US20030186611A1 - Polymer compositions and moulded bodies made therefrom - Google Patents

Polymer compositions and moulded bodies made therefrom Download PDF

Info

Publication number
US20030186611A1
US20030186611A1 US10/204,108 US20410802A US2003186611A1 US 20030186611 A1 US20030186611 A1 US 20030186611A1 US 20410802 A US20410802 A US 20410802A US 2003186611 A1 US2003186611 A1 US 2003186611A1
Authority
US
United States
Prior art keywords
molded article
material
sea
polymer composition
cellulose
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/204,108
Inventor
Stefan Zikeli
Thomas Endl
Michael Martl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZiAG Plant Engineering GmbH
Original Assignee
ZiAG Plant Engineering GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to DE10007794.3 priority Critical
Priority to DE2000107794 priority patent/DE10007794A1/en
Application filed by ZiAG Plant Engineering GmbH filed Critical ZiAG Plant Engineering GmbH
Assigned to ZIMMER AG reassignment ZIMMER AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ENDL, THOMAS, ZIKELI, STEFAN, MARTL, MICHAEL GERT
Publication of US20030186611A1 publication Critical patent/US20030186611A1/en
Application status is Abandoned legal-status Critical

Links

Images

Classifications

    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44Yarns or threads characterised by the purpose for which they are designed
    • D02G3/448Yarns or threads for use in medical applications
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02Cellulose; Modified cellulose
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00Compositions of proteins; Compositions of derivatives thereof
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08Composition of the spinning solution or the bath
    • D01F2/10Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material or construction of the yarn or other warp or weft elements used
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/04Alginic acid; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/01Natural vegetable fibres
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/01Natural vegetable fibres
    • D10B2201/02Cotton
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20Cellulose-derived artificial fibres
    • D10B2201/22Cellulose-derived artificial fibres made from cellulose solutions
    • D10B2201/24Viscose
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20Cellulose-derived artificial fibres
    • D10B2201/28Cellulose esters or ethers, e.g. cellulose acetate
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/022Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polypropylene
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/10Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00Wearing apparel
    • D10B2501/06Details of garments
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2503/00Domestic or personal
    • D10B2503/06Bed linen
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00Industrial
    • D10B2505/08Upholstery, mattresses
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139Open-ended, self-supporting conduit, cylinder, or tube-type article
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2915Rod, strand, filament or fiber including textile, cloth or fabric
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2929Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3146Strand material is composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/637Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/696Including strand or fiber material which is stated to have specific attributes [e.g., heat or fire resistance, chemical or solvent resistance, high absorption for aqueous compositions, water solubility, heat shrinkability, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/699Including particulate material other than strand or fiber material

Abstract

The invention relates to a polymer composition comprising a biologically degradable polymer and a material from sea plants and/or shells of sea animals or at least two components selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions. The invention additionally relates to a molded article comprising said polymer composition. Said molded article may be used packaging material or fibrous material, in the form of fibrous material as mixing component for the production of yarns, and in the form of fibrous material for the production of nonwoven fabrics or woven fabrics.

