EP1560957B1 - Fibres clivables a composants multiples a allongement eleve comportant de l'amidon et des polymeres - Google Patents

Fibres clivables a composants multiples a allongement eleve comportant de l'amidon et des polymeres Download PDF

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Publication number
EP1560957B1
EP1560957B1 EP02808136A EP02808136A EP1560957B1 EP 1560957 B1 EP1560957 B1 EP 1560957B1 EP 02808136 A EP02808136 A EP 02808136A EP 02808136 A EP02808136 A EP 02808136A EP 1560957 B1 EP1560957 B1 EP 1560957B1
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Prior art keywords
fiber
component
starch
fibers
split
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German (de)
English (en)
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EP1560957A1 (fr
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Eric Bryan Bond
Daniel Steven Wheeler
Kelyn Anne Arora
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Procter and Gamble Co
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Procter and Gamble Co
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/43832—Composite fibres side-by-side
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4266—Natural fibres not provided for in group D04H1/425
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/4383—Composite fibres sea-island
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
    • D04H1/5414—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres side-by-side
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D04H1/544—Olefin series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
    • D04H1/5412—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres sheath-core
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
    • D04H1/5416—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres sea-island
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
    • D04H1/5418—Mixed fibres, e.g. at least two chemically different fibres or fibre blends

Definitions

  • the present invention relates to splittable multicomponent fibers comprising starch and polymers and split fibers obtained from such splittable fibers.
  • the present invention also relates to a process for making split fibers.
  • the split fibers can have high elongation and can be used to make nonwoven webs and disposable articles.
  • nonwovens that can deliver softness and extensibility.
  • Soft nonwovens are gentle to the skin and are particularly useful in disposable products.
  • decreasing fiber diameters can improve softness of nonwovens and other substrates.
  • Nonwovens that are capable of high extensibility at relatively low force are also desired. These can be used to provide sustained fit in products and facilitate the use of various mechanical post-treatments.
  • it has been found that having both small fiber diameter and high extensibility is difficult to achieve. This is because when the fiber diameter is reduced, it is commonly because the spinning speed or draw ratio has been increased which decreases extensibility of the fiber.
  • Other ways to increase fiber extensibility of fine fibers include using higher-cost materials and or special mixing requirements.
  • the present invention can provide small diameter, extensible fibers in the form of split fibers obtained from splittable fibers splittable fibers that are cost-effective and easily processable.
  • the splittable fibers are made of natural starches and thermoplastic polymers.
  • the present invention also provides nonwoven articles and other substrates made from such split fibers.
  • the present invention is directed to splittable multicomponent fibers, to split fibers made from such splittable fibers, to a processes for making such splittable and split fibers, and to nonwovens substrates made from the split fibers.
  • the splittable multicomponent fibers comprise at least one nonencompassed segment of one component comprising thermoplastic starch and at least one nonencompassed segment of another component comprising a non-starch thermoplastic polymer.
  • said second component is capable of being split or removed from said first component to provide at least one split fiber consisting essentially of said first component; and (ii) wherein the split fiber of said first component has an Elongation to Break Ratio of greater than 1.0 as measured according to the ASTM Standard D3822 using a strain rate of 200% per minute applied to fiber samples having a 2.54cm (1 inch) gauge length.
  • nonencompassed segment means that the segment of the multicomponent fiber has at least one region of its lateral surface that is not encompassed by another segment of the multicomponent fiber.
  • the splittable multicomponent fiber will produce at least one split fiber comprising the thermoplastic polymer, and can also produce a plurality of split thermoplastic polymer fibers.
  • the splittable multicomponent fibers can also produce split fibers comprising the thermoplastic starch component.
  • the split fibers corresponding to the thermoplastic polymer component will have a greater elongation than directly spun thermoplastic fibers which have an equivalent mass through put as the thermoplastic polymer component of the multicomponent fiber and which have the same diameter as the split fiber. This allows small diameter fiber to be produced at low spinning speed, so as to provide improved elongation properties, compared to conventional methods whereby cost effective processes run at high spinning speeds tend to result in poorer elongation properties, or wherein formation of small diameter fibers with good elongation are typically made according to processes with low mass through-put, and consequently low cost effectiveness.
  • the configuration of the splittable multicomponent fibers may be side-by-side, segmented pie, hollow segmented pie, segmented ribbon, tipped multilobal, or any combination of configurations.
  • segments will split or be splittable from adjacent segments of the fiber wherein the adjacent segment or segments constitute a different component of the multicomponent fiber.
  • split fibers can be obtained from the multicomponent fibers hereof via chemical, mechanical, thermal, or other processes. Split fibers can also be obtained immediately upon formation of the multicomponent fiber, upon exit from the spinneret capillaries.
  • the splittable nature of the fibers hereof is due at least in part to differences in rheological, thermal, solubility, surface energy, extensibility and/or solidification differential behavior between the components of the multicomponent fiber.
  • the splittable multicomponent fibers provide improved extensibility in the split fibers because they can be spun under conditions such that the fibers have relatively low molecular orientation and relatively large diameters. This can occur by using relatively slow spinning speeds, not subjecting the fibers to large drawing forces, and/or by increasing the through put per hole in the spinneret.
  • fibers are drawn to smaller fiber diameters to increase the fiber strength and for a softer feel when used in a nonwoven. The drawing process, however, increases molecular orientation which results in a decrease in elongation to break of the fibers.
  • the split fibers of the present invention will have a higher elongation to break compared to fibers of the same diameter produced by direct spinning at equivalent mass through-put.
  • the split fibers of the present invention can also have improved softness when used in a nonwoven fabric as a result of the improved extensibility.
  • the present invention is also directed to nonwoven webs and disposable articles comprising the split fibers.
  • the nonwoven webs may also contain other synthetic or natural fibers blended with the split fibers of the present invention.
  • compositions, products, and processes described herein may comprise, consist essentially of, or consist of any or all of the required and/or optional components, ingredients, compositions, or steps described herein.
  • the specification contains a detailed description of (1) materials of the present invention, (2) configuration of the multicomponent fibers, (3) material properties of the multicomponent fiber and split fibers, (4) processes, and (5) articles.
  • Component A Thermoplastic Polymers
  • Suitable melting temperatures of the thermoplastic polymers, as well as the thermoplastic polymer component are from about 60°C to about 300°C, preferably from about 80°C to about 250°C and preferably from 100°C-215°C.
  • Thermoplastic polymers having a melting temperature (Tm) above 250°C may be used if plasticizers or diluents or other polymers are used to lower the observed melting temperature, such that the melting temperature of the composition of the thermoplastic polymer-containing component is within the above ranges. It may be desired to use a thermoplastic polymer having a glass transition (Tg) temperature of less than 0°C.
  • Tg glass transition
  • the thermoplastic polymer component has rheological characteristics suitable for melt spinning.
  • the molecular weight of the polymer should be sufficiently high to enable entanglement between polymer molecules and yet low enough to be melt spinnable.
  • suitable thermoplastic polymers can have molecular weights about 1,000,000 g/mol or below, preferably from about 5,000 g/mol to about 800,000 g/mol, more preferable from about 10,000 g/mol to about 700,000 g/mol and most preferably from about 20,000 g/mol to about 500,000 g/mol.
  • thermoplastic polymers desirably should be able to solidify fairly rapidly, preferably under extensional flow, as typically encountered in known processes as staple fibers (spin draw process) or spunbond/meltblown continuous filament process, and desirably can form a thermally stable fiber structure.
  • "Thermally stable fiber structure” as used herein is defined as not exhibiting significant melting or dimensional change at 25°C and ambient atmospheric pressure over a period of 24 hours at 50% relative humidity when diameter is measured and the fibers are placed in the environment within five minutes of their formation. Dimensional changes in measured fiber diameter greater than 25% difference, using as a basis the corresponding, original fiber diameter measurement, would be considered significant. If the original fiber is not round, the shortest diameter should be used for the calculation. The shortest diameter should also be used for the 24 hour measurement also.
  • Suitable thermoplastic polymers include polyolefins such as polyethylene or copolymers thereof, including low, high, linear low, or ultra low density polyethylenes, polypropylene or copolymers thereof, including atactic polypropylene; polybutylene or copolymers thereof; polyamides or copolymers thereof, such as Nylon 6, Nylon 11, Nylon 12, Nylon 46, Nylon 66; polyesters or copolymers thereof, such as polyethylene terephthalates; olefin carboxylic acid copolymers such as ethylene/acrylic acid copolymer, ethylene/maleic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/vinyl acetate copolymers or combinations thereof; polyacrylates, polymethacrylates, and their copolymers such as poly(methyl methacrylates).
  • polyolefins such as polyethylene or copolymers thereof, including low, high, linear low, or ultra low density polyethylenes, polypropylene or copo
  • thermoplastic polymers include polypropylene, polyethylene, polyamides, polyvinyl alcohol, ethylene acrylic acid, polyolefin carboxylic acid copolymers, polyesters, and combinations thereof.
  • Biodegradable thermoplastic polymers are also suitable for use herein.
  • Biodegradable materials are susceptible to being assimilated by microorganisms such as molds, fungi, and bacteria when the biodegradable material is buried in the ground or otherwise comes in contact with the microorganisms including contact under environmental conditions conducive to the growth of the microorganisms.
  • Suitable biodegradable polymers also include those biodegradable materials which are environmentally degradable using aerobic or anaerobic digestion procedures, or by virtue of being exposed to environmental elements such as sunlight, rain, moisture, wind, temperature, and the like.
  • the biodegradable thermoplastic polymers can be used individually or as a combination of biodegradable or non-biodegradable polymers.
  • Biodegradable polymers include polyesters containing aliphatic components.
  • the polyesters are ester polycondensates containing aliphatic constituents and poly(hydroxycarboxylic) acid.
  • the ester polycondensates include diacids/diol aliphatic polyesters such as polybutylene succinate, polybutylene succinate co-adipate, aliphatic/aromatic polyesters such as terpolymers made of butylenes diol, adipic acid and terephthalic acid.
  • the poly(hydroxycarboxylic) acids include lactic acid based homopolymers and copolymers, polyhydroxybutyrate (PHB), or other polyhydroxyalkanoate homopolymers and copolymers.
  • Such polyhydroxyalkanoates include copolymers of PHB with higher chain length monomers, such as C6 - C12, and higher, polyhydroxyalkanaotes, such as disclosed in US Patent RE 36,548 and US Patent 5,990,271
  • An example of a suitable commercially available poly lactic acid is NATUREWORKS from Cargill Dow and LACEA from Mitsui Chemical.
  • An example of a suitable commercially available diacid/diol aliphatic polyester is the polybutylene succinate/adipate copolymers sold as BIONOLLE 1000 and BIONOLLE 3000 from the Showa High Polymer Company, Ltd. Located in Tokyo, Japan.
  • An example of a suitable commercially available aliphatic/aromatic copolyester is the poly(tetramethylene adipate-co-terephthalate) sold as EASTAR BIO Copolyester from Eastman Chemical or ECOFLEX from BASF.
  • thermoplastic polymer component can contain a single polymer species or a blend of two or more non-starch thermoplastic polymers. Additionally, other materials, including but not limited to thermoplastic starch, can be present in the thermoplastic polymer component. Typically, non-starch, thermoplastic polymers are present in an amount of from about 51% to 100%, preferably from about 60% to about 95%, more preferably from about 70% to about 90%, by total weight of the thermoplastic polymer component.
  • Component B Thermoplastic Starch
  • the present invention relates to the use of starch, a low cost naturally occurring biopolymer.
  • the starch used in the present invention is thermoplastic, destructured starch.
  • the term "destructurized starch” is used to mean starch that is no longer in its naturally occurring granular structure.
  • the term “thermoplastic starch” or “TPS” is used to mean starch with a plasticizer for improving its thermoplastic flow properties so that it may be able to be spun into fibers.
  • Natural starch does not melt or flow like conventional thermoplastic polymers. Since natural starch generally has a granular structure, it desirably should be "destructurized”, or “destructured”, before it can be melt processed and spun like a thermoplastic material.
  • the granular structure of starch is characterized by granules comprising a structure of discrete amylopectin and amylose regions in a starch granule.
  • This granular structure is broken down during destructurization, which can be followed by a volume expansion of the starch component in he presence of the solvent or plasticizer.
  • Starch undergoing destructuring in the presence of the solvent or plasticizer also typically has an increase in viscosity versus non-destructured starch with the solvent or plasticizer.
  • the resulting destructurized starch can be in gelatinized form or, upon drying and or annealing, in crystalline form. However once broken down the natural granular structure of starch will not, in general, return.
  • the starch be fully destructured such that no lumps impacting the fiber spinning process are present.
  • the destructuring agent used to destructure the starch may remain with the starch during further processing, or may be transient, in that it is removed such that it does not remain in the fiber spun with the starch.
  • Starch can be destructured in a variety of different ways.
  • the starch can be destructurized with a solvent.
  • starch can be destructurized by subjecting a mixture of the starch and solvent to heat, which can be under pressurized conditions and shear, to gelatinize the starch, leading to destructurization.
  • Solvents can also act as plasticizers and may be desirably retained in the composition to perform as a plasticizer during later processing.
  • plasticizing agents that can act as solvents to destructure starch are described herein. These include the low molecular weight or monomeric plasticizers, such as but not limited to hydroxyl-containing plasticizers, including but not limited to the polyols, e.g. polyols such as mannitol, sorbitol, and glycerin. Water also can act as a solvent and plasticizer for starch.
  • plasticizer For starch to flow and be melt spinnable like a conventional thermoplastic polymer, it should have plasticizer present. If the destructuring agent is removed, it is the nature of the starch to in general remain destructured, however a plasticizer should be added to or otherwise included in the starch component to impart thermoplastic properties to the starch component in order to facilitate fiber spinning. Thus, the plasticizer present during spinning may be the same one used to destructure the starch. Alternately, especially when the destructuring agent is transient as described above (for example water), a separate or additional plasticizer may be added to the starch. Such additional plasticizer can be added prior to, during, or after the starch is destructured, as long as it remains in the starch for the fiber spinning step.
  • Suitable naturally occurring starches can include, but are not limited to, corn starch (including, for example, waxy maize starch), potato starch, sweet potato starch, wheat starch, sago palm starch, tapioca starch, rice starch, soybean starch, arrow root starch, bracken starch, lotus starch, cassava starch, high amylose corn starch, and commercial amylose powder. Blends of starch may also be used. Though all starches are useful herein, the present invention is most commonly practiced with natural starches derived from agricultural sources, which offer the advantages of being abundant in supply, easily replenishable and inexpensive in price.
  • Naturally occurring starches particularly corn starch (including, for example, waxy maize starch), and wheat starch, are starch polymers of choice due to their economy and availability. Modified starch may also be used. Modified starch is defined as non-substituted, or substituted, starch that has had its native molecular weight characteristics changed (i.e. the molecular weight is changed but no other changes are necessarily made to the starch). Molecular weight can be modified, preferably reduced, by any technique numerous of which are well known in the art.
  • thermomechanical method and the oxidation method offer an additional advantage when carried out in situ.
  • the exact chemical nature of the starch and molecular weight reduction method is not critical as long as the average molecular weight is provided at the desired level or range. Such techniques can also reduce molecular weight distribution.
  • Natural, unmodified starch generally has a very high average molecular weight and a broad molecular weight distribution (e.g. natural corn starch has an average molecular weight of up to about 60,000,000 grams/mole (g/mol)). It is desirable to reduce the molecular weight of the starch for use in the present invention. Molecular weight reduction can be obtained by any technique known in the art, including those discussed above. Ranges of molecular weight for destructured starch or starch blends added to the melt can be from about 3,000 g/mol to about 8,000,000 g/mol, preferably from about 10,000 g/mol to about 5,000,000 g/mol, and more preferably from about 20,000 g/mol to about 3,000,000 g/mol.
  • substituted starch can be used.
  • Chemical modifications of starch to provide substituted starch include, but are not limited to, etherification and esterification.
  • etherification and esterification For example, methyl, ethyl, or propyl (or larger aliphatic groups) can be substituted onto the starch using conventional etherification and esterification techniques as well known in the art.
  • Such substitution can be done when the starch is in natural, granular form or after it has been destructured. It will be appreciated that substitution can reduce the rate of biodegradability of the starch, but can also reduce the time, temperature, shear, and/or pressure conditions for destructurization.
  • the degree of substitution of the chemically substituted starch is typically, but not necessarily, from about 0.01 to about 3.0, and can also be from about 0.01 to about 0.06.
  • the thermoplastic starch comprises from about 51% to about 100%, preferably from about 60% to about 95%, more preferably from about 70% to about 90% by weight of the thermoplastic starch component.
  • the ratio of the starch component to the thermoplastic polymer will determine the percent of thermoplastic starch in the bicomponent fiber component.
  • the weight of starch in the composition includes starch and its naturally occurring bound water content.
  • bound water means the water found naturally occurring in starch and before mixing of starch with other components to make the composition of the present invention.
  • free water means the water that is added in making the composition of the present invention. A person of ordinary skill in the art would recognize that once the components are mixed in a composition, water can no longer be distinguished by its origin. Natural starch typically has a bound water content of about 5% to about 16% by weight of starch.
  • One or more plasticizers can be used in the present invention to destructurize the starch and enable the starch to flow, i.e. create a thermoplastic starch.
  • a plasticizer may be used as a destructuring agent for he starch. That plasticizer may remain in the destructured starch component to function as a plasticizer for the thermoplastic starch, or may be removed and substituted with a different plasticizer in the thermoplastic starch component.
  • the plasticizers may also improve the flexibility of the final products, which is believed to be due to the lowering of the glass transition temperature of the composition.
  • thermoplastic polymer component may be present to lower the polymer's melting temperature, modify flexibility of the final product, or improve overall compatibility with the thermoplastic starch blend. Furthermore, thermoplastic polymers with higher melting temperatures may be used if plasticizers or diluents are present which suppress the melting temperature of the polymer.
  • the plasticizers should be substantially compatible with the polymeric components of the present invention with which they are intermixed.
  • substantially compatible means when heated to a temperature above the softening and/or the melting temperature of the composition, the plasticizer is capable of forming a homogeneous mixture with polymer present in the component in which it is intermixed.
  • the plasticizers herein can include monomeric compounds and polymers.
  • the polymeric plasticizers will typically have a molecular weight of about 100,000 g/mol or less.
  • Polymeric plasticizers can include block copolymers and random copolymers, including terpolymers thereof.
  • the plasticizer has a low molecular weight plasticizer, for example a molecular weight of about 20,000 g/mol or less, or about 5,000 g/mol or less, or about 1,000 g/mol or less.
  • the plasticizers may be used alone or more than one plasticizer may be used in any particular component of the present invention.
  • the plasticizer can be, for example, an organic compound having at least one hydroxyl group, including polyols having two or more hydroxyls.
  • useful hydroxyl plasticizers include sugars such as glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose erythrose, and pentaerythritol; sugar alcohols such as erythritol, xylitol, malitol, mannitol and sorbitol; polyols such as glycerol (glycerin), ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, hexane triol, and the like, and polymers thereof; and mixtures thereof.
  • Suitable plasticizers especially include glycerine, mannitol, and sorbitol.
  • hydroxyl polymeric plasticizers such as poloxomers (polyoxyethylene /polyoxypropylene block copolymers) and poloxamines (polyoxyethylene/polyoxypropylene block copolymers of ethylene diamine). These copolymers are available as Pluronic® from BASF Corp., Parsippany, NJ. Suitable poloxamers and poloxamines are available as Synperonic® from ICI Chemicals, Wilmington, DE, or as Tetronic® from BASF Corp., Parsippany, NJ. Also suitable for use are hydroxy-containing polymers such as polyvinyl alcohol, ethylene vinyl alcohol, and copolymers and blends thereof.
  • hydrogen bond forming organic compounds including those which do not have hydroxyl group, including urea and urea derivatives; anhydrides of sugar alcohols such as sorbitan; animal proteins such as gelatin; vegetable proteins such as sunflower protein, soybean proteins, cotton seed proteins; and mixtures thereof.
  • plasticizers are phthalate esters, dimethyl and diethylsuccinate and related esters, glycerol triacetate, glycerol mono and diacetates, glycerol mono, di, and tripropionates, butanoates, stearates, lactic acid esters, citric acid esters, adipic acid esters, stearic acid esters, oleic acid esters, and other father acid esters which are biodegradable.
  • Aliphatic acids such as ethylene acrylic acid, ethylene maleic acid, butadiene acrylic acid, butadiene maleic acid, propylene acrylic acid, propylene maleic acid, and other hydrocarbon based acids.
  • the amount of plasticizer is dependent upon the molecular weight and amount of starch and the affinity of the plasticizer for the starch or thermoplastic polymer. Any amount that effectively plasticizes the starch can be used.
  • the plasticizer should sufficiently plasticize the starch component so that it can be processed effectively to form fibers.
  • the amount of plasticizer increases with increasing molecular weight of starch.
  • the plasticizer can be present in an amount of from about 2% to about 70%, and can also be from about 5% to about 55%, or from about 10% to about 50% of the component into which it is intermixed.
  • Polymeric incorporated into the starch component that function as plasticizers for the starch shall be counted as part of the plasticizer constituent of that component of the present invention.
  • Plasticizer is optional for the thermoplastic polymer components in the present invention at any effective levels, including the ranges above, and amounts below 2% are also included.
  • thermoplastic starch and thermoplastic polymer composition may be incorporated into the thermoplastic starch and thermoplastic polymer composition.
  • These optional ingredients may be present in quantities of about 49% or less, or from about 0.1% to about 30%, or from about 0.1% to about 10% by weight of the component.
  • the optional materials may be used to modify the processability and/or to modify physical properties such as elasticity, tensile strength and modulus of the final product.
  • Other benefits include, but are not limited to, stability including oxidative stability, brightness, color, flexibility, resiliency, workability, processing aids, viscosity modifiers, and odor control.
  • a preferred processing aid is magnesium stearate.
  • Another optional material that may be desired, particularly in the starch component is ethylene acrylic acid, commercially available as Primacore by Dow Chemical Company. Examples of optional ingredients are found in US application serial number 09/853,131 .
  • multicomponent is defmed as a fiber having more than one separate part in spatial relationship to one another at the exit from the extrusion equipment.
  • Component as used herein, is defined as a separate part of the fiber that has a spatial relationship to another part of the fiber.
  • the fibers of the present invention are, at least, bicomponent fibers.
  • the term multicomponent includes bicomponent, which is defined as a fiber having two separate parts in a spatial relationship to one another.
  • the different components of multicomponent fibers are arranged in substantially distinct regions across the cross-section of the fiber and extend continuously along the length of the fiber.
  • Multiconstituent components are defined as meaning the chemical species of matter or the material.
  • Multiconstituent fiber is defined to mean a fiber, or component thereof, containing more than one chemical species or material.
  • the multicomponent fibers of the present invention may be in many different configurations.
  • the multicomponent fibers of the present invention are splittable fibers.
  • Rheological, thermal, and solidification differential behavior can potentially cause splitting.
  • Splitting may also occur by a mechanical means such as ring-rolling, stress or strain, use of an abrasive, or differential stretching, and/or by fluid induced distortion, such as hydrodynamic or aerodynamic.
  • Spunbond structures, staple fibers, hollow fibers, shaped fibers, such as multi-lobal fibers and multicomponent fibers can all be produced by using the compositions and methods of the present invention.
  • the multicomponent fibers may be in a side-by-side, hollow segmented pie, segmented pie (i.e., solid segmented pie), ribbon, islands-in-the-sea configuration, tipped multilobal, or any combination thereof.
  • the fibers of the present invention may have different geometries that include round, elliptical, star shaped, rectangular, triangular, and other various eccentricities.
  • Various configuration of the splittable multicomponent fiber of the present invention are shown in the figures. Unless otherwise stated, Segment X in the figures described below may correspond to either the starch component or the thermoplastic polymer component, and Segment Y may correspond to either the starch component or the thermoplastic polymer component, however both X and Y shall not correspond to the same component.
  • thermoplastic starch component there may be any number of distinct segments flow through a single spinneret hole; typically, without limitation, the number of segments can range from 2 to about 256, or alternately from 4 to about 400, or from 8 to about 164, or from about 16 to about 64.
  • the ratio of the weight of the thermoplastic starch component to thermoplastic polymer component is generally from about 5:95 to about 95:5.
  • the weight percentage of thermoplastic starch component based on the total weight of the multicomponent fiber, can be lower than the weight percentage of thermoplastic polymer component, as this produces either more split fibers comprising the thermoplastic polymer or reduces the amount of the multicomponent fiber (starch component) that is removed.
  • the weight ratio of thermoplastic starch component to the thermoplastic polymer component for such multicomponent fibers can be, for example, from about 10:90 to about 65:35, and alternately can be from about 15:85 to about 50:50. In other embodiments, wherein it is also desired to retain and use starch fibers split from the multicomponent fiber, the weight ratio of starch component to thermoplastic polymer component can be adjusted in for the multicomponent fiber as desired to provided the desired proportion and size of split starch component and thermoplastic polymer component fibers.
  • split fiber is used to include fibers obtained upon separation, or splitting, of the multicomponent fiber into one or more fibers by separating one or more components of the multicomponent fiber. Splitting can be accomplished by any techniques in the art including, for example, chemical removal of a component, such as but not limiting to dissolving the component or by inclusion of an aid to facilitate separation of the components of the fiber, as well as mechanically removing a component, and combinations thereof. Mechanical splitting can be accomplished by application of force (including but not limited to drawing, hydroentangling, stretching etc.).
  • Multicomponent fibers having components that are not highly compatible with one another may split naturally upon spinning of the fibers or upon normal handling of the fibers once formed.
  • a component can be dissolved away by numerous techniques known in the art. These include, by way of example, exposure of the polymer to be dissolved with a plasticizer, or solvent or reactive medium (liquid or gas). Also, segments that are adjacent to one another that are made from components having significant differences in surface energy will tend to be more easily splittable, and may split naturally upon formation or upon exit from the spinneret capillary. Techniques for splitting multicomponent fibers are described in more detail below.
  • the first fiber diameter is the "parent" or splittable multicomponent.
  • the parent fiber splits When the parent fiber splits, it produces one or more "children" or split fibers that are smaller in diameter than the parent fiber.
  • the diameter of the splittable multicomponent fiber can be about 400 microns or less, and can also be about 200 microns or less, or about 100 microns or less.
  • the diameter of the split fibers is always less than the diameter of the multicomponent fiber and generally is about 50 microns or less, and can also be about 40 microns or less, about 30 microns, or about 25 microns or less.
  • the diameter of the split fibers typically can be about 2 microns or greater, and embodiments hereof can be about 5 microns or greater. Fiber diameter is controlled by parameters well known in the art including but not limited to spinning speed, mass through-put, and blend composition.
  • the diameter is determined as equivalent diameter.
  • the parent fiber is defined as a fiber having a relatively low draw down ratio.
  • the total fiber draw down ratio is defmed as the ratio of the fiber at its maximum diameter (which is typically results immediately after exiting the capillary) to the final fiber diameter in its end use.
  • the total parent fiber draw down ratio via either staple, spunbond, or meltblown process can be about 50 or less, and in embodiments hereof can be about 30 or less, or about 20 or less, or about 15 or less.
  • the fibers produced in the present invention may be environmentally degradable depending upon the amount of starch that is present, the polymer used, and the specific configuration of the fiber. "Environmentally degradable” is defined as being biodegradable, disintegratable, dispersible, flushable, or compostable or a combination thereof. In the present invention, the fibers, nonwoven webs, and articles may be environmentally degradable.
  • the fibers described herein are typically used to make disposable nonwoven articles.
  • the articles are commonly flushable.
  • flushable refers to materials which are capable of dissolving, dispersing, disintegrating, and/or decomposing in a septic disposal system such as a toilet to provide clearance when flushed down the toilet without clogging the toilet or any other sewage drainage pipe.
  • the fibers and resulting articles may also be aqueous responsive.
  • aqueous responsive as used herein means that when placed in water or flushed, an observable and measurable change will result Typical observations include noting that the article swells, pulls apart, dissolves, or observing a general weakened structure
  • the multicomponent and split fibers of the present invention can have low brittleness and have high toughness, for example a toughness of about 2MPa or greater. Toughness is defined as the area under the stress-strain curve.
  • the split fibers of the present invention corresponding to the non-starch thermoplastic polymer containing component of the present invention have enhanced extensibility or elongation. Extensibility or elongation is measured by elongation to break. Extensibility or elongation is defined as being capable of elongating under an applied force, but not necessarily recovering. Elongation to break is measured as the distance the fiber can be stretched until failure.
  • the elongation to break of the fibers hereof are tested according to ASTM standard D3822 except a strain rate of 200 %/min is used. Testing is performed on an MATS Synergie 400 tensile testing machine with a 10 N load cell and pneumatic grips. Tests are conducted at a rate of 5.08cm/minute (2 inches/minute) on samples with a 2.54cm(1 inch) gauge length. Samples are pulled to break. Peak stress and % elongation at break are recorded and averaged for 10 specimens.
  • the "Elongation to Break" of a fiber is defined as the elongation to break measured according to the above described test and conditions.
  • the Elongation to Break Ratio of the split fibers of the present invention is defined as the Elongation to Break of the split fiber of the present invention divided by the Elongation to Break of a monocomponent fiber made from the same composition as the split fiber under essentially identical fiber spinning conditions and parameters except as provided below.
  • the mass throughput of the monocomponent fiber should be the same as the total mass throughput as the corresponding component of the multicomponent fiber. For example, if the total mass through-put for thermoplastic polymer component is "x", and the multicomponent contains three (3) split fiber-forming segments, the mass through-put for forming the monocomponent fiber should still be "x".
  • the diameter of the monocomponent fiber should be the same as the equivalent diameter of the split fiber.
  • spinning speed for the monocomponent fiber may be higher than spinning speed for the multicomponent fiber, particularly when the multicomponent fiber contains two or split fiber-forming segments.
  • the dimensions of the spinneret capillary used to prepare the moncomponent fiber should be the same as that used to prepare the multicomponent fiber.
  • the Elongation to Break Ratio for the split fibers corresponding to the thermoplastic polymer component of the multicomponent fibers of the present invention should be greater than 1.0, and can be about 1.5 or greater, or about 2.0 or greater.
  • a benefit of the present invention is that small diameter fibers can be produced that are highly extensible at relatively high mass throughput.
  • Nonwoven products produced from the fibers of the present invention can exhibit desirable mechanical properties, particularly, strength, flexibility, softness, and absorbency. Measures of strength include dry and/or wet tensile strength. Flexibility is related to stiffness and can attribute to softness. Softness is generally described as a physiologically perceived attribute which is related to both flexibility and texture. Generally, smaller fiber diameters will result in softer nonwoven products. Absorbency relates to the products' ability to take up fluids as well as the capacity to retain them.
  • the split fibers corresponding to the thermoplastic polymer component of the multicomponent fibers of the present invention will be provided by the present inventions.
  • the present inventions may also provide split fibers of the thermoplastic starch component. These may be used in combination with or separate from the thermoplastic polymer component split fibers.
  • the first step in producing a multicomponent fiber can be a compounding or mixing step.
  • the raw materials are heated, typically under shear.
  • the shearing in the presence of heat can result in a homogeneous melt with proper selection of the composition.
  • the melt is then placed in an extruder where fibers are formed.
  • a collection of fibers is combined together using heat, pressure, chemical binder, mechanical entanglement, and combinations thereof resulting in the formation of a nonwoven web.
  • the nonwoven is then assembled into an article.
  • the objective of the compounding step is to produce a homogeneous melt composition for each component of the fibers.
  • the melt composition is homogeneous, meaning that a uniform distribution of ingredients in the melt is present.
  • the resultant melt composition(s) should be essentially free of water to spin fibers. Essentially free is defined as not creating substantial problems, such as causing bubbles to form which may ultimately break the fiber while spinning.
  • the free water content of the melt composition can be about 1% or less, about 0.5% or less, or about 0.15% of less.
  • the total water content includes the bound and free water.
  • the total water content (including bound water and free water) is about 1% or less.
  • the starch or polymers may need to be dried before processed and/or a vacuum is applied during processing to remove any free water.
  • the thermoplastic starch, or other components hereof can be dried at elevated temperatures, such as about 60°C, before spinning.
  • the drying temperature is determined by the chemical nature of a component's constituents. Therefore, different compositions can use different drying temperatures which can range from 20°C to 150°C and are, in general, below the melting temperature of the polymer. Drying of the components may, for example, be in series or as discrete steps combined with spinning. Such techniques for drying as are well known in the art can be used for the purposes of this invention.
  • any method known in the art or suitable for the purposes hereof can be used to combine the ingredients of the components of the present invention.
  • Such techniques will include heat, mixing, and pressure.
  • the particular order or mixing, temperatures, mixing speeds or time, and equipment can be varied, as will be understood by those skilled in the art, however temperature should be controlled such that the starch does not significantly degrade.
  • the resulting melt should be homogeneous.
  • a suitable method of mixing for a starch and plasticizer blend is as follows:
  • a suitable mixing device is a multiple mixing zone twin screw extruder with multiple injection points.
  • the multiple injection points can be used to add the destructurized starch and the polymer.
  • a twin screw batch mixer or a single screw extrusion system can also be used. As long as sufficient mixing and heating occurs, the particular equipment used is not critical.
  • An alternative method for compounding the materials comprises adding the plasticizer, starch, and polymer to an extrusion system where they are mixed in progressively increasing temperatures.
  • the first three zones may be heated to 90°, 120°, and 130° C, and the last three zones will be heated above the melting point of the polymer. This procedure results in minimal thermal degradation of the starch and for the starch to be fully destructured before intimate mixing with the thermoplastic materials.
  • thermoplastic starch An example of compounding destructured thermoplastic starch would be to use a Werner &Pfleiderer (30 mm diameter 40:1 length to diameter ratio) co-rotating twin-screw extruder set at 250RPM with the first two heat zones set at 50°C and the remaining five heating zones set 150°C. A vacuum is attached between the penultimate and last heat section pulling a vacuum of 1.013 MPa(10 atm).
  • Starch powder and plasticizer e.g., sorbitol
  • Processing aids can be added along with the starch or plasticizer. For example, magnesium separate can be added, for example, at a level of 0 -1 %, by weight, of the thermoplastic starch component.
  • the fibers of the present invention can be made by melt spinning. Melt spinning is differentiated from other spinning, such as wet or dry spinning from solution, where in such alternate methods a solvent is present in the melt and is eliminated by volatilizing or diffusing it out of the extrudate.
  • Spinning temperatures for the melts can range from about 105°C to about 300°C, and in some embodiments can be from about 130°C to about 250°C or from about 150°C to about 210°C.
  • the processing temperature is determined by the chemical nature, molecular weights and concentration of each component.
  • Fiber spinning speeds of about 10 meters/minute or greater can be used. In some embodiments hereof, the fiber spinning speed is from about 100 to about 7,000 meters/minute, or from about 300 to about 3,000 meters/minute, or from about 500 to about 2,000 meters/minute.
  • the fiber may be made by fiber spinning processes characterized by a high draw down ratio.
  • the draw down ratio is defined as the ratio of the fiber at its maximum diameter (which is typically occurs immediately after exiting the capillary of the spinneret in a conventional spinning process) to the final diameter of the formed fiber.
  • the fiber draw down ratio via either staple, spunbond, or meltblown process will typically be 1.5 or greater, and can be about 5 or greater, about 10 or greater, or about 12 or greater.
  • Continuous fibers can be produced through, for example, spunbond methods or meltblowing processes.
  • non-continuous (staple fibers) fibers can be produced according to conventional staple fiber processes as are well known in the art.
  • the various methods of fiber manufacturing can also be combined to produce a combination technique, as will be understood by those skilled in the art.
  • Hollow fibers for example, can be produced as described in US Patent 6,368,990 . Such methods as mentioned above for fiber spinning are well known and understood in the art.
  • the fibers spun can be collected subsequent for formation using conventional godet winding systems or through air drag attenuation devices. If the godet system is used, the fibers can be further oriented through post extrusion drawing at temperatures from about 50° to about 200° C. The drawn fibers may then be crimped and/or cut to form non-continuous fibers (staple fibers) used in a carding, airlaid, or fluidlaid process.
  • residual water levels typically be 1%, by weight of the fiber, or less, alternately 0.5% or less, or 0.15% or less.
  • Suitable multicomponent melt spinning equipment is commercially available from, for example, Hills Inc. located in Melbourne, Florida USA and is described in US Patent 5,162,074 (Hills, Inc.).
  • the spinneret capillary dimensions can vary depending upon desired fiber size and design, spinning conditions, and polymer properties. Suitable capillary dimensions include, but are not limited to, length-to-diameter ratio of 4 with a diameter of 0.350mm.
  • spinning of the fibers and compounding of the components can optionally be done in-line, with compounding, drying and spinning being a continuous process.
  • the residence time of each component in the spinline can have special significance when a high melting temperatures thermoplastic polymer is chosen to be spun with destructured starch.
  • Spinning equipment can be designed to minimize the exposure of the destructured starch component to high process temperature by minimizing the time and volume of destructured exposed in the spinneret.
  • the polymer supply lines to the spinneret can be sealed and separated until introduction into the bicomponent pack.
  • the at least two components can be introduced and processed in their separate extruders at different temperatures until introduced into the spinneret.
  • a suitable process for spinning bicomponent, segmented pie fiber with at least one destructured starch segment and at least one polypropylene segment is as follows.
  • the destructured starch component extruder profile may be 80°C, 150°C and 150°C in the first three zones of a three heater zone extruder with a starch composition similar to Example 5.
  • the transfer lines and melt pump heater temperatures may be 150°C for the starch component.
  • the polypropylene component extruder temperature profile may be 180°C, 230°C and 230°C in the first three zones of a three heater zone extruder.
  • the transfer lines and melt pump can be heated to 230°C. In this case the spinneret temperature can range from 180°C to 230°C.
  • the multicomponent fiber splits into the split fibers upon formation or upon exit from the capillary of the spinneret, without the application of fiber splitting techniques other than the conditions inherently present in the fiber spinning process.
  • split fibers can already be present.
  • Such fiber splitting results from differences in rheology, compatability or solidification kinetics of the different components of the adjacent segments of the multicomponent fiber. Components with substantially different surface energy will tend to split from one another with application of low levels of force, such as present during the normal fiber spinning process.
  • Polypropylene for example, has low surface energy compared unsubstituted starch, and can form multicomponent fibers with unsubstituted starch wherein the split fibers naturally form upon exit from the spinneret capillary. Differences in polymer component elongation or stiffness may also enhance the splitting off the multicomponent fibers upon exit from the spinneret. For example, reducing starch molecular weight tends to increase brittleness of the starch, thereby increasing the difference in elongation properties between the starch and the thermoplastic polymer and increasing the ability of he multicomponent fiber to split upon exit from the spinneret.
  • one or more components of the multicomponent fiber is separated from the multicomponent fiber by application of a post fiber formation step, which can be application of mechanical energy, thereby also providing least one component in the form of split fibers.
  • the fibers can be split via mechanical deformation without removal of the starch component in addition to the methods described above for starch component removal in a fiber after it has been split.
  • the mechanical deformation may come from, for example, elongation, bending, shearing on the surfaces of the fiber (abrasion for instance) or any other suitable method.
  • the starch component fibers retained, if desired, or removed via solvent extraction, mechanical destruction, e.g., via needle punching, high pressure fluid exposure or any other suitable means.
  • the starch component constituents are formulated such that the starch component is very brittle, which makes mechanical removal of the starch component easier.
  • one or more components can be separated from the multicomponent fiber, leaving at least one component in the form of split fibers.
  • Starch can be dissolved in a solvent, such as for example water or other polar solvent (e.g., C1 - C3 alcohol), such that fibers (nonwoven and woven are herby incorporated hereafter for any removal operation) can be passed through a solvent bath or sprayed with a high pressure fluid solvent to remove the starch component.
  • combinations of the above embodiments may be present in or applied to the multicomponent fibers.
  • Other methods as may be known to those in the art may also be used.
  • These fibers can be further treated if desired with application of finishes or impregnated with other materials.
  • the split fibers may be converted to fibrous webs and nonwovens by any suitable method known in the art.
  • Nonwoven substrates may be formed, for example, utilizing a variety of different bonding methods.
  • Continuous fibers can be formed into a web using industry standard spunbond or meltblown type technologies while staple fibers can be formed into a web using industry standard carding, airlaid, or wetlaid technologies.
  • Typical bonding methods include: calendar (pressure and heat), thru-air heat, mechanical entanglement, hydrodynamic entanglement, needle punching, and chemical bonding and/or resin bonding.
  • Thermally bondable fibers are required for the pressurized heat and thru-air heat bonding methods.
  • the nonwoven webs and substrates hereof can be made using the thermoplastic polymer component split fibers, the starch component split fibers, or a combination thereof. Additionally, the split fibers of the present invention can be combined with other fibers known in the art including, but not limited to, synthetic fibers and natural fibers. The split fibers hereof can be used for any purposes known in the art for fibers comprising the constituents included in the split fibers obtained according to the present invention.
  • the split fibers of the present invention may also be bonded or combined with other synthetic or natural fibers to make nonwoven articles.
  • the synthetic or natural fibers may be blended together in the forming process or used in discrete layers.
  • Suitable synthetic fibers include fibers made from polypropylene, polyethylene, polyester, polyacrylates, and copolymers thereof and mixtures thereof.
  • Natural fibers include cellulosic fibers and derivatives thereof. Suitable cellulosic fibers include those derived from any tree or vegetation, including hardwood fibers, softwood fibers, hemp, and cotton. Also included are fibers made from processed natural cellulosic resources such as rayon.
  • the split fibers of the present invention may be used to make nonwovens, including but not limited to those that contain 15%, by weight, or greater, of a plurality of fibers that are continuous or non-continuous and physically and/or chemically attached to one another.
  • the nonwoven may be in the form of a protective layer, a barrier layer, a liquid and/or air impervious layer, or an absorbent core or web.
  • the nonwoven may be combined with additional nonwovens or films to produce a layered product used either by itself or as a component in a complex combination of other materials, such as a baby diaper or feminine care pad.
  • a particular embodiment contemplated herein includes disposable, nonwoven articles. The products may find use in one of many different uses.
  • Suitable articles of the present invention include disposable nonwovens for hygiene, cleansing, surface treatment, and medical applications.
  • Hygiene applications include such items as wipes; diapers, particularly the top sheet or back sheet or as a protective layer covering elastics or other components of the diaper; and feminine pads or products, particularly the top sheet or backsheet.
  • the starches for use in the examples below are StarDri 1, StarDri 100, Ethylex 2015, or Ethylex 2035, all from Staley Chemical Co. The latter Staley materials are substituted starches.
  • the polypropylenes (PP) are Basell Profax PH-835, Basell PDC 1298, or Exxon/Mobil Achieve 3854.
  • the polyethylenes (PE) are Dow Chemicals Aspun 6811A, Dow Chemical Aspun 6830A, or Dow Chemical Aspun 6842A.
  • the glycerine is from Dow Chemical Company, Kosher Grade BU OPTIM* Glycerine 99.7%.
  • the sorbitol is from Archer-Daniels-Midland Co. (ADM), Crystalline NF/FCC 177440-2S.
  • the polyethylene acrylic acid is PRIMACOR 5980I from Dow Chemical Co.
  • Other polymers having similar chemical compositions that differ in molecular weight, molecular weight distribution, and/or co-monomer or defect level can also be used.
  • the process condition in Comparative Example 1 and Examples 1-12 use a mass through put of 0.8 ghm. The typical range of mass throughput is from about 0.1 to about 8 ghm.
  • Comparative Example 1 Solid polypropylene (PP) monocomponent fibers composed of Basell Profax PH-835 are prepared at a through-put of 0.8 grams per hole per minute (ghm) had an elongation-to-break of 181% when the fiber diameter was 18 ⁇ m when melt spun into fibers via a continuous filament process at a melt extrusion temperature of 190°C.
  • PP polypropylene
  • Example 1 Hollow Segmented Pie The bicomponent pack set-up contains 16-segmented pie configuration.
  • Component A is Basell Profax PH-835.
  • Component B is the TPS component and is compounded using 60 parts StarDri 1, 40 parts sorbitol, 15 parts Primacore 5980-I, and 1 part Magnesium Stearate. Each ingredient is added concurrently to an extrusion system where they are melted and mixed in progressively increasing temperatures. This procedure minimizes the thermal degradation to the starch that occurs when the starch is heated above 180°C for significant periods of time.
  • the spinneret processing temperature is 190°C.
  • the ratio of Component A to B is 4:1.
  • the mass throughput is 0.8 ghm.
  • the fiber velocity via mechanical winding is 500 meters/minute (m/min).
  • Component A readily splits from Component B under mechanical deformation.
  • the value is 643% at an average Component A filament diameter of 16 ⁇ m.
  • the TPS component, Component B can be readily removed via submersion in water to yield 8 PP fibers with similar elongation as the multicomponent fiber.
  • Example 2 Hollow Segmented Pie The bicomponent pack set-up contains 16-segmented pie configuration.
  • Component A is Basell Profax PH-835.
  • Component B is the TPS component and is compounded using 60 parts StarDri 1, 40 parts sorbitol, and 1 part Magnesium Stearate. Each ingredient is added concurrently to an extrusion system where they are melted and mixed in progressively increasing temperatures. This procedure minimizes the thermal degradation to the starch that occurs when the starch is heated above 180°C for significant periods of time.
  • the spinneret processing temperature is 190°C.
  • the ratio of Component A to B is 2.33:1.
  • the mass throughput is 0.8 ghm.
  • the fiber velocity via mechanical winding is 500 m/min.
  • Component A readily splits from Component B under mechanical deformation.
  • the value is 678% at an average Component A filament diameter of 16 ⁇ m.
  • the elongation-to-break is significantly higher in Example 1 at a smaller overall diameter.
  • the TPS component, Component B can be readily removed via submersion in water to yield 8 PP fibers with similar elongation as the multicomponent fiber.
  • Example 3 Hollow Segmented Pie The bicomponent pack set-up contains 16-segmented pie configuration.
  • Component A is Basell Profax PH-835.
  • Component B is the TPS component and is compounded using 60 parts StarDri 1, 40 parts sorbitol, and 1 part Magnesium Stearate. Each ingredient is added concurrently to an extrusion system where they are melted and mixed in progressively increasing temperatures. This procedure minimizes the thermal degradation to the starch that occurs when the starch is heated above 180°C for significant periods of time.
  • the spinneret processing temperature is 190°C.
  • the ratio of Component A to B is 9:1.
  • the mass throughput is 0.7 ghm.
  • the fiber velocity via mechanical winding is 500m/min.
  • Component A readily splits from Component B under mechanical deformation.
  • the value is 620% at an average Component A filament diameter of 16 ⁇ m.
  • the elongation-to-break is significantly higher in Example 1 at a smaller overall diameter.
  • the TPS component, Component B can be readily removed via submersion in water to yield 8 PP fibers with similar elongation as the multicomponent fiber.
  • Example 4 Hollow Segmented Pie The bicomponent pack set-up contains 16-segmented pie configuration.
  • Component A is Basell Profax PH-835.
  • Component B is the TPS component and is compounded using 60 parts StarDri 1, 40 parts sorbitol, and 1 part Magnesium Stearate. Each ingredient is added concurrently to an extrusion system where they are melted and mixed in progressively increasing temperatures. This procedure minimizes the thermal degradation to the starch that occurs when the starch is heated above 180°C for significant periods of time.
  • the spinneret processing temperature is 190°C.
  • the ratio of Component A to B is 1:1.
  • the mass throughput is 1.2ghm.
  • the fiber velocity via mechanical winding is 500 m/min.
  • Component A readily splits from Component B under mechanical deformation.
  • the value is 790% at an average Component A filament diameter of 16 ⁇ m.
  • the elongation-to-break is significantly higher in Example 1 at a smaller overall diameter.
  • the TPS component, Component B can be readily removed via submersion in water to yield 8 PP fibers with elongation as the multicomponent fiber.
  • Example 5 Hollow Segmented Pie The bicomponent pack set-up contains 16-segmented pie configuration.
  • Component A is Basell Profax PH-835.
  • Component B is the TPS component and is compounded using 60 parts StarDri 1, 40 parts sorbital.12 parts Dow Primacore 5980I, and 1 part Magnesium Stearate. Each ingredient is added concurrently to an extrusion system where they are melted and mixed in progressively increasing temperatures. This procedure minimizes the thermal degradation to the starch that occurs when the starch is heated above 180°C for significant periods of time.
  • the spinneret processing temperature is 190°C.
  • the ratio of Component A to B is 4:1.
  • the mass throughput is 0.8ghm.
  • the fiber velocity via mechanical winding is 500m/min.
  • Component A readily splits from Component B under mechanical deformation.
  • the value is 640% at an average Component A filament diameter of 16 ⁇ m.
  • the TPS component, Component B can be readily removed via submersion in water to yield 8 PP fibers with similar elongation as the multicomponent fiber.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Multicomponent Fibers (AREA)
  • Nonwoven Fabrics (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (19)

  1. Fibre à multicomposants pouvant être fractionnée obtenue par filage par fusion, ladite fibre comprenant:
    A) au moins un segment non entouré d'un premier composant comprenant un polymère thermoplastique qui n'est pas de l'amidon;
    B) au moins un segment non entouré d'un deuxième composant comprenant de l'amidon thermoplastique;
    dans laquelle:
    (i) ledit deuxième composant est susceptible d'être fractionné ou retiré dudit premier composant pour fournir au moins une fibre fendue constituée sensiblement dudit premier composant; et
    (ii) dans laquelle la fibre fractionnée dudit premier composant a un rapport d'allongement à la rupture supérieur à 1,0, ledit rapport étant défini comme l'allongement à la rupture de la fibre fractionnée dudit premier composant divisé par l'allongement à la rupture d'une fibre à monocomposant du même diamètre équivalent fabriquée à partir de la même composition que la fibre fractionnée pratiquement dans des conditions et paramètres de filage de fibre identiques si ce n'est que la vitesse de filage pour la fibre à monocomposant peut être plus élevée que la vitesse de filage pour la fibre à multicomposants de sorte que le rendement massique de la fibre à monocomposant est le même que le rendement massique total du premier composant de la fibre à multicomposants, dans laquelle l'allongement à la rupture est mesuré selon la norme ASTM D3822 en utilisant une vitesse de déformation de 200% par minute appliquée à des échantillons de fibre ayant une longueur de référence de 2,54cm (1 pouce).
  2. Fibre à multicomposants pouvant être fractionnée selon la revendication 1, où la fibre à multicomposants pouvant être fractionnée a une configuration choisie dans le groupe constitué de tarte en quartiers, tarte en quartiers creuse, côté-à-côté, ruban segmenté, multilobal apical, et leurs combinaisons.
  3. Fibre à multicomposants selon la revendication 1 ou la revendication 2, où la fibre à multicomposants pouvant être fractionnée a un diamètre de 400micromètres ou moins, en variante 200micromètres ou moins.
  4. Fibre à multicomposants selon l'une quelconque des revendications 1 à 3, dans laquelle ledit premier composant comprend une pluralité de segments distincts, et chacun desdits segments a un diamètre de 50micromètres ou moins, en variante 25micromètres ou moins.
  5. Fibre à multicomposants pouvant être fractionnée selon l'une quelconque des revendications 1 à 4, dans laquelle le polymère thermoplastique du composant A est choisi dans le groupe constitué de polyoléfines, polyesters, polyamides et leurs copolymères et combinaisons.
  6. Fibre à multicomposants pouvant être fractionnée selon l'une quelconque des revendications 1 à 4, dans laquelle ledit amidon thermoplastique comprend de l'amidon déstructuré et un plastifiant.
  7. Fibre à multicomposants pouvant être fractionnée selon l'une quelconque des revendications 1 à 6, dans laquelle ledit premier composant comprend jusqu'à 49% d'amidon et ledit deuxième composant comprend jusqu'à 49% en poids, d'un polymère thermoplastique qui n'est pas de l'amidon.
  8. Fibre à multicomposants pouvant être fractionnée selon l'une quelconque des revendications 1 à 7, dans laquelle le rapport d'allongement à la rupture est de 2,0 ou plus grand.
  9. Fibres fractionnées dérivées du premier composant de la fibre à multicomposants pouvant être fractionnée selon l'une quelconque des revendications 1 à 8.
  10. Fibres fractionnées selon la revendication 9, où lesdites fibres fractionnées comprennent en outre des fibres fractionnées dérivées du deuxième composant de ladite fibre à multicomposants pouvant être fractionnée.
  11. Procédé de fabrication de fibres, comprenant les étapes consistant à:
    (a) fournir une fibre à multicomposants filée en fusion ayant (i) au moins un segment non entouré d'un premier composant comprenant un polymère thermoplastique qui n'est pas de l'amidon et (ii) au moins un segment non entouré d'un deuxième composant comprenant de l'amidon thermoplastique;
    (b) fractionner au moins ledit deuxième composant de ladite fibre à multicomposants pour fournir au moins une fibre fractionnée dérivée dudit premier composant;
    dans laquelle la fibre fractionnée dudit premier composant a un rapport d'allongement à la rupture supérieur à 1,0, ledit rapport étant défini comme l'allongement à la rupture de la fibre fractionnée dudit premier composant divisé par l'allongement à la rupture d'une fibre à monocomposant du même diamètre équivalent fabriquée à partir de la même composition que la fibre fractionnée pratiquement dans des conditions et paramètres de filage de fibre identiques si ce n'est que la vitesse de filage pour la fibre à monocomposant peut être plus élevée que la vitesse de filage pour la fibre à multicomposants de sorte que le rendement massique de la fibre à monocomposant est le même que le rendement massique total du premier composant de la fibre à multicomposants, dans laquelle l'allongement à la rupture est mesuré selon la norme ASTM D3822 en utilisant une vitesse de déformation de 200% par minute appliquée à des échantillons de fibre ayant une longueur de référence de 2,54cm (1pouce).
  12. Procédé selon la revendication 11, dans lequel ledit rapport d'allongement à la rupture est de 1,5 ou plus grand.
  13. Procédé selon la revendication 11 ou la revendication 12, dans lequel le premier composant comprend une pluralité de segments distincts, et ledit procédé fournit une pluralité de fibres fractionnées dérivées dudit premier composant.
  14. Procédé selon la revendication 13, dans lequel ladite étape de fractionnement (b) fournit en outre des fibres fractionnées dérivées dudit deuxième composant.
  15. Procédé selon l'une quelconque des revendications 11 à 14, dans lequel ladite fibre à multicomposants est formée à partir d'une buse à filer, et ladite fibre à multicomposants se fractionne à la sortie de la buse à filer.
  16. Procédé selon l'une quelconque des revendications 11 à 15, dans lequel ladite étape de fractionnement comprend l'application d'énergie mécanique.
  17. Procédé selon l'une quelconque des revendications 11 à 16, dans lequel ladite étape de fractionnement comprend une dissolution dudit deuxième composant.
  18. Nappe non tissée comprenant les fibres fractionnées selon la revendication 9.
  19. Article jetable comprenant la nappe non tissée selon la revendication 18.
EP02808136A 2002-11-14 2002-11-14 Fibres clivables a composants multiples a allongement eleve comportant de l'amidon et des polymeres Expired - Lifetime EP1560957B1 (fr)

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US20130089747A1 (en) 2011-05-20 2013-04-11 William Maxwell Allen, Jr. Fibers of Polymer-Wax Compositions
JP2021008408A (ja) 2017-10-05 2021-01-28 味の素株式会社 光学活性ピロリドンカルボン酸またはそのアルカリ金属塩の製造方法

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WO1996019599A1 (fr) * 1994-12-22 1996-06-27 Biotec Biologische Naturverpackungen Gmbh Produits textiles techniques et non techniques et materiaux d'emballage

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DE4136694C2 (de) * 1991-11-07 1996-10-10 Inventa Ag Stärkefaser oder Stärke-modifizierte Faser, Verfahren zu ihrer Herstellung sowie ihre Verwendung
US5814404A (en) * 1994-06-03 1998-09-29 Minnesota Mining And Manufacturing Company Degradable multilayer melt blown microfibers
WO1996025538A1 (fr) * 1995-02-14 1996-08-22 Chisso Corporation Fibre biodegradable et textile non tisse

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Publication number Priority date Publication date Assignee Title
WO1996019599A1 (fr) * 1994-12-22 1996-06-27 Biotec Biologische Naturverpackungen Gmbh Produits textiles techniques et non techniques et materiaux d'emballage

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WO2004044287A1 (fr) 2004-05-27
ES2355896T3 (es) 2011-04-01
DE60238282D1 (de) 2010-12-23
CA2501988A1 (fr) 2004-05-27
AU2002368338A1 (en) 2004-06-03
JP4119431B2 (ja) 2008-07-16
ATE487816T1 (de) 2010-11-15
EP1560957A1 (fr) 2005-08-10

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