EP0440472B1 - Durch die Vernetzung von Holzstoffasern mit Polykarbonsäuren erhaltene elastische, voluminöse Faser - Google Patents

Durch die Vernetzung von Holzstoffasern mit Polykarbonsäuren erhaltene elastische, voluminöse Faser Download PDF

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Publication number
EP0440472B1
EP0440472B1 EP91300760A EP91300760A EP0440472B1 EP 0440472 B1 EP0440472 B1 EP 0440472B1 EP 91300760 A EP91300760 A EP 91300760A EP 91300760 A EP91300760 A EP 91300760A EP 0440472 B1 EP0440472 B1 EP 0440472B1
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fibers
wood pulp
crosslinked
drying
bulking
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EP0440472A1 (de
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Bruce Jerome Kokko
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Fort James Corp
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James River Corp of Virginia
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
    • 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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/20—Chemically or biochemically modified fibres

Definitions

  • the present invention relates generally to fibers exhibiting improved resilient bulking and absorbent properties and paper products comprising said fibers. More particularly, this invention relates to an improved method of preparing resilient bulking fibers by crosslinking wood pulp fibers with polycarboxylic acids.
  • resilient bulking fibers are useful for the preparation of bulkier and more absorbent paper structures. Such paper structures are useful for the manufacture of products such as handsheets, towels, tissues, filters, paperboard, diapers, sanitary napkins, hospital dressings and the like.
  • One method for obtaining resilient bulking fibers is by crosslinking cellulose fibers by treatment with a chemical compound.
  • US-A-3,819,470 discloses modified cellulosic fibers characterized by reduced swellability and a reduced capability of natural fiber-to-fiber bonding when compared to unmodified cellulosic fibers and having a substantive polymeric compound reacted with and attached to the fibers.
  • US-A-4,431,481 discloses modified cellulosic fibers produced by treating the fibers with copolymers of maleamic acid.
  • Other known techniques include treatment of fibers with cationic urea formaldehyde resins, (US-A-3,756,913), methylol ureas and melamines (US-A-3,440,135), formaldehyde (US-A-3,224,926), with the condensation product of acrolein and formaldehyde, (US-A-3,183,054), bis-acrylamides (EP-A-0,213,415), and treatment with glyoxal or glutaric dialdehyde (WO-A-88104704, US-A-4,822,453 and US-A-4,853,086).
  • US-A-4822453 proposes the use of an organic acid such as citric acid in combination with zinc nitrate as a catalyst for the crosslinking action.
  • crosslinking methods of the prior art tend to suffer from the disadvantages of toxicity, high cost, or poor effectiveness. Of these, toxicity is especially disadvantageous in view of the mounting concerns over the environment and safety of the workers. Because of these concerns, most currently available bulking fibers and the methods for making them are not commercially acceptable or will be challenged.
  • crosslinkers such as epichlorohydrin, divinylsulfone, bisacrylamides, formaldehyde, and formaldehyde-based reagents such as 4,5-dihydroxy-1,2-dimethylol-ethylene urea (common textile finish) present serious hazards to workers and consumers.
  • Formaldehyde-free reagents such as 4,5-dihydroxy-1, 2-dimethyl-ethylene urea, while safer, are very expensive.
  • Other formaldehyde-free reagents such as glyoxal, glutaric dialdehyde, and various resins, while generally considered non-hazardous and reasonably priced, are less effective at producing bulking resilient fibers.
  • treatment of cellulosic fibers with maleamic copolymers or other resins results in fibers having equivalent bulk to fibers without chemical treatment that were heated to the same elevated temperatures as utilized with the resin treatment.
  • Nit formation is particularly prevalent when faster reacting agents, such as aldehydic compounds, or when polymeric agents are used.
  • Practitioners of the art usually employ debonding agents, mechanical defibration such as hammermilling, and screening to reduce the nit and knot contents of treated fibers. Such measures tend to be costly and can be deleterious to fiber and paper quality.
