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EP0454373B1 - Gellan gum fibers - Google Patents

  • ️Wed Aug 23 1995

EP0454373B1 - Gellan gum fibers - Google Patents

Gellan gum fibers Download PDF

Info

Publication number
EP0454373B1
EP0454373B1 EP19910303521 EP91303521A EP0454373B1 EP 0454373 B1 EP0454373 B1 EP 0454373B1 EP 19910303521 EP19910303521 EP 19910303521 EP 91303521 A EP91303521 A EP 91303521A EP 0454373 B1 EP0454373 B1 EP 0454373B1 Authority
EP
European Patent Office
Prior art keywords
gum
fibers
gellan gum
gellan
alginate
Prior art date
1990-04-23
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.)
Expired - Lifetime
Application number
EP19910303521
Other languages
German (de)
French (fr)
Other versions
EP0454373A3 (en
EP0454373A2 (en
Inventor
George T. Colegrove
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.)
Monsanto Co
Original Assignee
Merck and Co Inc
Monsanto Co
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.)
1990-04-23
Filing date
1991-04-19
Publication date
1995-08-23
1991-04-19 Application filed by Merck and Co Inc, Monsanto Co filed Critical Merck and Co Inc
1991-10-30 Publication of EP0454373A2 publication Critical patent/EP0454373A2/en
1993-01-20 Publication of EP0454373A3 publication Critical patent/EP0454373A3/en
1995-08-23 Application granted granted Critical
1995-08-23 Publication of EP0454373B1 publication Critical patent/EP0454373B1/en
2011-04-19 Anticipated expiration legal-status Critical
Status Expired - Lifetime legal-status Critical Current

