US20080078514A1 - Methods for the preparation of cellulose fibers having superabsorbent particles adhered thereto - Google Patents
Methods for the preparation of cellulose fibers having superabsorbent particles adhered thereto Download PDFInfo
- Publication number
- US20080078514A1 US20080078514A1 US11/537,973 US53797306A US2008078514A1 US 20080078514 A1 US20080078514 A1 US 20080078514A1 US 53797306 A US53797306 A US 53797306A US 2008078514 A1 US2008078514 A1 US 2008078514A1
- Authority
- US
- United States
- Prior art keywords
- polymers
- cellulose
- fibers
- particles
- superabsorbent
- 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
Links
- 239000002245 particle Substances 0.000 title claims abstract description 81
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 38
- 239000005017 polysaccharide Substances 0.000 claims abstract description 38
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 32
- 229920002678 cellulose Polymers 0.000 claims abstract description 30
- 239000001913 cellulose Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000835 fiber Substances 0.000 claims description 81
- 150000004804 polysaccharides Chemical class 0.000 claims description 37
- 235000010980 cellulose Nutrition 0.000 claims description 31
- 239000002131 composite material Substances 0.000 claims description 30
- 229920002472 Starch Polymers 0.000 claims description 18
- 235000019698 starch Nutrition 0.000 claims description 18
- 229920002907 Guar gum Polymers 0.000 claims description 11
- 239000000665 guar gum Substances 0.000 claims description 11
- 235000010417 guar gum Nutrition 0.000 claims description 11
- 229960002154 guar gum Drugs 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 11
- 229920000247 superabsorbent polymer Polymers 0.000 claims description 10
- 235000010443 alginic acid Nutrition 0.000 claims description 9
- 229920000615 alginic acid Polymers 0.000 claims description 9
- 239000004583 superabsorbent polymers (SAPs) Substances 0.000 claims description 9
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 claims description 8
- 229920000926 Galactomannan Polymers 0.000 claims description 8
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 229920002581 Glucomannan Polymers 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229940046240 glucomannan Drugs 0.000 claims description 7
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 6
- 229920001661 Chitosan Polymers 0.000 claims description 5
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 5
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical class [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 5
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 229920001612 Hydroxyethyl starch Polymers 0.000 claims description 4
- 150000004781 alginic acids Chemical class 0.000 claims description 4
- 229920001525 carrageenan Polymers 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 229940050526 hydroxyethylstarch Drugs 0.000 claims description 4
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 3
- JDIBGQFKXXXXPN-UHFFFAOYSA-N bismuth(3+) Chemical class [Bi+3] JDIBGQFKXXXXPN-UHFFFAOYSA-N 0.000 claims description 3
- FRWDHMWMHYXNLW-UHFFFAOYSA-N boron(3+) Chemical class [B+3] FRWDHMWMHYXNLW-UHFFFAOYSA-N 0.000 claims description 3
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical class [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 3
- 108010064470 polyaspartate Proteins 0.000 claims 2
- 229920001059 synthetic polymer Polymers 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000007900 aqueous suspension Substances 0.000 abstract description 4
- 150000004676 glycans Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 21
- 239000002250 absorbent Substances 0.000 description 16
- 230000002745 absorbent Effects 0.000 description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 13
- 241001122767 Theaceae Species 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 229920001477 hydrophilic polymer Polymers 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000000123 paper Substances 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920005615 natural polymer Polymers 0.000 description 5
- 230000003993 interaction Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920013683 Celanese Polymers 0.000 description 3
- 206010021639 Incontinence Diseases 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 241000218657 Picea Species 0.000 description 2
- 235000005018 Pinus echinata Nutrition 0.000 description 2
- 241001236219 Pinus echinata Species 0.000 description 2
- 235000017339 Pinus palustris Nutrition 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VZZHAYFWMLLWGG-UHFFFAOYSA-K triazanium;bismuth;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].[NH4+].[NH4+].[Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O VZZHAYFWMLLWGG-UHFFFAOYSA-K 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- KJLPSBMDOIVXSN-UHFFFAOYSA-N 4-[4-[2-[4-(3,4-dicarboxyphenoxy)phenyl]propan-2-yl]phenoxy]phthalic acid Chemical compound C=1C=C(OC=2C=C(C(C(O)=O)=CC=2)C(O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 KJLPSBMDOIVXSN-UHFFFAOYSA-N 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002752 Konjac Polymers 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 1
- KLMDYFUUSKOJAX-UHFFFAOYSA-K aluminum;acetate;dihydroxide Chemical compound CC(=O)O[Al](O)O KLMDYFUUSKOJAX-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000252 konjac Substances 0.000 description 1
- 235000019823 konjac gum Nutrition 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000213 tara gum Substances 0.000 description 1
- 235000010491 tara gum Nutrition 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- CAYKLJBSARHIDI-UHFFFAOYSA-K trichloroalumane;hydrate Chemical compound O.Cl[Al](Cl)Cl CAYKLJBSARHIDI-UHFFFAOYSA-K 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
Definitions
- Personal care absorbent products such as infant diapers, adult incontinent pads, and feminine care products, typically contain an absorbent core that includes superabsorbent polymer particles distributed within a fibrous matrix.
- Superabsorbents are water-swellable, generally water-insoluble absorbent materials having a high absorbent capacity for body fluids.
- Superabsorbent polymers (SAPS) in common use are mostly derived from acrylic acid, which is itself derived from petroleum oil, a non-renewable raw material. Acrylic acid polymers and SAPs are generally recognized as not being biodegradable. Despite their wide use, some segments of the absorbent products market are concerned about the use of nonrenewable petroleum oil derived materials and their non-biodegradable nature.
- Acrylic acid based polymers also comprise a meaningful portion of the cost structure of diapers and incontinent pads. Users of SAP are interested in lower cost SAPs. The high cost derives in part from the cost structure for the manufacture of acrylic acid which, in turn, depends upon the fluctuating price of petroleum oil. Also, when diapers are discarded after use they normally contain considerably less than their maximum or theoretical content of body fluids. In other words, in terms of their fluid holding capacity, they are “over-designed”. This “over-design” constitutes an inefficiency in the use of SAP. The inefficiency results in part from the fact that SAPs are designed to have high gel strength (as demonstrated by high absorbency under load or AUL).
- the high gel strength (upon swelling) of currently used SAP particles helps them to retain a lot of void space between particles, which is helpful for rapid fluid uptake.
- this high “void volume” simultaneously results in there being a lot of interstitial (between particle) liquid in the product in the saturated state.
- interstitial liquid the “rewet” value or “wet feeling” of an absorbent product is compromised.
- U.S. southern pine fluff pulp is commonly used in conjunction with the SAP. This fluff is recognized worldwide as the preferred fiber for absorbent products. The preference is based on the fluff pulp's advantageous high fiber length (about 2.8 mm) and its relative ease of processing from a wetland pulp sheet to an airlaid web.
- Fluff pulp is also made from renewable and biodegradable cellulose pulp fibers. Compared to SAP, these fibers are inexpensive on a per mass basis, but tend to be more expensive on a per unit of liquid held basis. These fluff pulp fibers mostly absorb within the interstices between fibers. For this reason, a fibrous matrix readily releases acquired liquid on application of pressure. The tendency to release acquired liquid can result in significant skin wetness during use of an absorbent product that includes a core formed exclusively from cellulosic fibers. Such products also tend to leak acquired liquid because liquid is not effectively retained in such a fibrous absorbent core.
- Superabsorbent composites in fiber form have a distinct advantage over particle forms in some applications. Such superabsorbent composite fibers can be made into a pad form directly. Liquid acquisition will be more uniform compared to a fiber pad with shifting superabsorbent particles.
- Biodegradable renewable fibers such as cellulose fiber is ideally suitable for such a fibrous superabsorbent composite material, if it can be treated and made to have strong affinity to superabsorbent particles. In this way, the superabsorbent material can be used in absorbent product designs that are efficient.
- the invention provides a method for adhering superabsorbent particles to cellulose fibers, comprising adding a plurality of superabsorbent particles to a first aqueous mixture comprising cellulose treated with a polysaccharide polymer to provide a second aqueous mixture; and mixing the second aqueous mixture with a water-miscible solvent to provide cellulose fibers having superabsorbent particles adhered thereto.
- the method includes applying a crosslinking agent to the cellulose treated with the polysaccharide in the first aqueous mixture prior to adding the particles.
- FIG. 1 is a scanning electron microscope photograph (13 ⁇ ) of representative fibers with adhered superabsorbent particles made in accordance with the method of the invention (Sample 3, Table 1);
- FIG. 2 is a scanning electron microscope photograph (100 ⁇ ) of representative fibers with adhered superabsorbent particles made in accordance with the method of the invention (Sample 3, Table 1);
- FIG. 3 is a scanning electron microscope photograph (13 ⁇ ) of representative fibers with adhered superabsorbent particles made in accordance with the method of the invention (Sample 4, Table 1);
- FIG. 4 is a scanning electron microscope photograph (100 ⁇ ) of representative fibers with adhered superabsorbent particles made in accordance with the method of the invention (Sample 4, Table 1).
- the present invention provides a method for adhering particles (e.g., superabsorbent particles) to cellulose fibers.
- the method includes the steps of adding a plurality of particles to a first aqueous mixture comprising cellulose treated with a polysaccharide polymer to provide a second aqueous mixture; and mixing the second aqueous mixture with a water-miscible solvent to provide cellulose fibers having particles adhered thereto.
- the method includes applying a crosslinking agent to the cellulose treated with the polysaccharide in the first aqueous mixture prior to adding the particles.
- the product fibers are obtained by filtration.
- the method further includes the steps of drying the cellulose fibers having particles adhered thereto to provide partially-dried composite fibers (30-50% consistency).