  • the present invention overcomes the problems and disadvantages of the prior art directed to papermaking by providing high bulking resilient fibers with little or no nits or knots obtained through crosslinking of wood pulp fibers with polycarboxylic acids such as citric acid.
  • Another object of the present invention is to increase the anionicity of the fibers such that the fibers are more receptive to specific additives and are themselves more conducive to making acceptable paper substrates.
  • a resilient bulking fiber comprising individualized crosslinked wood pulp cellulosic fibers having intra-fiber chemical bonds characterised in that the intra-fiber crosslink bonds derive from a polycarboxylic acid, and the degree of crosslinking is at least that sufficient to induce in said individualized fibers at least one of the following, namely twisting, curling and resilient bulking tendency.
  • crosslinking is intra-fiber; that is the crosslink bonds are primarily between cellulose molecules of a single fiber. This is in contrast to inter-fiber cross-linking where the bonds are formed between cellulose molecules of different fibers.
  • the resulting dry bulking fibers can be incorporated into products through conventional papermaking techniques. These fibers resist relaxation during papermaking, retaining their bulking behaviour throughout the papermaking process.
  • the invention further provides the use of polycarboxylic acid as the cross-linking agent to induce twisting and curling in individualized wood pulp cellulosic fibers by the formation of intra-fiber crosslink bonds.
  • an absorbent paper product comprising cross-linked wood pulp cellulose fibers in accordance with the invention to provide improved bulking and absorbent properties.
  • the crosslinked fibers may contain both intra-fiber and interfiber bonds.
  • the paper product may also contain non-crosslinked fibers which may be wood fibers and which may comprise the majority of the product on a weight basis. Examples of wood fibers are pre-dried and never dried Scandinavian bleached spruce kraft, Southern pine bleached kraft, secondary fibers, Southern and Northern softwood krafts and never dried Northern softwood bleached kraft.
  • the paper products may be, for example, handsheets, towels, tissues, filters, paperboard, diapers, sanitary napkins and hospital dressings.
  • Fig. 1 graphically depicts the Attenuated Total Reflectance (ATR) of CAFC fibers (cf Example 4).
  • Fig. 2 graphically depicts the ATR spectrum of TC fibers (cf Example 2).
  • Fig. 3 graphically depicts the ATR spectrum of CA fibers (cf Example 6).
  • Fig. 4 is a microphotograph of fibers that were oven dried and cured without citric acid.
  • Fig. 5 is a microphotograph of fibers that were oven dried and cured with citric acid.
  • resilient bulking fibers and a method for their preparation by crosslinking individualized wood pulp cellulose fibers with polycarboxylic acids.
  • individualized crosslinked fibers refers to cellulosic fibers that have primarily intrafiber chemical crosslink bonds. That is, the crosslink bonds are primarily between cellulose molecules of a single fiber, rather than between cellulose molecules of separate fibers.
  • the cellulose fibers are treated with an aqueous solution comprising a polycarboxylic acid and, if desired, an additional agent such as sodium hydroxide or other caustic agent or a coreactant/accelerator. It is preferable to select the coreactant/accelerator from the class of inorganic phosphorus compounds. It is more preferable to select the coreactant/accelerator from the group consisting of phosphates, phosphites, hypophosphites, pyrophosphates and metaphosphates. It is most preferable to use an inorganic phosphorus compound such as monosodium phosphate.
  • Dry lap or never dried wood pulp fibers can be used, although it is preferable to use never dried fibers. It is our experience that starting with the never-dried fiber results in maximum bulking levels after crosslinking regardless of the type of cellulose crosslinker used. Not wishing to be bound by any theory, it is believed that never-dried fibers allow for homogeneous distribution of crosslinking chemical in the cell wall, remain in a more individualized state during the crosslinking process, and more readily adopt twisted and curled configurations than do predried fibers.
  • wood pulp fibers may be used, although it is preferable to use chemical thermal mechanical pulps, Southern and Northern softwood bleached kraft pulps, and secondary fibers.