Links

  • 239000000835 fiber Substances 0.000 title claims description 40
  • 229920002148 Gellan gum Polymers 0.000 title claims description 32
  • 235000010492 gellan gum Nutrition 0.000 title claims description 29
  • 239000000216 gellan gum Substances 0.000 title claims description 29
  • 235000010443 alginic acid Nutrition 0.000 claims description 13
  • 229920000615 alginic acid Polymers 0.000 claims description 13
  • 238000000034 method Methods 0.000 claims description 9
  • 229920001285 xanthan gum Polymers 0.000 claims description 7
  • 235000010493 xanthan gum Nutrition 0.000 claims description 7
  • 239000000230 xanthan gum Substances 0.000 claims description 7
  • 229920000161 Locust bean gum Polymers 0.000 claims description 6
  • 235000010420 locust bean gum Nutrition 0.000 claims description 6
  • 239000000711 locust bean gum Substances 0.000 claims description 6
  • 150000003839 salts Chemical class 0.000 claims description 6
  • FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
  • 239000011777 magnesium Substances 0.000 claims description 4
  • 229910052749 magnesium Inorganic materials 0.000 claims description 4
  • 230000001112 coagulating effect Effects 0.000 claims description 3
  • GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims 2
  • OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
  • 229910052791 calcium Inorganic materials 0.000 claims 1
  • 239000011575 calcium Substances 0.000 claims 1
  • 239000000243 solution Substances 0.000 description 16
  • 229920001282 polysaccharide Polymers 0.000 description 9
  • 239000005017 polysaccharide Substances 0.000 description 9
  • 150000004804 polysaccharides Chemical class 0.000 description 9
  • XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
  • 230000015572 biosynthetic process Effects 0.000 description 7
  • FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 6
  • 229940072056 alginate Drugs 0.000 description 6
  • KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
  • 150000001768 cations Chemical class 0.000 description 5
  • 229940082509 xanthan gum Drugs 0.000 description 5
  • IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
  • BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
  • JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
  • CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
  • 235000010410 calcium alginate Nutrition 0.000 description 4
  • 239000000648 calcium alginate Substances 0.000 description 4
  • 229960002681 calcium alginate Drugs 0.000 description 4
  • OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 4
  • 239000000499 gel Substances 0.000 description 4
  • 239000000463 material Substances 0.000 description 4
  • 235000010413 sodium alginate Nutrition 0.000 description 4
  • 239000000661 sodium alginate Substances 0.000 description 4
  • IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
  • UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
  • 239000001110 calcium chloride Substances 0.000 description 3
  • 229910001628 calcium chloride Inorganic materials 0.000 description 3
  • 238000001125 extrusion Methods 0.000 description 3
  • 229940005550 sodium alginate Drugs 0.000 description 3
  • 240000008886 Ceratonia siliqua Species 0.000 description 2
  • 235000013912 Ceratonia siliqua Nutrition 0.000 description 2
  • 244000303965 Cyamopsis psoralioides Species 0.000 description 2
  • KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
  • 229920002907 Guar gum Polymers 0.000 description 2
  • 241000199919 Phaeophyceae Species 0.000 description 2
  • 206010052428 Wound Diseases 0.000 description 2
  • 208000027418 Wounds and injury Diseases 0.000 description 2
  • 230000002745 absorbent Effects 0.000 description 2
  • 239000002250 absorbent Substances 0.000 description 2
  • 239000000783 alginic acid Substances 0.000 description 2
  • 229960001126 alginic acid Drugs 0.000 description 2
  • 150000004781 alginic acids Chemical class 0.000 description 2
  • 239000007864 aqueous solution Substances 0.000 description 2
  • 229910001424 calcium ion Inorganic materials 0.000 description 2
  • 150000001720 carbohydrates Chemical class 0.000 description 2
  • 235000014633 carbohydrates Nutrition 0.000 description 2
  • 239000008367 deionised water Substances 0.000 description 2
  • 229910021641 deionized water Inorganic materials 0.000 description 2
  • 239000004744 fabric Substances 0.000 description 2
  • 238000000855 fermentation Methods 0.000 description 2
  • 230000004151 fermentation Effects 0.000 description 2
  • 235000010417 guar gum Nutrition 0.000 description 2
  • 239000000665 guar gum Substances 0.000 description 2
  • 229960002154 guar gum Drugs 0.000 description 2
  • 238000009940 knitting Methods 0.000 description 2
  • 229910001425 magnesium ion Inorganic materials 0.000 description 2
  • 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
  • 235000019341 magnesium sulphate Nutrition 0.000 description 2
  • 229910052757 nitrogen Inorganic materials 0.000 description 2
  • 235000015097 nutrients Nutrition 0.000 description 2
  • -1 salt alginate Chemical class 0.000 description 2
  • 239000003352 sequestering agent Substances 0.000 description 2
  • 239000001509 sodium citrate Substances 0.000 description 2
  • NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
  • FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
  • GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
  • 229910001415 sodium ion Inorganic materials 0.000 description 2
  • 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
  • RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
  • BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
  • 235000013913 Ceratonia Nutrition 0.000 description 1
  • 241001060815 Ceratonia Species 0.000 description 1
  • 229920000742 Cotton Polymers 0.000 description 1
