2020-02-18 Domtar Paper Company, Llc Surface enhanced pulp fibers at a substrate surface
US10704165B2 (en) 2012-08-24 2020-07-07 Domtar Paper Company, Llc Surface enhanced pulp fibers, methods of making surface enhanced pulp fibers, products incorporating surface enhanced pulp fibers, and methods of making products incorporating surface enhanced pulp fibers
US10710930B2 (en) 2014-02-21 2020-07-14 Domtar Paper Company, Llc Surface enhanced pulp fibers in fiber cement
US11473245B2 (en) 2016-08-01 2022-10-18 Domtar Paper Company Llc Surface enhanced pulp fibers at a substrate surface
US11499269B2 (en) 2016-10-18 2022-11-15 Domtar Paper Company Llc Method for production of filler loaded surface enhanced pulp fibers
US11608596B2 (en) 2019-03-26 2023-03-21 Domtar Paper Company, Llc Paper products subjected to a surface treatment comprising enzyme-treated surface enhanced pulp fibers and methods of making the same
US12104327B2 (en) 2019-09-23 2024-10-01 Domtar Paper Company, Llc Tissues and paper towels incorporating surface enhanced pulp fibers and methods of making the same
US12116732B2 (en) 2019-09-23 2024-10-15 Domtar Paper Company, Llc Paper products incorporating surface enhanced pulp fibers and having decoupled wet and dry strengths and methods of making the same

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WO1997034047A1 (en) * 1996-03-13 1997-09-18 The Procter & Gamble Company Tissue paper containing chemically softened coarse cellulose fibers
WO1998023813A1 (en) * 1996-11-26 1998-06-04 Kimberly-Clark Worldwide, Inc. Method of making sanitary paper products from recycled newspapers
WO1998027278A1 (en) * 1996-12-17 1998-06-25 Kimberly-Clark Worldwide, Inc. Fractionation process for cellulosic fibers
US6024834A (en) * 1996-12-17 2000-02-15 Kimberly-Clark Worldwide, Inc. Fractionation process for cellulosic fibers
US6080266A (en) * 1996-12-17 2000-06-27 Kimberly-Clark Worldwide, Inc. Fractionation process for cellulosic fibers
US5882743A (en) * 1997-04-21 1999-03-16 Kimberly-Clark Worldwide, Inc. Absorbent folded hand towel
US6146494A (en) * 1997-06-12 2000-11-14 The Procter & Gamble Company Modified cellulosic fibers and fibrous webs containing these fibers
WO2000019005A1 (en) * 1998-09-30 2000-04-06 Kimberly-Clark Worldwide, Inc. A sanitary paper product made by modifying coarse fibers and process thereof
US8002949B2 (en) * 2001-04-09 2011-08-23 Kruger Products L.P. Tissue products containing softness
GB2390609B (en) * 2001-04-09 2005-11-09 Scott Paper Ltd Tissue products containing softness
US7597780B2 (en) 2001-04-09 2009-10-06 Philip Buder Tissue products containing softness
WO2002081819A1 (en) * 2001-04-09 2002-10-17 Scott Paper Limited Tissue products containing softness
GB2390609A (en) * 2001-04-09 2004-01-14 Scott Paper Ltd Tissue products containing softness
US10704165B2 (en) 2012-08-24 2020-07-07 Domtar Paper Company, Llc Surface enhanced pulp fibers, methods of making surface enhanced pulp fibers, products incorporating surface enhanced pulp fibers, and methods of making products incorporating surface enhanced pulp fibers
US10975499B2 (en) 2012-08-24 2021-04-13 Domtar Paper Company, Llc Surface enhanced pulp fibers, methods of making surface enhanced pulp fibers, products incorporating surface enhanced pulp fibers, and methods of making products incorporating surface enhanced pulp fibers
US10563356B2 (en) 2014-02-21 2020-02-18 Domtar Paper Company, Llc Surface enhanced pulp fibers at a substrate surface
US10710930B2 (en) 2014-02-21 2020-07-14 Domtar Paper Company, Llc Surface enhanced pulp fibers in fiber cement
US11473245B2 (en) 2016-08-01 2022-10-18 Domtar Paper Company Llc Surface enhanced pulp fibers at a substrate surface
US11499269B2 (en) 2016-10-18 2022-11-15 Domtar Paper Company Llc Method for production of filler loaded surface enhanced pulp fibers
WO2019152969A1 (en) * 2018-02-05 2019-08-08 Pande Harshad Paper products and pulps with surface enhanced pulp fibers and increased absorbency, and methods of making same
US11441271B2 (en) 2018-02-05 2022-09-13 Domtar Paper Company Llc Paper products and pulps with surface enhanced pulp fibers and increased absorbency, and methods of making same
US12104324B2 (en) 2018-02-05 2024-10-01 Domtar Paper Company, Llc Paper products and pulps with surface enhanced pulp fibers and increased absorbency, and methods of making same
US11608596B2 (en) 2019-03-26 2023-03-21 Domtar Paper Company, Llc Paper products subjected to a surface treatment comprising enzyme-treated surface enhanced pulp fibers and methods of making the same
US12104327B2 (en) 2019-09-23 2024-10-01 Domtar Paper Company, Llc Tissues and paper towels incorporating surface enhanced pulp fibers and methods of making the same
US12116732B2 (en) 2019-09-23 2024-10-15 Domtar Paper Company, Llc Paper products incorporating surface enhanced pulp fibers and having decoupled wet and dry strengths and methods of making the same

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DE69525946T2 (de) 2002-11-28
EP0772716A1 (en) 1997-05-14
DE69525946D1 (de) 2002-04-25
AU2969995A (en) 1996-03-04
JPH10503684A (ja) 1998-04-07
CN1200780A (zh) 1998-12-02
CA2194670A1 (en) 1996-02-15
CA2194670C (en) 2002-09-17
EP0772716B1 (en) 2002-03-20
MX9700759A (es) 1998-10-31
BR9508461A (pt) 1998-06-09

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