  • individualized wood pulp cellulosic fibers are crosslinked by a polycarboxylic acid.
  • the degree of crosslinking is at least that sufficient to induce twisting and curling and/or resilient bulking tendency in said individualized fibers.
  • the upper limit would be reached when the degree of crosslinking renders the fibers unfit for the intended use.
  • Individualized crosslinked fibers according to this invention thus include those crosslinked by from less than 1 mole % to more than 25 mole %, calculated on a cellulosic anhydroglucose molar basis, of a polycarboxylic acid crosslinking agent, although from 1 to 25 mole % is preferred.
  • any polycarboxylic acid known to crosslink cellulose may be used to crosslink the fibers according to the present invention.
  • Preferred polycarboxylic acids include citric acid, propane tricarboxylic acid, maleic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and benzene tetracarboxylic acid. It is also contemplated to use polycarboxylic acid precursors and derivatives that will produce the polycarboxylic acid under the reaction conditions utilized to crosslink the fibers.
  • the most preferred polycarboxylic acid is citric acid because it is an inexpensive, nontoxic, environmentally safe, readily available, naturally occurring polycarboxylic acid.
  • the polycarboxylic acid may be present in any concentration in the aqueous solution to allow for a sufficient number of crosslinks. It is advantageous to use in the range of a 3-10% aqueous solution of polycarboxylic acid, with about a 5% aqueous solution being most preferred.
  • a caustic agent may be used, if desired, including sodium hydroxide.
  • the fibers may be dewatered by conventional papermaking techniques, for example, through the use of a screw press.
  • the dewatering is done to any consistency, although higher consistencies are desirable for economical drying.
  • the fibers are dewatered to a consistency of at least 30%.
  • it is important to minimize compression forces experienced by the fibers prior to crosslinking and particularly during dewatering.
  • the dewatered fibers may be dried by any method that allows individualization of fibers (i.e., minimizes nits, knots, fisheyes, etc.).
  • the fibers may be azeotropically dried in a solvent, preferably toluene.
  • the filtered (i.e. dewatered) fibers may be fluff dried using a hot gas such as air or superheated steam.
  • the fibers After the fibers have been dried to an individualized state, they are then cured by conventionally known means to bring about the crosslinking reaction.
  • the fibers may be cured by heating them at a temperature in the range of from 150°C to 180°C for in the range of about one-half of a minute to about ten minutes.
  • Drying and curing can be accomplished either separately or concurrently in either batch or continuous operations.
  • Drying and curing of the treated fibers can be achieved by any means that allows heating of the fibers to elevated temperatures, for example, ovens, or heating in hot gas streams such as air, steam, superheated steam, or inert gases such as argon or nitrogen. It is preferred to use reducing atmospheres during drying and curing, such as is achievable with systems like superheated steam or inert gases like nitrogen and argon, to minimize charring, darkening, and degradation of the fibers.
  • the cured fibers thus prepared can then be dispersed for use.
  • the dispersion step involves contacting the cured fibers with water at an elevated temperature.
  • These bulking fibers may then be used -- alone or in blends -- to prepare products that exhibit improved bulking and absorbent properties.
  • the improvement in absorbency relates both to faster rate of absorbency and to increased fluid-holding capacity.
  • the amounts of crosslinked fibers used to prepare the products are readily determinable by those skilled in the art. For instance, filtration and absorbent product applications will often be made 100% from the fibers of the present invention.
  • towel and tissue paper products may be made by blending fibers according to the present invention with a majority of conventional wood pulp fibers. In such applications, it may be preferable to use crosslinked fibers in an amount of 25% or less by weight of the paper product.
  • NSWK Northern bleached softwood kraft fibers
  • Example 1 was repeated without citric acid to produce fibers hereafter referred to as "TC".
  • Example 1 was repeated except that no sodium hydroxide was added to the citric acid solution , the fibers were fluff dried with hot air in lieu of azeotrope drying in toluene, and curing was done at 180°C for 2.8 minutes.