- the partially-dried composite fibers can be fiberized to provide partially-dried fiberized composite fibers.
- the partially-dried fiberized composite fibers can be further dried to provide dried fiberized cellulose fibers having particles adhered thereto.
- cellulose fibers that have been treated with a hydrophilic polysaccharide are combined with superabsorbent particles.
- suitable cellulosic fibers are derived primarily from wood pulp.
- Suitable wood pulp fibers for use with the invention can be obtained from well-known chemical processes such as the kraft and sulfite processes, with or without subsequent bleaching. Pulp fibers can also be processed by thermomechanical, chemithermomechanical methods, or combinations thereof. A high alpha cellulose pulp is also a suitable wood pulp fiber. The preferred pulp fiber is produced by chemical methods. Ground wood fibers, recycled or secondary wood pulp fibers, and bleached and unbleached wood pulp fibers can be used. Softwoods and hardwoods can be used. Suitable fibers are commercially available from a number of companies, including Weyerhaeuser Company.
- suitable cellulosic fibers produced from southern pine that are usable with the present invention are available from Weyerhaeuser Company under the designations CF416, NF405, PL416, FR516, and NB416.
- Other suitable fibers include northern softwood and eucalyptus fibers.
- hydrophilic polysaccharide polymer refers to any one of a variety of polysaccharide polymers that are hydrophilic and that have a tendency to associate with cellulose.
- Representative hydrophilic polysaccharide polymers include natural polymers, such as galactomannan polymers, glucomannan polymers, alginic acids, carageenans, starches and starch derivatives such as carboxymethyl starch, and hydroxyethyl starch, and cellulose derivatives such as such as carboxymethyl cellulose, hydroxyethyl cellulose.
- the hydrophilic polysaccharide polymer is a galactomannan polymer.
- Representative galactomannan polymers include guar gum, locust bean gum, and tara gum.
- the hydrophilic polysaccharide polymer is a glucomannan polymer.
- Representative glucomannan polymers include konjac gum.
- the cellulose treated with hydrophilic polysaccharide polymer includes from about 1 to about 20 percent by weight hydrophilic polysaccharide polymer based on the weight of cellulose.
- hydrophilic polysaccharide polymer treated cellulose is prepared by dissolving a desired amount of the hydrophilic polysaccharide polymer in water (e.g., 10 g in 1000 mL water) to provide a solution and then adding cellulose fibers (e.g., 1.00 g) with mixing to provide a suspension.
- the treated fibers are obtained by filtration and drying (e.g., 1.0% by weight hydrophilic polysaccharide polymer treated cellulose).
- an aqueous mixture of cellulose fibers treated with a hydrophilic polysaccharide polymer are treated with a crosslinking agent prior to the addition of the superabsorbent particles.
- a crosslinking agent will depend on the nature of the particles to be adhered to the fibers. If the particles are highly crosslinked, added crosslinking agent is not required. However, if the particles are not adequately crosslinked to provide sufficient insolubility in water, then the crosslinking agent is used.
- Suitable crosslinking agents include crosslinking agents that are reactive toward hydroxyl groups and carboxyl groups.
- Representative crosslinking agents include metallic crosslinking agents, such as aluminum (III) compounds, titanium (IV) compounds, bismuth (III) compounds, boron (III) compounds, and zirconium (IV) compounds.
- metallic crosslinking agents such as aluminum (III) compounds, titanium (IV) compounds, bismuth (III) compounds, boron (III) compounds, and zirconium (IV) compounds.
- the numerals in parentheses in the preceding list of metallic crosslinking agents refers to the valency of the metal.
- Representative metallic crosslinking agents include aluminum sulfate; aluminum hydroxide; dihydroxy aluminum acetate (stabilized with boric acid); other aluminum salts of carboxylic acids and inorganic acids; other aluminum complexes, such as Ultrion 8186 from Nalco Company (aluminum chloride hydroxide); boric acid; sodium metaborate; ammonium zirconium carbonate (AZC); zirconium compounds containing inorganic ions or organic ions or neutral ligands; bismuth ammonium citrate (BAC); other bismuth salts of carboxylic acids and inorganic acids; titanium (IV) compounds, such as titanium (IV) bis(triethylaminato) bis(isopropoxide) (commercially available from the Dupont Company under the designation Tyzor TE); and other titanates with alkoxide or carboxylate ligands.
- aluminum complexes such as Ultrion 8186 from Nalco Company (aluminum chloride hydroxide); boric acid; sodium metabor
- the crosslinking agent is applied in an amount up to about 20 percent by weight based on the total weight of the treated cellulose fibers.
- the amount of first crosslinking agent applied to the treated cellulose will vary depending on the crosslinking agent.
- the fibers have an aluminum content up to about 2.0% by weight based on the weight of the composite fibers for aluminum crosslinked fibers, a titanium content of up to about 4.5% by weight based on the weight of the composite fibers for titanium crosslinked fibers, a zirconium content of up to about 6.0% by weight based on the weight of the composite fibers for zirconium crosslinked fibers, and a bismuth content up to about 5.0% by weight based on the weight of the composite fibers for bismuth crosslinked fibers.
- a plurality of superabsorbent particles is added to the first aqueous suspension including the cellulose treated with a hydrophilic polysaccharide polymer that has been optionally treated with a crosslinking agent
- Suitable particles include those derived from synthetic hydrophilic polymers (e.g., superabsorbent polymers or SAPs), such as polyacrylic acids, polyacrylamides, and polyaspartic acids; and hydrophilic polymers (e.g., superabsorbent polymers) derived natural polymers, such as celluloses (e.g., carboxymethyl cellulose), alginates, chitosans, and starches (e.g., carboxymethyl starch).
- SAPs synthetic hydrophilic polymers
- SAPs polyacrylic acids, polyacrylamides, and polyaspartic acids
- hydrophilic polymers e.g., superabsorbent polymers
- celluloses e.g., carboxymethyl cellulose
- alginates e.g., chito
- Superabsorbent particles in the product cellulose fibers are be present in an amount form about 50 to about 80% by weight of the product fibers.
- the polysaccharide treated fiber in the product cellulose fibers are present in an amount form about 20 to 50%, by weight of the product fibers.
- the cellulose fibers having superabsorbent particles attached thereto are obtained by mixing the second aqueous mixture including the plurality of superabsorbent particles and treated cellulose with a water-miscible solvent.
- Suitable water-miscible solvents include water-miscible alcohols and ketones.
- Representative water-miscible solvents include acetone, methanol, ethanol, isopropanol, and mixtures thereof.
- the water-miscible solvent is ethanol.
- the water-miscible solvent is isopropanol.
- the volume of water-miscible solvent added to the gel ranges from about 1:1 to about 1:5 water to water-miscible solvent.
- mixing the gel with the water-miscible solvent includes stirring to provide fibers with adhered superabsorbent particles.
- the mixing step and the use of the water-miscible solvent controls the rate of dehydration and solvent exchange and provides fiber with adhering superabsorbent particles.
- Mixing can be carried out using a variety of devices including overhead stirrers, Hobart mixers, British disintegrators, and blenders.
- the invention provides a method for adhering superabsorbent particles to cellulose fibers, comprising adding a plurality of particles to a first aqueous mixture comprising cellulose treated with a polysaccharide polymer to provide a second aqueous mixture; and mixing the second aqueous suspension with a water-miscible solvent to provide cellulose fibers having superabsorbent particles adhered thereto.
- the method further comprising adding a crosslinking agent to the cellulose treated with polysaccharide in the first aqueous suspension prior to adding the particles.
- the methods of the invention provide cellulose fibers having superabsorbent particles adhered thereto.
- the cellulose fibers having particles adhered thereto include cellulose fibers treated with a hydrophilic polysaccharide polymer and the adhered superabsorbent particles include synthetic hydrophilic polymers (e.g., superabsorbent polymers or SAPs), such as polyacrylic acids, polyacrylamides, and polyaspartic acids; and hydrophilic polymers (e.g., superabsorbent polymers) derived natural polymers, such as celluloses (e.g., carboxymethyl cellulose), alginates, chitosans, and starches (e.g., carboxymethyl starch).
- synthetic hydrophilic polymers e.g., superabsorbent polymers or SAPs
- SAPs synthetic hydrophilic polymers
- polyacrylic acids e.g., polyacrylic acids, polyacrylamides, and polyaspartic acids
- hydrophilic polymers e.g., superabsorbent polymers
- derived natural polymers such as celluloses (e.g., carb
- the cellulose fibers having particles adhered thereto include cellulose fibers treated with a hydrophilic polysaccharide polymer and a crosslinking agent and the adhered superabsorbent particles include synthetic hydrophilic polymers (e.g., superabsorbent polymers or SAPs), such as polyacrylic acids, polyacrylamides, and polyaspartic acids; and hydrophilic polymers (e.g., superabsorbent polymers) derived natural polymers, such as celluloses (e.g., carboxymethyl cellulose), alginates, chitosans, and starches (e.g., carboxymethyl starch).
- synthetic hydrophilic polymers e.g., superabsorbent polymers or SAPs
- SAPs synthetic hydrophilic polymers
- polyacrylic acids e.g., polyacrylic acids, polyacrylamides, and polyaspartic acids
- hydrophilic polymers e.g., superabsorbent polymers
- derived natural polymers such as celluloses
- suitable hydrophilic polysaccharide polymers include natural polymers, such as galactomannan polymers, glucomannan polymers, alginic acids, carageenans, starches and starch derivatives such as carboxymethyl starch, and hydroxyethyl starch, and cellulose derivatives such as such as carboxymethyl cellulose, hydroxyethyl cellulose.
- the polysaccharide is guar gum.