  • 239000001879 Curdlan Substances 0.000 description 1
  • 229920002558 Curdlan Polymers 0.000 description 1
  • RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
  • FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
  • LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
  • 229920002527 Glycogen Polymers 0.000 description 1
  • DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
  • JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
  • 229910019142 PO4 Inorganic materials 0.000 description 1
  • ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
  • HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 description 1
  • 239000004373 Pullulan Substances 0.000 description 1
  • 229920001218 Pullulan Polymers 0.000 description 1
  • 206010040070 Septic Shock Diseases 0.000 description 1
  • 241000790234 Sphingomonas elodea Species 0.000 description 1
  • 229920002472 Starch Polymers 0.000 description 1
  • 206010044248 Toxic shock syndrome Diseases 0.000 description 1
  • 231100000650 Toxic shock syndrome Toxicity 0.000 description 1
  • 241000589636 Xanthomonas campestris Species 0.000 description 1
  • 239000000654 additive Substances 0.000 description 1
  • REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
  • 235000010407 ammonium alginate Nutrition 0.000 description 1
  • 239000000728 ammonium alginate Substances 0.000 description 1
  • KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 1
  • 150000001450 anions Chemical class 0.000 description 1
  • 230000000844 anti-bacterial effect Effects 0.000 description 1
  • 230000000843 anti-fungal effect Effects 0.000 description 1
  • 230000000845 anti-microbial effect Effects 0.000 description 1
  • 229940121375 antifungal agent Drugs 0.000 description 1
  • WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
  • 230000001851 biosynthetic effect Effects 0.000 description 1
  • 229940043431 ceratonia Drugs 0.000 description 1
  • 235000013351 cheese Nutrition 0.000 description 1
  • 239000007795 chemical reaction product Substances 0.000 description 1
  • 239000003795 chemical substances by application Substances 0.000 description 1
  • 238000013270 controlled release Methods 0.000 description 1
  • 238000001816 cooling Methods 0.000 description 1
  • 238000004132 cross linking Methods 0.000 description 1
  • 235000019316 curdlan Nutrition 0.000 description 1
  • 229940078035 curdlan Drugs 0.000 description 1
  • 239000012153 distilled water Substances 0.000 description 1
  • 125000004185 ester group Chemical group 0.000 description 1
  • 230000032050 esterification Effects 0.000 description 1
  • 238000005886 esterification reaction Methods 0.000 description 1
  • 150000002170 ethers Chemical class 0.000 description 1
  • 210000000416 exudates and transudate Anatomy 0.000 description 1
  • 238000007380 fibre production Methods 0.000 description 1
  • 239000012467 final product Substances 0.000 description 1
  • 235000013305 food Nutrition 0.000 description 1
  • 238000001879 gelation Methods 0.000 description 1
  • 229940050410 gluconate Drugs 0.000 description 1
  • 229940096919 glycogen Drugs 0.000 description 1
  • 238000010438 heat treatment Methods 0.000 description 1
  • 230000007062 hydrolysis Effects 0.000 description 1
  • 238000006460 hydrolysis reaction Methods 0.000 description 1
  • 230000003301 hydrolyzing effect Effects 0.000 description 1
  • 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
  • 235000015243 ice cream Nutrition 0.000 description 1
  • 238000005342 ion exchange Methods 0.000 description 1
  • 239000007788 liquid Substances 0.000 description 1
  • 239000003589 local anesthetic agent Substances 0.000 description 1
  • 229960005015 local anesthetics Drugs 0.000 description 1
  • 159000000003 magnesium salts Chemical class 0.000 description 1
  • 239000004745 nonwoven fabric Substances 0.000 description 1
  • 239000008177 pharmaceutical agent Substances 0.000 description 1
  • NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
  • 239000010452 phosphate Substances 0.000 description 1
  • 229910052700 potassium Inorganic materials 0.000 description 1
  • 235000010408 potassium alginate Nutrition 0.000 description 1
  • 239000000737 potassium alginate Substances 0.000 description 1
  • 238000002360 preparation method Methods 0.000 description 1
  • 229960004919 procaine Drugs 0.000 description 1
  • MFDFERRIHVXMIY-UHFFFAOYSA-N procaine Chemical compound CCN(CC)CCOC(=O)C1=CC=C(N)C=C1 MFDFERRIHVXMIY-UHFFFAOYSA-N 0.000 description 1
  • 239000000047 product Substances 0.000 description 1
  • 235000010409 propane-1,2-diol alginate Nutrition 0.000 description 1
  • 239000000770 propane-1,2-diol alginate Substances 0.000 description 1
  • 235000019423 pullulan Nutrition 0.000 description 1
  • 235000013580 sausages Nutrition 0.000 description 1
  • 238000007493 shaping process Methods 0.000 description 1
  • 239000002002 slurry Substances 0.000 description 1
  • 229910052708 sodium Inorganic materials 0.000 description 1
  • 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
  • 241000894007 species Species 0.000 description 1
  • 238000009987 spinning Methods 0.000 description 1
  • 239000003381 stabilizer Substances 0.000 description 1
  • 235000019698 starch Nutrition 0.000 description 1
  • 239000008107 starch Substances 0.000 description 1
  • FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 description 1
  • 230000008961 swelling Effects 0.000 description 1
  • 229940095064 tartrate Drugs 0.000 description 1
  • 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
  • 239000002562 thickening agent Substances 0.000 description 1
  • 238000009941 weaving Methods 0.000 description 1
  • 239000003357 wound healing promoting agent Substances 0.000 description 1
  • 239000002759 woven fabric Substances 0.000 description 1

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments

Definitions

  • GB-A-653,341 is an example of an early disclosure of the use of calcium alginate materials in surgical dressings. The earliest such materials were calcium alginate fibers, but they suffered from the disadvantage of being quite insoluble in water or wound exudate matter. Later a portion of the calcium ions in calcium alginate was exchanged with other cations, whose alginate salts are soluble. GB-A-653,341 therefore proposed that some of the calcium ions be replaced with sodium ions, to form a mixed salt alginate.
  • alginate fibers have been proposed which involve shaping the fibers as by weaving or knitting into sheets or pads. These materials are useful because they absorb water and swell but retain their shape and structural integrity.
  • GB-A-1 207 352 describes a water absorbent product of absorbent fibers prepared from one of several fiber forming materials, including guar gum.
  • the guar gum fibers are formed by adding guar to an organic liquid, e.g. isopropyl alcohol, and adding the resulting slurry to excess water to precipitate a hydrate of the guar. The hydrate is then extruded into a coagulating bath to form the fibers.
  • gellan gum fibers may be produced by extrusion of a gum solution into a gelling bath.
  • the process advantageously, does not require esterification and subsequent hydrolysis.
  • the process also produces hybrid fibers comprising gellan and one or more additional gums.
  • gellan gum is meant the extracellularly produced gum made by the heteropolysaccharide-producing bacterium Pseudomonas elodea , ATCC 31461, by the whole culture fermentation under a variety of conditions of a medium comprising: a fermentable carbohydrate, a nitrogen source, and other appropriate nutrients. Included is the native, deacylated, partially deacylated, and clarified forms therefore. Gellan gum is also known as S-60.
  • deacylated gellan gum described in U.S-A-4,326,052.
  • gellan gum solutions containing 2-6% gum are extruded through fine orifices into coagulating baths containing various cations to produce filamentous fibers which can be used in wound dressings, catamenial devices, etc.
  • Gellan gum may be used by itself or in combination with other polysaccharides such as alginates, xanthan gum, and locust bean gum. Solutions may be extruded cold (room temperature-50°C) or hot (50°-80°C); if hot, the addition of another gum is usually necessary. Gellan gum is especially useful for producing fibers containing magnesium for controlled release of that cation.
  • the fibers may also contain known wound healing agents.
  • the bath of gelling salts is an aqueous solution of 0.5-5% of a soluble salt, the cation of which may be mono-, di-, or tri-valent and selected from those of Groups I, II, and III of the Perodic Table, especially Na+, K+, Ca++, Mg++, and Al+++. Ca++ and Mg++ are especially preferred.
  • the anion may be chloride sulfate, lactate, phosphate, carbonate, gluconate, or tartrate. Residence time is the bath is 5 seconds - 5 minutes.
  • a second polysaccharide When a second polysaccharide is used it is one which exhibits a high viscosity when hot; in particular, algin, xanthan gum, and locust bean gum or combinations of these.
  • the second gum can replace up to 33 1/3% of the gellan gum; i.e., up to 2% of a 6% gum solution may be comprised of one or more of a second polysaccharide.
  • the ratio of gellan gum to said second gum is at least 2:1.
  • algin is meant the soluble derivatives of alginic acid, which may be chemically extracted from all species of Phaeophyceae , brown algae.
  • the term is intended to include the soluble salts of alginic acid (e.g., sodium, potassium, or ammonium alginate) and the salts of its ethers (e.g., propylene glycol alginate).
  • xanthan gum is meant the biosynthetic polysaccharide produced by the organism Xanthomonas campestris by the whole culture fermentation of a medium comprising a fermentable carbohydrate, a nitrogen source and appropriate other nutrients.