  • the resultant fibers are hereafter referred to as "CAFC".
  • Example 4 was repeated without citric acid to generate fibers hereafter referred to as "FC".
  • Example 4 was repeated without the oven curing step to generate fibers hereafter referred to as "CA".
  • Example 4 was repeated without citric acid and without the oven curing step to generate fibers hereafter referred to as "FD".
  • the citric acid crosslinking reaction rendered the NSWK fiber more anionic. This was readily apparent by treating the crosslinked fibers with methylene blue. A deep blue color was retained in the crosslinked fibers, whereas little dye was taken up by the untreated NSWK fibers.
  • the total charge of citric acid crosslinked fibers, made according to Example 4 was 76 meq/100 g.
  • the total charge of untreated fibers was 4 meq/100 g.
  • This anionicity is a further advantage of the fibers of the present invention over those prepared according to the past art, as the polycarboxylic acid crosslinked fibers should be more receptive to cationic additives important to papermaking. For example, the strength of sheets made from the crosslinked fibers should be recoverable without compromising the bulk enhancement by incorporation of a cationic strength resin.
  • the polycarboxylic acid crosslinking reaction did not appear to damage the NSWK fibers. Thus, the average fiber length was not changed by the crosslinking reaction. Furthermore, the integrity of the fibers was unchanged by the crosslinking reaction as evidenced by microscopic examination (compare Figures 4 and 5). There was some brightness reduction due to the crosslinking reaction (see Table 1).
  • Example 4 Partial neutralization of the citric acid prior to fiber treatment is not necessary (See Example 4) for the successful preparation of high bulking resilient fibers as described above.
  • Examples 1-3 were repeated without the use of sodium hydroxide in the preparation of the treatment solution, and the resultant fibers (i.e. CAT fibers) had equivalent performance to that of the CATC fibers (compare data in Table 4 with that in Table 1). Since the citric acid treated fibers were at 25% consistency prior to drying, 39% of available citric acid (i.e. that acid contained in the dry fiber prior to curing) had reacted with the NSWK fibers to produce the CAT fibers described in this example.
  • Example 10 was repeated except a treatment solution containing only 5 wt% citric acid was used.
  • Table 4 comparable bulking performance is observed with the resultant CAT fibers relative to those prepared with solutions having twice the level of citric acid. Furthermore, there is a marked improvement in brightness accompanying the reduction of citric acid in the treatment bath. It should also be noted that 53% of the available citric acid had reacted with the NSWK fibers to produce the CAT fibers described in this example.
  • Example 10 was repeated except a 3 wt% aqueous solution of citric acid was used for the treatment. As can be seen in Table 4, there was a slight reduction in the bulking ability realized with the CAT fiber prepared under these conditions. Nevertheless, a 2% bulk enhancement is predicted for every 1% incorporation of these fibers in a NSWK furnish. Furthermore, essentially no reduction in brightness was observed with these fibers relative to the control. As was the case with the CAT fibers prepared according to Example 10, about 39% of the available citric acid had reacted with the NSWK fibers to produce the CAT fibers described in this example.
  • the percent bound citric acid levels as determined by titration (7) are consistently lower than those determined by ion chromatography.
  • the latter method is considered to be more reliable as it is not predicated on an assumption of the number of active equivalents of carboxyl functionality during base hydrolysis.
  • the citric acid crosslinking treatment is effective at producing bulk and resiliency enhancement in a wide variety of wood pulps. Different wood pulps were treated according to Example 13, unless otherwise stated, and made into pressed 65 g/m2 handsheets. The bulk data is provided in Table 6.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Paper (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Measurement Of Radiation (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (33)

  1. Individualisierte vernetzte Holzstoffcellulosefasern mit in der Faser befindlichen chemischen Bindungen, dadurch gekennzeichnet, daß die Vernetzungsbindungen innerhalb der Faser von einer Polycarbonsäure abgeleitet sind und der Vernetzungsgrad mindestens ausreicht, um in diesen individualisierten Fasern ein Verdrillen, Kräuseln oder elastisches Ausdehnen auszulösen.
