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EP0440472B1 - Fibres élastiques à bouffant élevé obtenues par réticulation de fibres de pâte de bois avec des acides polycarboxyliques - Google Patents

Fibres élastiques à bouffant élevé obtenues par réticulation de fibres de pâte de bois avec des acides polycarboxyliques 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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Prior art keywords
fibers
wood pulp
crosslinked
drying
bulking
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German (de)
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EP0440472A1 (fr
Inventor
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)
  • Biochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Measurement Of Radiation (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (33)

  1. Fibres cellulosiques de pâte de bois réticulées individualisées ayant des liaisons chimiques à l'intérieur des fibres, caractérisées en ce que les liaisons de réticulation à l'intérieur des fibres proviennent d'un acide polycarboxylique et que le degré de réticulation est au moins suffisant pour induire dans ces fibres individualisées au moins l'une des tendances suivantes, à savoir, torsion, ondulation , bouffant élastique.
  2. Fibres cellulosiques de pâte de bois individualisées suivant la revendication 1, réticulées par une quantité de 1 à 25% en moles calculée sur une base molaire d'anhydroglucose cellulosique, d'un agent de réticulation de type acide polycarboxylique.
  3. Fibres cellulosiques de pâte de bois individualisées suivant les revendications 1 ou 2, dans lesquelles l'agent de réticulation de type acide polycarboxylique est choisi parmi l'acide citrique et l'acide butanetétracarboxylique.
  4. Pâte bouffante fibreuse élastique comprenant des fibres cellulosiques de pâte de bois réticulées individualisées suivant l'une quelconque des revendications 1 à 3.
  5. Procédé pour la préparation de fibres bouffantes élastiques par:
    (a) mise en contact des fibres cellulosiques de pâte de bois avec un agent de réticulation;
    (b) individualisation des fibres cellulosiques; et
    (c) durcissement des fibres cellulosiques individualisées pour former des liaisons de réticulation à l'intérieur des fibres dérivées de cet agent de réticulation entre des molécules de cellulose à l'intérieur des fibres individuelles des fibres cellulosiques,
    caractérisé en ce qu'un acide polycarboxylique est employé en tant qu'agent de réticulation.
  6. Procédé suivant la revendication 5, dans lequel l'étape (a) comprend le mélange des fibres cellulosiques de pâte de bois avec une solution aqueuse d'acide polycarboxylique.
  7. Procédé suivant la revendication 6, dans lequel l'étape (b) comprend l'élimination de l'eau et le séchage des fibres.
  8. Procédé suivant la revendication 7, dans lequel l'élimination de l'eau comprend le pressage des fibres cellulosiques à travers une presse à vis.
  9. Procédé suivant les revendications 7 ou 8, dans lequel les fibres sont débarrassées d'eau jusqu'à une consistance d'au moins 30%.
  10. Procédé suivant l'une quelconque des revendications 7 à 9, dans lequel le séchage comprend un séchage donnant du bouffant.
  11. Procédé suivant la revendication 10, dans lequel le séchage donnant du bouffant est effectué avec des gaz chauds.
  12. Procédé suivant l'une quelconque des revendications 7 à 11, dans lequel le séchage est effectué avec de la vapeur surchauffée.
  13. Procédé suivant l'une quelconque des revendications 7 à 12, dans lequel le séchage est effectué dans une atmosphère réductrice.
  14. Procédé suivant l'une quelconque des revendications 7 à 9, dans lequel l'étape de séchage comprend le séchage azéotropique des fibres dans un solvant.
  15. Procédé suivant l'une quelconque des revendications 7 à 14, dans lequel l'étape de séchage est réalisée à une température inférieure à celle qui est utilisée pour le durcissement dans l'étape (c).
  16. Procédé suivant l'une quelconque des revendications 5 à 15, dans lequel le durcissement est effectué dans une atmosphère réductrice.
  17. Procédé suivant l'une quelconque des revendications 6 à 16, dans lequel cette solution aqueuse est une solution aqueuse de 3 à 10% d'un acide polycarboxylique.
  18. Procédé suivant l'une quelconque des revendications 6 à 17, dans lequel la solution aqueuse comprend un agent caustique.
  19. Procédé suivant l'une quelconque des revendications 6 à 17, dans lequel la solution aqueuse comprend de l'acide citrique et un coréactif/accélérateur.
  20. Procédé suivant la revendication 19, dans lequel ce coréactif/accélérateur est choisi parmi des phosphates, des phosphites, des hypophosphites, des pyrophosphates et des métaphosphates.
  21. Procédé suivant la revendication 20, dans lequel le coréactif/accélérateur est du phosphate monosodique.
  22. Procédé suivant l'une quelconque des revendications 5 à 21, dans lequel cet acide polycarboxylique est choisi parmi l'acide citrique et l'acide butanetétracarboxylique.
  23. Procédé suivant l'une quelconque des revendications 5 à 22, dans lequel l'étape de durcissement comprend le chauffage des fibres à une température comprise dans la gamme de 150 à 180°C pendant une période de temps comprise dans la gamme de 0,5 à 10 minutes.
  24. Procédé suivant l'une quelconque des revendications 5 à 23, dans lequel ces fibres de pâte de bois sont choisies parmi des pâtes mécaniques thermiques chimiques, des pâtes pour papier d'emballage fort blanchies de bois tendres du Nord et du Sud, et des fibres secondaires.
  25. Procédé suivant l'une quelconque des revendications 5 à 24, dans lequel ces fibres de pâte de bois sont des fibres jamais séchées.
  26. Produit amélioré de papier absorbant et bouffant élastique comprenant des fibres cellulosiques de pâte de bois réticulées pour fournir des propriétés améliorées de bouffant et d'absorption, caractérisé en ce que les fibres réticulées sont suivant l'une quelconque des revendications 1 à 3 ou sont obtenues par un procédé suivant l'une quelconque des revendications 5 à 25.
  27. Produit de papier suivant la revendication 26, dans lequel ces fibres cellulosiques de pâte de bois réticulées contiennent à la fois des liaisons à l'intérieur des fibres et entre les fibres.
  28. Produit de papier suivant les revendications 26 ou 27 comprenant de plus des fibres non réticulées.
  29. Produit de papier suivant la revendication 28, dans lequel ces fibres non réticulées constituent la majorité de ce produit, sur une base pondérale.
  30. Produit de papier suivant les revendication 28 ou 29, dans lequel ces fibres non réticulées sont des fibres de bois.
  31. Produit de papier suivant la revendication 30, dans lequel ces fibres de bois sont choisies parmi des fibres blanchies pour papier d'emballage fort de sapin de Scandinavie pré-séchées ou jamais séchées, des fibres blanchies pour papier d'emballage fort de pin du Sud, des fibres secondaires, des fibres pour papier d'emballage fort de bois tendre du Sud, des fibres pour papier d'emballage fort de bois tendre du Nord et des fibres pour papier d'emballage fort de bois tendre du Nord, jamais séchées.
  32. Produit de papier suivant l'une quelconque des revendications 26 à 31, dans lequel ce produit de papier est choisi parmi des serviettes, des torchons, des mouchoirs, des filtres, du carton, des couches, des serviettes hygiéniques et des pansements pour hôpitaux.
  33. Utilisation d'un acide polycarboxylique en tant qu'agent de réticulation pour induire une torsion ou une ondulation dans des fibres cellulosiques de pâte de bois individualisées par la formation de liaisons de réticulation à l'intérieur des fibres.
EP91300760A 1990-02-01 1991-01-31 Fibres élastiques à bouffant élevé obtenues par réticulation de fibres de pâte de bois avec des acides polycarboxyliques Expired - Lifetime EP0440472B1 (fr)

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

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EP0440472B1 true EP0440472B1 (fr) 1995-08-16

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EP (1) EP0440472B1 (fr)
AT (1) ATE126556T1 (fr)
CA (1) CA2035402A1 (fr)
DE (1) DE69112089T2 (fr)
ES (1) ES2075339T3 (fr)
FI (1) FI910467L (fr)

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0484101A2 (fr) * 1990-10-31 1992-05-06 James River Corporation Of Virginia Serviette en papier à couche volumineuse
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 (fr) * 1992-01-13 1993-07-22 Weyerhaeuser Company Procede et dispositif de reticulation de fibres de cellulose individualisees
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
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US6184271B1 (en) 1994-03-25 2001-02-06 Weyerhaeuser Company Absorbent composite containing polymaleic acid crosslinked cellulosic fibers
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US6340411B1 (en) 1992-08-17 2002-01-22 Weyerhaeuser Company Fibrous product containing densifying agent
US6379499B1 (en) 1999-09-28 2002-04-30 University Of Georgia Research Foundation, Inc. Polymer-aldehyde additives to improve paper properties
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US6524653B1 (en) 2000-11-01 2003-02-25 Niponi, Llc Cellulose-based fire retardant composition
US6533989B1 (en) 2000-08-03 2003-03-18 Kimberly-Clark Worldwide, Inc. Multi-chamber process and apparatus for forming a stabilized absorbent web
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US6695950B1 (en) 1999-08-17 2004-02-24 National Starch And Chemical Investment Holding Corporation Aldehyde modified cellulose pulp for the preparation of high strength paper products
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WO2003062818A1 (fr) * 2002-01-23 2003-07-31 Lenzing Aktiengesellschaft Procede de determination spectroscopique de constituants de viscose
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US5437418A (en) * 1987-01-20 1995-08-01 Weyerhaeuser Company Apparatus for crosslinking individualized cellulose fibers
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US5137537A (en) * 1989-11-07 1992-08-11 The Procter & Gamble Cellulose Company Absorbent structure containing individualized, polycarboxylic acid crosslinked wood pulp cellulose fibers
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US5531728A (en) * 1990-01-23 1996-07-02 The Procter & Gamble Company Absorbent structures containing thermally-bonded stiffened fibers and superabsorbent material
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EP0484101A2 (fr) * 1990-10-31 1992-05-06 James River Corporation Of Virginia Serviette en papier à couche volumineuse
EP0484101A3 (en) * 1990-10-31 1992-07-22 James River Corporation Of Virginia Paper towels having bulky inner layer
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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
US5147345A (en) * 1991-08-12 1992-09-15 The Procter & Gamble Company High efficiency absorbent articles for incontinence management
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US5352480A (en) * 1992-08-17 1994-10-04 Weyerhaeuser Company Method for binding particles to fibers using reactivatable binders
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US6425979B1 (en) 1992-08-17 2002-07-30 Weyerhaeuser Company Method for making superabsorbent containing diapers
US6627249B2 (en) 1992-08-17 2003-09-30 Weyerhaeuser Company Method of enhancing blood absorbence by superabsorbent material
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US5308896A (en) * 1992-08-17 1994-05-03 Weyerhaeuser Company Particle binders for high bulk fibers
US6461553B1 (en) 1992-08-17 2002-10-08 Weyerhaeuser Method of binding binder treated particles to fibers
US6340411B1 (en) 1992-08-17 2002-01-22 Weyerhaeuser Company Fibrous product containing densifying agent
US5300192A (en) * 1992-08-17 1994-04-05 Weyerhaeuser Company Wet laid fiber sheet manufacturing with reactivatable binders for binding particles to fibers
US6391453B1 (en) 1992-08-17 2002-05-21 Weyernaeuser Company Binder treated particles
US6395395B1 (en) 1992-08-17 2002-05-28 Weyerhaeuser Company Method and compositions for enhancing blood absorbence by superabsorbent materials
US6184271B1 (en) 1994-03-25 2001-02-06 Weyerhaeuser Company Absorbent composite containing polymaleic acid crosslinked cellulosic fibers
US6620865B2 (en) 1994-03-25 2003-09-16 Weyerhaeuser Company Polycarboxylic acid crosslinked cellulosic fibers
US6306251B1 (en) 1994-03-25 2001-10-23 Weyerhaeuser Company Multi-ply cellulosic products using high-bulk cellulosic fibers
US6716306B2 (en) 1994-03-25 2004-04-06 Weyerhaeuser Company High bulk cellulose fibers crosslinked with tartaric acid and method of making same
US5998511A (en) * 1994-03-25 1999-12-07 Weyerhaeuser Company Polymeric polycarboxylic acid crosslinked cellulosic fibers
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
US6582553B2 (en) 1994-03-25 2003-06-24 Weyerhaeuser Company High bulk cellulosic fibers crosslinked with malic acid and process for making the same
US6020536A (en) * 1996-06-28 2000-02-01 Sca Hygiene Products Ab Absorbent body for absorbent articles
US6695950B1 (en) 1999-08-17 2004-02-24 National Starch And Chemical Investment Holding Corporation Aldehyde modified cellulose pulp for the preparation of high strength paper products
US6379499B1 (en) 1999-09-28 2002-04-30 University Of Georgia Research Foundation, Inc. Polymer-aldehyde additives to improve paper properties
US6627041B2 (en) 2000-03-06 2003-09-30 Georgia-Pacific Corporation Method of bleaching and providing papermaking fibers with durable curl
US6533978B1 (en) 2000-08-03 2003-03-18 Kimberly-Clark Worldwide, Inc. Process and apparatus for forming a stabilized absorbent web
US6533989B1 (en) 2000-08-03 2003-03-18 Kimberly-Clark Worldwide, Inc. Multi-chamber process and apparatus for forming a stabilized absorbent web
US6524653B1 (en) 2000-11-01 2003-02-25 Niponi, Llc Cellulose-based fire retardant composition
US6673266B2 (en) 2000-11-01 2004-01-06 Niponi, Llc Fire-retardant petroleum composition
WO2015114520A1 (fr) * 2014-01-31 2015-08-06 Kimberly-Clark Worldwide, Inc. Tissu ayant une liaison hydrogène réduite
US9127408B2 (en) 2014-01-31 2015-09-08 Kimberly-Clark Worldwide, Inc. Tissue having reduced hydrogen bonding
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DE69112089D1 (de) 1995-09-21
FI910467A0 (fi) 1991-01-31
CA2035402A1 (fr) 1991-08-02
DE69112089T2 (de) 1996-01-11
EP0440472A1 (fr) 1991-08-07
ES2075339T3 (es) 1995-10-01
FI910467L (fi) 1991-08-02
ATE126556T1 (de) 1995-09-15

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