  • Xanthan gum preparation is described in numerous publications and patents, e.g., U.S. Patents 3,671,398; 3,594,280; 3,591,578; 3,481,889; 3,433,708; 3,427,226; 3,391,061; 3,391,060; 3,271,267; 3,251,749; and 3,020,206.
  • Locust bean gum is an extract of the locust bean or carob, Ceratonia siligua . It is commercially available and used as a stabilizer in foods such as ice cream, sausages, and cheese.
  • Gellan gum is normally gelled by heating an aqueous solution to dissolve the gum then simply cooling to produce a gel, provided cations are present. It is also known that solutions may be prepared cold in distilled or deionized water by the addition of a small amount of sequestrant.
  • the sequestrants which can be used in this invention include trisodium orthophosphate (TSP), ethylenediaminetetraacetic acid (EDTA), sodium citrate, tetrasodium pyrophosphate (TSPP), sodium hexametaphosphate (Calgon) and the like.
  • Gellan gum fibers can therefore be prepared by forcing a solution of 2.0% deacylated, clarified gellan gum containing 0.25% sodium citrate in deionized water through a nozzle having a diameter of eleven thousandth of an inch into a 2% calcium chloride bath where fiber formation immediately occurs.
  • Gellan gum is particularly useful for forming fibers containing magnesium ions as it also gels in the presence of magnesium salts.
  • the 2% gellan gum solution above was also forced into a bath containing 2% magnesium sulfate wherein fiber formation also immediately occurred.
  • Fibers containing a source of magnesium are valuable additives to catamenial devices such as tampons where magnesium ions are said to prevent toxic shock syndrome.
  • Magnesium alginate is soluble in water; therefore it cannot be formed by useful methods but must be formed by ion exchange from insoluble calcium alginate fibers already produced by the usual methods.
  • a small amount can be formed simultaneously with gellan gum fibers however, by incorporating sodium alginate into gellan gum solutions before extrusion into the gelling bath.
  • Fiber formation from hot solutions is more complicated.
  • Gellan gum solutions have high viscosity when cold but low viscosity when heated, which makes it possible to prepare more concentrated solutions which gel more rapidly with higher gel strength. Fiber production by extrusion from hot gum solutions into a bath were not successful, however, because the low viscosity solution dispersed into flocs without forming a continuous fiber. It has been found that the addition of another polysaccharide which produces more viscosity at temperatures of 50-80°C make fiber formation possible.
  • the high viscosity thickeners xanthan gum and locust bean gum or a combination of the two also produced fibers when combined with the gellan gum at levels of 0.5-1.0%.
  • the fibers of this invention can be used in various forms. If a non-woven fabric is to be prepared, and this is the fabric of choice, a cotton card may be used to form a web, which may then be cross-lapped and then needle punched in conventional equipment.
  • the fibers may be carded and then spun into a yarn, which can be woven in a conventional loom. Alternatively, the fibers may be collected in a spinning box, according to the method of Tallis (GB-A-568,177) and woven. If a knitted fabric is to be prepared, the fibers can be prepared as a continuous filament yarn (again according to GB-A-568,177) which is then knitted on a conventional knitting machine.
  • the fiber end product (e.g., a pad) may include one or more antimicrobial (for example, antibacterial or antifungal) agents and/or one or more local anesthetics (for example, procaine) and additionally or alternatively one or more pharmaceutical agents.
  • antimicrobial for example, antibacterial or antifungal
  • local anesthetics for example, procaine