- suitable crosslinking agents include of aluminum (III) compounds, titanium (IV) compounds, bismuth (III) compounds, boron (III) compounds, and zirconium (IV) compounds. Representative crosslinking agents are described above.
- FIGS. 1-4 Representative cellulose fibers having superabsorbent particles adhered thereto are shown in FIGS. 1-4 .
- FIG. 1 is a scanning electron microscope photograph (13 ⁇ ) of representative cellulose fibers having adhered superabsorbent particles (Sample 3, Table 1).
- FIG. 2 is a scanning electron microscope photograph (100 ⁇ ) of representative cellulose fibers having adhered superabsorbent particles (Sample 3, Table 1).
- FIG. 3 is a scanning electron microscope photograph (13 ⁇ ) of representative cellulose fibers having adhered superabsorbent particles (Sample 4, Table 1).
- FIG. 4 is a scanning electron microscope photograph (100 ⁇ ) of representative cellulose fibers having adhered superabsorbent particles (Sample 4, Table 1).
- the fibers are prepared by a process that includes optionally treating an aqueous mixture of a plurality of superabsorbent particles and cellulose treated with a hydrophilic polysaccharide polymer with a metal crosslinking agent to provide a mixture, and then further mixing the mixture with a water-miscible solvent.
- the fibers produced by the method are substantially insoluble in water while being capable of absorbing water.
- the agent When a crosslinking agent is optionally used before adding superabsorbent particles to the aqueous solution containing the cellulose fiber treated with the hydrophilic polysaccharide polymer, the agent provides additional crosslinking of the polymers of the superabsorbent particles. This is suitable when the particles are not sufficiently crosslinked (or under crosslinked by design). When the particles are highly crosslinked, this additional crosslinking is not used to prevent loss of absorbent capacity of the product composite fibers. When a crosslinking agent is optionally used, the agent can also provide additional crosslinks between polymer molecules of the superabsorbent particles and the hydrophilic polymer bound to the cellulose fibers.
- the superabsorbent particles used should not be highly crosslinked.
- the metal crosslink arises as a consequence of an associative interaction (e.g., bonding) between functional groups on the hydrophilic polymers (e.g., carboxy, carboxylate, or hydroxyl groups) and a multi-valent metal species (see description of crosslinking agents above).
- the superabsorbent particles and the treated cellulose fiber contain hydrophilic polymers that can form metal crosslinks.
- Suitable multi-valent metal species include metal ions having a valency of three or greater and that are capable of forming an associative interaction with a polymer (e.g., reactive toward associative interaction with the polymer's carboxy, carboxylate, or hydroxyl groups).
- the polymers are intermolecularly crosslinked when the multi-valent metal species forms an associative interaction with functional groups on two or more polymer molecules.
- a crosslink may be formed within one polymer molecule or may be formed between two or more polymer molecules.
- the product fibers are highly absorptive.
- the fibers have a Free Swell Capacity of from about 30 to about 60 g/g (0.9% saline solution), a Centrifuge Retention Capacity (CRC) of from about 15 to about 35 g/g (0.9% saline solution), and an Absorbency Under Load (AUL) of from about 15 to about 30 g/g (0.9% saline solution).
- the product fibers are useful as a superabsorbent in personal care absorbent products (e.g., infant diapers, feminine care products and adult incontinence products).
- the fibers have the ability to absorb water, saline solutions and biological fluids such as urine and the fibrous form also helps in wicking.
- the fibers are useful in a variety of other applications, including, for example, wound dressings, cable wrap, absorbent sheets or bags, and packaging materials.
- the tea bag material has an absorbency determined as follows:
- Kontes 90 mm ULTRA-WARE filter set up with fritted glass (coarse) filter plate. clamped to stand; 2 L glass bottle with outlet tube near bottom of bottle; rubber stopper with glass tube through the stopper that fits the bottle (air inlet); TYGON tubing; stainless steel rod/plexiglass plunger assembly (71 mm diameter); stainless steel weight with hole drill through to place over plunger (plunger and weight 867 g); VWR 9.0 cm filter papers (Qualitative 413 catalog number 28310-048) cut down to 80 mm size; double-stick SCOTCH tape; and 0.9% saline.
- Filter paper should be at equilibrium by now, zero scale.
- Guar gum (4.0 g) was dissolved in 3200 ml of deionized water.
- Northern kraft spruce (NKS) pulp (40.0 g) was dispersed in the guar gum solution and oven dried at 105° C. This material was used for binding superabsorbent composite particles.
- Aluminum sulfate octadecahydrate 0.035 g was dissolved in 50 ml of deionized water at 80° C. Guar gum treated cellulose fiber (prepared as described as in Example 1) 1.2 g was then dispersed in the aluminum sulfate solution for 15 minutes. Commercial superabsorbent particles (SANWET IM-4500 from Hoechst Celanese) 2.8 g was added to the fiber slurry and mixed for 2 minutes. To the swollen mass of fiber gel was added 150 ml of isopropanol and mixed for 5 minutes to obtain composite fiber with attached superabsorbent particles. The composite fiber obtained was then filtered. The fiber mass was partially dried in the oven at 66° C., The fiber mass was then fiberized and dried in the oven at 66° C.
- SANWET IM-4500 from Hoechst Celanese
- T-bag test gave free swell of 39.75 g/g; centrifuge capacity of 19.86 g/g; and AUL of 27.36 g/g (at 0.3 psi) for 0.9% saline solution.
- Guar gum treated cellulose fiber (prepared as described as in Example 1) 1.2 g was then dispersed in 50 ml of deionized water at 80° C. for 15 minutes.
- Commercial superabsorbent particles (SANWET IM-4500 from Hoechst Celanese) 2.8 g was added to the fiber slurry and mixed for 2 minutes.
- To the swollen mass of fiber gel was added 150 ml of isopropanol and mixed to obtain composite fiber with attached superabsorbent particles.
- the composite fiber obtained was the filtered.
- the fiber mass was partially dried in the oven at 66° C.
- the fiber mass was then fiberized and dried in the oven at 66° C.
- T-bag test gave free swell of 40.50 g/g; centrifuge capacity of 23.54 g/g; and AUL of 28.15 g/g (at 0.3 psi) for 0.9% saline solution.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
- Personal care absorbent products, such as infant diapers, adult incontinent pads, and feminine care products, typically contain an absorbent core that includes superabsorbent polymer particles distributed within a fibrous matrix. Superabsorbents are water-swellable, generally water-insoluble absorbent materials having a high absorbent capacity for body fluids. Superabsorbent polymers (SAPS) in common use are mostly derived from acrylic acid, which is itself derived from petroleum oil, a non-renewable raw material. Acrylic acid polymers and SAPs are generally recognized as not being biodegradable. Despite their wide use, some segments of the absorbent products market are concerned about the use of nonrenewable petroleum oil derived materials and their non-biodegradable nature. Acrylic acid based polymers also comprise a meaningful portion of the cost structure of diapers and incontinent pads. Users of SAP are interested in lower cost SAPs. The high cost derives in part from the cost structure for the manufacture of acrylic acid which, in turn, depends upon the fluctuating price of petroleum oil. Also, when diapers are discarded after use they normally contain considerably less than their maximum or theoretical content of body fluids. In other words, in terms of their fluid holding capacity, they are “over-designed”. This “over-design” constitutes an inefficiency in the use of SAP. The inefficiency results in part from the fact that SAPs are designed to have high gel strength (as demonstrated by high absorbency under load or AUL). The high gel strength (upon swelling) of currently used SAP particles helps them to retain a lot of void space between particles, which is helpful for rapid fluid uptake. However, this high “void volume” simultaneously results in there being a lot of interstitial (between particle) liquid in the product in the saturated state. When there is a lot of interstitial liquid the “rewet” value or “wet feeling” of an absorbent product is compromised.
- In personal care absorbent products, U.S. southern pine fluff pulp is commonly used in conjunction with the SAP. This fluff is recognized worldwide as the preferred fiber for absorbent products. The preference is based on the fluff pulp's advantageous high fiber length (about 2.8 mm) and its relative ease of processing from a wetland pulp sheet to an airlaid web. Fluff pulp is also made from renewable and biodegradable cellulose pulp fibers. Compared to SAP, these fibers are inexpensive on a per mass basis, but tend to be more expensive on a per unit of liquid held basis. These fluff pulp fibers mostly absorb within the interstices between fibers. For this reason, a fibrous matrix readily releases acquired liquid on application of pressure. The tendency to release acquired liquid can result in significant skin wetness during use of an absorbent product that includes a core formed exclusively from cellulosic fibers. Such products also tend to leak acquired liquid because liquid is not effectively retained in such a fibrous absorbent core.
- Superabsorbent composites in fiber form have a distinct advantage over particle forms in some applications. Such superabsorbent composite fibers can be made into a pad form directly. Liquid acquisition will be more uniform compared to a fiber pad with shifting superabsorbent particles.
- A need therefore exists for fibrous superabsorbent materials that have the ability to have superabsorbent particles attached to the fibers. Biodegradable renewable fibers such as cellulose fiber is ideally suitable for such a fibrous superabsorbent composite material, if it can be treated and made to have strong affinity to superabsorbent particles. In this way, the superabsorbent material can be used in absorbent product designs that are efficient. These and other objectives are accomplished by the invention set forth below.
- The invention provides a method for adhering superabsorbent particles to cellulose fibers, comprising adding a plurality of superabsorbent particles to a first aqueous mixture comprising cellulose treated with a polysaccharide polymer to provide a second aqueous mixture; and mixing the second aqueous mixture with a water-miscible solvent to provide cellulose fibers having superabsorbent particles adhered thereto. In one embodiment, the method includes applying a crosslinking agent to the cellulose treated with the polysaccharide in the first aqueous mixture prior to adding the particles.
- The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
-
FIG. 1 is a scanning electron microscope photograph (13×) of representative fibers with adhered superabsorbent particles made in accordance with the method of the invention (Sample 3, Table 1); -
FIG. 2 is a scanning electron microscope photograph (100×) of representative fibers with adhered superabsorbent particles made in accordance with the method of the invention (Sample 3, Table 1); -
FIG. 3 is a scanning electron microscope photograph (13×) of representative fibers with adhered superabsorbent particles made in accordance with the method of the invention (Sample 4, Table 1); and -
FIG. 4 is a scanning electron microscope photograph (100×) of representative fibers with adhered superabsorbent particles made in accordance with the method of the invention (Sample 4, Table 1). - In one aspect, the present invention provides a method for adhering particles (e.g., superabsorbent particles) to cellulose fibers. The method includes the steps of adding a plurality of particles to a first aqueous mixture comprising cellulose treated with a polysaccharide polymer to provide a second aqueous mixture; and mixing the second aqueous mixture with a water-miscible solvent to provide cellulose fibers having particles adhered thereto. In one embodiment, the method includes applying a crosslinking agent to the cellulose treated with the polysaccharide in the first aqueous mixture prior to adding the particles.
- The product fibers are obtained by filtration. In one embodiment, the method further includes the steps of drying the cellulose fibers having particles adhered thereto to provide partially-dried composite fibers (30-50% consistency). The partially-dried composite fibers can be fiberized to provide partially-dried fiberized composite fibers. The partially-dried fiberized composite fibers can be further dried to provide dried fiberized cellulose fibers having particles adhered thereto.
- In the method, cellulose fibers that have been treated with a hydrophilic polysaccharide are combined with superabsorbent particles.
- Although available from other sources, suitable cellulosic fibers are derived primarily from wood pulp. Suitable wood pulp fibers for use with the invention can be obtained from well-known chemical processes such as the kraft and sulfite processes, with or without subsequent bleaching. Pulp fibers can also be processed by thermomechanical, chemithermomechanical methods, or combinations thereof. A high alpha cellulose pulp is also a suitable wood pulp fiber. The preferred pulp fiber is produced by chemical methods. Ground wood fibers, recycled or secondary wood pulp fibers, and bleached and unbleached wood pulp fibers can be used. Softwoods and hardwoods can be used. Suitable fibers are commercially available from a number of companies, including Weyerhaeuser Company. For example, suitable cellulosic fibers produced from southern pine that are usable with the present invention are available from Weyerhaeuser Company under the designations CF416, NF405, PL416, FR516, and NB416. Other suitable fibers include northern softwood and eucalyptus fibers.
- As used herein, the term “hydrophilic polysaccharide polymer” refers to any one of a variety of polysaccharide polymers that are hydrophilic and that have a tendency to associate with cellulose. Representative hydrophilic polysaccharide polymers include natural polymers, such as galactomannan polymers, glucomannan polymers, alginic acids, carageenans, starches and starch derivatives such as carboxymethyl starch, and hydroxyethyl starch, and cellulose derivatives such as such as carboxymethyl cellulose, hydroxyethyl cellulose. In one embodiment, the hydrophilic polysaccharide polymer is a galactomannan polymer. Representative galactomannan polymers include guar gum, locust bean gum, and tara gum. In one embodiment, the hydrophilic polysaccharide polymer is a glucomannan polymer. Representative glucomannan polymers include konjac gum. The cellulose treated with hydrophilic polysaccharide polymer includes from about 1 to about 20 percent by weight hydrophilic polysaccharide polymer based on the weight of cellulose.
- The preparation of representative cellulose fibers treated with a hydrophilic polysaccharide polymer (e.g., guar gum treated cellulose fibers) is described in Example 1. In general, hydrophilic polysaccharide polymer treated cellulose is prepared by dissolving a desired amount of the hydrophilic polysaccharide polymer in water (e.g., 10 g in 1000 mL water) to provide a solution and then adding cellulose fibers (e.g., 1.00 g) with mixing to provide a suspension. The treated fibers are obtained by filtration and drying (e.g., 1.0% by weight hydrophilic polysaccharide polymer treated cellulose).
- In one embodiment, an aqueous mixture of cellulose fibers treated with a hydrophilic polysaccharide polymer are treated with a crosslinking agent prior to the addition of the superabsorbent particles. The use of a crosslinking agent will depend on the nature of the particles to be adhered to the fibers. If the particles are highly crosslinked, added crosslinking agent is not required. However, if the particles are not adequately crosslinked to provide sufficient insolubility in water, then the crosslinking agent is used.
- Suitable crosslinking agents include crosslinking agents that are reactive toward hydroxyl groups and carboxyl groups. Representative crosslinking agents include metallic crosslinking agents, such as aluminum (III) compounds, titanium (IV) compounds, bismuth (III) compounds, boron (III) compounds, and zirconium (IV) compounds. The numerals in parentheses in the preceding list of metallic crosslinking agents refers to the valency of the metal.
- Representative metallic crosslinking agents include aluminum sulfate; aluminum hydroxide; dihydroxy aluminum acetate (stabilized with boric acid); other aluminum salts of carboxylic acids and inorganic acids; other aluminum complexes, such as Ultrion 8186 from Nalco Company (aluminum chloride hydroxide); boric acid; sodium metaborate; ammonium zirconium carbonate (AZC); zirconium compounds containing inorganic ions or organic ions or neutral ligands; bismuth ammonium citrate (BAC); other bismuth salts of carboxylic acids and inorganic acids; titanium (IV) compounds, such as titanium (IV) bis(triethylaminato) bis(isopropoxide) (commercially available from the Dupont Company under the designation Tyzor TE); and other titanates with alkoxide or carboxylate ligands.
- The crosslinking agent is applied in an amount up to about 20 percent by weight based on the total weight of the treated cellulose fibers. The amount of first crosslinking agent applied to the treated cellulose will vary depending on the crosslinking agent. In general, the fibers have an aluminum content up to about 2.0% by weight based on the weight of the composite fibers for aluminum crosslinked fibers, a titanium content of up to about 4.5% by weight based on the weight of the composite fibers for titanium crosslinked fibers, a zirconium content of up to about 6.0% by weight based on the weight of the composite fibers for zirconium crosslinked fibers, and a bismuth content up to about 5.0% by weight based on the weight of the composite fibers for bismuth crosslinked fibers.
- In the method, a plurality of superabsorbent particles is added to the first aqueous suspension including the cellulose treated with a hydrophilic polysaccharide polymer that has been optionally treated with a crosslinking agent, Suitable particles include those derived from synthetic hydrophilic polymers (e.g., superabsorbent polymers or SAPs), such as polyacrylic acids, polyacrylamides, and polyaspartic acids; and hydrophilic polymers (e.g., superabsorbent polymers) derived natural polymers, such as celluloses (e.g., carboxymethyl cellulose), alginates, chitosans, and starches (e.g., carboxymethyl starch). The combination of a carboxyalkyl cellulose and either a glucomannan or galactomannan polymer is not considered to be a superabsorbent particle in the context of this invention.
- Superabsorbent particles in the product cellulose fibers are be present in an amount form about 50 to about 80% by weight of the product fibers. The polysaccharide treated fiber in the product cellulose fibers are present in an amount form about 20 to 50%, by weight of the product fibers.
- The cellulose fibers having superabsorbent particles attached thereto are obtained by mixing the second aqueous mixture including the plurality of superabsorbent particles and treated cellulose with a water-miscible solvent. Suitable water-miscible solvents include water-miscible alcohols and ketones. Representative water-miscible solvents include acetone, methanol, ethanol, isopropanol, and mixtures thereof. In one embodiment, the water-miscible solvent is ethanol. In another embodiment, the water-miscible solvent is isopropanol.
- The volume of water-miscible solvent added to the gel ranges from about 1:1 to about 1:5 water to water-miscible solvent.
- In the method, mixing the gel with the water-miscible solvent includes stirring to provide fibers with adhered superabsorbent particles. The mixing step and the use of the water-miscible solvent controls the rate of dehydration and solvent exchange and provides fiber with adhering superabsorbent particles. Mixing can be carried out using a variety of devices including overhead stirrers, Hobart mixers, British disintegrators, and blenders.
- Thus, in one embodiment, the invention provides a method for adhering superabsorbent particles to cellulose fibers, comprising adding a plurality of particles to a first aqueous mixture comprising cellulose treated with a polysaccharide polymer to provide a second aqueous mixture; and mixing the second aqueous suspension with a water-miscible solvent to provide cellulose fibers having superabsorbent particles adhered thereto.
- As noted above, in another embodiment, the method further comprising adding a crosslinking agent to the cellulose treated with polysaccharide in the first aqueous suspension prior to adding the particles.
- The methods of the invention provide cellulose fibers having superabsorbent particles adhered thereto.
- In one embodiment, the cellulose fibers having particles adhered thereto, include cellulose fibers treated with a hydrophilic polysaccharide polymer and the adhered superabsorbent particles include synthetic hydrophilic polymers (e.g., superabsorbent polymers or SAPs), such as polyacrylic acids, polyacrylamides, and polyaspartic acids; and hydrophilic polymers (e.g., superabsorbent polymers) derived natural polymers, such as celluloses (e.g., carboxymethyl cellulose), alginates, chitosans, and starches (e.g., carboxymethyl starch).
- In another embodiment, the cellulose fibers having particles adhered thereto, include cellulose fibers treated with a hydrophilic polysaccharide polymer and a crosslinking agent and the adhered superabsorbent particles include synthetic hydrophilic polymers (e.g., superabsorbent polymers or SAPs), such as polyacrylic acids, polyacrylamides, and polyaspartic acids; and hydrophilic polymers (e.g., superabsorbent polymers) derived natural polymers, such as celluloses (e.g., carboxymethyl cellulose), alginates, chitosans, and starches (e.g., carboxymethyl starch).
- As noted above, suitable hydrophilic polysaccharide polymers include natural polymers, such as galactomannan polymers, glucomannan polymers, alginic acids, carageenans, starches and starch derivatives such as carboxymethyl starch, and hydroxyethyl starch, and cellulose derivatives such as such as carboxymethyl cellulose, hydroxyethyl cellulose. In one embodiment, the polysaccharide is guar gum.
- For hydrophilic polysaccharide treated cellulose fibers also treated with a crosslinking agent suitable crosslinking agents include of aluminum (III) compounds, titanium (IV) compounds, bismuth (III) compounds, boron (III) compounds, and zirconium (IV) compounds. Representative crosslinking agents are described above.
- Representative cellulose fibers having superabsorbent particles adhered thereto are shown in
FIGS. 1-4 .FIG. 1 is a scanning electron microscope photograph (13×) of representative cellulose fibers having adhered superabsorbent particles (Sample 3, Table 1).FIG. 2 is a scanning electron microscope photograph (100×) of representative cellulose fibers having adhered superabsorbent particles (Sample 3, Table 1).FIG. 3 is a scanning electron microscope photograph (13×) of representative cellulose fibers having adhered superabsorbent particles (Sample 4, Table 1).FIG. 4 is a scanning electron microscope photograph (100×) of representative cellulose fibers having adhered superabsorbent particles (Sample 4, Table 1). - The fibers are prepared by a process that includes optionally treating an aqueous mixture of a plurality of superabsorbent particles and cellulose treated with a hydrophilic polysaccharide polymer with a metal crosslinking agent to provide a mixture, and then further mixing the mixture with a water-miscible solvent. The fibers produced by the method are substantially insoluble in water while being capable of absorbing water.
- When a crosslinking agent is optionally used before adding superabsorbent particles to the aqueous solution containing the cellulose fiber treated with the hydrophilic polysaccharide polymer, the agent provides additional crosslinking of the polymers of the superabsorbent particles. This is suitable when the particles are not sufficiently crosslinked (or under crosslinked by design). When the particles are highly crosslinked, this additional crosslinking is not used to prevent loss of absorbent capacity of the product composite fibers. When a crosslinking agent is optionally used, the agent can also provide additional crosslinks between polymer molecules of the superabsorbent particles and the hydrophilic polymer bound to the cellulose fibers. To take advantage of this favorable attractions between superabsorbent particles and the hydrophilic polysaccharide treated cellulose fibers, the superabsorbent particles used should not be highly crosslinked. The metal crosslink arises as a consequence of an associative interaction (e.g., bonding) between functional groups on the hydrophilic polymers (e.g., carboxy, carboxylate, or hydroxyl groups) and a multi-valent metal species (see description of crosslinking agents above). The superabsorbent particles and the treated cellulose fiber contain hydrophilic polymers that can form metal crosslinks. Suitable multi-valent metal species include metal ions having a valency of three or greater and that are capable of forming an associative interaction with a polymer (e.g., reactive toward associative interaction with the polymer's carboxy, carboxylate, or hydroxyl groups). The polymers are intermolecularly crosslinked when the multi-valent metal species forms an associative interaction with functional groups on two or more polymer molecules. A crosslink may be formed within one polymer molecule or may be formed between two or more polymer molecules.
- The product fibers are highly absorptive. The fibers have a Free Swell Capacity of from about 30 to about 60 g/g (0.9% saline solution), a Centrifuge Retention Capacity (CRC) of from about 15 to about 35 g/g (0.9% saline solution), and an Absorbency Under Load (AUL) of from about 15 to about 30 g/g (0.9% saline solution).
- The product fibers are useful as a superabsorbent in personal care absorbent products (e.g., infant diapers, feminine care products and adult incontinence products). The fibers have the ability to absorb water, saline solutions and biological fluids such as urine and the fibrous form also helps in wicking. The fibers are useful in a variety of other applications, including, for example, wound dressings, cable wrap, absorbent sheets or bags, and packaging materials.
- The preparations of representative fibers are described in Examples 2 and 3 The composition and liquid absorbent characteristics of representative fibers are summarized in the Table 1. In Table 1, for the superabsorbent particle and the polysaccharide polymer treated cellulose, the values in parentheses refer to the relative weight of each in the composite superabsorbent fiber (wgt % total wgt); “Crosslinking agent/4 g” refers to the amount of crosslinking agent applied per 4 g product; “SANIWET-4500” refers to a synthetic superabsorbent particle (a polyacrylic acid particle) commercially available from Hoechst Celanese; “NKS pulp with 10% GG” refers to northern kraft spruce (NKS) pulp treated with 10 weight % guar gum; and “with wash” refers to washing the treated fibers with 100% ethanol or 100% isopropanol before drying.
- The materials, procedure, and calculations to determine tree swell capacity (g/g) and centrifuge retention capacity (CRC) (g/g) were as follows.
- Test Materials:
- Japanese pie-made empty tea bags (available from Drugstore.com, IN PURSUIT OF TEA polyester tea bags 93 mm.×70 mm with fold-over flap. (http:www.mesh.ne.jp/tokiwa/)).
- Balance (4 decimal place accuracy, 0.0001 g for air-dried superabsorbent polymer (ADS SAP) and tea bag weights); timer; 1% saline; drip rack with clips (NLM 211); and lab centrifuge (NLM 211, Spin-X spin extractor, model 776S, 3,300 RPM, 120v).
- Test Procedure:
- 1. Determine solids content of ADS.
- 2. Pre-weigh tea bags to nearest 0.0001 g and record.
- 3. Accurately weigh 0.2025 g.+/−0.0025 g of test material (SAP), record and place into pre-weighed tea bag (air-dried (AD) bag weight). (ADS weight+AD bag weight=total dry weight).
- 4. Fold tea bag edge over closing bag.
- 5. Fill a container (at least 3 inches deep) with at least 2 inches with 1% saline.
- 6. Hold tea bag (with test sample) flat and shake to distribute test material evenly through bag.
- 7. Lay tea bag onto surface of saline and start timer.
- 8. Soak bags for specified time (e.g., 30 minutes).
- 9. Remove tea bags carefully, being careful not to spill any contents from bags, hang from a clip on drip rack for 3 minutes.
- 10. Carefully remove each bag, weigh, and record (drip weight).
- 11. Place tea bags onto centrifuge walls, being careful not to let them touch and careful to balance evenly around wall.
- 12. Lock down lid and start timer. Spin for 75 seconds.
- 13. Unlock lid and remove bags. Weigh each bag and record weight (centrifuge weight).
- Calculations:
- The tea bag material has an absorbency determined as follows:
- Free Swell Capacity, factor=5.78
- Centrifuge Capacity, factor 0.50
- Z=Oven dry SAP wt (g)/Air dry SAP wt (g)
- Free Capacity (g/g):
-
- Centrifuge Retention Capacity (g/g):
-
- The materials, procedure, and calculations to determine AUL were as follows.
- Test Materials:
- Mettler Toledo PB 3002 balance and BALANCE-LINK software or other compatible balance and software, Software set-up: record weight from balance every 30 sec (this will be a negative number. Software can place each value into EXCEL spreadsheet.
- Kontes 90 mm ULTRA-WARE filter set up with fritted glass (coarse) filter plate. clamped to stand; 2 L glass bottle with outlet tube near bottom of bottle; rubber stopper with glass tube through the stopper that fits the bottle (air inlet); TYGON tubing; stainless steel rod/plexiglass plunger assembly (71 mm diameter); stainless steel weight with hole drill through to place over plunger (plunger and weight=867 g); VWR 9.0 cm filter papers (Qualitative 413 catalog number 28310-048) cut down to 80 mm size; double-stick SCOTCH tape; and 0.9% saline.
- Test Procedure:
- 1. Level filter set-up with small level.
- 2. Adjust filter height or fluid level in bottle so that fritted glass filter and saline level in bottle are at same height.
- 3. Make sure that there are no kinks in tubing or air bubbles in tubing or under fritted glass filter plate.
- 4. Place filter paper into filter and place stainless steel weight onto filter paper.
- 5, Wait for 5-10 min while filter paper becomes fully wetted and reaches equilibrium with applied weight.
- 6. Zero balance.
- 7. While waiting for filter paper to reach equilibrium prepare plunger with double stick tape on bottom.
- 8. Place plunger (with tape) onto separate scale and zero scale.
- 9. Place plunger into dry test material so that a monolayer of material is stuck to the bottom by the double stick tape.
- 10. Weigh the plunger and test material on zeroed scale and record weight of dry test material (dry material weight 0.15 g+/−0.05 g).
- 11. Filter paper should be at equilibrium by now, zero scale.
- 12. Start balance recording software.
- 13. Remove weight and place plunger and test material into filter assembly.
- 14. Place weight onto plunger assembly.
- 15. Wait for test to complete (30 or 60 min)
- 16. Stop balance recording software.
- Calculations:
-
- A=balance reading (g)*−1 (weight of saline absorbed by test material)
- B=dry weight of test material (this can be corrected for moisture by multiplying the AD weight by solids %).
- AUL (g/g)=A/B (g 1% saline/1 g test material)
- The following examples are provided for the purpose of illustrating, not limiting, the invention.
- In this example, the preparation of representative guar gum treated cellulose fibers is described.
- Guar gum (4.0 g) was dissolved in 3200 ml of deionized water. Northern kraft spruce (NKS) pulp (40.0 g) was dispersed in the guar gum solution and oven dried at 105° C. This material was used for binding superabsorbent composite particles.
- In this example, the preparation of a representative fibrous superabsorbent composite containing cellulose and commercial superabsorbent particles crosslinked with aluminum sulfate.
- Aluminum sulfate octadecahydrate 0.035 g was dissolved in 50 ml of deionized water at 80° C. Guar gum treated cellulose fiber (prepared as described as in Example 1) 1.2 g was then dispersed in the aluminum sulfate solution for 15 minutes. Commercial superabsorbent particles (SANWET IM-4500 from Hoechst Celanese) 2.8 g was added to the fiber slurry and mixed for 2 minutes. To the swollen mass of fiber gel was added 150 ml of isopropanol and mixed for 5 minutes to obtain composite fiber with attached superabsorbent particles. The composite fiber obtained was then filtered. The fiber mass was partially dried in the oven at 66° C., The fiber mass was then fiberized and dried in the oven at 66° C.
- T-bag test gave free swell of 39.75 g/g; centrifuge capacity of 19.86 g/g; and AUL of 27.36 g/g (at 0.3 psi) for 0.9% saline solution.
- In this example, the preparation of a representative fibrous superabsorbent composite containing cellulose and commercial superabsorbent particles without added crosslinking agent.
- Guar gum treated cellulose fiber (prepared as described as in Example 1) 1.2 g was then dispersed in 50 ml of deionized water at 80° C. for 15 minutes. Commercial superabsorbent particles (SANWET IM-4500 from Hoechst Celanese) 2.8 g was added to the fiber slurry and mixed for 2 minutes. To the swollen mass of fiber gel was added 150 ml of isopropanol and mixed to obtain composite fiber with attached superabsorbent particles. The composite fiber obtained was the filtered. The fiber mass was partially dried in the oven at 66° C. The fiber mass was then fiberized and dried in the oven at 66° C.
- T-bag test gave free swell of 40.50 g/g; centrifuge capacity of 23.54 g/g; and AUL of 28.15 g/g (at 0.3 psi) for 0.9% saline solution.
-
TABLE 1 Composition and Absorbent Properties of Composite Superabsorbent Fiber from Synthetic Superabsorbent and Galactomannan Treated Cellulose Polysaccharide polymer treated Superabsorbent particle cellulose Free Swell CRC AUL Sample (wgt % total wgt) (wgt % total wgt) Crosslinking agent/4 g (g/g) (g/g) (g/g) 1 SANWETIM-4500 (50%) NKS pulp with 10% GG (50%) 0.017 g Al2(SO4)3 with wash 35.3 15.62 23.31 2 SANWETIM-4500 (50%) NKS pulp with 10% GG (50%) — 33.95 16.61 23.8 3 SANWETIM-4500 (70%) NKS pulp with 10% GG (30%) 0.017 g Al2(SO4)3 with wash 39.75 19.86 27.36 4 SANWETIM-4500 (70%) NKS pulp with 10% GG (30%) — 40.5 23.54 28.15 - White illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.
Claims (17)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/537,973 US20080078514A1 (en) | 2006-10-02 | 2006-10-02 | Methods for the preparation of cellulose fibers having superabsorbent particles adhered thereto |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/537,973 US20080078514A1 (en) | 2006-10-02 | 2006-10-02 | Methods for the preparation of cellulose fibers having superabsorbent particles adhered thereto |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20080078514A1 true US20080078514A1 (en) | 2008-04-03 |
Family
ID=39259986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/537,973 Abandoned US20080078514A1 (en) | 2006-10-02 | 2006-10-02 | Methods for the preparation of cellulose fibers having superabsorbent particles adhered thereto |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US20080078514A1 (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080079188A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of mixed polymer superabsorbent fibers |
| US20080081843A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of superabsorbent particles containing carboxyalkyl cellulose |
| US20080081165A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Fibrous superabsorbent composite containing cellulose |
| US20080079187A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of mixed polymer superabsorbent fibers containing cellulose |
| US20080082065A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Mixed polymer superabsorbent fibers containing cellulose |
| US20080319107A1 (en) * | 2007-06-25 | 2008-12-25 | Weyerhaeuser Co. | Fibrous blend and methods of preparation |
| US20080318772A1 (en) * | 2007-06-25 | 2008-12-25 | Weyerhaeuser Co. | Mixed polymer composite fiber and cellulose fiber |
| US7625463B2 (en) | 2006-10-02 | 2009-12-01 | Weyerhaeuser Nr Company | Methods for the preparation of fibrous superabsorbent composite containing cellulose |
| US20090325799A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Biodegradable Superabsorbent Particles |
| US20090326180A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Biodegradable Superabsorbent Particles Containing Cellulose Fiber |
| US20090324731A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Method for Making Biodegradable Superabsorbent Particles |
| US20090325800A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Fibers Having Biodegradable Superabsorbent Particles Attached Thereto |
| US20090321030A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Method for Making Fiber Having Biodegradable Superabsorbent Particles Attached Thereto |
| US20090325797A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Biodegradable Superabsorbent Particles |
| US20090321029A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Method for making biodegradable superabsorbent particles |
| US7749317B2 (en) | 2007-06-25 | 2010-07-06 | Weyerhaeuser Nr Company | Fibrous blend and method of making |
| US7785710B2 (en) | 2006-10-02 | 2010-08-31 | Weyerhaeuser Nr Company | Superabsorbent particles containing carboxyalkyl cellulose and temporary metal crosslinks |
| US11718912B2 (en) | 2019-07-30 | 2023-08-08 | Applied Materials, Inc. | Methods and apparatus for calibrating concentration sensors for precursor delivery |
| US12194169B2 (en) | 2020-04-06 | 2025-01-14 | Nuro, Inc. | Methods and apparatus for sanitizing an autonomous vehicle |
Citations (55)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3645836A (en) * | 1968-09-05 | 1972-02-29 | David Torr | Water-absorption fibrous materials and method of making the same |
| US4028290A (en) * | 1975-10-23 | 1977-06-07 | Hercules Incorporated | Highly absorbent modified polysaccharides |
| US4128692A (en) * | 1974-08-27 | 1978-12-05 | Hercules Incorporated | Superabsorbent cellulosic fibers having a coating of a water insoluble, water absorbent polymer and method of making the same |
| US4143163A (en) * | 1976-06-30 | 1979-03-06 | Maxfibe, Inc. | Coated fibrous cellulose product and process |
| US4273118A (en) * | 1979-06-04 | 1981-06-16 | Avtex Fibers Inc. | Fibers of high fluid holding capacity |
| US4319956A (en) * | 1980-06-16 | 1982-03-16 | The Dexter Corporation | Nonwoven web material for medical towels and the like |
| US4605401A (en) * | 1981-10-16 | 1986-08-12 | Chemische Fabrik Stockhausen Gmbh | Material for the absorption of water, aqueous solutions and aqueous body fluids |
| US4624868A (en) * | 1979-12-17 | 1986-11-25 | Colgate-Palmolive Company | Borated polysaccharide absorbents and absorbent products |
| US4693713A (en) * | 1981-07-16 | 1987-09-15 | Miroslav Chmelir | Absorbents for blood and serous body fluids |
| US4952550A (en) * | 1989-03-09 | 1990-08-28 | Micro Vesicular Systems, Inc. | Particulate absorbent material |
| US4959341A (en) * | 1989-03-09 | 1990-09-25 | Micro Vesicular Systems, Inc. | Biodegradable superabsorbing sponge |
| US5231122A (en) * | 1988-04-11 | 1993-07-27 | Faricerca S.P.A. | Fibrous composition for absorbent pads, a method for the manufacture of an absorbent material from such a composition, and an absorbent material produced by the method |
| US5425725A (en) * | 1993-10-29 | 1995-06-20 | Kimberly-Clark Corporation | Absorbent article which includes superabsorbent material and hydrophilic fibers located in discrete pockets |
| US5470964A (en) * | 1992-02-14 | 1995-11-28 | Kimberly-Clark Corporation | Process for the preparation of modified polysaccharides having improved absorbent properties |
| US5498705A (en) * | 1995-02-22 | 1996-03-12 | Kimberly-Clark Corporation | Modified polysaccharides having improved absorbent properties and process for the preparation thereof |
| US5550189A (en) * | 1992-04-17 | 1996-08-27 | Kimberly-Clark Corporation | Modified polysaccharides having improved absorbent properties and process for the preparation thereof |
| US5612411A (en) * | 1992-11-18 | 1997-03-18 | Kimberly-Clark Corporation | Absorbent phycocolloids and a method for their manufacture |
| US5688776A (en) * | 1992-03-20 | 1997-11-18 | Basf Aktiengesellschaft | Crosslinked polysaccharides, process for their preparation and their use |
| US5736595A (en) * | 1993-05-03 | 1998-04-07 | Chemische Fabrik Stockhausen Gmbh | Polymer composition, absorbent material composition, their production and their use |
| US5801116A (en) * | 1995-04-07 | 1998-09-01 | Rhodia Inc. | Process for producing polysaccharides and their use as absorbent materials |
| US5847031A (en) * | 1993-05-03 | 1998-12-08 | Chemische Fabrik Stockhausen Gmbh | Polymer composition, absorbent composition, their production and use |
| US6162541A (en) * | 1997-11-18 | 2000-12-19 | Solutia Inc. | Superabsorbing compositions and processes for preparing same |
| US6296936B1 (en) * | 1996-09-04 | 2001-10-02 | Kimberly-Clark Worldwide, Inc. | Coform material having improved fluid handling and method for producing |
| US6331619B1 (en) * | 1996-12-18 | 2001-12-18 | Sca Hygiene Products Zeist B.V. | Superabsorbent material and method for producing said material |
| US20030027787A1 (en) * | 2000-11-10 | 2003-02-06 | Group Lysac Inc./Lysac Group Inc. | Crosslinked polysaccharide, obtained by crosslinking with substituted polyethylene glycol, as superabsorbant |
| US20030068944A1 (en) * | 2001-10-08 | 2003-04-10 | The Procter & Gamble Company | Absorbent articles for feminine protection with gel-forming polysaccharide-comprising wings |
| US6562743B1 (en) * | 1998-12-24 | 2003-05-13 | Bki Holding Corporation | Absorbent structures of chemically treated cellulose fibers |
| US20030144642A1 (en) * | 1999-09-21 | 2003-07-31 | Weyerhaeuser Company | Absorbent composite having fibrous bands |
| US20030232965A1 (en) * | 2002-04-24 | 2003-12-18 | David Bergeron | Synergistic compositions of polysaccharides as natural and biodegradable absorbent materials or super absorbents |
| US20040024092A1 (en) * | 2002-07-26 | 2004-02-05 | Soerens Dave Allen | Fluid storage material including particles secured with a crosslinkable binder composition and method of making same |
| US6689934B2 (en) * | 2001-12-14 | 2004-02-10 | Kimberly-Clark Worldwide, Inc. | Absorbent materials having improved fluid intake and lock-up properties |
| US6713460B2 (en) * | 1999-05-11 | 2004-03-30 | Groupe Lysac Inc. | Glass-like polysaccharide useful as absorbent for liquids |
| US6765042B1 (en) * | 1998-12-16 | 2004-07-20 | Sca Hygiene Products Zeist B.V. | Acidic superabsorbent polysaccharides |
| US20040236260A1 (en) * | 2000-07-12 | 2004-11-25 | Bryan Griffiths | Multi-layered wound dressing |
| US6846924B1 (en) * | 1996-01-10 | 2005-01-25 | Sca Hygiene Products Ab | Method of producing an absorbent material, an absorbent material and absorbent articles including the material in question |
| US20050214541A1 (en) * | 2003-09-29 | 2005-09-29 | Le Groupe Lysac Inc. | Polysaccharide phyllosilicate absorbent or superabsorbent nanocomposite materials |
| US6998367B2 (en) * | 2001-12-06 | 2006-02-14 | Kimberly-Clark Worldwide, Inc. | Absorbent composition containing transitional crosslinking points |
| US20060142477A1 (en) * | 2004-12-29 | 2006-06-29 | Glasser Wolfgang G | Method for making sulfoalkylated cellulose polymer network |
| US20060147689A1 (en) * | 2004-12-30 | 2006-07-06 | Raj Wallajapet | Absorbent composites containing biodegradable reinforcing fibers |
| US20070179291A1 (en) * | 2003-03-26 | 2007-08-02 | Le Groupe Lysac, Inc. | Starch network as absorbent or superabsorbent materials and their preparation by extrusion |
| US7306039B2 (en) * | 2003-08-13 | 2007-12-11 | Bj Services Company | Methods of using crosslinkable compositions |
| US20080009616A1 (en) * | 2004-06-21 | 2008-01-10 | Markus Frank | Water-Absorbing Polysaccharide and Method for Producing the Same |
| US7321007B2 (en) * | 2002-09-24 | 2008-01-22 | The Procter & Gamble Company | Liquid absorbent thermoplastic composition comprising superabsorbent material particles of substantially angle-lacking shape |
| US20080081843A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of superabsorbent particles containing carboxyalkyl cellulose |
| US20080082065A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Mixed polymer superabsorbent fibers containing cellulose |
| US20080082064A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Crosslinked carboxyalkyl cellulose fibers having permanent and non-permanent crosslinks |
| US20080082067A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Cellulose fibers having superabsorbent particles adhered thereto |
| US20080081189A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Mixed Polymer Superabsorbent Fibers And Method For Their Preparation |
| US20080078515A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of fibrous superabsorbent composite containing cellulose |
| US20080081165A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Fibrous superabsorbent composite containing cellulose |
| US20080081190A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Mixed polymer superabsorbent fibers |
| US20080079187A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of mixed polymer superabsorbent fibers containing cellulose |
| US20080079188A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of mixed polymer superabsorbent fibers |
| US20080081191A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Superabsorbent particles containing carboxyalkyl cellulose |
| US7407912B2 (en) * | 2001-05-25 | 2008-08-05 | Stockhausen Gmbh | Supersuperabsorbent polymers |
-
2006
- 2006-10-02 US US11/537,973 patent/US20080078514A1/en not_active Abandoned
Patent Citations (55)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3645836A (en) * | 1968-09-05 | 1972-02-29 | David Torr | Water-absorption fibrous materials and method of making the same |
| US4128692A (en) * | 1974-08-27 | 1978-12-05 | Hercules Incorporated | Superabsorbent cellulosic fibers having a coating of a water insoluble, water absorbent polymer and method of making the same |
| US4028290A (en) * | 1975-10-23 | 1977-06-07 | Hercules Incorporated | Highly absorbent modified polysaccharides |
| US4143163A (en) * | 1976-06-30 | 1979-03-06 | Maxfibe, Inc. | Coated fibrous cellulose product and process |
| US4273118A (en) * | 1979-06-04 | 1981-06-16 | Avtex Fibers Inc. | Fibers of high fluid holding capacity |
| US4624868A (en) * | 1979-12-17 | 1986-11-25 | Colgate-Palmolive Company | Borated polysaccharide absorbents and absorbent products |
| US4319956A (en) * | 1980-06-16 | 1982-03-16 | The Dexter Corporation | Nonwoven web material for medical towels and the like |
| US4693713A (en) * | 1981-07-16 | 1987-09-15 | Miroslav Chmelir | Absorbents for blood and serous body fluids |
| US4605401A (en) * | 1981-10-16 | 1986-08-12 | Chemische Fabrik Stockhausen Gmbh | Material for the absorption of water, aqueous solutions and aqueous body fluids |
| US5231122A (en) * | 1988-04-11 | 1993-07-27 | Faricerca S.P.A. | Fibrous composition for absorbent pads, a method for the manufacture of an absorbent material from such a composition, and an absorbent material produced by the method |
| US4952550A (en) * | 1989-03-09 | 1990-08-28 | Micro Vesicular Systems, Inc. | Particulate absorbent material |
| US4959341A (en) * | 1989-03-09 | 1990-09-25 | Micro Vesicular Systems, Inc. | Biodegradable superabsorbing sponge |
| US5470964A (en) * | 1992-02-14 | 1995-11-28 | Kimberly-Clark Corporation | Process for the preparation of modified polysaccharides having improved absorbent properties |
| US5688776A (en) * | 1992-03-20 | 1997-11-18 | Basf Aktiengesellschaft | Crosslinked polysaccharides, process for their preparation and their use |
| US5550189A (en) * | 1992-04-17 | 1996-08-27 | Kimberly-Clark Corporation | Modified polysaccharides having improved absorbent properties and process for the preparation thereof |
| US5612411A (en) * | 1992-11-18 | 1997-03-18 | Kimberly-Clark Corporation | Absorbent phycocolloids and a method for their manufacture |
| US5847031A (en) * | 1993-05-03 | 1998-12-08 | Chemische Fabrik Stockhausen Gmbh | Polymer composition, absorbent composition, their production and use |
| US5736595A (en) * | 1993-05-03 | 1998-04-07 | Chemische Fabrik Stockhausen Gmbh | Polymer composition, absorbent material composition, their production and their use |
| US5425725A (en) * | 1993-10-29 | 1995-06-20 | Kimberly-Clark Corporation | Absorbent article which includes superabsorbent material and hydrophilic fibers located in discrete pockets |
| US5498705A (en) * | 1995-02-22 | 1996-03-12 | Kimberly-Clark Corporation | Modified polysaccharides having improved absorbent properties and process for the preparation thereof |
| US5801116A (en) * | 1995-04-07 | 1998-09-01 | Rhodia Inc. | Process for producing polysaccharides and their use as absorbent materials |
| US6846924B1 (en) * | 1996-01-10 | 2005-01-25 | Sca Hygiene Products Ab | Method of producing an absorbent material, an absorbent material and absorbent articles including the material in question |
| US6296936B1 (en) * | 1996-09-04 | 2001-10-02 | Kimberly-Clark Worldwide, Inc. | Coform material having improved fluid handling and method for producing |
| US6331619B1 (en) * | 1996-12-18 | 2001-12-18 | Sca Hygiene Products Zeist B.V. | Superabsorbent material and method for producing said material |
| US6162541A (en) * | 1997-11-18 | 2000-12-19 | Solutia Inc. | Superabsorbing compositions and processes for preparing same |
| US6765042B1 (en) * | 1998-12-16 | 2004-07-20 | Sca Hygiene Products Zeist B.V. | Acidic superabsorbent polysaccharides |
| US6562743B1 (en) * | 1998-12-24 | 2003-05-13 | Bki Holding Corporation | Absorbent structures of chemically treated cellulose fibers |
| US6713460B2 (en) * | 1999-05-11 | 2004-03-30 | Groupe Lysac Inc. | Glass-like polysaccharide useful as absorbent for liquids |
| US20030144642A1 (en) * | 1999-09-21 | 2003-07-31 | Weyerhaeuser Company | Absorbent composite having fibrous bands |
| US20040236260A1 (en) * | 2000-07-12 | 2004-11-25 | Bryan Griffiths | Multi-layered wound dressing |
| US20030027787A1 (en) * | 2000-11-10 | 2003-02-06 | Group Lysac Inc./Lysac Group Inc. | Crosslinked polysaccharide, obtained by crosslinking with substituted polyethylene glycol, as superabsorbant |
| US7407912B2 (en) * | 2001-05-25 | 2008-08-05 | Stockhausen Gmbh | Supersuperabsorbent polymers |
| US20030068944A1 (en) * | 2001-10-08 | 2003-04-10 | The Procter & Gamble Company | Absorbent articles for feminine protection with gel-forming polysaccharide-comprising wings |
| US6998367B2 (en) * | 2001-12-06 | 2006-02-14 | Kimberly-Clark Worldwide, Inc. | Absorbent composition containing transitional crosslinking points |
| US6689934B2 (en) * | 2001-12-14 | 2004-02-10 | Kimberly-Clark Worldwide, Inc. | Absorbent materials having improved fluid intake and lock-up properties |
| US20030232965A1 (en) * | 2002-04-24 | 2003-12-18 | David Bergeron | Synergistic compositions of polysaccharides as natural and biodegradable absorbent materials or super absorbents |
| US20040024092A1 (en) * | 2002-07-26 | 2004-02-05 | Soerens Dave Allen | Fluid storage material including particles secured with a crosslinkable binder composition and method of making same |
| US7321007B2 (en) * | 2002-09-24 | 2008-01-22 | The Procter & Gamble Company | Liquid absorbent thermoplastic composition comprising superabsorbent material particles of substantially angle-lacking shape |
| US20070179291A1 (en) * | 2003-03-26 | 2007-08-02 | Le Groupe Lysac, Inc. | Starch network as absorbent or superabsorbent materials and their preparation by extrusion |
| US7306039B2 (en) * | 2003-08-13 | 2007-12-11 | Bj Services Company | Methods of using crosslinkable compositions |
| US20050214541A1 (en) * | 2003-09-29 | 2005-09-29 | Le Groupe Lysac Inc. | Polysaccharide phyllosilicate absorbent or superabsorbent nanocomposite materials |
| US20080009616A1 (en) * | 2004-06-21 | 2008-01-10 | Markus Frank | Water-Absorbing Polysaccharide and Method for Producing the Same |
| US20060142477A1 (en) * | 2004-12-29 | 2006-06-29 | Glasser Wolfgang G | Method for making sulfoalkylated cellulose polymer network |
| US20060147689A1 (en) * | 2004-12-30 | 2006-07-06 | Raj Wallajapet | Absorbent composites containing biodegradable reinforcing fibers |
| US20080078515A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of fibrous superabsorbent composite containing cellulose |
| US20080082064A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Crosslinked carboxyalkyl cellulose fibers having permanent and non-permanent crosslinks |
| US20080082067A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Cellulose fibers having superabsorbent particles adhered thereto |
| US20080081189A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Mixed Polymer Superabsorbent Fibers And Method For Their Preparation |
| US20080082065A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Mixed polymer superabsorbent fibers containing cellulose |
| US20080081165A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Fibrous superabsorbent composite containing cellulose |
| US20080081190A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Mixed polymer superabsorbent fibers |
| US20080079187A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of mixed polymer superabsorbent fibers containing cellulose |
| US20080079188A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of mixed polymer superabsorbent fibers |
| US20080081191A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Superabsorbent particles containing carboxyalkyl cellulose |
| US20080081843A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of superabsorbent particles containing carboxyalkyl cellulose |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7645806B2 (en) | 2006-10-02 | 2010-01-12 | Weyerhaeuser Nr Company | Methods for the preparation of superabsorbent particles containing carboxyalkyl cellulose |
| US20080081843A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of superabsorbent particles containing carboxyalkyl cellulose |
| US20080081165A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Fibrous superabsorbent composite containing cellulose |
| US20080079187A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of mixed polymer superabsorbent fibers containing cellulose |
| US20080082065A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Mixed polymer superabsorbent fibers containing cellulose |
| US7785710B2 (en) | 2006-10-02 | 2010-08-31 | Weyerhaeuser Nr Company | Superabsorbent particles containing carboxyalkyl cellulose and temporary metal crosslinks |
| US20080079188A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of mixed polymer superabsorbent fibers |
| US7717995B2 (en) | 2006-10-02 | 2010-05-18 | Weyerhaeuser Nr Company | Methods for the preparation of mixed polymer superabsorbent fibers containing cellulose |
| US7625463B2 (en) | 2006-10-02 | 2009-12-01 | Weyerhaeuser Nr Company | Methods for the preparation of fibrous superabsorbent composite containing cellulose |
| US7749317B2 (en) | 2007-06-25 | 2010-07-06 | Weyerhaeuser Nr Company | Fibrous blend and method of making |
| US7591891B2 (en) | 2007-06-25 | 2009-09-22 | Weyerhaeuser Nr Company | Fibrous blend and methods of preparation |
| US20080319107A1 (en) * | 2007-06-25 | 2008-12-25 | Weyerhaeuser Co. | Fibrous blend and methods of preparation |
| US20080318772A1 (en) * | 2007-06-25 | 2008-12-25 | Weyerhaeuser Co. | Mixed polymer composite fiber and cellulose fiber |
| US20090325797A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Biodegradable Superabsorbent Particles |
| US7833384B2 (en) | 2008-06-30 | 2010-11-16 | Weyerhaeuser Nr Company | Method for making fiber having biodegradable superabsorbent particles attached thereto |
| US20090321029A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Method for making biodegradable superabsorbent particles |
| US20090325799A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Biodegradable Superabsorbent Particles |
| US20090321030A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Method for Making Fiber Having Biodegradable Superabsorbent Particles Attached Thereto |
| US20090325800A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Fibers Having Biodegradable Superabsorbent Particles Attached Thereto |
| US20090324731A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Method for Making Biodegradable Superabsorbent Particles |
| US20090326180A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Biodegradable Superabsorbent Particles Containing Cellulose Fiber |
| US7959762B2 (en) | 2008-06-30 | 2011-06-14 | Weyerhaeuser Nr Company | Method for making biodegradable superabsorbent particles |
| US8084391B2 (en) | 2008-06-30 | 2011-12-27 | Weyerhaeuser Nr Company | Fibers having biodegradable superabsorbent particles attached thereto |
| US8101543B2 (en) | 2008-06-30 | 2012-01-24 | Weyerhaeuser Nr Company | Biodegradable superabsorbent particles |
| US8641869B2 (en) | 2008-06-30 | 2014-02-04 | Weyerhaeuser Nr Company | Method for making biodegradable superabsorbent particles |
| US11718912B2 (en) | 2019-07-30 | 2023-08-08 | Applied Materials, Inc. | Methods and apparatus for calibrating concentration sensors for precursor delivery |
| US12194169B2 (en) | 2020-04-06 | 2025-01-14 | Nuro, Inc. | Methods and apparatus for sanitizing an autonomous vehicle |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20080082067A1 (en) | Cellulose fibers having superabsorbent particles adhered thereto | |
| US8084391B2 (en) | Fibers having biodegradable superabsorbent particles attached thereto | |
| US7455902B2 (en) | Mixed polymer superabsorbent fibers | |
| US20080078514A1 (en) | Methods for the preparation of cellulose fibers having superabsorbent particles adhered thereto | |
| US20080082065A1 (en) | Mixed polymer superabsorbent fibers containing cellulose | |
| US7833384B2 (en) | Method for making fiber having biodegradable superabsorbent particles attached thereto | |
| US7625463B2 (en) | Methods for the preparation of fibrous superabsorbent composite containing cellulose | |
| US7785710B2 (en) | Superabsorbent particles containing carboxyalkyl cellulose and temporary metal crosslinks | |
| US7749317B2 (en) | Fibrous blend and method of making | |
| US7717995B2 (en) | Methods for the preparation of mixed polymer superabsorbent fibers containing cellulose | |
| US7959762B2 (en) | Method for making biodegradable superabsorbent particles | |
| US20080081165A1 (en) | Fibrous superabsorbent composite containing cellulose | |
| US7645806B2 (en) | Methods for the preparation of superabsorbent particles containing carboxyalkyl cellulose | |
| EP1925323A1 (en) | Mixed polymer superabsorbent fibers and method for their preparation | |
| US8101543B2 (en) | Biodegradable superabsorbent particles | |
| US20080079188A1 (en) | Methods for the preparation of mixed polymer superabsorbent fibers | |
| EP1920787A2 (en) | Crosslinked carboxyalkyl cellulose fibers having permanent and non-permanent crosslinks and methods for its preparation | |
| US20080318772A1 (en) | Mixed polymer composite fiber and cellulose fiber | |
| US8641869B2 (en) | Method for making biodegradable superabsorbent particles | |
| US20080147032A1 (en) | Methods for the preparation crosslinked carboxyalkyl cellulose fibers having non-permanent and temporary crosslinks | |
| US20090326180A1 (en) | Biodegradable Superabsorbent Particles Containing Cellulose Fiber | |
| US7591891B2 (en) | Fibrous blend and methods of preparation | |
| US20080082066A1 (en) | Crosslinked carboxyalkyl cellulose fibers having non-permanent and temporary crosslinks | |
| US20080319108A1 (en) | Method of making a mixed polymer composite fiber and cellulose fiber | |
| EP1911467A1 (en) | Mixed polymer superabsorbent fibers containing cellulose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: WEYERHAEUSER COMPANY, WASHINGTON Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WEERAWARNA, S. ANANDA;SU, BING;REEL/FRAME:018724/0814 Effective date: 20061201 |
|
| AS | Assignment |
Owner name: WEYERHAEUSER NR COMPANY, WASHINGTON Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WEYERHAEUSER COMPANY;REEL/FRAME:022835/0233 Effective date: 20090421 Owner name: WEYERHAEUSER NR COMPANY,WASHINGTON Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WEYERHAEUSER COMPANY;REEL/FRAME:022835/0233 Effective date: 20090421 |
|
| STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |