EP1828450B1 - Structures polymeres comprenant un agent d'association et procedes de production desdites structures - Google Patents

Structures polymeres comprenant un agent d'association et procedes de production desdites structures Download PDF

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Publication number
EP1828450B1
EP1828450B1 EP05854923.9A EP05854923A EP1828450B1 EP 1828450 B1 EP1828450 B1 EP 1828450B1 EP 05854923 A EP05854923 A EP 05854923A EP 1828450 B1 EP1828450 B1 EP 1828450B1
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Prior art keywords
fiber
hydroxyl polymer
polymer
hydroxyl
fibers
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German (de)
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EP1828450A2 (fr
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Larry Neil Mackey
Stephen Wayne Heinzman
Gregory Charles Gordon
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from US11/018,746 external-priority patent/US20060134410A1/en
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments

Definitions

  • the present invention relates to hydroxyl polymers, more particularly, to polymeric structures, especially fibers, comprising an association agent, fibrous structures comprising such polymeric structures and processes for making such polymeric structures and/or fibrous structures.
  • Polymeric structures such as fibers and/or films, comprising hydroxyl polymers are known in the art.
  • WO 03/066942 A1 discloses non-thermoplastic starch fibers having no melting point and having apparent wet tensile stress greater than about 0.2 MPa.
  • the fibers can be manufactured from a composition comprising a modified starch and a cross-linking agents.
  • WO 2004/108832 A2 discloses cross-linking systems suitable for use in a polymer melt composition wherein the polymer melt composition comprises a hydroxyl polymer.
  • EP 1132427 A1 discloses melt processable starch compositions which contain starch and additives.
  • the additives can be plasticizers or diluents.
  • polymeric structures, especially in the form of fibers, comprising an association agent wherein the polymeric structures exhibit an apparent peak wet tensile stress greater than 0.2 MPa and/or an average fiber diameter of less than 10 ⁇ m have been until now unobtainable.
  • polymeric structures that comprise an association agent wherein the polymeric structures exhibit an apparent peak wet tensile stress greater than 0.2 MPa and/or an average fiber diameter of less than 10 ⁇ m, webs comprising such polymeric structures and processes for making such polymeric structures.
  • the present invention fulfills the needs described above by providing polymeric structures as recited in claim 1 comprising an association agent and/or webs comprising such polymeric structures and processes for making such polymeric structures and/or webs.
  • a non-naturally occurring polymeric structure in the form of a fiber wherein the fiber comprises a hydroxyl polymer and an association agent, wherein the polymeric structure exhibits an apparent peak wet tensile stress greater than 0.2 MPa is provided.
  • a process for making a polymeric structure comprising an association agent comprising the steps of:
  • the present invention provides a polymeric structure comprising an association agent, a web comprising such a polymeric structure and a process for making such a polymeric structure and/or web.
  • Polymeric structure as used herein means any physical structure formed as a result of processing a hydroxyl polymer-containing composition in accordance with the present invention.
  • Nonlimiting examples of polymeric structures in accordance with the present invention include fibers, films and/or foams.
  • the polymeric structures of the present invention are non-naturally occurring physical structures. In other words, they are man-made physical structures.
  • Fiber or “filament” as used herein means a slender, thin, and highly flexible object having a major axis which is very long, compared to the fiber's two mutually-orthogonal axes that are perpendicular to the major axis.
  • a fiber may exhibit an aspect ratio of the major's axis length to an equivalent diameter of the fiber's cross-section perpendicular to the major axis greater than 100/1, more specifically greater than 500/1, and still more specifically greater than 1000/1, and even more specifically, greater than 5000/1.
  • the fibers may be continuous or substantially continuous fibers or they may be discontinuous fibers.
  • the hydroxyl polymer fibers of the present invention may have an average fiber diameter of less than about 50 ⁇ m and/or less than about 20 ⁇ m and/or less than about 10 ⁇ m and/or less than about 8 ⁇ m and/or less than about 6 ⁇ m and/or less than about 4 ⁇ m as measured by the Average Fiber Diameter Test Method described herein.
  • Such a fiber may exhibit an average fiber diameter of greater than about 1 ⁇ m and/or greater than about 2 ⁇ m and/or greater than about 3 ⁇ m.
  • the hydroxyl polymer fibers of the present invention may include melt blown fibers, dry spun fibers, rotary spun fibers, spunbond fibers, staple fibers, hollow fibers, shaped fibers, such as multi-lobal fibers and multicomponent fibers, especially bicomponent fibers.
  • the multicomponent fibers, especially bicomponent fibers may be in a side-by-side, sheath-core, segmented pie, ribbon, islands-in-the-sea configuration, or any combination thereof.
  • the sheath may be continuous or non-continuous around the core.
  • the ratio of the weight of the sheath to the core can be from about 5:95 to about 95:5.
  • the hydroxyl polymer fibers of the present invention may have different geometries that include round, elliptical, star shaped, rectangular, and other various eccentricities.
  • the polymeric structures of the present invention may include a multiconstituent polymeric structure, such as a multicomponent fiber, comprising a hydroxyl polymer and an association agent of the present invention along with another polymer.
  • a multicomponent fiber as used herein, means a fiber having more than one separate part in spatial relationship to one another.
  • Multicomponent fibers include bicomponent fibers, which is defined as a fiber having two separate parts in a spatial relationship to one another. The different components of multicomponent fibers can be arranged in substantially distinct regions across the cross-section of the fiber and extend continuously along the length of the fiber.
  • a nonlimiting example of such a multicomponent fiber is a bicomponent fiber in which the hydroxyl polymer of the present invention represents the core of the fiber and another polymer represents the sheath, which surrounds or substantially surrounds the core of the fiber.
  • the hydroxyl polymer-containing composition from which such a polymeric structure is derived may include both the hydroxyl polymer and the other polymer.
  • the sheath may comprise a hydroxyl polymer and a crosslinking system having a crosslinking agent
  • the core may comprise a hydroxyl polymer and a crosslinking system having a crosslinking agent.
  • the hydroxyl polymer may be the same or different and the crosslinking agent may be the same or different.
  • the level of hydroxyl polymer may be the same or different and the level of crosslinking agent may be the same or different.
  • One or more polymeric structures of the present invention may be incorporated into a multi-polymeric structure product, such as a fibrous structure and/or web, if the polymeric structures are in the form of fibers.
  • a multi-polymeric structure product may ultimately be incorporated into a commercial product, such as a single- or multi-ply sanitary tissue product, such as facial tissue, bath tissue, paper towels and/or wipes, feminine care products, diapers, writing papers, cores, such as tissue cores, and other types of paper products.
  • a "fibrous structure” as used herein means a single web structure that comprises at least one fiber.
  • a fibrous structure of the present invention may comprise one or more fibers, wherein at least one of the fibers comprises a hydroxyl polymer fiber.
  • a fibrous structure of the present invention may comprise a plurality of fibers, wherein at least one (sometimes a majority, even all) of the fibers comprises a hydroxyl polymer fiber.
  • the fibrous structures of the present invention may be layered such that one layer of the fibrous structure may comprise a different composition of fibers and/or materials from another layer of the same fibrous structure.
  • "Web" as used herein means a physical structure that comprises at least one planar surface.
  • a web is a physical structure that comprises two planar surfaces.
  • a web may be a film, if no fibers are present within the web.
  • a web that comprises one or more fibers may be a fibrous structure.
  • One or more hydroxyl polymer fibers of the present invention may be associated together to form a web.
  • numerous fibers are collected, such as on a forming wire and/or belt and/or three dimensional molding member, in order to the association of the fibers into a web.
  • a web and/or fibrous structure of the present invention exhibits an initial total wet tensile of greater than about 10 g/2.54 cm (10 g/in).
  • Hydroxyl polymer as used herein means any polymer that contains greater than 10% and/or greater than 20% and/or greater than 25% by weight hydroxyl groups.
  • Hydroxyl polymer-containing composition as used herein means a composition that comprises a hydroxyl polymer (substituted or unsubstituted).
  • Unsubstituted hydroxyl polymer and/or "unsubstituted form of a hydroxyl polymer” and/or “unsubstituted form of a substituted hydroxyl polymer” as used herein means a hydroxyl polymer in which all of its original hydroxyl moieties are intact. In other words, no derivatized hydroxyl moieties exist in the hydroxyl polymer. For example, a hydroxyethyl starch is not an unsubstituted hydroxyl polymer. The mere removal of the hydrogen from the oxygen in the hydroxyl moieties does not create a substituted hydroxyl polymer.
  • Substituted hydroxyl polymer and/or “substituted form of a hydroxyl polymer” and/or “substituted form of an unsubstituted hydroxyl polymer” as used herein means a hydroxyl polymer comprising at least one derivative of an original hydroxyl moiety. In other words, at least one oxygen originally present in a hydroxyl moiety is covalently bonded to a moiety other than hydrogen.
  • association agent means an agent that is capable of interacting with a hydroxyl polymer to influence the hydroxyl polymer-containing composition's properties, especially the hydroxyl polymer-containing composition's spinning (rheological) properties, without covalently binding to the hydroxyl polymer.
  • Non-naturally occurring as used herein with respect to "non-naturally occurring fiber” means that the fiber is not found in nature in that form. In other words, some chemical processing of materials needs to occur in order to obtain the non-naturally occurring fiber.
  • a wood pulp fiber is a naturally occurring fiber, however, if the wood pulp fiber is chemically processed, such as via a lyocell-type process, a solution of cellulose is formed. The solution of cellulose may then be spun into a fiber. Accordingly, this spun fiber would be considered to be a non-naturally occurring fiber since it is not directly obtainable from nature in its present form.
  • Naturally occurring means that a fiber and/or a material is found in nature in its present form.
  • An example of a naturally occurring fiber is a wood pulp fiber.
  • “Apparent Peak Wet Tensile Stress,” or simply “Wet Tensile Stress,” is a condition existing within a polymeric structure, such as a fiber, at the point of its maximum (i.e., "peak") stress as a result of strain by external forces, and more specifically elongation forces, as described in the Apparent Peak Wet Tensile Stress Test Method described herein below.
  • the stress is "apparent” because a change, if any, in the polymeric structures average thickness, such as a fiber's average fiber diameter, resulting from the polymeric structure's elongation, is not taken into consideration for the purposes of determining the apparent peak wet tensile stress of a polymeric structure.
  • the apparent peak wet tensile stress of the polymeric structures is proportional to their wet tensile strength and is used herein to quantitatively estimate the latter.
  • Weight average molecular weight as used herein means the weight average molecular weight as determined using gel permeation chromatography according to the protocol found in Colloids and Surfaces A. Physico Chemical & Engineering Aspects, Vol. 162, 2000, pg. 107-121 .
  • Polymer as used herein generally includes, but is not limited to, homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, etc., and blends and modifications thereof.
  • polymer includes all possible geometric configurations of the material. The configurations include, but are not limited to, isotactic, atactic, syndiotactic, and random symmetries.
  • Spinning process temperature means the temperature at which the hydroxyl polymer polymeric structures in the form of fibers are attenuated at the external surface of the spinning die as the hydroxyl polymer polymeric structures are formed.
  • the hydroxyl polymer fibers of the present invention may be a polymeric structure. In other words, one or more polymers may form the fiber.
  • the hydroxyl polymer fibers of the present invention may be continuous or substantially continuous.
  • a fiber is continuous if it exhibits a length greater than about 2.54 cm (1 inch) and/or greater than 5.08 cm (2 inches).
  • the hydroxyl polymer fibers of the present invention may be produced by crosslinking two or more hydroxyl polymers together.
  • a suitable crosslinking system for achieving crosslinking of the hydroxyl polymer comprises a crosslinking agent and optionally a crosslinking facilitator, wherein the hydroxyl polymer is crosslinked by the crosslinking agent.
  • An example of a suitable crosslinking system for use in the present invention is described in U.S. Patent Application Publication 2004/0249066 .
  • the hydroxyl polymer fiber of the present invention exhibits no melting point. In other words, it degrades before melting.
  • the webs of the present invention may include pulp fibers, such as cellulose fibers and/or other polymer fibers besides the hydroxyl polymer fibers.
  • a hydroxyl polymer fiber of the present invention exhibits an apparent peak wet tensile stress greater than 0.2 MPa and/or greater than 0.5 MPa and/or greater than 1 MPa and/or
  • a hydroxyl polymer fiber of the present invention comprises at least about 50% and/or at least about 60% and/or at least about 70% to about 100% and/or to about 95% and/or to about 90% by weight of the fiber of a hydroxyl polymer.
  • a hydroxyl polymer fiber of the present invention exhibits a pH of less than about 7 and/or less than about 6 and/or less than about 5 and/or less than about 4.5 and/or less than about 4.
  • a hydroxyl polymer fiber of the present invention comprises an association agent.
  • the association agent may be separate and discrete from the hydroxyl polymer. In other words, the association agent may not be covalently bound to an oxygen atom of a hydroxyl moiety of the hydroxyl polymer.
  • Hydroxyl polymers in accordance with the present invention include any unsubstituted hydroxyl-containing polymer, for example, native dent corn starch hydroxyl polymer and/or acid-thinned dent corn starch hydroxyl polymer and/or any substituted hydroxyl-containing polymer, for example, hydroxyethyl starch hydroxyl polymer.
  • the hydroxyl polymer of the present invention includes greater than 10% and/or greater than 20% and/or greater than 25% by weight hydroxyl moieties.
  • Nonlimiting examples of hydroxyl polymers in accordance with the present invention include polyols, such as polyvinyl alcohol, polyvinyl alcohol derivatives, polyvinyl alcohol copolymers, starch, starch derivatives, starch copolymers, chitosan, chitosan derivatives, chitosan copolymers, cellulose, cellulose derivatives such as cellulose ether and ester derivatives, cellulose copolymers, gums, arabinans, galactans, proteins and various other polysaccharides and mixtures thereof.
  • polyols such as polyvinyl alcohol, polyvinyl alcohol derivatives, polyvinyl alcohol copolymers, starch, starch derivatives, starch copolymers, chitosan, chitosan derivatives, chitosan copolymers, cellulose, cellulose derivatives such as cellulose ether and ester derivatives, cellulose copolymers, gums, arabinans, galactans, proteins and various other polysacchari
  • Classes of hydroxyl polymers are defined by the hydroxyl polymer backbone.
  • polyvinyl alcohol and polyvinyl alcohol derivatives and polyvinyl alcohol copolymers are in the class of polyvinyl alcohol hydroxyl polymers whereas starch and starch derivatives are in the class of starch hydroxyl polymers.
  • the hydroxyl polymers of the present invention may have a weight average molecular weight of greater than about 10,000 g/mol and/or greater than about 40,000 g/mol and/or from about 10,000 to about 80,000,000 g/mol and/or from about 10,000 to about 40,000,000 g/mol and/or from about 10,000 to about 10,000,000 g/mol.
  • Higher and lower molecular weight hydroxyl polymers may be used in combination with hydroxyl polymers having weight average molecular weights within the above ranges.
  • hydroxyl polymers such as polysaccharides, for example natural starches
  • a natural starch can be acid-thinned, hydroxy-ethylated, hydroxypropylated, and/or oxidized.
  • the hydroxyl polymer may comprise native dent corn starch hydroxyl polymer.
  • the hydroxyl polymer of the present invention comprises a starch hydroxyl polymer.
  • the starch hydroxyl polymer may be acid thinned starch hydroxyl polymer and/or alkaline cooked starch hydroxyl polymer.
  • the starch hydroxyl polymer may be derived from corn, potato, wheat, tapioca and the like.
  • the weight ratio of amylose to amylopectin in the starch hydroxyl polymer may be from about 10:90 to about 99:1 respectively.
  • the starch hydroxyl polymer comprises from at least about 10% and/or at least about 20% to about 99% and/or to about 90% by weight of amylose.
  • Polysaccharides as used herein means natural polysaccharides and polysaccharide derivatives or modified polysaccharides. Suitable polysaccharides include, but are not limited to, starches, starch derivatives, chitosan, chitosan derivatives, cellulose derivatives, gums, arabinans, galactans and mixtures thereof.
  • the polyvinylalcohol has no "y" and/or "z" units.
  • Polyvinyl alcohols herein can be grafted with other monomers to modify its properties.
  • a wide range of monomers has been successfully grafted to polyvinyl alcohol.
  • Nonlimiting examples of such monomers include vinyl acetate, styrene, acrylamide, acrylic acid, 2-hydroxyethyl methacrylate, acrylonitrile, 1,3-butadiene, methyl methacrylate, methacrylic acid, vinylidene chloride, vinyl chloride, vinyl amine and a variety of acrylate esters.
  • the hydroxyl polymer-containing compositions of the present invention contains an association agent.
  • the association agent is capable of associating, typically other than by covalent bond, with the hydroxyl polymer, particularly the hydroxyl moieties thereof.
  • the association agent is an amine oxide selected from the group consisting of cetyldimethylamine oxide, lauryldimethylamine oxide and cocamidopropylamine oxide.
  • a suitable amine oxide is commercially available from Stepan Company under the tradename Ammonyl CO.
  • the association agent may be present in the polymeric structure, such as the fiber, at a level from greater than 0% to less than about 100%.
  • the association agent is present in the polymeric structure at a level of from greater than 0% and/or from at least about 0.001% and/or at least about 0.01% and/or at least about 0.1% and/or at least about 1% to about 50% and/or to about 40% and/or to about 30% and/or to about 15% and/or to about 10% and/or to about 5% and/or to about 3%.
  • the hydroxyl polymer-containing composition of the present invention may comprise an unsubstituted hydroxyl polymer and/or a substituted hydroxyl polymer.
  • the hydroxyl polymer-containing composition may be a blend and/or mixture of polymers, such as two or more different hydroxyl polymers, for example an unsubstituted hydroxyl polymer (i.e., native dent corn starch hydroxyl polymer) and a substituted hydroxyl polymer (i.e., a hydroxyethyl starch hydroxyl polymer).
  • the hydroxyl polymer-containing composition may comprise two or more different classes of hydroxyl polymers, such as a starch hydroxyl polymer and a polyvinyl alcohol hydroxyl polymer.
  • Optional ingredients for example fillers both inorganic and organic and/or fibers and/or foaming agents may also be included in the hydroxyl polymer-containing composition and/or in the fibrous structure made therefrom.
  • the hydroxyl polymer-containing composition may already be formed.
  • the hydroxyl polymer may be solubilized via contact with a liquid, such as water, in order to form the hydroxyl polymer-containing composition.
  • a liquid such as water
  • Such a liquid may be considered for the purposes of the present invention as performing the function of an external plasticizer.
  • any other suitable processes known to those skilled in the art to produce the hydroxyl polymer-containing composition such that the hydroxyl polymer-containing composition exhibits suitable properties for polymer processing the composition into a polymeric structure in accordance with the present invention may be used.
  • the hydroxyl polymer-containing composition may have and/or be exposed to a temperature of from about 23°C to about 140°C and/or from about 50°C to about 130°C and/or from about 65°C to about 100°C and/or from about 65°C to about 95°C and/or from about 70°C to about 90°C when making polymeric structures from the hydroxyl polymer-containing composition.
  • the hydroxyl polymer-containing composition may have and/or be exposed to a temperature that is generally higher when making film and/or foam polymeric structures, as described below.
  • the pH of the hydroxyl polymer-containing composition may be from about 2.5 to about 11 and/or from about 2.5 to about 10 and/or from about 3 to about 9.5 and/or from about 3 to about 8.5 and/or from about 3.2 to about 8 and/or from about 3.2 to about 7.5.
  • a hydroxyl polymer-containing composition of the present invention may comprise at least about 5% and/or at least about 15% and/or from at least about 20% and/or 30% and/or 40% and/or 45% and/or 50% to about 75% and/or 80% and/or 85% and/or 90% and/or 95% and/or 99.5% by weight of the hydroxyl polymer-containing composition of a hydroxyl polymer.
  • the hydroxyl polymer may have a weight average molecular weight greater than about 10,000 g/mol prior to crosslinking.
  • a crosslinking system may be present in the hydroxyl polymer-containing composition and/or may be added to the hydroxyl polymer-containing composition before polymer processing of the hydroxyl polymer-containing composition.
  • the hydroxyl polymer-containing composition may comprise a) at least about 5% and/or at least about 15% and/or from at least about 20% and/or 30% and/or 40% and/or 45% and/or 50% to about 75% and/or 80% and/or 85% by weight of the hydroxyl polymer-containing composition of a hydroxyl polymer; b) a crosslinking system comprising from about 0.1% to about 10% by weight of the hydroxyl polymer-containing composition of a crosslinking agent; and c) from about 10% and/or 15% and/or 20% to about 50% and/or 55% and/or 60% and/or 70% by weight of the hydroxyl polymer-containing composition of external plasticizer e.g., water.
  • external plasticizer e.g., water.
  • the crosslinking system of the present invention may further comprise, in addition to the crosslinking agent, a crosslinking facilitator.
  • Crosslinking facilitator as used herein means any material that is capable of activating a crosslinking agent thereby transforming the crosslinking agent from its unactivated state to its activated state.
  • the crosslinking agent Upon crosslinking the hydroxyl polymer, the crosslinking agent becomes an integral part of the polymeric structure as a result of crosslinking the hydroxyl polymer as shown in the following schematic representation:
  • the crosslinking facilitator may include derivatives of the material that may exist after the transformation/activation of the crosslinking agent.
  • a crosslinking facilitator salt being chemically changed to its acid form and vice versa.
  • Nonlimiting examples of suitable crosslinking facilitators include acids having a pKa of between 2 and 6 or salts thereof.
  • the crosslinking facilitators may be Bronsted Acids and/or salts thereof, preferably ammonium salts thereof.
  • metal salts such as magnesium and zinc salts
  • Bronsted Acids and/or salts thereof can be used alone or in combination with Bronsted Acids and/or salts thereof, as crosslinking facilitators.
  • Nonlimiting examples of suitable crosslinking facilitators include acetic acid, benzoic acid, citric acid, formic acid, glycolic acid, lactic acid, maleic acid, phthalic acid, phosphoric acid, succinic acid and mixtures thereof and/or their salts, preferably their ammonium salts, such as ammonium glycolate, ammonium citrate, ammonium sulfate, and ammonium chloride.
  • a hydroxyl polymer-containing composition of the present invention may be prepared using a screw extruder, such as a vented twin screw extruder.
  • a barrel 10 of an APV Baker (Peterborough, England) twin screw extruder is schematically illustrated in Fig. 1A .
  • the barrel 10 is separated into eight zones, identified as zones 1-8.
  • the barrel 10 encloses the extrusion screw and mixing elements, schematically shown in Fig. 1B , and serves as a containment vessel during the extrusion process.
  • a solid feed port 12 is disposed in zone 1 and a liquid feed port 14 is disposed in zone 1.
  • a vent 16 is included in zone 7 for cooling and decreasing the liquid, such as water, content of the mixture prior to exiting the extruder.
  • An optional vent stuffer commercially available from APV Baker, can be employed to prevent the hydroxyl polymer-containing composition from exiting through the vent 16.
  • the flow of the hydroxyl polymer-containing composition through the barrel 10 is from zone 1 exiting the barrel 10 at zone 8.
  • a screw and mixing element configuration for the twin screw extruder is schematically illustrated in Fig 1B .
  • the twin screw extruder comprises a plurality of twin lead screws (TLS) (designated A and B) and single lead screws (SLS) (designated C and D) installed in series. Screw elements (A - D) are characterized by the number of continuous leads and the pitch of these leads.
  • a lead is a flight (at a given helix angle) that wraps the core of the screw element.
  • the number of leads indicates the number of flights wrapping the core at any given location along the length of the screw. Increasing the number of leads reduces the volumetric capacity of the screw and increases the pressure generating capability of the screw.
  • the pitch of the screw is the distance needed for a flight to complete one revolution of the core. It is expressed as the number of screw element diameters per one complete revolution of a flight. Decreasing the pitch of the screw increases the pressure generated by the screw and decreases the volumetric capacity of the screw.
  • the length of a screw element is reported as the ratio of length of the element divided by the diameter of the element.
  • Screw element A is a TLS with a 1.0 pitch and a 1.5 length ratio.
  • Screw element B is a TLS with a 1.0 pitch and a 1.0 L/D ratio.
  • Screw element C is a SLS with a 1 ⁇ 4 pitch and a 1.0 length ratio.
  • Screw element D is a SLS and a 1 ⁇ 4 pitch and a 1 ⁇ 2 length ratio.
  • Bilobal paddles, E serving as mixing elements, are also included in series with the SLS and TLS screw elements in order to enhance mixing.
  • zone 1 the hydroxyl polymer is fed into the solid feed port at a rate of 230 grams/minute using a K-Tron (Pitman,NJ) loss-in-weight feeder.
  • This hydroxyl polymer is combined inside the extruder (zone 1) with water, an external plasticizer, added at the liquid feed at a rate of 146 grams/minute using a Milton Roy (Ivyland, PA) diaphragm pump (7.2 l (1.9 gallon) per hour pump head) to form an hydroxyl polymer/water slurry.
  • This slurry is then conveyed down the barrel of the extruder and cooked, in the presence of an alkaline agent, such as ammonium hydroxide and/or sodium hydroxide.
  • an alkaline agent such as ammonium hydroxide and/or sodium hydroxide.
  • the cooking causes a hydrogen from at least one hydroxyl moiety on the hydroxyl polymer to become disassociated with the hydroxyl moiety and thus create a negative charge on the oxygen atom of the former hydroxyl moiety.
  • This oxygen atom is now open for association by an association agent, such as a quaternary ammonium compound, for example a quaternary amine. Accordingly, an association agent is added to the hydroxyl polymer/water slurry, thus creating an associated hydroxyl polymer.
  • Table 1 describes the temperature, pressure, and corresponding function of each zone of the extruder.
  • Table I Zone Temp.(°F) Pressure Description of Screw Purpose 1 70 Low Feeding/Conveying Feeding and Mixing 2 70 Low Conveying Mixing and Conveying 3 70 Low Conveying Mixing and Conveying 4 130 Low Pressure/ Decreased Conveying Conveying and Heating 5 300 Medium Pressure Generating Cooking at Pressure and Temperature 6 250 High Reversing Cooking at Pressure and Temperature 7 210 Low Conveying Cooling and Conveying (with venting) 8 210 Low Pressure Generating Conveying
  • part of the associated hydroxyl polymer/water slurry can be dumped and another part (100g) can be fed into a Zenith®, type PEP II (Sanford NC) and pumped into a SMX style static mixer (Koch-Glitsch, Woodridge, Illinois).
  • the static mixer is used to combine additional additives such as crosslinking agents, crosslinking facilitators, external plasticizers, such as water, with the associated hydroxyl polymer/water slurry to form an associated hydroxyl polymer-containing composition.
  • the additives are pumped into the static mixer via PREP 100 HPLC pumps (Chrom Tech, Apple Valley MN). These pumps provide high pressure, low volume addition capability.
  • the associated hydroxyl polymer-containing composition of the present invention is ready to be polymer processed into a hydroxyl polymer polymeric structure.
  • Polymer processing as used herein means any operation and/or process by which a polymeric structure comprising a hydroxyl polymer is formed from a hydroxyl polymer-containing composition.
  • Nonlimiting examples of polymer processing operations include extrusion, molding and/or fiber spinning.
  • Extrusion and molding either casting or blown
  • Molding typically produce films, sheets and various profile extrusions.
  • Molding may include injection molding, blown molding and/or compression molding.
  • Fiber spinning may include spun bonding, melt blowing, continuous filament producing, rotary spinning and/or tow fiber producing.
  • the hydroxyl polymer-containing composition can be subjected to one or more polymer processing operations such that the hydroxyl polymer-containing composition is processed into a polymeric structure in the form of a fiber comprising the hydroxyl polymer and optionally, a crosslinking system, according to the present invention.
  • the crosslinking system via the crosslinking agent crosslinks hydroxyl polymers together to produce the polymeric structure of the present invention, with or without being subjected to a curing step.
  • the crosslinking system in accordance with the present invention acceptably crosslinks, as determined by the Initial Total Wet Tensile Test Method described herein, the hydroxyl polymers of a processed hydroxyl polymer-containing composition together via the crosslinking agent to form an integral polymeric structure.
  • the crosslinking agent is a "building block" for the polymeric structure. Without the crosslinking agent, no polymeric structure in accordance with the present invention could be formed.
  • Polymeric structures of the present invention do not include coatings and/or other surface treatments that are applied to a pre-existing form, such as a coating on a fiber, film or foam.
  • the polymeric structure produced via a polymer processing operation may be cured at a curing temperature of from about 110°C to about 315°C and/or from about 110°C to about 250°C and/or from about 110°C to about 200°C and/or from about 120°C to about 195°C and/or from about 130°C to about 185°C for a time period of from about 0.01 and/or 1 and/or 5 and/or 15 seconds to about 60 minutes and/or from about 20 seconds to about 45 minutes and/or from about 30 seconds to about 30 minutes.
  • Alternative curing methods may include radiation methods such as UV, e-beam, IR and other temperature-raising methods.
  • the polymeric structure may also be cured at room temperature for days, either after curing at above room temperature or instead of curing at above room temperature.
  • the polymeric structure may exhibit an initial total wet tensile, as measured by the Initial Total Wet Tensile Test Method described herein, of at least about 1.18 g/cm (3 g/in) and/or at least about 1.97 g/cm (5 g/in) and/or at least about 5.91 g/cm (15 g/in) and/or at least about 9.84 g/cm (25 g/in) to about 51.
  • a polymeric structure of the present invention may comprise from at least about 20% and/or 30% and/or 40% and/or 45% and/or 50% to about 75% and/or 80% and/or 85% and/or 90% and/or 95% and/or 99.5% by weight of the polymeric structure of a hydroxyl polymer.
  • a hydroxyl polymer-containing composition is prepared according to the Synthesis of a Hydroxyl Polymer-Containing Composition described above. As shown in Fig. 2 , the hydroxyl polymer-containing composition may be processed into a polymeric structure.
  • the hydroxyl polymer-containing composition present in an extruder 102 is pumped to a die 104 using pump 103, such as a Zenith®, type PEP II, having a capacity of 0.6 cubic centimeters per revolution (cc/rev), manufactured by Parker Hannifin Corporation, Zenith Pumps division, of Sanford, NC, USA.
  • pump 103 such as a Zenith®, type PEP II, having a capacity of 0.6 cubic centimeters per revolution (cc/rev), manufactured by Parker Hannifin Corporation, Zenith Pumps division, of Sanford, NC, USA.
  • the hydroxyl polymer's, such as starch, flow to die 104 is controlled by adjusting the number of revolutions per minute (rpm) of the pump 103.
  • Pipes connecting the extruder 102, the pump 103, the die 104, and optionally a mixer 116 are electrically heated and thermostatically controlled to 65°C.
  • the die 104 has several rows of circular extrusion nozzles 200 spaced from one another at a pitch P ( Fig. 3 ) of about 1.524 millimeters (about 0.060 inches).
  • the nozzles 200 have individual inner diameters D2 of about 0.305 millimeters (about 0.012 inches) and individual outside diameters (D1) of about 0.813 millimeters (about 0.032 inches).
  • Each individual nozzle 200 is encircled by an annular and divergently flared orifice 250 formed in a plate 260 ( Figs. 3 and 4 ) having a thickness of about 1.9 millimeters (about 0.075 inches).
  • a pattern of a plurality of the divergently flared orifices 250 in the plate 260 correspond to a pattern of extrusion nozzles 200.
  • the orifices 250 have a larger diameter D4 ( Figs. 3 and 4 ) of about 1.372 millimeters (about 0.054 inches) and a smaller diameter D3 of 1.17 millimeters (about 0.046 inches) for attenuation air.
  • the plate 260 was fixed so that the embryonic fibers 110 being extruded through the nozzles 200 are surrounded and attenuated by generally cylindrical, humidified air streams supplied through the orifices 250.
  • the nozzles can extend to a distance from about 1.5 mm to about 4 mm, and more specifically from about 2 mm to about 3 mm, beyond a surface 261 of the plate 260 ( Fig. 3 ).
  • a plurality of boundary-air orifices 300 is formed by plugging nozzles of two outside rows on each side of the plurality of nozzles, as viewed in plane, so that each of the boundary-layer orifice comprised a annular aperture 250 described herein above. Additionally, every other row and every other column of the remaining capillary nozzles are blocked, increasing the spacing between active capillary nozzles
  • Attenuation air can be provided by heating compressed air from a source 106 by an electrical-resistance heater 108, for example, a heater manufactured by Chromalox, Division of Emerson Electric, of Pittsburgh, PA, USA.
  • the attenuating air has an absolute pressure from about 130 kPa to about 310 kPa, measured in the pipe 115.
  • the polymeric structure fibers 110 being extruded have a moisture content of from about 20% and/or 25% to about 50% and/or 55% by weight.
  • the polymer structure fibers 110 are dried by a drying air stream 109 having a temperature from about 149° C (about 300° F) to about 315° C (about 600° F) by an electrical resistance heater (not shown) supplied through drying nozzles 112 and discharged at an angle generally perpendicular relative to the general orientation of the embryonic fibers being extruded.
  • the polymeric structure fibers are dried from about 45% moisture content to about 15% moisture content (i.e., from a consistency of about 55% to a consistency of about 85%) and are collected on a collection device 111, such as, for example, a movable foraminous belt.
  • polymeric structures of the present invention may be made by any suitable process known to those skilled in the art.
  • a nonlimiting example of a suitable process for making a polymeric structure according to the present invention comprises the step of obtaining a polymeric structure comprising an hydroxyl polymer from a hydroxyl polymer-containing composition comprising a substituted form of the hydroxyl polymer.
  • a process for making a polymeric structure comprising an hydroxyl polymer wherein the process comprises the step of polymer processing a hydroxyl polymer-containing composition comprising an hydroxyl polymer into a polymeric structure comprising the hydroxyl polymer, is provided.
  • a process for making a polymeric structure comprising an hydroxyl polymer comprising the steps of:
  • a hydroxyl polymer specifically one or more hydroxyl moieties present on the hydroxyl polymer, is associated, during an associating step, with an association agent for a time sufficient to permit a polymeric structure comprising the hydroxyl polymer and association agent to be formed.
  • the association agent temporarily impacts the properties of the hydroxyl polymer in a manner such that it can be spun and/or otherwise polymer processed into a polymeric structure, such as a fiber.
  • the associating step may comprise subjecting the hydroxyl polymer to an alkaline pH.
  • the associating step may comprise subjecting the hydroxyl polymer to a pH of greater than 7 and/or at least about 7.5 and/or at least about 8 and/or at least about 8.5.
  • an alkaline agent may be used in the associating step.
  • suitable alkaline agents may be selected from the group consisting of sodium hydroxide calcium hydroxide, magnesium hydroxide, potassium hydroxide, ammonium hydroxide and mixtures thereof.
  • the associating step may occur at a temperature in the range of from about 70°C to about 140°C and/or from about 70°C to about 120°C and/or from about 75°C to about 100°C.
  • the associating step may comprise interacting the hydroxyl polymer with an association agent to form an associated hydroxyl polymer.
  • the step of obtaining a fiber from the associated hydroxyl polymer may comprise subjecting the associated hydroxyl polymer to an acidic pH.
  • the step of obtaining a fiber from the associated hydroxyl polymer may comprise subjecting the associated hydroxyl polymer to a pH of less than 7 and/or less than about 6 and/or less than about 5 and/or less than about 4.5 and/or less than about 4.
  • an acidic agent may be used in the obtaining a fiber step.
  • Nonlimiting examples of suitable acidic agents may be selected from the group consisting of: acetic acid, benzoic acid, citric acid, formic acid, glycolic acid, lactic acid, maleic acid, phthalic acid, phosphoric acid, succinic acid and mixtures thereof and/or their salts, preferably their ammonium salts, such as ammonium glycolate, ammonium citrate, ammonium sulfate, ammonium chloride, and mixtures thereof.
  • the obtaining a fiber step may occur at a temperature in the range of from about 60°C to about 100° and/or from about 70°C to about 95°C.
  • the step of obtaining a polymeric structure may comprise spinning the associated hydroxyl polymer such that a fiber comprising a hydroxyl polymer and an association agent is formed.
  • the spinning may be any suitable spinning operation known to those skilled in the art.
  • the process of the present invention may further comprise a step of collecting a plurality of the fibers to form a web.
  • the following test has been designed to measure the apparent peak wet tensile stress of a starch fiber during the first minutes of the fiber being moistened -- to reflect a consumer's real-life expectations as to the strength properties of the end product, such as, for example, a toilet tissue, during its use.
  • the water droplet velocity and the water droplet diameter of the mist generated by the humidifier can be measured using photogrammetric techniques. Images can be captured using a Nikon®, Model D1, of Japan, 3-megapixel digital camera equipped with a 37 mm coupling ring, a Nikon® PB-6 bellows, and a Nikon® auto-focus AF Micro Nikkor® 200 mm 1:4D lens. Each pixel had the dimension of about 3.5 micrometer assuming a square pixel. Images can be taken in shadow mode using a Nano Twin Flash (High-Speed Photo-Systeme, of Wedel, Germany). Any number of commercially available image-processing packages can be used to process the images. The dwell time between the two flashes of this system is set at 5, 10, and 20 microsecond. The distance traveled by water droplets between flashes is used to calculate droplet velocity.
  • Water droplets were found to be from about 12 microns to about 25 microns in diameter.
  • the velocity of the water droplets at a distance of about (25 ⁇ 5) mm from the outlet of the flexible hose was calculated to be about 27 meters per second (m/sec), ranging from about 15 m/sec to about 50 m/sec.
  • m/sec meters per second
  • the flexible hose is positioned so that the mist stream totally engulfs the fiber thereby thoroughly wetting the fiber.
  • the distance between the outlet of the flexible hose and the fiber is adjusted until the mist stream stalls at or just past the fiber.
  • FSR is based on a design similar to that described in an article titled " A Filament Stretching Device For Measurement Of Extensional Viscosity,” published by J. Rheology 37 (6), 1993, pages 1081-1102 (Tirtaatmadja and Sridhar), incorporated herein by reference, with the following modifications:
  • a wide-bandwidth single-channel signal-conditioning module Model 5B41-06, manufactured by Analog Devices Co. of Norwood, MA, USA can be used to condition the signal from the force transducer, Model 405A, manufactured by Aurora Scientific Inc., of Aurora, Ontario, Canada.
  • hydroxyl polymer for example Eclipse G starch (acid thinned dent corn starch of approximate average molecular weight of 3,000,000 g/mol, from A. E. Staley Manufacturing Corporation of Decatur, IL, USA), 10.00 grams of a hydroxyl polymer, for example 10% Celvol 310 solution in water (Ethenol, homopolymer from Celanese Ltd.
  • Eclipse G starch acid thinned dent corn starch of approximate average molecular weight of 3,000,000 g/mol, from A. E. Staley Manufacturing Corporation of Decatur, IL, USA
  • Celvol 310 solution in water Ethenol, homopolymer from Celanese Ltd.
  • a crosslinking agent for example Parez® 490 from Lanxess Corp. (formerly Bayer Corp.), Pittsburgh, PA, USA, (3% urea-glyoxal resin based on the weight of the starch), and 4.00 grams of a crosslinking facilitator, for example 25% Ammonium chloride solution (4% based on the weight of the starch) are added to the beaker and mixed. Then the mixture is cooled to a temperature of about 40°C. A portion of the mixture is transferred to a 10 cubic centimeter (cc) syringe and is extruded therefrom to form a fiber. The fiber is manually elongated so that the fiber has a diameter between about 10 ⁇ m and about 100 ⁇ m.
  • a crosslinking agent for example Parez® 490 from Lanxess Corp. (formerly Bayer Corp.), Pittsburgh, PA, USA, (3% urea-glyoxal resin based on the weight of the starch)
  • a crosslinking facilitator for example 25% Ammoni
  • the fiber is suspended in an ambient air for approximately one minute to allow the fiber to dry and solidify.
  • the fiber is placed on an aluminum pan and is cured in a convection oven for about 10 minutes at a temperature of about 130°C.
  • the cured fiber is then placed in a room having a constant temperature of about 22°C and a constant relative humidity of about 25% for about 24 hours.
  • a coupon 90 ( Fig. 6 ) can be used to support the fiber 110.
  • the coupon 90 can be manufactured from an ordinary office copy paper or a similar light material.
  • the coupon 90 comprises a rectangular structure having the overall size of about 20 millimeters by about 8 millimeters, with a rectangle cutout 91 sized about 9 millimeters by about 5 millimeters in the center of the coupon 90.
  • the ends 110a, 110b of the fiber 110 can be secured to the ends of the coupon 90 with an adhesive tape 95 (such as, for example, a conventional Scotch tape), or otherwise, so that the fiber 110 spans the distance (of about 9 millimeters in the instant example) of the cut-out 91 in the center of the coupon 90, as shown in Fig. 6 .
  • the coupon 90 may have a hole 98 in the top portion of the coupon 90, structured to receive a suitable hook mounted on the upper plate of the force transducer.
  • the fiber's diameter can be measured with an optical microscope at 3 positions and averaged to obtain the average fiber diameter used in calculations.
  • the coupon 90 can then be mounted onto a fiber-stretching rheometer (not shown) so that the fiber 110 is substantially parallel to the direction of the load "P" ( Fig. 6 ) to be applied. Side portions of the coupon 90 that are parallel to the fiber 110 can be cut (along lines 92, Fig. 6 ), so that the fiber 110 is the only element receiving the load.
  • the fiber 110 can be sufficiently moistened.
  • an ultrasonic humidifier (not shown) can be turned on, with a rubber hose positioned about 200 millimeters (about 8 inches) away from the fiber so as to direct the output mist directly at the fiber.
  • the fiber 110 can be exposed to the vapor for about one minute, after which the force load P can be applied to the fiber 110.
  • the fiber 110 continues to be exposed to the vapor during the application of the force load that imparts elongation force to the fiber 110. Care should be taken to ensure that the fiber 110 is continuously within the main stream of the humidifier output as the force is applied to the fiber.
  • droplets of water are typically visible on or around the fiber 110.
  • the humidifier, its contents, and the fiber 110 are allowed to equilibrate to an ambient temperature before use.
  • the wet tensile stress can be calculated in units of MegaPascals (MPa).
  • the test can be repeated multiple times, for example eight times.
  • the results of wet tensile stress measurements of eight fibers are averaged.
  • the force readings from the force transducer are corrected for the mass of the residual coupon by subtracting the average force transducer signal collected after the fiber had broken from the entire set of force readings.
  • the stress at failure for the fiber can be calculated by taking the maximum force generated on the fiber divided by the cross-sectional area of the fiber based on the optical microscope measurements of the fiber's average fiber diameter measured prior to conducting the test.
  • the actual beginning plate separation (bps) can be dependent on a particular sample tested, but is recorded in order to calculate the actual engineering strain of the sample.
  • a web comprising fibers of appropriate basis weight (approximately 5 to 20 grams/square meter) is cut into a rectangular shape, approximately 20 mm by 35 mm.
  • the sample is then coated using a SEM sputter coater (EMS Inc, PA, USA) with gold so as to make the fibers relatively opaque. Typical coating thickness is between 50 and 250 nm.
  • the sample is then mounted between two standard microscope slides and compressed together using small binder clips.
  • the sample is imaged using a 10X objective on an Olympus BHS microscope with the microscope light-collimating lens moved as far from the objective lens as possible. Images are captured using a Nikon D1 digital camera.
  • a Glass microscope micrometer is used to calibrate the spatial distances of the images.
  • the approximate resolution of the images is 1 ⁇ m/pixel. Images will typically show a distinct bimodal distribution in the intensity histogram corresponding to the fibers and the background. Camera adjustments or different basis weights are used to achieve an acceptable bimodal distribution. Typically 10 images per sample are taken and the image analysis results averaged.
  • the images are analyzed in a similar manner to that described by B. Pourdeyhimi, R. and R. Dent in "Measuring fiber diameter distribution in nonwovens" (Textile Res. J. 69(4) 233-236, 1999 ).
  • Digital images are analyzed by computer using the MATLAB (Version. 6.3) and the MATLAB Image Processing Tool Box (Version 3.)The image is first converted into a grayscale. The image is then binarized into black and white pixels using a threshold value that minimizes the intraclass variance of the thresholded black and white pixels. Once the image has been binarized, the image is skeltonized to locate the center of each fiber in the image. The distance transform of the binarized image is also computed.
  • the scalar product of the skeltonized image and the distance map provides an image whose pixel intensity is either zero or the radius of the fiber at that location. Pixels within one radius of the junction between two overlapping fibers are not counted if the distance they represent is smaller than the radius of the junction. The remaining pixels are then used to compute a length-weighted histogram of fiber diameters contained in the image.
  • An electronic tensile tester (Thwing-Albert EJA Materials Tester, Thwing-Albert Instrument Co., 10960 Dutton Rd., Philadelphia, Pa., 19154) is used and operated at a crosshead speed of 4.0 inch (about 10.16 cm) per minute and a gauge length of 2.54 cm (1.0 inch), using a strip of a polymeric structure of 2.54 cm (1 inch) wide and a length greater than 7.62 cm (3 inches) long. The two ends of the strip are placed in the upper jaws of the machine, and the center of the strip is placed around a stainless steel peg (0.5 cm in diameter).
  • the initial result of the test is an array of data in the form load (grams force) versus crosshead displacement (centimeters from starting point).
  • MD machine direction
  • CD cross-machine direction, i.e., 90° from MD.
  • the MD and CD wet tensile strengths are determined using the above equipment and calculations in the following manner:
  • the Initial Total Wet Tensile value is then normalized for the basis weight of the strip from which it was tested.
  • the initial total wet tensile of a polymeric structure comprising a crosslinking system of the present invention is at least 1.18 g/cm (3 g/in) and/or at least 1.57 g/cm (4 g/in) and/or at least 1.97 g/cm (5 g/in), then the crosslinking system is acceptable and is within the scope of the present invention.
  • the initial total wet tensile is less than or equal to about 23.62 g/cm (60 g/in) and/or less than or equal to about 21.65 g/cm (55 g/in) and/or less than or equal to about 19.69 g/cm (50 g/in).
  • association agent is present in a polymeric structure, such as a fiber, and/or in a fibrous structure and/or in a sanitary tissue product
  • standard test methods namely HPLC-mass spectroscopy or GC-mass spectroscopy or capillary electrophoresis-mass spectroscopy, examples of such methods are described in Vogt, Carla; Heinig, Katja. Trace analysis of surfactants using chromatographic and electrophoretic techniques. Fresenius' Journal of Analytical Chemistry (1999), 363(7), 612-618. CODEN: FJACES ISSN:0937-0633 . CAN 130:283696 AN 1999:255335 CAPLUS

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Claims (9)

  1. Procédé pour former une nappe non tissée moulée, texturée, lacée par filage, à partir d'une préforme de substrat fibreux caractérisé par l'étape consistant à :
    fournir une préforme de substrat ayant une longueur moyenne de fibre, f1 et une grille de formage (10), ladite grille de formage comprenant un élément de treillis supérieur (20) ayant une hauteur, hc égale ou supérieure à f1 et un élément de treillis sous-jacent (30) en contact intime avec ledit élément de treillis supérieur, dans lequel ledit élément de treillis supérieur (20) a un diamètre ouvert efficace, dc et ledit élément de treillis sous-jacent (30) a un diamètre ouvert efficace, df, et dans lequel dc 2/df 2 est supérieur ou égal à 50 et est inférieur ou égal à 300,
    placer ladite préforme de substrat fibreux en contact avec ladite grille de formage,
    soumettre simultanément ledit substrat à un procédé d'enchevêtrement par voie hydraulique.
  2. Procédé selon la revendication 1, dans lequel ladite grille de formage (10) est un cylindre pouvant tourner.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, dans lequel ledit procédé d'enchevêtrement par voie hydraulique comprend, en outre, la mise en contact de ladite préforme de substrat fibreux avec au moins un jet d'eau avant la mise en contact dudit substrat avec ladite grille de formage, ledit au moins un jet d'eau étant dirigé sur ladite préforme de substrat fibreux approximativement perpendiculaire à ladite préforme de substrat fibreux.
  4. Procédé selon l'une quelconque des revendications 1, 2, ou 3, dans lequel ladite préforme de substrat fibreux est choisie dans le groupe constitué d'une préforme de substrat cardée et une préforme de substrat appliquée par jet d'air.
  5. Appareil pour former une nappe non tissée texturée lacée par filage comprenant :
    (a) une grille de formage (10), ladite grille de formage est caractérisée en ce qu'un élément de treillis supérieur (20) ayant un diamètre ouvert efficace, dc et un élément de treillis sous-jacent (30) ayant un diamètre ouvert efficace, df est en contact intime avec ledit élément de treillis supérieur, dc 2/df 2 étant supérieur ou égal à 50 et étant inférieur ou égal à 300 ; et
    (b) un moyen d'enchevêtrement par voie hydraulique en association avec ladite grille de formage.
  6. Appareil selon la revendication 5, dans lequel ladite grille de formage est sous la forme d'un cylindre.
  7. Appareil selon la revendication 5 ou la revendication 6, dans lequel ladite grille de formage entoure un cylindre de support rotatif perméable aux liquides.
  8. Appareil selon l'une quelconque des revendications 5, 6, ou 7, dans lequel ledit moyen d'enchevêtrement par voie hydraulique comprend au moins un jet d'eau qui est approximativement perpendiculaire à ladite grille de formage.
  9. Appareil selon l'une quelconque des revendications 5, 6, 7, ou 8, dans lequel ledit élément de treillis supérieur et ledit élément de treillis sous-jacent comprennent des motifs géométriques identiques ou différents choisis dans le groupe constitué de carré, circulaire, elliptique, rectangulaire, pentagonal, hexagonal, en losange, en losange arrondi, en os de chien, triangulaire, et leurs combinaisons.
EP05854923.9A 2004-12-20 2005-12-20 Structures polymeres comprenant un agent d'association et procedes de production desdites structures Not-in-force EP1828450B1 (fr)

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US11/018,746 US20060134410A1 (en) 2004-12-20 2004-12-20 Polymeric structures comprising an unsubstituted hydroxyl polymer and processes for making same
US11/295,939 US8273453B2 (en) 2004-12-20 2005-12-07 Structures comprising an association agent and processes for making same
PCT/US2005/046284 WO2006069120A2 (fr) 2004-12-20 2005-12-20 Structures polymeres comprenant un agent d'association et procedes de production desdites structures

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US8921244B2 (en) * 2005-08-22 2014-12-30 The Procter & Gamble Company Hydroxyl polymer fiber fibrous structures and processes for making same
US7972986B2 (en) 2007-07-17 2011-07-05 The Procter & Gamble Company Fibrous structures and methods for making same
US10024000B2 (en) 2007-07-17 2018-07-17 The Procter & Gamble Company Fibrous structures and methods for making same
US8852474B2 (en) 2007-07-17 2014-10-07 The Procter & Gamble Company Process for making fibrous structures
AU2010313458B2 (en) 2009-11-02 2014-03-20 The Procter & Gamble Company Fibrous structures and methods for making same
CA2779719C (fr) 2009-11-02 2014-05-27 The Proctor & Gamble Company Elements fibreux et structures fibreuses les employant
JP5770262B2 (ja) 2010-03-31 2015-08-26 ザ プロクター アンド ギャンブルカンパニー 繊維性構造体及びその製造方法

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GB937253A (en) * 1960-03-23 1963-09-18 Algemene Kunstzijde Unie Nv Improvements in or relating to the manufacture of viscose rayon
GB1165958A (en) * 1966-02-12 1969-10-01 Hoechst Ag Process for the Manufacture of Films and Filamentary Materials made from Viscose

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MXPA00012782A (es) * 2000-03-07 2005-05-12 Procter & Gamble Composiciones de almidon procesables por fusion.
TW200411094A (en) * 2002-02-01 2004-07-01 Procter & Gamble Non-thermoplastic starch fibers and starch composition for making same and process for making non-thermoplastic starch fibers
US7947766B2 (en) * 2003-06-06 2011-05-24 The Procter & Gamble Company Crosslinking systems for hydroxyl polymers

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GB937253A (en) * 1960-03-23 1963-09-18 Algemene Kunstzijde Unie Nv Improvements in or relating to the manufacture of viscose rayon
GB1165958A (en) * 1966-02-12 1969-10-01 Hoechst Ag Process for the Manufacture of Films and Filamentary Materials made from Viscose

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CA2591596A1 (fr) 2006-06-29
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AU2005319271B2 (en) 2009-06-11
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WO2006069120A3 (fr) 2006-08-03
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