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Materials For Medical Uses (AREA)
  • Artificial Filaments (AREA)

Description

    BACKGROUND OF THIS INVENTION

  • Alginate fibers have been known for use in surgical dressings for some time. GB-A-653,341 is an example of an early disclosure of the use of calcium alginate materials in surgical dressings. The earliest such materials were calcium alginate fibers, but they suffered from the disadvantage of being quite insoluble in water or wound exudate matter. Later a portion of the calcium ions in calcium alginate was exchanged with other cations, whose alginate salts are soluble. GB-A-653,341 therefore proposed that some of the calcium ions be replaced with sodium ions, to form a mixed salt alginate.

  • Other uses for alginate fibers have been proposed which involve shaping the fibers as by weaving or knitting into sheets or pads. These materials are useful because they absorb water and swell but retain their shape and structural integrity.

  • Other polysaccharides have been proposed for fiber formation. For example, Burrow

    et al

    . (EP-A-232,121) have described cross-linked polysaccharides (starch, gellan, curdlan, pullulan, and glycogen) fibers. These cross-linked fibers are produced by extruding a dissolved carboxylate ester of the polysaccharide while simultaneously hydrolyzing the ester groups and cross-linking the resultant hydroxyl groups.

  • GB-A-1 207 352 describes a water absorbent product of absorbent fibers prepared from one of several fiber forming materials, including guar gum. The guar gum fibers are formed by adding guar to an organic liquid, e.g. isopropyl alcohol, and adding the resulting slurry to excess water to precipitate a hydrate of the guar. The hydrate is then extruded into a coagulating bath to form the fibers.

    • SUMMARY OF THIS INVENTION

  • It has now been found that gellan gum fibers may be produced by extrusion of a gum solution into a gelling bath. The process, advantageously, does not require esterification and subsequent hydrolysis. The process also produces hybrid fibers comprising gellan and one or more additional gums.

    • DETAILED DESCRIPTION

  • By the term "gellan gum", as used herein, is meant the extracellularly produced gum made by the heteropolysaccharide-producing bacterium

    Pseudomonas elodea

    , ATCC 31461, by the whole culture fermentation under a variety of conditions of a medium comprising: a fermentable carbohydrate, a nitrogen source, and other appropriate nutrients. Included is the native, deacylated, partially deacylated, and clarified forms therefore. Gellan gum is also known as S-60.

  • Processes for producing gellan gum are well-known in the art, e.g., U.S. Patents 4,326,052, 4,326,053, 4,377,636, 4,385,126, and 4,503,084.

  • Particularly preferred is deacylated gellan gum, described in U.S-A-4,326,052.

  • In general, gellan gum solutions containing 2-6% gum (percentages herein are on a wt./wt. basis unless stated otherwise) are extruded through fine orifices into coagulating baths containing various cations to produce filamentous fibers which can be used in wound dressings, catamenial devices, etc. Gellan gum may be used by itself or in combination with other polysaccharides such as alginates, xanthan gum, and locust bean gum. Solutions may be extruded cold (room temperature-50°C) or hot (50°-80°C); if hot, the addition of another gum is usually necessary. Gellan gum is especially useful for producing fibers containing magnesium for controlled release of that cation. The fibers may also contain known wound healing agents.

  • When the gellan gum is co-extruded with other polysaccharides, this produces fibers with hybrid properties.

  • The bath of gelling salts is an aqueous solution of 0.5-5% of a soluble salt, the cation of which may be mono-, di-, or tri-valent and selected from those of Groups I, II, and III of the Perodic Table, especially Na⁺, K⁺, Ca⁺⁺, Mg⁺⁺, and Al⁺⁺⁺. Ca⁺⁺ and Mg⁺⁺ are especially preferred. The anion may be chloride sulfate, lactate, phosphate, carbonate, gluconate, or tartrate. Residence time is the bath is 5 seconds - 5 minutes.

  • When a second polysaccharide is used it is one which exhibits a high viscosity when hot; in particular, algin, xanthan gum, and locust bean gum or combinations of these. The second gum can replace up to 33 1/3% of the gellan gum; i.e., up to 2% of a 6% gum solution may be comprised of one or more of a second polysaccharide.

  • In the final product, therefore, the ratio of gellan gum to said second gum is at least 2:1.

  • By algin is meant the soluble derivatives of alginic acid, which may be chemically extracted from all species of

    Phaeophyceae

    , brown algae. The term is intended to include the soluble salts of alginic acid (e.g., sodium, potassium, or ammonium alginate) and the salts of its ethers (e.g., propylene glycol alginate).

  • By xanthan gum is meant the biosynthetic polysaccharide produced by the organism

    Xanthomonas campestris

    by the whole culture fermentation of a medium comprising a fermentable carbohydrate, a nitrogen source and appropriate other nutrients.

  • Xanthan gum preparation is described in numerous publications and patents, e.g., U.S. Patents 3,671,398; 3,594,280; 3,591,578; 3,481,889; 3,433,708; 3,427,226; 3,391,061; 3,391,060; 3,271,267; 3,251,749; and 3,020,206.

  • Locust bean gum (lbg) is an extract of the locust bean or carob,

    Ceratonia siligua

    . It is commercially available and used as a stabilizer in foods such as ice cream, sausages, and cheese.

  • Gellan gum is normally gelled by heating an aqueous solution to dissolve the gum then simply cooling to produce a gel, provided cations are present. It is also known that solutions may be prepared cold in distilled or deionized water by the addition of a small amount of sequestrant. The sequestrants which can be used in this invention include trisodium orthophosphate (TSP), ethylenediaminetetraacetic acid (EDTA), sodium citrate, tetrasodium pyrophosphate (TSPP), sodium hexametaphosphate (Calgon) and the like. Gellan gum fibers can therefore be prepared by forcing a solution of 2.0% deacylated, clarified gellan gum containing 0.25% sodium citrate in deionized water through a nozzle having a diameter of eleven thousandth of an inch into a 2% calcium chloride bath where fiber formation immediately occurs.

  • Gellan gum is particularly useful for forming fibers containing magnesium ions as it also gels in the presence of magnesium salts. The 2% gellan gum solution above was also forced into a bath containing 2% magnesium sulfate wherein fiber formation also immediately occurred. Fibers containing a source of magnesium are valuable additives to catamenial devices such as tampons where magnesium ions are said to prevent toxic shock syndrome. Magnesium alginate is soluble in water; therefore it cannot be formed by useful methods but must be formed by ion exchange from insoluble calcium alginate fibers already produced by the usual methods. A small amount can be formed simultaneously with gellan gum fibers however, by incorporating sodium alginate into gellan gum solutions before extrusion into the gelling bath. Up to about 25% sodium alginate based on the weight of the gellan gum is possible without destroying the fiber integrity. Thus, 2.0% gellan gum plus 0.5% alginate having a viscosity of 95,000 cP as measured on a Brookfield LVT viscometer, spindle 4, 6 rpm, 25°C was extruded into a bath containing 2% magnesium sulfate wherein gelation and fiber formation immediately occurred. Since the alginate tends to swell slightly the bath may also contain up to 50% of a lower alcohol such as isopropanol to minimize swelling. The same solution above was extruded into a 2% calcium chloride bath wherein fiber formation immediately occurred.

  • Fiber formation from hot solutions is more complicated. Gellan gum solutions have high viscosity when cold but low viscosity when heated, which makes it possible to prepare more concentrated solutions which gel more rapidly with higher gel strength. Fiber production by extrusion from hot gum solutions into a bath were not successful, however, because the low viscosity solution dispersed into flocs without forming a continuous fiber. It has been found that the addition of another polysaccharide which produces more viscosity at temperatures of 50-80°C make fiber formation possible. Thus, a hot 4% gellan gum solution forced through a nozzle into a 2% calcium chloride bath instantly dispersed while a 4% gellan gum solution containing 1% sodium alginate having a viscosity of 4,400 cP as measured on a Brookfield LVT viscometer, spindle 4, 60 rpm, 70°C formed fibers under the same conditions. The high viscosity thickeners xanthan gum and locust bean gum or a combination of the two also produced fibers when combined with the gellan gum at levels of 0.5-1.0%.

  • The fibers of this invention can be used in various forms. If a non-woven fabric is to be prepared, and this is the fabric of choice, a cotton card may be used to form a web, which may then be cross-lapped and then needle punched in conventional equipment.

  • If a woven fabric is to be prepared, the fibers may be carded and then spun into a yarn, which can be woven in a conventional loom. Alternatively, the fibers may be collected in a spinning box, according to the method of Tallis (GB-A-568,177) and woven. If a knitted fabric is to be prepared, the fibers can be prepared as a continuous filament yarn (again according to GB-A-568,177) which is then knitted on a conventional knitting machine.