Description

  • The invention relates to a polymer composition comprising a biologically degradable polymer, as well as to the use thereof of the production of a molded article, the molded article produced from said polymer composition, a method for the production thereof and the use thereof, and to an article of clothing comprising the molded article in form of fibers. [0001]
  • Polymer compositions with different additives for the production of molded articles are known. [0002]
  • U.S. Pat. No. 5,766,746 describes a nonwoven fabric made of cellulose fibers, which comprise a flame-resistant phosphoric component. [0003]
  • U.S. Pat. No. 5,565,007 describes modified rayon fibers, with a modifying agent for improving the dyeing properties of the fibers. [0004]
  • U.S. Pat. No. 4,055,702 discloses melt-spun, cold-drawn fibers from a synthetic organic polymer with additives. Said additives may be receptors, flame-resistant rendering agents, antistatic agents, stabilizers, mildew inhibitors or antioxidants. [0005]
  • “Lenzinger Berichte”, 76/97, page 126 moreover discloses a lyocell fiber spun from a cellulose solution in N-methylmorpholine-N-oxide (hereinafter called “NMMNO”), into which may be incorporated 0.5 to 5 weight-%, relative to the cellulose weight, of cross-linking agents for improving the wet abrasion value. It is additionally described to incorporate lyocell fibers, carboxymethylchitin, carboxymethylchitosan or polyethylene imine for improving the fungicidal properties, polyethylene imine for the adsorption of metal ions and dyes, hyaluronic acid for improving the bactericidal properties, xanthene, guar, carubin, bassorin or starch for improving hydrophilicity, water adsorption and water vapor permeability, or starch for the accelerated enzymatic hydrolysis. [0006]
  • WO 98/58015 describes a composition contaning fine particles of solid matter for the addition to a formable solution of cellulose in an aqueous tertiary amine oxide. The composition is made of solid particles, tertiary amine oxide, water and at least another substance. Said other substance may be a stabilizer or a dispersing agent. The solid particles may be pigments. [0007]
  • Furthermore, it is known that high concentrations of iron and transitional metals influence the stability of a spinning mass of cellulose, NMMNO and water. High iron concentrations decrease the disintegration temperature of the solution to such an extent that explosion-like disintegration reactions of the solution may occur. The disintegration and stabilization of cellulose solved in NMMNO is described in “Das Papier”, F. A. Buitenhuijs 40. year, volume 12, 1986, which also mentions the influence of iron—Fe(III) on said cellulose solutions. With an addition of 500 ppm of Fe(III) more than 40% of the NMMNO were transformed into the disintegration product N-methylmorpholine (“NMM”), whereby the addition of Cu[0008] +2 also reduces the stability of the solution. With the addition of copper to an NMMO cellulose solution free of copper the disintegration temperature (T onset ° C.) was reduced from 175° C. to 114° C. in the presence of 900 mg copper/kg of the mass. Moreover described is the positive effect of stabilizers such as propyl gallate and ellagic acid.
  • The addition of additives to fibers moreover causes difficulties in preserving the properties of the fibers such as mechanical stabilities, fiber elongations, loop strength, abrasion resistance, dye receptivity. [0009]
  • JP 1228916 describes a film made of two layers of woven material or nonwoven fabric, between which fine flakes of algae material such as Rhodophyceae are filled by means of adhesives or by hot welding. Thus, a film is obtained which, when used, improves the health. [0010]
  • Said film has, however, the disadvantage that the finely grounded (comminuted) algae material is present in hollow spaces between said two layers, so that the algae material escapes when the film is torn and is separated from the environment by the layers. [0011]
  • U.S. Pat. Nos. 4,421,583 and 4,562,110 describe a method, wherein fiber material is produced from alginate. For this purpose, alginate is obtained from the sea plants by means of an extraction method, and the so obtained soluble alginate is directly spun to form fibers. [0012]
  • DE 19544097 describes a method of producing molded articles from polysaccharide mixtures by dissolving cellulose and a second polysaccharide in an organic polysaccharide solvent mixable with water, which may likewise contain a second solvent, by molding the solution under pressure through a nozzle to form molded articles and by solidifying the molded articles by means of coagulation in a coagulating bath. Apart from cellulose, hexoses with glycosidic 1,4 and 1,6 linkage, uronic acids and starch, especially pullulan, carubin, buaran, hyaluronic acid, pectin, algin, carrageenan or xanthene are mentioned therein as second polysaccharides. Moreover, it is described that, apart from a second polysaccharide, also a third polysaccharide, preferably chitin, chitosan or, respectively, a corresponding derivative may be used. The molded articles obtained according to this method are used as means for binding water and/or heavy metals, as fiber having bactericidal and/or fungicidal properties or as yarn with an increased degradation velocity in the stomach of ruminants. [0013]
  • The use of nucleation agents in the production of molded articles from thermoplastic high polymers, especially α-olefinic polymers is described in U.S. Pat. No. 3,367,926. As nucleation agents amino acids, the salts thereof and proteins are, inter alia, mentioned. [0014]
  • For reducing the fibrillation tendency in cellulosic molded articles it is known to apply defibrillation agents on the freshly spun or dried fiber in a subsequent treatment step. All previously known defibrillation agents are cross-linking agents. [0015]
  • According to EP-A-0 538 977 cellulose fibers are treated in an alkaline medium with a chemical reagent comprising 2 to 6 functional groups capable of reacting with cellulose, in order to reduce the fibrillation tendency. [0016]
  • Another method for the reduction of the fibrillation tendency of cellulosic molded articles by means of a textile auxiliary agent is described in WO 99/19555. So far a solution for reducing the fibrillation of the cellulose fibers during the spinning process has not as yet been found. [0017]
  • It is, therefore, the object of the present invention to provide a polymer composition containing an additive, with a good stability and proccesability, as well as a molded article produced therefrom having a small fibrillation tendency, and a method for the production thereof. [0018]
  • This object is solved by a polymer composition comprising a biologically degradable polymer and a material from sea plants and/or shells of sea animals, by a molded article produced therefrom as well as by a method for the production thereof according to claims 1 to 6 and 12 to 25. [0019]
  • The object is additionally solved by a polymer composition comprising a biologically degradable polymer and at least two components selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions, by a molded article produced therefrom and by a method for the production thereof according to claims 7 to 25. [0020]
  • The biologically degradable polymer is preferably selected from the group consisting of cellulose, modified cellulose, latex, vegetable or animal protein, especially cellulose, and mixtures thereof. Polyamides, polyurethanes and mixtures thereof may likewise be used, as far as they are biologically degradable. The polymer composition according to the invention and the molded article produced therefrom preferably contain no polymers which are not biologically non-degradable, or mixtures thereof. [0021]
  • The polymer compositions according to the invention may also contain polymers which are not biologically degradable. Certain polymer solvents such as DMAc, DMSO or DMF etc. can also solve synthetic polymers such as aromatic polyamides (aramides), polyacrylonitrile (PACN) or polyvinyl alcohols (PVA), which, again, may be combined to form polymer compositions in combination with known cellulose solvents such as LiCl/DMAc, DMSO/PF, tertiary amine oxides/water. [0022]
  • Examples for modified cellulose include carboxethyl cellulose, methyl cellulose, nitrate cellulose, copper cellulose, viscose xanthogenate, cellulose carbamate and cellulose acetate. Examples for fibers from polycondensation and polymerization products are polyamides substituted with methyl, hydroxy or benzyl groups. Examples for polyurethanes are those formed on the basis of polyesterpolyolen. [0023]
  • The sea plant material is preferably selected from the group consisting of algae, kelp and seaweed, especially algae. Examples for algae include brown algae, green algae, red algae, blue algae or mixtures thereof. Examples for brown algae are Ascophyllum spp., [0024] Ascophyllum nodosum, Alaria esculenta, Fucus serratus, Fucus spiralis, Fucus vesiculosus, Laminaria saccharine, Laminaria hyperborea, Laminaria digitata, Laminaria echroleuca and mixtures thereof. Examples for red algae include Asparagopsis armata, Chondrus cripus, Maerl beaches, Mastocarpus stellatus, Palmaria palmata and mixtures thereof. Examples for green algae are Enteromorpha compressa, Ulva rigida and mixtures thereof, Examples for blue algae are Dermocarpa, Nostoc, Hapalosiphon, Hormogoneae, Porchlorone. A classification of algae can be inferred from the Botanic Textbook for Colleges [Lehrbuch der Botanik für Hochschulen] E. Strasburger; F. Noll; H. Schenk; A. F. W. Schimper; 33. edition, Gustav Fischer Verlag, Stuttgart-Jena-New York; 1991.
  • The sea plant material can be obtained in different ways. At first, it is harvested, whereby there are three different harvesting methods: [0025]
  • 1. the sea plant material washed ashore is collected, [0026]
  • 2. the sea plants are cut from stones, or [0027]
  • 3. the sea plants are collected in the sea by divers. [0028]
  • The sea plant material obtained according to the third method has the best quality and is rich in vitamins, minerals, minor elements and polysaccharides. For the purpose of the present invention the sea plant material harvested according to this method is preferably used. [0029]
  • The harvested material can be processed in different ways. The sea plant material can be dried at temperatures of up to 450° C. and grounded by using ultrasound, wet ball mills, pin-type mills or counterrotating mills, whereby a powder is obtained, which may, if required, still be subjected to cycloning for the classifying thereof. A so obtained powder may be used according to the invention. Said sea plant material powder may, in addition, be subjected to an extraction method, for instance, with vapor, water or an alcohol such as ethanol, whereby a liquid extract is obtained. Said extract may likewise be used according to the invention. [0030]
  • The harvested sea plant material can moreover be subjected to a cryocomminution, whereby it is comminuted into particles of approximately 100 μm at −50° C. If desired, the so obtained material may additionally be comminuted, whereby particles having a size of approximately 6 to approximately 10 μm are obtained. [0031]
  • The material from the outer shell of sea animals is preferably selected out of sea sediments, grounded shells of crabs or mussels, lobsters, crustaceans, shrimps, corals. [0032]
  • A typical composition of a mixture of natural origin is shown in table 1. [0033]
    TABLE 1
    Components (%)
    Vitamins 0.2%
    Proteins 5.7%
    Fats 2.6%
    Humidity 10.7%
    Ash 15.4%
    Carbohydrates 65.6%
  • Minerals of a mixture of natural origin according to table 1 are shown in table 2.1. [0034]
    TABLE 2.1
    Concentration Concentration Concentration
    ELEMENT [mg/kg] ELEMENT [mg/kg] ELEMENT [mg/kg]
    Sodium 41,800 Iron 895 Aluminum 1,930
    Magnesium 2,130 Nickel 35 Sulfur 15,640
    Calcium 19,000 Copper 6 Molybdenum 16
    Manganese 1,235 Chlorine 36,800 Cobalt 12
    Phosphor 2,110 Iodine 624 Tin <1
    Mercury 2 Lead <1 Boron 194
    Fluorine 326 Zinc 35 Strontium 749
  • Minerals of a mixture (humidity 94%, ignition residue 90%) of natural origin are shown in table 2.2. [0035]
    TABLE 2.2
    Concentration Concentration Concentration
    ELEMENT [mg/kg] ELEMENT [mg/kg] ELEMENT [mg/kg]
    Sodium 5,100 Iron 2,040 Aluminum <5
    Magnesium 24,000 Nickel 14 Sulfur 4,500
    Calcium 350,000 Copper 10 Molybdenum 39
    Manganese 125 Chlorine 1,880 Cobalt 6
    Phosphor 800 Iodine 181 Tin <5
    Mercury <0.3 Lead 460 Boron 17
    Fluorine 200 Zinc 37
  • The material from sea animal shells can, in the case of sea sediments, be used directly. If materials from the shells of crabs or mussels, lobsters, crustaceans, shrimps are used, the same is grounded. [0036]
  • Mixtures from sea plant materials and shells of sea animals as well as the extracted products thereof may likewise be used. The quantitative composition of sea plant materials and the shells of sea animals is preferably 50 weight-% to 50 weight-%. Sea plant materials are preferably used according to the invention. [0037]
  • The material from sea plants and/or shells of sea animals may be present in the polymer composition and the molded article produced therefrom in an amount of 0.1 to 30 weight-%, preferably 0.1 to 15 weight-%, more preferably 1 to 8 weight-%, especially 1 to 4 weight-%, based on the weight of the biologically degradable polymer. Especially if the molded article is present in the form of a fiber, the amount of material from sea plants and/or shells of sea animals is preferably 0.1 to 15 weight-%, especially 1 to 5 weight-%. [0038]
  • An example for a material from sea plants used according to the invention is a powder from [0039] Ascophyllum nodosum having a particle size of 95% <40 μm, which contains 5.7 weight-% protein, 2.6 weight-% fat, 7.0 weight-% fibrous components, 10.7 weight-% humidity, 15.4 weight-% ash and 58.6 weight-% carbohydrates. It moreover contains vitamins and minor elements such as ascorbic acid, tocopherols, carotene, barium, niacin, vitamin K, riboflavin, nickel, vanadium, thiamin, folic acid, folinic acid, biotin and vitamin B12. In addition, it contains amino acids such as alanine, arginine, asparagic acid, glutamic acid, glycin, leucine, lysine, serine, threonine, tyrosine, valine and methionine.
  • According to another embodiment the polymer composition comprises a biologically degradable polymer and at least two components selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions. The components may be of synthetic nature or of a natural origin. Said components may be used in a dried form or with a humidity, which preferably ranges between 5 and 15%. [0040]
  • In a preferred embodiment the polymer composition comprises a biologically degradable polymer and at least three components, especially preferably at least four components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions. [0041]
  • The polymer composition comprises especially preferably a biologically degradable polymer and at least two components selected from the group consisting of saccharides and the derivatives thereof and amino acids. [0042]
  • The at least two components selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions may be present in the polymer composition and the molded article produced therefrom in an amount of 0.1 to 30 weight-%, preferably 0.1 to 15 weight-%, especially in an amount of 4 to 10 weight-%, based on the weight of the biologically degradable polymer. [0043]
  • The saccharides may be used in amounts of 0.05 to 9 weight-%, preferably in amounts of 2 to 6 weight-%, the vitamins in amounts of 0.00007 to 0.04 weight-%, preferably in amounts of 0.003 to 0.03 weight-%, the proteins and/or amino acids in amounts of 0.005 to 4 weight-%, preferably in amounts of 0.2 to 0.7 weight-%, and the metal ions and the counterions thereof in amounts of 0.01 to 9 weight-%, preferably in amounts of 0.5 to 1.6 weight-%, based on the weight of the biologically degradable polymer. [0044]
  • The biologically degradable polymer is preferably selected from the same group as in the preceding embodiment. [0045]
  • The saccharides or the derivatives thereof used may be selected from the group consisting of monosaccharides, oligosaccharides and polysaccharides. Mixtures containing alginic acid, laminarin, mannitol and methylpentosanes are preferably used. [0046]
  • The used proteins contain preferably alanine, arginine, asparagic acid, glutamic acid, glycin, leucine, lysine, serine, threonine, tyrosine, valine and methionine. [0047]
  • The amino acids are preferably the same ones contained in the proteins as used. [0048]
  • Furthermore, the used vitamins may be selected from the group consisting of ascorbic acid, tocopherol, carotene, niacin (vitamin B3), phytonadione (vitamin K), riboflavin, thiamin, folic acid, folinic acid, biotin, retinol (vitamin A), pyridoxine (vitamin B6) and cyanocobalamin (vitamin B[0049] 12).
  • The metal ions may be selected from the group consisting of aluminum, antimony, barium, boron, calcium, chromium, iron, germanium, gold, potassium, cobalt, copper, lanthanum, lithium, magnesium, manganese, molybdenum, sodium, rubidium, selenium, silicon, thallium, titan, vanadium, tungsten, zinc and tin. [0050]
  • The counterions of the metal ions may, for example, be fluoride, chloride, bromide, iodide, nitrate, phosphate, carbonate and sulfate. The amount of metal ions or, respectively, the pertinent counterions is adjusted such that, when the at least two components or, respectively, the polymer composition are ashed, an ash content in the range of 5-95%, preferably a range of 10-60% is formed. [0051]
  • For the purposes according to the invention particles of the material from sea plants and/or shells of sea animals or the at least two components selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions in the particle-size range of 200 to 400 μm, preferably of 150 to 300 μm may be used. Smaller sized particles may also be used, such as at 1 to 100 μm, preferably 0.1 to 10 μm, more preferably 0.1 to 7 μm, especially 1 to 5 μm (measuring method: laser diffraction apparatus: Sympatec Rhodos). Also grain size mixtures of a uniform material or, respectively, different algae material may be used. [0052]
  • In order to obtain the material from sea plants and/or shells of sea animals or the at least two components in this fineness, the material from sea plants and/or shells of sea animals or the at least two components may be grounded, for instance, with commercially available pin-type mills, whereupon the fine fraction is then separated by means of corresponding classifiers. Such a classifying process for toner for the development of electrostatic pictures is described in DE 19803107, whereby a fine fraction is classified out of the product at approximately 5 μm. [0053]