  2. Individualisierte vernetzte Holzstoffcellulosefasern nach Anspruch 1, die mit 1 bis 25 Mol-%, berechnet auf der Molbasis von Celluloseanhydroglucose, eines Polycarbonsäurevernetzungsmittels vernetzt sind.
  3. Individualisierte vernetzte Holzstoffcellulosefasern nach Anspruch 1 oder 2, in denen das Polycarbonsäurevernetzungsmittel aus Citronensäure und Butantetracarbonsäure ausgewählt ist.
  4. Elastische faserartige Dickpulpe, die individualisierte vernetzte Holzstoffcellulosefasern nach einem der Ansprüche 1 bis 3 umfaßt.
  5. Verfahren zur Herstellung elastischer Dickfasern durch:
    a) Inkontaktbringen von Holzpulpecellulosefasern mit einem Vernetzungsmittel,
    b) Individualisierung der Cellulosefasern und
    c) Härten der individualisierten Cellulosefasern, um innerhalb der Faser befindliche, von diesem Vernetzungsmittel abgeleitete Vernetzungsbindungen zwischen Cellulosemolekülen innerhalb individueller Fasern der Cellulosefasern zu bilden,
    dadurch gekennzeichnet, daß eine Polycarbonsäure als Vernetzungsmittel verwendet wird.
  6. Verfahren nach Anspruch 5, bei dem in Schritt (a) die Holzpulpecellulosefasern mit einer wäßrigen Lösung von Polycarbonsäure vermischt werden.
  7. Verfahren nach Anspruch 6, bei dem in Schritt (b) die Fasern entwässert und getrocknet werden.
  8. Verfahren nach Anspruch 7, bei dem die Fasern beim Entwässern durch eine Schneckenpresse gepreßt werden.
  9. Verfahren nach Anspruch 7 oder 8, bei dem die Fasern bis zu einer Konsistenz von mindestens 30 % entwässert werden.
  10. Verfahren nach einem der Ansprüche 7 bis 9, bei dem das Trocknen Auflockerungstrocknen umfaßt.
  11. Verfahren nach Anspruch 10, bei dem das Auflockerungstrocknen mit heißen Gasen durchgeführt wird.
  12. Verfahren nach einem der Ansprüche 7 bis 11, bei dem das Trocknen mit supererhitztem Dampf durchgeführt wird.
  13. Verfahren nach einem der Ansprüche 7 bis 12, bei dem das Trocknen in einer Reduktionsatmosphäre erfolgt.
  14. Verfahren nach einem der Ansprüche 7 bis 9, bei dem im Trockenschritt die Fasern azeotrop in einem Lösungsmittel getrocknet werden.
  15. Verfahren nach einem der Ansprüche 7 bis 14, bei dem der Trockenschritt bei einer niedrigeren Temperatur als das Härten in Schritt (c) durchgeführt wird.
  16. Verfahren nach einem der Ansprüche 5 bis 15, bei dem das Härten in einer Reduktionsatmosphäre erfolgt.
  17. Verfahren nach einem der Ansprüche 6 bis 16, bei dem die wäßrige Lösung eine 3 - 10%ige wäßrige Lösung einer Polycarbonsäure ist.
  18. Verfahren nach einem der Ansprüche 6 bis 17, bei dem die wäßrige Lösung ein Ätzmittel umfaßt.
  19. Verfahren nach einem der Ansprüche 6 bis 17, bei dem die wäßrige Lösung Citronensäure und/oder einen Coreaktanten/Beschleuniger umfaßt.
  20. Verfahren nach Anspruch 19, bei dem der Coreaktant/Beschleuniger aus Phosphaten, Phosphiten, Hypophosphiten, Pyrophosphaten und Methaphosphaten ausgewählt ist.
  21. Verfahren nach Anspruch 20, bei dem der Coreaktant/Beschleuniger Mononatriumphosphat ist.
  22. Verfahren nach einem der Ansprüche 5 bis 21, bei dem die Polycarbonsäure aus Citronensäure und Butantetracarbonsäure ausgewählt ist.
  23. Verfahren nach einem der Ansprüche 5 bis 22, bei dem beim Härtungsschritt die Fasern über einen Zeitraum von 0,5 bis 10 Minuten bei einer Temperatur im Bereich von 150 bis 180°C erhitzt werden.
  24. Verfahren nach einem der Ansprüche 5 bis 23, bei dem die Holzpulpefasern aus chemisch-thermischen mechanischen Pulpen, gebleichten Kraftpulpen aus Southern und Northern Softwood (südlichem und nördlichem Weichholz) und Sekundärfasern ausgewählt sind.
  25. Verfahren nach einem der Ansprüche 5 bis 24, bei dem die Holzpulpefasern niemals getrocknete Fasern darstellen.
  26. Verbessertes elastisches absorbierendes Dickdruckpapier, das vernetzte Holzpulpecellulosefasern umfaßt, die ihm verbesserte Ausdehnungs- und Absorptionseigenschaften verleihen, dadurch gekennzeichnet, daß die vernetzten Fasern einem der Ansprüche 1 bis 3 entsprechen oder nach einem Verfahren der Ansprüche 5 bis 25 hergestellt wurden.
  27. Papierprodukt nach Anspruch 26, bei dem die vernetzten Holzpulpecellulosefasern Bindungen aufweisen, die sich sowohl innerhalb der Faser als auch zwischen den Fasern befinden.
  28. Papierprodukt nach Anspruch 26 oder 27, das außerdem nichtvernetzte Fasern umfaßt.
  29. Papierprodukt nach Anspruch 28, bei dem die nichtvernetzten Fasern den größten Teil des Produkts auf Gewichtsbasis ausmachen.
  30. Papierprodukt nach Anspruch 28 oder 29, bei dem die nichtvernetzten Fasern Holzfasern sind.
  31. Papierprodukt nach Anspruch 30, bei dem die Holzfasern aus vorgetrocknetem oder niemals getrocknetem Scandinavian Spruce Kraft (gebleicht), Southern Pine Kraft (gebleicht), Sekundärfasern, Southern Softwood Kraft, Northern Softwood Kraft sowie niemals getrocknetem gebleichtem Northern Softwood Kraft ausgewählt sind.
  32. Papierprodukt nach einem der Ansprüche 26 bis 31, bei dem das Papierprodukt aus Handtüchern, Trockentüchern, mehrlagigem Papier, Filtern, Pappe, Windeln, Monatsbinden und im Krankenhaus verwendeten Verbänden ausgewählt ist.
  33. Verwendung von Polycarbonsäure als Vernetzungsmittel, um in individualisierten Holzpulpecellulosefasern durch die Bildung von Vernetzungsbindungen innerhalb der Fasern ein Verdrillen oder Kräuseln auszulösen.
EP91300760A 1990-02-01 1991-01-31 Durch die Vernetzung von Holzstoffasern mit Polykarbonsäuren erhaltene elastische, voluminöse Faser Expired - Lifetime EP0440472B1 (de)

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US47340490A 1990-02-01 1990-02-01
US473404 1990-02-01

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EP (1) EP0440472B1 (de)
AT (1) ATE126556T1 (de)
CA (1) CA2035402A1 (de)
DE (1) DE69112089T2 (de)
ES (1) ES2075339T3 (de)
FI (1) FI910467A7 (de)

Cited By (34)

* Cited by examiner, † Cited by third party
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EP0484101A3 (en) * 1990-10-31 1992-07-22 James River Corporation Of Virginia Paper towels having bulky inner layer
US5137537A (en) * 1989-11-07 1992-08-11 The Procter & Gamble Cellulose Company Absorbent structure containing individualized, polycarboxylic acid crosslinked wood pulp cellulose fibers
US5147345A (en) * 1991-08-12 1992-09-15 The Procter & Gamble Company High efficiency absorbent articles for incontinence management
US5183707A (en) * 1989-11-07 1993-02-02 The Procter & Gamble Cellulose Company Individualized, polycarboxylic acid crosslinked fibers
US5190563A (en) * 1989-11-07 1993-03-02 The Proctor & Gamble Co. Process for preparing individualized, polycarboxylic acid crosslinked fibers
US5199953A (en) * 1990-09-14 1993-04-06 Ortec, Inc. Process for reducing discoloration of cellulosic fibers, treated at a high temperature with a solution of a polycarboxylic acid and boric acid or borate
US5217445A (en) * 1990-01-23 1993-06-08 The Procter & Gamble Company Absorbent structures containing superabsorbent material and web of wetlaid stiffened fibers
WO1993014264A1 (en) * 1992-01-13 1993-07-22 Weyerhaeuser Company Method and apparatus for crosslinking individualized cellulose fibers
US5234423A (en) * 1991-06-13 1993-08-10 The Procter & Gamble Company Absorbent article with elastic waist feature and enhanced absorbency
US5300192A (en) * 1992-08-17 1994-04-05 Weyerhaeuser Company Wet laid fiber sheet manufacturing with reactivatable binders for binding particles to fibers
US5308896A (en) * 1992-08-17 1994-05-03 Weyerhaeuser Company Particle binders for high bulk fibers
US5324391A (en) * 1990-10-31 1994-06-28 Weyerhaeuser Company Method for crosslinking cellulose fibers
US5352480A (en) * 1992-08-17 1994-10-04 Weyerhaeuser Company Method for binding particles to fibers using reactivatable binders
US5387207A (en) * 1991-08-12 1995-02-07 The Procter & Gamble Company Thin-unit-wet absorbent foam materials for aqueous body fluids and process for making same
US5531728A (en) * 1990-01-23 1996-07-02 The Procter & Gamble Company Absorbent structures containing thermally-bonded stiffened fibers and superabsorbent material
US5556976A (en) * 1987-01-20 1996-09-17 Jewell; Richard A. Reactive cyclic N-sulfatoimides and cellulose crosslinked with the imides
US5840787A (en) * 1994-03-25 1998-11-24 Weyerhaeuser Company Cellulosic products using high-bulk cellulosic fibers
US5906894A (en) * 1994-03-25 1999-05-25 Weyerhaeuser Company Multi-ply cellulosic products using high-bulk cellulosic fibers
US5998511A (en) * 1994-03-25 1999-12-07 Weyerhaeuser Company Polymeric polycarboxylic acid crosslinked cellulosic fibers
US6020536A (en) * 1996-06-28 2000-02-01 Sca Hygiene Products Ab Absorbent body for absorbent articles
US6184271B1 (en) 1994-03-25 2001-02-06 Weyerhaeuser Company Absorbent composite containing polymaleic acid crosslinked cellulosic fibers
US6306251B1 (en) 1994-03-25 2001-10-23 Weyerhaeuser Company Multi-ply cellulosic products using high-bulk cellulosic fibers
US6340411B1 (en) 1992-08-17 2002-01-22 Weyerhaeuser Company Fibrous product containing densifying agent
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US6627041B2 (en) 2000-03-06 2003-09-30 Georgia-Pacific Corporation Method of bleaching and providing papermaking fibers with durable curl
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EP0440472A1 (de) 1991-08-07
ATE126556T1 (de) 1995-09-15
ES2075339T3 (es) 1995-10-01
FI910467L (fi) 1991-08-02
DE69112089D1 (de) 1995-09-21
FI910467A7 (fi) 1991-08-02
DE69112089T2 (de) 1996-01-11
CA2035402A1 (en) 1991-08-02
FI910467A0 (fi) 1991-01-31

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