  • The fiber end product (e.g., a pad) may include one or more antimicrobial (for example, antibacterial or antifungal) agents and/or one or more local anesthetics (for example, procaine) and additionally or alternatively one or more pharmaceutical agents.

Claims (4)

  1. A fiber comprising gellan gum and one or more of a second gum, which is algin, xanthan, or locust bean gum, wherein the ratio gellan gum to said second gum is at least 2:1.

  2. A method of producing gellan gum fibers which comprises extruding a 2-6% gellan gum solution into a coagulating bath comprising 0.5-5.0% gelling salts.

  3. The method of Claim 2 wherein the gelling salts are of calcium or magnesium.

  4. The method of Claim 2 wherein the gum solution comprises one or more of a second gum, which is algin, xanthan, or locust bean gum, and wherein the ratio of gellan to said second gum is at least 2:1.

EP19910303521 1990-04-23 1991-04-19 Gellan gum fibers Expired - Lifetime EP0454373B1 (en)

Applications Claiming Priority (2)

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US51341290A 1990-04-23 1990-04-23
US513412 1990-04-23

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EP0454373A3 EP0454373A3 (en) 1993-01-20
EP0454373B1 true EP0454373B1 (en) 1995-08-23

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JP (1) JP2557572B2 (en)
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US6387978B2 (en) 1996-07-11 2002-05-14 Boston Scientific Corporation Medical devices comprising ionically and non-ionically crosslinked polymer hydrogels having improved mechanical properties
USRE38158E1 (en) 1994-07-27 2003-06-24 Minnesota Mining And Manufacturing Company Adhesive sealant composition

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US5531716A (en) * 1993-09-29 1996-07-02 Hercules Incorporated Medical devices subject to triggered disintegration
AU4526296A (en) * 1994-12-27 1996-07-19 Monsanto Company Gelled, alcohol-free carbonated beverage
GB2310668B (en) * 1996-02-28 2000-04-19 Johnson & Johnson Medical Solid polysaccharide materials for use as wound dressings
US6368356B1 (en) 1996-07-11 2002-04-09 Scimed Life Systems, Inc. Medical devices comprising hydrogel polymers having improved mechanical properties
KR100525693B1 (en) 1996-08-27 2005-11-03 산에이겐 에후.에후. 아이. 가부시키가이샤 Novel Use of Native Gellan Gum
US6453608B1 (en) * 1997-10-31 2002-09-24 Monsanto Company Gellan gum seed coating
US6913765B2 (en) 2001-03-21 2005-07-05 Scimed Life Systems, Inc. Controlling resorption of bioresorbable medical implant material
US8685943B2 (en) 2003-03-12 2014-04-01 Hill's Pet Nutrition, Inc. Methods for reducing diarrhea in a companion animal
EP1666075A1 (en) 2004-10-04 2006-06-07 Switch Biotech Aktiengesellschaft Wound dressing compositions, especially for delivery of protease inhibitors
GB201500430D0 (en) 2015-01-12 2015-02-25 Univ Birmingham Dressing
WO2018078562A1 (en) * 2016-10-26 2018-05-03 Association For The Advancement Of Tissue Engineering And Cell Based Technologies & Therapies (A4Tec) Fibers with segments, their preparation and applications thereof

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GB1207352A (en) * 1967-10-16 1970-09-30 David Torr Disposable absorbent products
JPS63267361A (en) * 1987-04-24 1988-11-04 San Ei Chem Ind Ltd Gelled substance carrying perfume or the like

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE38158E1 (en) 1994-07-27 2003-06-24 Minnesota Mining And Manufacturing Company Adhesive sealant composition
US6387978B2 (en) 1996-07-11 2002-05-14 Boston Scientific Corporation Medical devices comprising ionically and non-ionically crosslinked polymer hydrogels having improved mechanical properties

Also Published As

Publication number Publication date
CA2040959A1 (en) 1991-10-24
JPH04222223A (en) 1992-08-12
EP0454373A3 (en) 1993-01-20
EP0454373A2 (en) 1991-10-30
DE69112260D1 (en) 1995-09-28
DE69112260T2 (en) 1996-04-11
JP2557572B2 (en) 1996-11-27

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