  • Given this process, however, only the fine fraction can be obtained, and the main fraction is thereby not used in the polymer composition according to the invention. [0054]
  • Another possibility to obtain the material from sea plants and/or shells of sea animals or the at least two components in the required particle size resides in disintegrating the material from sea plants and/or shells of sea animals or the at least two components by means of jet mills with static or rotating internal or external classifiers. Jet mills typically comprise a flat cylindrical mill chamber, around which a plurality of jet nozzles distributed about the periphery are arranged. The grinding is substantially based on a mutual exchange of kinetic energy. The disintegration achieved by particle impact is followed by a classifying zone towards the center of the mill chamber, whereby the fine fraction is discharged by means of static or rotating internal or external classifiers. The coarse fraction remains in the milling space by means of centrifugal forces and is further grounded. A portion of the components being hard to mill may be discharged from the milling space through suitable apertures. Corresponding jet mills are described, for example, in the U.S. Pat. No. 1,935,344, in EP 888818, EP 603602, DE 3620440. [0055]
  • A typical particle size distribution is shown in FIG. 1. [0056]
  • The molded articles according to the invention can be produced from the polymer composition according to the invention with conventional methods, whereby the biologically degradable polymer and the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions are at first mixed to produce the polymer composition and the molded article can then be produced. [0057]
  • The continuous or discontinuous mixing of the biologically degradable polymer and the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions can take place with apparatus and on the basis of methods described in WO 96/33221, U.S. Pat. No. 5,626,810 and WO 96/33934. [0058]
  • The molded article according to the invention especially preferably provided in the form of fibers, most preferably in the form of cellulose fibers. The molded article according to the invention may also be provided in the form of an endless filament, or membrane, or in the form of a hose or a flat film. [0059]
  • Methods of producing the cellulose fibers according to the invention such as the lyocell or NMMO methods, the rayon or viscose methods or the carbamate method are known. [0060]
  • The lyocell method may be performed according to the following description. For producing a moldable mass and the cellulose fibers according to the invention a solution from cellulose, NMMNO and water is produced by first forming a suspension from cellulose, NMMNO and water, whereby said suspension is continuously transported by rotating elements over a heat exchange surface in a layer having a thickness of 1 to 20 mm and under a reduced pressure. During this process water is evaporated until a homogenous cellulose solution is formed. The so obtained cellulose solutions may contain an amount of cellulose of 2 to 30 weight-%, an amount of NMMNO of 68 to 82 weight-% and an amount of water of 2 to 17 weight-%. If desired, additives like anorganic salts, anorganic oxides, finely distributed organic substances or stabilizers may be added to said solution. [0061]
  • The material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions are then continuously or discontinuously added to the so obtained cellulose solution in the form of powder, a powder suspension or in a liquid form, as extract or suspension. [0062]
  • In dependence on the method the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions may also be added after or during the continuous disintegration of the dry cellulose, e.g. in the form of algae material in the original size, as powder or highly concentrated powder suspension. The powder suspension can be produced in water or any optional solvent in the desired concentration required for the method. [0063]
  • Furthermore, it is possible to subject the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions to a pulping process with simultaneous disintegration, or to feed to a refiner. The pulping can be carried out either in water, in caustic solutions or in the solvent required for dissolving the cellulose at a later stage. Here, too, the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions may be added in a solid, powdery, suspension-like or in liquid form. [0064]
  • In the presence of a derivatization agent and/or a solvent known for the dissolving process the polymer composition enriched with the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions can be transferred into a moldable extrusion mass. [0065]
  • Another possibility of adding the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions resides in the addition during a continuously controlled dissolving process as is described in EP 356419, U.S. Pat. No. 5,049,690 and U.S. Pat. No. 5,330,567. [0066]
  • Alternatively, the addition may be carried out discontinuously by obtaining a master batch of the cellulose solution. Preferably the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions is added continuously. [0067]
  • The material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions may be added in any other stage of the production process for the molded article. It can, for instance, be fed into a pipeline system, where it is correspondingly mixed by static mixing elements or, respectively, stirring elements such as known inline refiners or homogenizers, e.g. apparatus from Ultra Turrax, positioned therein. If the process is carried out in the continuous batch operation, e.g. by means of a stirred vessel cascade, the algae material can be introduced in a solid, powdery, suspension-like or liquid form at the point which is optimal for the process. The fine distribution can be achieved with known stirring elements adjusted to the method. [0068]
  • In dependence on the applied particle size the formed incorporated extrusion or spinning mass can be filtrated prior or after the incorporation. In response to the fineness of the applied product the filtration may also be omitted in spinning methods using large nozzle diameters. [0069]
  • If the spinning masses are very sensitive, the material can, in a suited form, directly be fed upstream of the spinning nozzle or the extrusion die via an injection location. [0070]
  • If the algae material or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions are liquid, it is additionally possible to feed them to the continuously spun thread during the spinning process. [0071]
  • The so obtained cellulose solution is spun according to conventional methods such as the dry-jet-wet method, the wet-spinning method, the melt-blown method, the pot spinning method, the funnel spinning method or the dry spinning method. When the spinning takes place according to the dry-jet-wet spinning method, the yarn sheet can also be cooled in the air gap between the nozzle and the coagulating bath by quenching. An air gap of 10-50 mm has proved to be suitable. The parameters for the cooling air are preferably air temperatures of 5-35° C. with a relative humidity of up to 100%. Patent documents U.S. Pat. No. 5,589,125 and 5,939,000 as well as EP 0574870 B1 and WO 98/07911 describe spinning methods for the production of cellulose fibers according to the NMMO method. [0072]
  • If required, the formed molded articles are subjected to the conventional subsequent chemical fiber treatment methods for filaments or staple fibers. [0073]
  • Obtained is a cellulose fiber according to the invention with a material from sea plants and/or shells of sea animals or with at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions, preferably at least three components, especially preferably at least four components. [0074]
  • Apart from the spinning method also extrusion methods for the production of flat films, round films, skins (sausage skins) and membranes can be used. [0075]
  • The viscose method can be carried through as follows. Pulp with approximately 90 to 92 weight-% of α-cellulose is treated with aqueous NaOH. Afterwards the cellulose is transformed into cellulose xanthogenate by means of conversion with carbon disulfide, and a viscose solution is obtained by adding aqueous NaOH under constant stirring. Said viscose solution contains approximately 6 weight-% cellulose, 6 weight-% NaOH and 32 weight-% carbon disulfide, based on the cellulose content. After the suspension was stirred, the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions are added either as powder or liquid extract. If desired, common additives such as surfactants, dispersing agents or stabilizers can be added. [0076]
  • The material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions can, again, be added at any stage of the process. [0077]
  • The so obtained solution is then spun to form fibers, as is, for instance, described in U.S. Pat. No. 4,144,097. [0078]
  • The carbamate method can be carried out as follows. For this purpose, cellulose carbamate is produced from pulp with approximately 90 to 95 weight-% of α-cellulose, as is described, for example, in U.S. Pat. No. 5,906,926 or in DE 19635707. Alkali cellulose is thereby produced from the applied pulp by treating it with aqueous NaOH. After the defibration the alkali cellulose is subjected to maturing and the caustic soda solution is then washed out. The so activated cellulose is mixed with urea and water and is introduced into a solvent in a reactor. The so obtained mixture is heated. The obtained carbamate is separated and a carbamate spinning solution is produced therefrom, which is described in DE 19757958. The material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions are added to said spinning solution. [0079]
  • The so obtained spinning solution is spun to form fibers according to known methods, and cellulose fibers according to the invention are obtained. [0080]
  • It has surprisingly been found that, despite the addition of an additive, the cellulose fibers according to the invention show the same excellent properties as cellulose fibers without additives, namely in view of their fineness, breaking force, breaking force variation, elongation, wet elongation, breaking tenacity, wet tenacity, fineness-related loop strength, wet abrasion upon breakage, wet abrasion variation and wet modulus, and have, at the same time, the positive properties conferred by the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions. This is especially surprising, as the addition of additives to spinning masses from cellulose, NMMNO and water has the drawback that the same discolor at the temperature of application, are not resistant to storage and incorporate impurities into the final cellulose products. [0081]
  • Furthermore, it could surprisingly be proved that the ionic components incorporated with the material remain in the fiber compound even when subjected to a forming method with an aqueous bath liquid, and do not escape into the spinning bath during the short spinning period. [0082]
  • After the spinning process the pH-value of the produced staple fiber was determined according to the DIN method 54 275. In comparison to a fiber not incorporated with sea plants and/or shells of sea animals the pH-value of the incorporated fiber increased, which indicates the extraction of ionic fiber components. By said property, in connection with the body humidity, the bioactivity of the skin can positively and healthfully be influenced when articles of clothing are worn. [0083]
  • Moreover, it has shown that by the addition of the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions, the fibrillation of the fibers, produced according to the lyocell method, is reduced. Thus, the fiber according to the invention, e.g. a cellulose fiber incorporated with algae, can be applied in a more favorable manner during the subsequent textile treatment of the fiber. [0084]
  • Despite the incorporation of a material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions, which is rich in iron and metal concentrations if a sea plant is concerned, advantageously no disintegration of a spinning solution from cellulose, NMMNO and water is observed. It has, on the contrary, shown that the disintegration temperature of such a spinning solution even increased when material from sea plants and/or shells of sea animals was added. This means that despite the presence of metal ions, no negative influence on the stability of the spinning mass could be observed. [0085]
  • By the incorporation of the material from sea plants and the incorporation of metals connected therewith, therefore, also chemical reactions on the fiber material may be carried out, such as ion exchange processes by the incorporated metal ions (e.g. increase of the hydrogen ion concentration in the fibrous material) or the deacetylation of chitin. [0086]
  • Another advantage conferred upon the molded articles according to the invention by the addition of material from sea plants and/or shells of sea animals or at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions is the homogenous incorporation of the active substances into the fiber matrix with different produceable fiber diameters. Moreover, the processing as monofilament or endless filament yarn is feasible. This results in a particularly favorable application of technical articles. [0087]
  • Especially if the molded article according to the invention is produced from a polymer composition containing exclusively biologically degradable material, the complete biological degradability thereof is an advantage. [0088]
  • The molded articles according to the invention may be used as packaging material, fiber material, nonwoven fabrics, textile compounds, fibrous webs, fiber fleeces, needlefelts, upholstery cotton wool, woven fabrics, knitted fabrics, as home textiles such as bed linen, as filling material, flocking fabric, hospital textiles such as sheets, diapers or mattresses, as fabrics for heating blankets, shoe inserts and dressings. Additional possibilities of using the same are described the Dictionary for textile interior design [Lexikon der textilen Raumausstattung], Buch und Medien Verlag Buurmann KG, ISBN 3-98047-440-2. [0089]
  • If a woven fabric is produced from the molded article according to the invention in the form of fibers, it may either consist of said fibers exclusively or contain an additional component. Said additional component can be selected out of the group consisting of cotton wool, lyocell, rayon, carbacell, polyester, polyamide, cellulose acetate, acrylate, polypropylene or mixtures thereof. The fibers containing a material from sea plants and/or shells of sea animals are present in the woven fabric preferably in an amount of up to approximately 70 weight-%. The material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions are present in the woven fabric preferably in an amount of 1 to 10 weight-%. [0090]
  • If the molded article is provided in the form of a fibrous material or a woven fabric, articles of clothing such as jumpers, jackets, dresses, suits, t-shirts, underwear or the like can be produced therefrom. [0091]
  • The articles of clothing produced from said fibers or woven fabrics according to the invention are extremely comfortable to wear and in general improve the state of health of the individual wearing said article of clothing. The health-improving effect of sea plant materials is, for instance, described in JP 1228916. [0092]
  • Due to the high portion of negative ions in the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions the pH-value of the skin is positively influenced in as far as it arranges for alkaline and thus healthy conditions on the skin. In addition, the skin temperature is increased more when wearing the articles of clothing according to the invention, in contrast to wearing an article of clothing made of fibers without the material from sea plants and/or shells of sea animals or the at least two components, selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions, whereby a positive effect is exerted on the blood circulation of the skin. [0093]
  • Due to the incorporated elements the fiber according to the invention passes the active substances on to the body, namely via the liquid present during the wearing in response to the body humidity. Due to the cellulosic material articles of clothing having good breathing properties can thus be produced. Moreover, the active substances can purposively be supplied to the skin, as is common in cosmetics or Thalami therapy. Due to the incorporation the active substances remain in the fiber or the woven fabric for a long time, even after frequent washing. [0094]
  • The minor elements and the vitamins supplied via the woven fabric made of the fibers according to the invention can support the body due to the remineralizing, stimulating and heating effect. [0095]
  • If the fiber according to the invention is provided in the form of staple fibers or disintegrated filaments, surfaces of carriers such as woven fabrics or films can be flocked therewith. For this purpose the surface of the carrier to be flocked is treated with an adhesive and the staple fibers or disintegrated filaments are applied thereon. [0096]
  • The invention will hereinafter by explained by means of examples. [0097]
  • COMPARATIVE EXAMPLE 1 Without Admixture
  • 3,086 g NMMNO (59.8%), 308 g MoDo, DP 500, dry contents 94%,1.8 propylgallate (0.63% related to the cellulose contents) were mixed, and the so obtained mixture was heated to 94° C. Obtained was a discontinuously produced spinning solution having a cellulose content of 11.8% and a viscosity of 4,765 Pa·s. The so obtained spinning solution was spun to form fibers, whereby the following spinning conditions were observed: [0098]
    Temperature of the store tank 90° C.
    Temperature spinning block, nozzle 80° C.
    Spinning bath  4° C.
    Spinning bath concentration (start) 0% (distilled water)
    Spinning bath concentration (end) 5% NMMNO
    Spinning pump 20.0 cm3/min.
    Nozzle filter 19200 M/cm2
    Spinning nozzle 495 Hole 70 μm; Au/Pt
    Final drawing-off 25 m/min.
  • The fibers were cut to a staple length of 40 mm, were washed free of a solvent and finished with a 10 g/l lubrication (50% Leomin OR-50% Leomin WG (nitrogen-containing fatty acid polyglycol ester Clariant GmbH)) at 45° C. or, respectively, the fat add-on for the better continued processing of the fibers was applied, and dried at 105° C. Subsequent to the drying a fiber humidity of 11% was adjusted. An additional bleaching process prior to the drying was not performed in this case. [0099]
  • The spinning behavior of the spinning solution obtained according the present example was good. [0100]
    TABLE 3
    Fiber data comparative example 1
    Comparative
    Example 1
    Fineness - Titer [dtex] 1.48
    Breaking tenacity dry [cN/tex] 42.20
    Breaking tenacity wet [cN/tex] 36.30
    Breaking tenacity loop [cN/tex] 15.20
    Breaking elongation - dry [%] 15.50
    Breaking elongation - wet [%] 15.20
    Wet modulus [cN/tex] 202.00
  • COMPARATIVE EXAMPLE 2 Without Admixture: Treatment of the Filaments in the Air Gap
  • The spinning solution was produced analogously to comparative example 1. The spinning solution was spun to fibers, whereby, in deviation from comparative example 1, the temperature of the spinning block was adjusted to 95° C. and the temperature of the nozzle to 105° C. In the air gap between the nozzle and the coagulating bath the yarn sheet was quenched with humid air (temperature: 20° C., humidity: 70%). [0101]
  • Otherwise, the test performance was carried out like in comparative example 1. [0102]
    TABLE 4
    Fiber data comparative example 2
    Comparative
    Example 2
    Fineness - Titer [dtex] 1.25
    Breaking tenacity dry [cN/tex] 45.10
    Breaking tenacity wet [cN/tex] 37.10
    Breaking tenacity loop [cN/tex] 22.10
    Breaking elongation - dry [%] 15.40
    Breaking elongation - wet [%] 18.50
    Wet modulus [cN/tex] 234.00
  • EXAMPLE 1
  • 3,156 g NMMNO (61.4%), 315 g MoDo, DP 500, dry contents 94%, 1.9 g propylgallate (0.63% related to the cellulose content) as well as 11.6 g of a powder—shown in table 1—(in total 3.9% related to the cellulose content) were mixed and heated to 94° C. Obtained was a spinning solution having a solids content of 12.4% and a viscosity of 6,424 Pa·s. The so produced spinning solution was spun to fibers like in comparative example 1, [0103]
    TABLE 5
    Fiber data example 1
    Example 1
    Fineness - Titer [dtex] 1.40
    Breaking tenacity dry [cN/tex] 38.60
    Breaking tenacity wet [cN/tex] 30.70
    Breaking tenacity loop [cN/tex] 11.40
    Breaking elongation - dry [%] 12.40
    Breaking elongation - wet [%] 13.00
    Wet modulus [cN/tex] 199.00
  • EXAMPLE 2
  • Analogously to example 1, 2.951 g NMMNO (60.84%), 305 g MoDo, DP 500, dry contents 94%, 1.8 g propylgallate (0.63% related to the cellulose content) as well as 17.5 g of the mixture used in table 1—(in total 6.1% related to the cellulose content) were mixed and heated to 94° C. Obtained was a spinning solution having a solids content of 12.9% and a viscosity of 7.801 Pa·s. The so produced spinning solution was spun to fibers like in comparative example 1. [0104]
    TABLE 6
    Fiber data example 2
    Example 2
    Fineness - Titer [dtex] 1.48
    Breaking tenacity dry [cN/tex] 36.60
    Breaking tenacity wet [cN/tex] 32.40
    Breaking tenacity loop [cN/tex] 13.30
    Breaking elongation - dry [%] 12.10
    Breaking elongation - wet [%] 13.50
    Wet modulus [cN/tex] 188.00
  • EXAMPLE 3
  • Analogously to example 1, 2,750 g NMMNO (60.3%), 305 g MoDo, DP 500, dry contents 94%, 1.7 g propylgallate (0.63% related to the cellulose content) as well as 11.2 g of a powder—shown in table 2.2— (in total 4.1% related to the cellulose content) were mixed and heated to 94° C. Obtained was a spinning solution having a solids content of 13% and a viscosity of 6.352 Pa·s. The so produced spinning solution was spun to fibers like in comparative example 1. [0105]
    TABLE 7
    Fiber data example 3
    Example 3
    Fineness - Titer [dtex] 1.41
    Breaking tenacity dry [cN/tex] 33.40
    Breaking tenacity wet [cN/tex] 29.20
    Breaking tenacity loop [cN/tex] 9.00
    Breaking elongation - dry [%] 12.60
    Breaking elongation - wet [%] 8.60
    Wet modulus [cN/tex] 182.00
  • EXAMPLE 4
  • Analogously to example 3, 3,345 g NMMNO (59.5%), 318 g MoDo, DP 500, dry contents 94%, 1.9 g propylgallate (0.63% related to the cellulose content) as well as 23.6 g of a mixture similar to the one used in table 3 (in total 7.9% related to the cellulose content) were mixed and heated to 94° C. The mixture used in this example differs from the one used in example 3 above all by a higher potassium content and a lower calcium content (˜12.6% to ˜35%). Obtained was a spinning solution having a solids content of 12.4% and a viscosity of 7.218 Pa·s. The so produced spinning solution was spun to fibers like in comparative example 1. [0106]
    TABLE 8
    Fiber data example 4
    Example 4
    Fineness - Titer [dtex] 1.42
    Breaking tenacity dry [cN/tex] 41.40
    Breaking tenacity wet [cN/tex] 32.90
    Breaking tenacity loop [cN/tex] 8.30
    Breaking elongation - dry [%] 11.90
    Breaking elongation - wet [%] 12.00
    Wet modulus [cN/tex] 212.00
  • EXAMPLE 5
  • 3,204 g NMMNO (59.5%), 318 g MoDo, DP 500, dry contents 94.4%, 1.9 g propylgallate (0.63% related to the cellulose content) and 25.4 g brown algae (8.5% related to the cellulose content) of the type Laminaria were mixed, and the so obtained mixture was heated to 94° C. Obtained was a discontinuously produced spinning solution having a cellulose content of 13.24% and a viscosity of 6.565 Pa·s. The so obtained spinning solution was spun to fibers, whereby the following spinning conditions were observed: [0107]
    Temperature of the store tank 90° C.
    Temperature spinning block, nozzle 80° C.
    Spinning bath  4° C.
    Spinning bath concentration (start) 0% (distilled water)
    Spinning bath concentration (end) 7% NMMNO
    Spinning pump 20.0 cm3/min.
    Nozzle filter 19200 M/cm2
    Spinning nozzle 495 Hole 70 μm; Au/Pt
    Final drawing-off 30 m/min.
  • The fibers were cut to a staple length of 40 mm, were washed free of a solvent and finished with a 10 g/l lubrication (50% Leomin OR-50% Leomin WG (nitrogen-containing fatty acid polyglycol ester Clariant GmbH)) at 45° C. or, respectively, the fat add-on for the better continued processing of the fibers was applied, and dried at 105° C. Subsequent to the drying a fiber humidity of 10% was adjusted. An additional bleaching process prior to the drying was not performed in this case. [0108]
  • The spinning behavior of the spinning solution obtained according the present example was good. [0109]
  • The following table 9 shows the physical properties of the so obtained cellulose fibers. [0110]
    TABLE 9
    Fineness [dtex] 1.42
    Breaking force [cN] 5.85
    Breaking force variation [%] 15.8
    Elongation [%] 11.9
    Wet elongation [%] 12.0
    Breaking tenacity [cN/tex] 41.4
    Breaking tenacity wet [cN/tex] 32.9
    Loop breaking tenacity [cN/tex] 8.3
    Wet abrasion upon breakage [turns] 10
    Wet abrasion variation [%] 19.7
    Wet modulus [cN/tex] 212
  • The elementary analyses of the applied material from sea plants, brown algae [0111] Laminaria digitata and the fiber sample with incorporated brown algae is shown in the following table 10.
    TABLE 10
    Fiber sample with incorporated
    Brown algae brown algae material
    Analyses [mg/kg] material Laminaria digitata
    Sodium 28,300 460
    Magnesium 51,300 3,400
    Calcium 126,000 8,100
    Chromium 850 50
    Manganese 670 55
    Iron 32,600 2,000
    Nickel 210 20
    Copper 30 8
    Molybdenum <5 <5
    Cobalt 19 <5
  • FIG. 2 moreover shows that a spinning solution with 8.5% [0112] Laminaria digitata is stable over thermal disintegration up to approximately 200° C.
  • EXAMPLE 6
  • 3,687 g NMMNO (62%), 381 g MoDo, DP 500, dry contents 94.4%, 2.27 g propylgallate (0.63% related to the cellulose content) and 3.6 g brown algae flour [0113] Laminaria digitata (1% related to the cellulose content) were mixed and heated to 94° C. Obtained was a spinning solution having a cellulose content of 12.78% and a viscosity of 8.424 Pa·s. The so produced spinning solution was spun to fibers like in comparative example 1.
  • The physical properties of the so obtained cellulose fibers are shown in the following table 11. [0114]
    Fineness [dtex] 1.40
    Breaking force [cN] 6.10
    Breaking force variation [%] 21.8
    Elongation [%] 13.0
    Wet elongation [%] 12.7
    Breaking tenacity [cN/tex] 42.4
    Breaking tenacity wet [cN/tex] 37.7
    Loop breaking tenacity [cN/tex] 8.81
    Wet abrasion upon breakage [turns] 14
    Wet abrasion variation [%] 34.7
    Wet modulus [cN/tex] 254
  • The so obtained fibers were spun to a yarn. The spinning was carried out under the conditions 63% relative air humidity and 20° C. by means of carding, stretching and spinning with a rotor spinning machine, to form 75 g of yarn with approximately 20 tex. FIG. 3 shows that the spinning solution with 1% [0115] Laminaria digitata, related to the cellulose content, is stable up to a temperature of approximately 200° C.
  • EXAMPLE 7
  • A cellulose xanthogenate was produced from a mixture of 33 weight-% cellulose, 17 weight-% caustic soda solution and 50 weight-% water by adding 32% carbon disulfide related to cellulose. Thereafter the xanthogenate was transferred by stirring for 2 hours, with the addition of diluted caustic soda solution, into a spinning solution with 6 weight-% cellulose, 6 weight-% NaOH and substantially water and reaction products resulting from the xanthate production. To the so obtained viscose solution 0.9 weight-% of brown algae material were added to the spinning solution. The viscose solution was allowed to stand for approximately 6 hours under a vacuum for degassing and thereupon filtrated. The so obtained viscose solution had a maturity level of 10° Hottenroth and was spun to fibers. [0116]
  • The spinning conditions were: [0117]
    Nozzle [n/μm] 1,053/60
    Hole throughput [g/hole/min.] 0.07
    Temperature of coagulating bath [° C.] 30
    Sulfuric acid in the coagulating bath [%] 10.8
    Sodium sulfate in the coagulating bath [%] 20.0
    Zinc sulfate in the coagulating bath [%] 1.5
    Drawing-off speed [m/min.] 36
  • The physical properties of the so obtained rayon fibers are shown in the following table 12. [0118]
    TABLE 12
    Fineness - Titer [dtex] 1.7
    Breaking tenacity dry [cN/tex] 21.7
    Breaking tenacity wet [cN/tex] 12.4
    Fineness-related loop strength [cN/tex] 6.0
    Breaking elongation - dry [%] 14.2
    Breaking elongation - wet [%] 15.8
    Wet modulus [cN/tex] 2.9
  • EXAMPLE 8
  • Rayon fibers were produced in accordance with example 7, except for the fact that 0.1 weight-% of brown algae material instead of 0.9 weight-% were added to the spinning solution. [0119]
  • The physical properties of the so obtained viscose or rayon fibers are shown in table 13. [0120]
    TABLE 13
    Fineness - Titer [dtex] 1.7
    Breaking tenacity dry [cN/tex] 23.7
    Breaking tenacity wet [cN/tex] 14.1
    Loop strength [cN/tex] 6.5
    Breaking elongation - dry [%] 16.9
    Breaking elongation - wet [%] 18.5
    Wet modulus [cN/tex] 3.0
  • COMPARATIVE EXAMPLE 3
  • As comparison, a viscose fiber was produced in accordance with example 7, except for the fact that no brown algae material was added. [0121]
  • The physical properties of said viscose fiber are shown in table 14. [0122]
    TABLE 14
    Fineness - Titer [dtex] 1.7
    Breaking tenacity dry [cN/tex] 24.8
    Breaking tenacity wet [cN/tex] 14.2
    Loop strength [cN/tex] 6.4
    Breaking elongation - dry [%] 17.2
    Breaking elongation - wet [%] 21.1
    Wet modulus [cN/tex] 2.9
  • EXAMPLE 9
  • For the production of cellulose carbamate an alkali cellulose was first produced from a chemical pulp with 92-95% alpha-content (Ketchikan). The caustic soda solution was washed out of the matured alkali cellulose (35 weight-% cell; 15 weight-% NaOH; 50 weight-% water) with water. After squeezing out the so activated cellulose (70 weight-% water) 10 kg of the squeezed out activated cellulose were mixed with urea (1.5 kg) in a kneader. The urea is thereby separated in the water contained in the cellulose and is evenly distributed in the cellulose. Said cellulose pulp was transferred into a reactor equipped with stirrer and reflux cooler, into which o-xylol (30 kg) had been fed. The contents in the reactor was then heated for approximately 2 hours at 145° C. and filtered off. [0123]
  • The so obtained residue was passed back into the reactor, into which approximately 25 kg water had been fed. The xylol still adhering to the carbamate was stripped off at 88° C. After the filtration the carbamate was washed out with hot water (50° C.) and with cold water. Thereafter the carabamate was squeezed out. [0124]
  • 3.45 kg Stark-solution were produced from 1.02 kg of said carbamate with 1.1 kg caustic soda solution (30 weight-%), 1.30 kg water and with the corresponding amount of brown algae (0.03 kg). All reactants were pre-cooled. The reaction itself took place at a temperature of 0° C. (Composition of the Stark-lye: 11.0 weight-% cell, 9.5 weight-% NaOH). [0125]
  • A spinning mass (5 kg) was produced from the cooled Stark-solution by adding 1.55 kg cooled caustic soda solution (3.03 weight-%) at a temperature of 0° C. The cooled spinning mass was filtrated through a filter with degrees of fineness of 10-40 μm and was spun. [0126]
  • The following spinning conditions were observed: [0127]
    Nozzle [n/μm] 36/60
    Hole throughput [g/hole/min.] 0.11
    Temperature of coagulating bath [° C.] 35
    Sulfuric acid in the coagulating bath [%] 90
    Sodium sulfate in the coagulating bath [%] 140
    Drawing-off speed [m/min.] 30
  • The physical properties of the so obtained Carbacell® fibers are shown in table 15. [0128]
    TABLE 15
    Fineness - Titer [dtex] 3.1
    Breaking tenacity dry [cN/tex] 14.8
    Breaking tenacity wet [cN/tex] 5.7
    Loop strength [cN/tex] 7.5
    Breaking elongation - dry [%] 4.0
    Breaking elongation - wet [%] 4.7
    Wet modulus [cN/tex] 100
  • EXAMPLE 10
  • Carbacell® fibers were produced in accordance with example 9, except for the fact that 0.1 weight-% of brown algae flour instead of 0.6 weight-% were added to the spinning mass. [0129]
  • The physical properties of the so obtained Carbacell® fibers are shown in the following table 16. [0130]
    Fineness - Titer [dtex] 3.3
    Breaking tenacity dry [cN/tex] 17.8
    Breaking tenacity wet [cN/tex] 5.8
    Loop strength [cN/tex] 7.5
    Breaking elongation - dry [%] 4.6
    Breaking elongation - wet [%] 5.4
    Wet modulus [cN/tex] 129
  • COMPARATIVE EXAMPLE 4
  • Carbacell® fibers were produced in accordance with example 9, except for the fact that no brown algae flour was added. [0131]
  • The physical properties of the so obtained fibers are shown in the following table 17. [0132]
    TABLE 17
    Fineness - Titer [dtex] 3.1
    Breaking tenacity dry [cN/tex] 18.0
    Breaking tenacity wet [cN/tex] 5.8
    Loop strength [cN/tex] 7.9
    Breaking elongation - dry [%] 4.7
    Breaking elongation - wet [%] 5.5
    Wet modulus [cN/tex] 135
  • EXAMPLES 11 TO 15
  • Lyocell cellulose fibers were continuously produced in accordance with example 5, whereby the respective amounts, the conditions of the continuously performed process and the physical properties of the obtained fibers are shown in the following table 18. [0133]
    TABLE 18
    Example Example Example Example Example
    Unit 11 12 13 14 15
    Pulp
    Type Alicell Modo Alicell Alicell Alicell
    VLV Drown VLF VLV VLV
    Dissolving
    DP Pulp 9 540 530 540 540 540
    Feed hole kg/h 161.8 161.8 173.0 167.2 161.7
    Cellulose % 13.0% 13.0% 12.0% 12.5% 13.0%
    Water % 10.7% 10.7% 11.3% 11.0% 10.7%
    NMMO % 76.3% 76.3% 76.7% 76.5% 76.3%
    Solution flow kg/h 138.5 138.5 150.0 144.0 138.5
    Vapor kg/h 23.3 23.3 23.0 23.2 23.3
    condensate
    System pressure mbar 55 55 55 55 55
    abs.
    Spinning temp. ° C. 117 110 72 80 117
    Fiber draft 10.9 10.9 4.3 10.5 11.81
    Titer dtex 1.3 1.3 1.3 1.3 1.18
    Air gap height mm 20 20 7 12 20
    Air quantity Nm3/h 130 130 130 180 135
    Air temperature ° C. 17.5 18.5 17.2 17.9 19
    Hole throughput g/hole 0.030 0.060 0.028 0.134 0.028
    min
    Hole diameter μ 100 100 65 100 100
    Brown algae g/h 181.9 182.3 1528.0 1531.8 2704.0
    powder Amount
    Coagulating bath ° C. 20 20 6 6 20
    temperature
    Spinning bath % 20 20 20 20 20
    concentration NMMO
    Final drawing-off m/mm 35 70 30 150 35
    Titer dtex 1.40 1.42 1.38 1.40 1.21
    Strength dry cn/tex 42.1 41.4 41.8 42.4 41
    Elongation dry % 12.8 11.9 13.0 13.2 13.8
    Wet strength cn/tex 32.9 34.8 37.7 37.7 33.4
    Wet elongation % 12.0 12.3 12.7 12.0 12.8
    Loop strength cn/tex 15.4 13 8.3 8.9 13.8
    Wet modulus cn/tex 238 254 212 212 242
  • EXAMPLE 16
  • Based on the fibers produced in accordance with comparative example 1 and 2 and in accordance with examples 1 to 4 cryo-breaks in liquid nitrogen were produced, whereof photographs were taken by means of a field emission electron-scanning microscope (Joel 6330 F) after the fibers had been sputtered with platinum. [0134]
  • The fiber produced according to comparative example 1 or 2 according to the standard process shows a splinted break. The fibrillary structure can clearly be recognized on the broken surface. The strong orientation of the fibrilla can be seen on the standing out longitudinal ridges and on the strongly fissured structure along the longitudinal axis. [0135]
  • The photographs of the fibers from examples 1 to 4 show something completely different. The partly blunt and clean broken surfaces can clearly be recognized. Moreover, it can be recognized that the distinct high longitudinal orientation in the fiber according to comparative example 1 is much less distinct in examples 1 to 4. [0136]
  • On the basis of the electron-scanning microscope photographs striking differences in the structure of the fiber were detected. [0137]
  • Above all, the strongly repressed longitudinal orientation shows that the use according to the invention of material from sea plants and/or shells of sea animals or of at least two components selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions results in a smaller fibrillation of the fibers during the production of cellulose fibers. [0138]
  • It had been especially interesting and unexpected that mixtures with different substances contained therein show said effect, as all previously known defibrillation agents are cross-linking agents. The smaller fibrillation is presumably due to a change of the crystallization properties of the cellulose during the extrusion. [0139]

Claims (25)

1. Polymer composition comprising a biologically degradable polymer and a material from sea plants and/or shells of sea animals:
2. Polymer composition according to claim 1, wherein the material from sea plants is selected from the group consisting of algae, kelp, seaweed and mixtures thereof.
3. Polymer composition according to claim 2, wherein the material from sea plants is selected from the group consisting of brown algae, green algae, red algae, blue algae and mixtures thereof.
4. Polymer composition according to one of the preceding claims, wherein the material from the shells of sea animals is selected from the group consisting of sea sediments and grounded shells of crabs, lobsters, crustaceans and mussels and mixtures thereof.
5. Polymer composition according to one of the preceding claims, wherein the material from sea plants and/or shells of sea animals is provided in an amount of 0.1 to 30 weight-% based on the weight of the biologically degradable polymer.
6. Polymer composition according to one of the preceding claims, wherein the biologically degradable polymer is cellulose and the material from sea plants are algae.
7. Polymer composition comprising a biologically degradable polymer and at least two components selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions.
8. Polymer composition according to claim 7, wherein at least three components are present.
9. Polymer composition according to claim 7, wherein at least four components are present.
10. Polymer composition according to one of claims 7 to 9, wherein the at least two components are provided in an amount of 0.1 to 30 weight-% based on the weight of the biologically degradable polymer.
11. Polymer composition according to one of claims 7 to 10, wherein the at least two components are selected from the group consisting of saccharides and the derivatives thereof and amino acids.
12. Polymer composition according to one of the preceding claims, wherein the biologically degradable polymer is selected from the group consisting of cellulose, modified cellulose, latex, vegetable and animal protein, and mixtures thereof.
13. Molded article comprising a polymer composition according to one of the preceding claims.
14. Molded article according to claim 13, wherein the molded article is selected from the group consisting of tanks, films, membranes, woven fabrics and fibers.
15. Molded article according to claim 14, wherein the fibers are staple fibers, monofilaments or endless filaments.
16. Use of the molded article according to one of claims 13 to 15 as packaging material or fibrous material.
17. Use of the molded article according to one of claims 13 to 15 in the form of a fibrous material as mixing component for the production of yarns.
18. Use of the molded article according to one of claims 13 to 15 in the form of a fibrous material for the production of nonwoven fabrics or woven fabrics.
19. Use of the molded article according to one of claims 13 to 15 in the form of a fibrous material for the production of nonwoven fabrics or woven fabrics, wherein a component selected from the group consisting of cotton wool, lyocell, rayon, carbacell, polyester, polyamide, cellulose acetate, acrylate, polypropylene or mixtures thereof is additionally present in the nonwoven fabric or woven fabric.
20. Use of the molded article according to claim 19, wherein 0.1 to 30 weight-% of the additional component are contained.
21. Woven fabric comprising a molded article according to one of claims 13 to 15.
22. Nonwoven fabric comprising a molded article according to one of claims 13 to 15.
23. Article of clothing comprising a molded article according to one of claims 13 or 15.
24. Method of producing a molded article according to one of claims 13 to 15, comprising the following steps:
(A) continuously or discontinuously mixing the biologically degradable polymer and the material from sea plants and/or shells of sea animals or the at least two components selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions,
(B) producing a moldable mass,
(C) processing the mass obtained in (B) to form a molded article, and
(D) subsequently treating the produced molded article.
25. Method according to claim 24, wherein a molded article according to one of claims 13 to 15 is produced.
US10/204,108 2000-02-21 2001-01-08 Polymer compositions and moulded bodies made therefrom Abandoned US20030186611A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE10007794.3 2000-02-21
DE2000107794 DE10007794A1 (en) 2000-02-21 2000-02-21 Composition useful for making containers, films, membranes and fibers, comprises a biodegradable polymer and a marine plant or shell material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/567,021 US7951237B2 (en) 2000-02-21 2006-12-05 Polymer composition and molded articles produced therefrom
US13/049,468 US8496748B2 (en) 2000-02-21 2011-03-16 Polymer composition and molded articles produced therefrom

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/567,021 Division US7951237B2 (en) 2000-02-21 2006-12-05 Polymer composition and molded articles produced therefrom

Publications (1)

Publication Number Publication Date
US20030186611A1 true US20030186611A1 (en) 2003-10-02

Family

ID=7631672

Family Applications (3)

Application Number Title Priority Date Filing Date
US10/204,108 Abandoned US20030186611A1 (en) 2000-02-21 2001-01-08 Polymer compositions and moulded bodies made therefrom
US11/567,021 Active US7951237B2 (en) 2000-02-21 2006-12-05 Polymer composition and molded articles produced therefrom
US13/049,468 Active US8496748B2 (en) 2000-02-21 2011-03-16 Polymer composition and molded articles produced therefrom

Family Applications After (2)

Application Number Title Priority Date Filing Date
US11/567,021 Active US7951237B2 (en) 2000-02-21 2006-12-05 Polymer composition and molded articles produced therefrom
US13/049,468 Active US8496748B2 (en) 2000-02-21 2011-03-16 Polymer composition and molded articles produced therefrom

Country Status (15)

Country Link
US (3) US20030186611A1 (en)
EP (1) EP1259564B1 (en)
CN (2) CN1246374C (en)
AT (1) AT283897T (en)
AU (1) AU7207901A (en)
BR (1) BR0108585A (en)
CA (1) CA2399954C (en)
DE (1) DE10007794A1 (en)
ES (1) ES2228913T3 (en)
NO (1) NO330413B1 (en)
PT (1) PT1259564E (en)
RU (1) RU2255945C2 (en)
TW (1) TWI292416B (en)
WO (1) WO2001062844A1 (en)
ZA (1) ZA200206366B (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050189675A1 (en) * 2002-07-12 2005-09-01 Sigrid Redlinger Process for the production of cellulosic moulded bodies
US20050234229A1 (en) * 2002-05-24 2005-10-20 Fritz Loth Method for the production of cellulose carbamate moulded bodies
US7314570B2 (en) 2001-08-20 2008-01-01 Zimmer A.G. Method for removing heavy metals from media containing heavy metals by means of a Lyocell moulded body, cellulosic moulded body comprising absorbed heavy metals, and the use of the same
US20090127750A1 (en) * 2004-04-16 2009-05-21 Birla Research Institute For Applied Science Process for making cellulose fibre, filaments or films
US20090197994A1 (en) * 2006-10-24 2009-08-06 Korea Institute Of Energy Research Algae fiber-reinforced bicomposite and method for preparing the same
US20100248572A1 (en) * 2007-09-18 2010-09-30 Lenzing Aktiengesellschaft Lyocell Fiber
US20100297408A1 (en) * 2008-01-22 2010-11-25 Sigrid Redlinger Process For The Treatment Of Cellulosic Molded Bodies
US20110172624A1 (en) * 2008-09-22 2011-07-14 Lenzing Aktiengesellschaft Use of lyocell fibers as well as articles containing lyocell fibers
US20110212150A1 (en) * 2008-09-22 2011-09-01 Lenzing Aktiengesellschaft Process for the treatment of cellulosic molded bones
US20110237146A1 (en) * 2008-12-10 2011-09-29 Teijin Aramid Gmbh Knitted fabric
US20130093112A1 (en) * 2010-04-08 2013-04-18 List Holding Ag Process for producing a product
US8574400B1 (en) 2012-05-25 2013-11-05 Kimberly-Clark Worldwide, Inc. Tissue comprising macroalgae
US9074324B2 (en) 2013-06-10 2015-07-07 Kimberly-Clark Worldwide, Inc. Layered tissue structures comprising macroalgae
US9499941B2 (en) 2012-05-25 2016-11-22 Kimberly-Clark Worldwide, Inc. High strength macroalgae pulps

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10216273A1 (en) * 2002-04-12 2003-10-30 Zimmer Ag Polymer composition comprising a biodegradable polymer and a material selected from herbs of the Asteraceae Familia and / or extracts thereof and / or one or more ingredients thereof
KR100575378B1 (en) * 2004-11-10 2006-04-25 주식회사 효성 Process for preparing a cellulose fiber
DE102004061179A1 (en) * 2004-12-16 2006-06-22 Ofa Bamberg Gmbh Elastic thread comprises flexible core, twisting filament formed from cellulose fiber which contains algae and an active substances delivered to the skin under the influence of temperature and/or humidity
WO2007125546A1 (en) * 2006-05-01 2007-11-08 Bnt Force Biodegradable Polymers Pvt Ltd., Novel biodegradable polymer composition useful for the preparation of biodegradable plastic and a process for the preparation of said composition
DE102007054702B4 (en) * 2007-11-14 2018-10-18 Smartpolymer Gmbh A process for the production of cellulose molded bodies of cellulose molded bodies, and its use
AT506268B1 (en) * 2008-01-11 2014-08-15 Chemiefaser Lenzing Ag microfiber
ES2660688T3 (en) * 2008-09-11 2018-03-23 Albany International Corp. pervious web for making tissue, towel or nonwoven
GB0907323D0 (en) * 2009-04-29 2009-06-10 Dynea Oy Composite material comprising crosslinkable resin of proteinous material
JP2013527329A (en) 2010-03-25 2013-06-27 レンツィング アクチェンゲゼルシャフト The use of cellulose fibers
CN104144984A (en) 2011-08-24 2014-11-12 阿尔吉斯有限责任公司 Macrophyte-based bioplastic
CN102532569B (en) * 2012-01-20 2013-10-02 甘肃华羚生物技术研究中心 Preparation method of yak milk casein edible film
CN102643609B (en) * 2012-05-04 2014-11-26 舟山市普陀丰达环保节能科技有限公司 Aqueous anti-corrosive coating used in seawater environment
WO2014035351A1 (en) * 2012-08-30 2014-03-06 Ptt Global Chemical Public Company Limited A bio-based polymer additive, a process for preparing the bio-based polymer additive and a biodegradable polymer composition comprising said bio-based polymer additive
CN103590124B (en) * 2012-12-27 2015-07-15 青岛海芬海洋生物科技有限公司 Preparation method of enteromorpha regenerated cellulose fibers
CN103628165B (en) * 2012-12-27 2016-03-30 青岛海芬海洋生物科技有限公司 The method of preparing protein fiber Enteromorpha
AT514137A1 (en) 2013-04-05 2014-10-15 Lenzing Akiengesellschaft Polysaccharide, and methods for their preparation
AT514136A1 (en) 2013-04-05 2014-10-15 Lenzing Akiengesellschaft Polysaccharide with increased Fibrillationsvermögen and processes for their preparation
AT514468A1 (en) 2013-06-17 2015-01-15 Lenzing Akiengesellschaft Highly absorbent polysaccharide and their use
AT514475B1 (en) * 2013-06-17 2016-11-15 Chemiefaser Lenzing Ag Polysaccharide, and methods for their preparation
AT514474B1 (en) 2013-06-18 2016-02-15 Chemiefaser Lenzing Ag Polysaccharide, and methods for their preparation
DE102014004258A1 (en) 2014-03-19 2015-09-24 Bauerfeind Ag Fibers and yarns with occlusal
EP3204540A1 (en) * 2014-10-10 2017-08-16 The Procter and Gamble Company Soluble fibrous structures and methods for making same
CL2015001932A1 (en) * 2015-07-07 2015-11-20 Jose Zaldivar Larrain Francisco Material comprising a mixture of brown algae, cellulose and adhesive material, and process for their preparation.
DE102015217382A1 (en) 2015-09-11 2017-03-16 Bauerfeind Ag Polymer compositions, fibers and yarns with petrolatum and / or oleic acid oils
AT518061B1 (en) * 2016-04-28 2017-07-15 Chemiefaser Lenzing Ag modified viscose

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4333484A (en) * 1978-08-02 1982-06-08 Philip Morris Incorporated Modified cellulosic smoking material and method for its preparation
US4994285A (en) * 1986-10-22 1991-02-19 Asahi Kasei Kogyo Kabushiki Kaisha Edible body and process for preparation thereof
US5205863A (en) * 1991-11-14 1993-04-27 International Communications & Energy Agricultural biodegradable plastics
US5244945A (en) * 1992-07-20 1993-09-14 International Communications & Energy Synthesis of plastics from recycled paper and sugar cane
US5288318A (en) * 1993-07-01 1994-02-22 The United States Of America As Represented By The Secretary Of The Army Cellulose acetate and starch based biodegradable injection molded plastics compositions and methods of manufacture
US5472569A (en) * 1992-04-16 1995-12-05 Cartiera Favini S.P.A. Paper comprising cellulose fiber and seaweed particles in integral form
US5759569A (en) * 1995-01-10 1998-06-02 The Procter & Gamble Company Biodegradable articles made from certain trans-polymers and blends thereof with other biodegradable components
US6103790A (en) * 1994-03-01 2000-08-15 Elf Atochem S.A. Cellulose microfibril-reinforced polymers and their applications

Family Cites Families (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1935344A (en) * 1931-06-16 1933-11-14 American Pulverizing Corp Camd Impact pulverizer
NL302327A (en) * 1963-02-20 1900-01-01
US3367926A (en) * 1964-03-25 1968-02-06 Dow Chemical Co Modification of crystalline structure of crystallizable high polymers
US4055702A (en) * 1974-03-29 1977-10-25 M & T Chemicals Inc. Additive-containing fibers
US4144097A (en) * 1978-04-19 1979-03-13 Atlantic Richfield Company Luminescent solar collector
US4246221A (en) * 1979-03-02 1981-01-20 Akzona Incorporated Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent
IE49193B1 (en) * 1979-04-18 1985-08-21 Courtaulds Ltd Process for making a non-woven alginate fabric useful as a wound dressing
AU546556B2 (en) * 1981-08-18 1985-09-05 Courtaulds Plc Alginate fibre material and process
US4663163A (en) * 1983-02-14 1987-05-05 Hou Kenneth C Modified polysaccharide supports
US5059654A (en) * 1983-02-14 1991-10-22 Cuno Inc. Affinity matrices of modified polysaccharide supports
US4791063A (en) * 1983-02-14 1988-12-13 Cuno Incorporated Polyionene transformed modified polysaccharide supports
US4606824A (en) * 1984-10-26 1986-08-19 Chaokang Chu Modified cellulose separation matrix
DE3620440A1 (en) 1986-06-18 1987-12-23 Indutec Industrietechnik Gmbh Two-stage opposing jet comminution method operated under pressure for enlarging the surface area of fine grained to granular bulk materials
JPH01228916A (en) 1988-03-09 1989-09-12 Satomitsu Kitamura Seaweed-filled sheet
AT392972B (en) 1988-08-16 1991-07-25 Chemiefaser Lenzing Ag A process for the preparation of solutions of cellulose, as well as means for carrying out the method
US5330567A (en) * 1988-08-16 1994-07-19 Lenzing Aktiengesellschaft Process and arrangement for preparing a solution of cellulose
US4908137A (en) * 1989-04-11 1990-03-13 Cuno, Incorporated Heavy metal removal process
US5045210A (en) * 1989-04-11 1991-09-03 Cuno, Incorporated Heavy metal removal process
DE3925356A1 (en) * 1989-07-31 1991-02-07 Degussa N, N'-disubstituted and N, N, N '- / N, N', N'-trisubstituted thioureas and methods for producing (ii)
JPH03269059A (en) * 1990-03-19 1991-11-29 Sumitomo Metal Ind Ltd Polymer composition
US5219646A (en) * 1990-05-11 1993-06-15 E. I. Du Pont De Nemours And Company Polyester blends and their use in compostable products such as disposable diapers
DE4027786A1 (en) 1990-09-04 1992-04-09 Marcel Huder Mixts. of vegetable or animal components including natural fibre - can be processed as thermoplastics e.g. by baking into useful articles, packaging, etc. with easy disposal after use
GB9122318D0 (en) 1991-10-21 1991-12-04 Courtaulds Plc Treatment of elongate members
FR2685679B1 (en) 1991-12-31 1994-04-01 Troadec Jean Rene film-forming composition for the elaboration of a substantially biodegradable film.
ATA53792A (en) * 1992-03-17 1995-02-15 Chemiefaser Lenzing Ag A process for producing cellulosic molded bodies, apparatus for performing the method and using a spinner
DE4308524C1 (en) 1992-06-16 1994-09-22 Thueringisches Inst Textil A process for preparing cellulose fibers and filaments by the dry-wet extrusion process
CN1027599C (en) 1992-07-14 1995-02-08 纺织工业部纺织科学研究院 Method for making organism functional medical adhesive-bonded cloth and its products
JP3082886B2 (en) 1992-11-16 2000-08-28 日本電信電話株式会社 Power storage type temperature difference cell power generation system
DE4243438C2 (en) 1992-12-22 1996-06-05 Hosokawa Alpine Ag Method and apparatus for fluidized-bed jet milling
TR28441A (en) * 1993-05-24 1996-07-04 Courtaulds Fibres Holdings Ltd spinning cells can be used in coagulation of lyocell filaments.
AT400581B (en) * 1993-10-19 1996-01-25 Chemiefaser Lenzing Ag A process for the preparation of solutions of cellulose
EP0683251B1 (en) * 1994-05-17 1998-07-08 DyStar Textilfarben GmbH &amp; Co. Deutschland KG Amination of cellulosic synthetic fibres
JP2555545B2 (en) 1994-06-22 1996-11-20 大倉工業株式会社 The method for producing a cellulose-chitosan-based molded products
DE4422118A1 (en) 1994-06-24 1996-01-04 Merck Patent Gmbh Preparations of monodisperse spherical oxide particles
US5766746A (en) * 1994-11-07 1998-06-16 Lenzing Aktiengesellschaft Flame retardant non-woven textile article
AT402410B (en) 1995-04-19 1997-05-26 Chemiefaser Lenzing Ag A process for producing a cellulosic suspension
AT409130B (en) 1995-04-25 2002-05-27 Chemiefaser Lenzing Ag to keep using a device and give a homogeneous cellulose suspension
DE19544097C1 (en) 1995-11-27 1997-07-10 Thueringisches Inst Textil Moulding solution of cellulose and more water-soluble polysaccharide component
JP3696327B2 (en) * 1996-03-22 2005-09-14 パイオニア株式会社 The information recording apparatus and method, and information reproducing apparatus and method
DE19618271C2 (en) * 1996-05-07 1999-10-28 Edmund Zimmermann A process for producing moldings from fibrous plant parts and / or natural fibers, and corresponding moldings
CN1230579C (en) 1996-08-23 2005-12-07 韦尔豪泽公司 Method for preparing Liaosaier fibre
DE19635707C1 (en) 1996-09-03 1998-04-02 Inst Textil & Faserforschung Production of cellulose carbamate from cellulose
FR2757173A1 (en) 1996-12-17 1998-06-19 Warner Lambert Co Polymeric compositions of non-animal origin for film formation
JPH10231241A (en) 1997-02-19 1998-09-02 T T S Gijutsu Kenkyusho:Kk Tablet necessitating no water in taking medicine, dry emulsion and its production
DE19715617A1 (en) * 1997-04-15 1998-10-22 Zimmer Ag A process for the preparation of modified cellulose
WO1998051709A1 (en) * 1997-05-13 1998-11-19 Young Keun Hong Aqueous cellulose solution and rayon fiber produced from the same
AT404846B (en) 1997-06-16 1999-03-25 Chemiefaser Lenzing Ag Composition containing fine solid particles
DE19728382C2 (en) 1997-07-03 2003-03-13 Hosokawa Alpine Ag & Co Method and apparatus for fluidized-bed jet milling
AT2256U1 (en) 1997-10-15 1998-07-27 Chemiefaser Lenzing Ag A process for treatment of cellulosic molded bodies
DE19757958A1 (en) 1997-12-24 1999-07-01 Lurgi Zimmer Ag Two-stage production of cellulose carbamate solution for the production of spinning solutions used in the manufacture of regenerated cellulose fibers.
DE19803107A1 (en) 1998-01-28 1999-07-29 Hosokawa Alpine Ag Process for the air classification of toner
DE19849185C2 (en) 1998-10-26 2000-08-17 Buna Sow Leuna Olefinverb Gmbh A process for the fabrication of compostable starch foam parts with increased moisture resistance
JP2002069475A (en) 2000-08-24 2002-03-08 Ikeda Shokken Kk Method of manufacturing oil and fat containing high percentage of docosahexaenoic acid
US20040109853A1 (en) * 2002-09-09 2004-06-10 Reactive Surfaces, Ltd. Biological active coating components, coatings, and coated surfaces
US7123280B2 (en) * 2003-09-29 2006-10-17 Konica Minolta Photo Imaging, Inc. Thermal transfer image receiving sheet and image forming method using the same
AR048727A1 (en) * 2004-05-03 2006-05-17 Leprino Foods Co mixed cheeses and methods of preparing such cheeses
US7585537B2 (en) * 2004-05-03 2009-09-08 Leprino Foods Company Cheese and methods of making such cheese
US7579033B2 (en) * 2004-05-03 2009-08-25 Leprino Foods Company Methods for making soft or firm/semi-hard ripened and unripened cheese and cheeses prepared by such methods

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4333484A (en) * 1978-08-02 1982-06-08 Philip Morris Incorporated Modified cellulosic smoking material and method for its preparation
US4994285A (en) * 1986-10-22 1991-02-19 Asahi Kasei Kogyo Kabushiki Kaisha Edible body and process for preparation thereof
US5205863A (en) * 1991-11-14 1993-04-27 International Communications & Energy Agricultural biodegradable plastics
US5472569A (en) * 1992-04-16 1995-12-05 Cartiera Favini S.P.A. Paper comprising cellulose fiber and seaweed particles in integral form
US5244945A (en) * 1992-07-20 1993-09-14 International Communications & Energy Synthesis of plastics from recycled paper and sugar cane
US5288318A (en) * 1993-07-01 1994-02-22 The United States Of America As Represented By The Secretary Of The Army Cellulose acetate and starch based biodegradable injection molded plastics compositions and methods of manufacture
US6103790A (en) * 1994-03-01 2000-08-15 Elf Atochem S.A. Cellulose microfibril-reinforced polymers and their applications
US5759569A (en) * 1995-01-10 1998-06-02 The Procter & Gamble Company Biodegradable articles made from certain trans-polymers and blends thereof with other biodegradable components

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7314570B2 (en) 2001-08-20 2008-01-01 Zimmer A.G. Method for removing heavy metals from media containing heavy metals by means of a Lyocell moulded body, cellulosic moulded body comprising absorbed heavy metals, and the use of the same
US20050234229A1 (en) * 2002-05-24 2005-10-20 Fritz Loth Method for the production of cellulose carbamate moulded bodies
US20050189675A1 (en) * 2002-07-12 2005-09-01 Sigrid Redlinger Process for the production of cellulosic moulded bodies
US20100289177A1 (en) * 2002-07-12 2010-11-18 Sigrid Redlinger Method for the production of shaped cellulose bodies
US20090127750A1 (en) * 2004-04-16 2009-05-21 Birla Research Institute For Applied Science Process for making cellulose fibre, filaments or films
US7938993B2 (en) * 2004-04-16 2011-05-10 Birla Research Institute For Applied Sciences Process for making cellulose fibre, filaments or films
US20090197994A1 (en) * 2006-10-24 2009-08-06 Korea Institute Of Energy Research Algae fiber-reinforced bicomposite and method for preparing the same
US8633120B2 (en) 2007-09-18 2014-01-21 Lenzing Aktiengesellschaft Lyocell fiber
JP2010539345A (en) * 2007-09-18 2010-12-16 レンツィング・アクチエンゲゼルシャフトLenzing AG Lyocell fiber
US20100248572A1 (en) * 2007-09-18 2010-09-30 Lenzing Aktiengesellschaft Lyocell Fiber
US20100297408A1 (en) * 2008-01-22 2010-11-25 Sigrid Redlinger Process For The Treatment Of Cellulosic Molded Bodies
US8524326B2 (en) 2008-01-22 2013-09-03 Lenzing Aktiengesellschaft Process for the treatment of cellulosic molded bodies
US20110212150A1 (en) * 2008-09-22 2011-09-01 Lenzing Aktiengesellschaft Process for the treatment of cellulosic molded bones
US20110172624A1 (en) * 2008-09-22 2011-07-14 Lenzing Aktiengesellschaft Use of lyocell fibers as well as articles containing lyocell fibers
US20110237146A1 (en) * 2008-12-10 2011-09-29 Teijin Aramid Gmbh Knitted fabric
US20130093112A1 (en) * 2010-04-08 2013-04-18 List Holding Ag Process for producing a product
US9555558B2 (en) * 2010-04-08 2017-01-31 List Holding Ag Process for producing a product
US8574400B1 (en) 2012-05-25 2013-11-05 Kimberly-Clark Worldwide, Inc. Tissue comprising macroalgae
US8771468B2 (en) 2012-05-25 2014-07-08 Kimberly-Clark Worldwide, Inc. Tissue comprising macroalgae
US9499941B2 (en) 2012-05-25 2016-11-22 Kimberly-Clark Worldwide, Inc. High strength macroalgae pulps
US9074324B2 (en) 2013-06-10 2015-07-07 Kimberly-Clark Worldwide, Inc. Layered tissue structures comprising macroalgae

Also Published As

Publication number Publication date
BR0108585A (en) 2003-04-29
NO20023945L (en) 2002-10-21
CA2399954C (en) 2007-10-16
AU7207901A (en) 2001-09-03
CN1660926A (en) 2005-08-31
CN100376625C (en) 2008-03-26
CA2399954A1 (en) 2001-08-30
AT283897T (en) 2004-12-15
CN1246374C (en) 2006-03-22
ZA200206366B (en) 2005-02-23
RU2255945C2 (en) 2005-07-10
EP1259564A1 (en) 2002-11-27
DE10007794A1 (en) 2001-06-28
EP1259564B1 (en) 2004-12-01
TWI292416B (en) 2008-01-11
PT1259564E (en) 2005-04-29
NO20023945D0 (en) 2002-08-20
US8496748B2 (en) 2013-07-30
CN1404504A (en) 2003-03-19
US20110200776A1 (en) 2011-08-18
US7951237B2 (en) 2011-05-31
NO330413B1 (en) 2011-04-11
RU2002125112A (en) 2004-01-10
ES2228913T3 (en) 2005-04-16
US20070161311A1 (en) 2007-07-12
WO2001062844A1 (en) 2001-08-30

Similar Documents

Publication Publication Date Title
Choudhury Textile preparation and dyeing
US5985301A (en) Antibacterial cellulose fiber and production process thereof
Agboh et al. Chitin and chitosan fibers
EP0794223B1 (en) Process for producing articles of regenerated chitin-chitosan containing material and the resulting articles
EP0619848B1 (en) A product containing silicon dioxide and a method for its preparation
KR100579353B1 (en) Method for removing heavy metals from media containing heavy metals by means of a lyocell moulded body, cellulosic moulded body comprising adsorbed heavy metals, and the use of the same
CN100359063C (en) Thread using bamboo skin and its producing method
AT510254B1 (en) A process for producing cellulosic multicomponent fibers
DE4136694C2 (en) Starch fiber or starch-modified fiber, processes for their preparation and their use
Bredereck et al. Man–made cellulosics
EP1819851B1 (en) Filling material and use of cellulosic staple fibers as filling fibre
WO2004013388A1 (en) Porous fiber
US20050230860A1 (en) Process for the preparation of a cellulose solution for spinning of fibres, filaments or films therefrom
EP0789790B1 (en) Regenerated cellulose moulding and process for producing it
DD142898A5 (en) A shaped cellulosic articles prepared from a cellulose-containing solution
WO1998012369A1 (en) Chitosan-containing acrylic fibers and process for preparing the same
US8962821B2 (en) Method for preparing regenerated cellulose fiber by two-step coagulating bath process
DE3690798C2 (en) Edible mass and processes for their preparation
CN102597343A (en) Iodegradable fibre and its process of manufacture
AT505905B1 (en) Cellulose powder and process for its manufacture
CN101029420A (en) Bamboo-carbon viscose fibre and its production
EP1679394A1 (en) Fiber yarn and fabric using the same
Lee et al. Fiber formation and physical properties of chitosan fiber crosslinked by epichlorohydrin in a wet spinning system: the effect of the concentration of the crosslinking agent epichlorohydrin
KR100611890B1 (en) A process for preparing a highly homogeneous cellulose solution
US6427933B1 (en) Method for manufacturing crystalline superfine silk powder

Legal Events

Date Code Title Description
AS Assignment

Owner name: ZIMMER AG, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZIKELI, STEFAN;ENDL, THOMAS;MARTL, MICHAEL GERT;REEL/FRAME:013519/0037;SIGNING DATES FROM 20021030 TO 20021106

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION