US20190330770A1 - Wet-laid microfibers including polyolefin and thermoplastic starch - Google Patents
Wet-laid microfibers including polyolefin and thermoplastic starch Download PDFInfo
- Publication number
- US20190330770A1 US20190330770A1 US16/467,516 US201616467516A US2019330770A1 US 20190330770 A1 US20190330770 A1 US 20190330770A1 US 201616467516 A US201616467516 A US 201616467516A US 2019330770 A1 US2019330770 A1 US 2019330770A1
- Authority
- US
- United States
- Prior art keywords
- microfibers
- meltblown
- starch
- blend
- spinning
- 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.)
- Pending
Links
- 229920001410 Microfiber Polymers 0.000 title claims abstract description 65
- 239000003658 microfiber Substances 0.000 title claims abstract description 65
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 45
- 229920008262 Thermoplastic starch Polymers 0.000 title claims abstract description 22
- 239000004628 starch-based polymer Substances 0.000 title claims abstract description 22
- 239000000835 fiber Substances 0.000 claims abstract description 115
- 239000000203 mixture Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000009987 spinning Methods 0.000 claims abstract description 43
- 230000008569 process Effects 0.000 claims abstract description 30
- 239000000155 melt Substances 0.000 claims abstract description 21
- 229920000881 Modified starch Polymers 0.000 claims abstract description 20
- 235000019426 modified starch Nutrition 0.000 claims abstract description 20
- 239000004368 Modified starch Substances 0.000 claims abstract description 19
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 18
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000002250 absorbent Substances 0.000 claims abstract description 13
- 230000002745 absorbent Effects 0.000 claims abstract description 13
- 238000005520 cutting process Methods 0.000 claims abstract description 8
- 229920002472 Starch Polymers 0.000 claims description 49
- 235000019698 starch Nutrition 0.000 claims description 49
- 239000008107 starch Substances 0.000 claims description 37
- -1 polypropylene Polymers 0.000 claims description 29
- 239000004743 Polypropylene Substances 0.000 claims description 25
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 13
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 240000007594 Oryza sativa Species 0.000 claims description 10
- 235000007164 Oryza sativa Nutrition 0.000 claims description 10
- 240000008042 Zea mays Species 0.000 claims description 10
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 10
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 10
- 235000005822 corn Nutrition 0.000 claims description 10
- 235000009566 rice Nutrition 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 240000003183 Manihot esculenta Species 0.000 claims description 7
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 7
- 235000000378 Caryota urens Nutrition 0.000 claims description 5
- 240000000163 Cycas revoluta Species 0.000 claims description 5
- 235000008601 Cycas revoluta Nutrition 0.000 claims description 5
- 244000017020 Ipomoea batatas Species 0.000 claims description 5
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 5
- 244000151018 Maranta arundinacea Species 0.000 claims description 5
- 235000010804 Maranta arundinacea Nutrition 0.000 claims description 5
- 235000010103 Metroxylon rumphii Nutrition 0.000 claims description 5
- 244000061456 Solanum tuberosum Species 0.000 claims description 5
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 5
- 240000006394 Sorghum bicolor Species 0.000 claims description 5
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 5
- 235000012419 Thalia geniculata Nutrition 0.000 claims description 5
- 235000021307 Triticum Nutrition 0.000 claims description 5
- 239000004464 cereal grain Substances 0.000 claims description 5
- 235000012015 potatoes Nutrition 0.000 claims description 5
- 244000098338 Triticum aestivum Species 0.000 claims 2
- 239000000463 material Substances 0.000 description 19
- 229920000856 Amylose Polymers 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 13
- 239000004014 plasticizer Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000011162 core material Substances 0.000 description 7
- 229920000747 poly(lactic acid) Polymers 0.000 description 7
- 239000004626 polylactic acid Substances 0.000 description 7
- 229920005629 polypropylene homopolymer Polymers 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 229920000945 Amylopectin Polymers 0.000 description 6
- 229920003317 Fusabond® Polymers 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 229920001222 biopolymer Polymers 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 241000209140 Triticum Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000001815 facial effect Effects 0.000 description 3
- 238000012681 fiber drawing Methods 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 239000012815 thermoplastic material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QNMKGMUGYVWVFQ-UHFFFAOYSA-N 2alpha-Hydroxyursolic acid Natural products CC12CC(O)C(O)C(C)(C)C1CCC1(C)C2CC=C2C3C(C)C(C)(C)CCC3(C(O)=O)CCC21C QNMKGMUGYVWVFQ-UHFFFAOYSA-N 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- HFGSQOYIOKBQOW-ZSDYHTTISA-N corosolic acid Chemical compound C1[C@@H](O)[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C HFGSQOYIOKBQOW-ZSDYHTTISA-N 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose 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](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 229920001685 Amylomaize Polymers 0.000 description 1
- MJBPUQUGJNAPAZ-AWEZNQCLSA-N Butin Natural products C1([C@@H]2CC(=O)C3=CC=C(C=C3O2)O)=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-AWEZNQCLSA-N 0.000 description 1
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- YTBSYETUWUMLBZ-IUYQGCFVSA-N D-erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 1
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 206010056474 Erythrosis Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- 206010021639 Incontinence Diseases 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- VAALVBPLSFRYMJ-XXMNONFOSA-N O=C1OC(=O)[C@@H]([C@@H](C23)C4)[C@H]1[C@@H]4C3[C@@H]1C[C@H]2[C@H]2C(=O)OC(=O)[C@@H]12 Chemical compound O=C1OC(=O)[C@@H]([C@@H](C23)C4)[C@H]1[C@@H]4C3[C@@H]1C[C@H]2[C@H]2C(=O)OC(=O)[C@@H]12 VAALVBPLSFRYMJ-XXMNONFOSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001278 adipic acid derivatives Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000021120 animal protein Nutrition 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical class [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 150000004648 butanoic acid derivatives Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 210000001520 comb Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001341 hydroxy propyl starch Substances 0.000 description 1
- 229940050526 hydroxyethylstarch Drugs 0.000 description 1
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 150000003903 lactic acid esters Chemical class 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 230000002175 menstrual effect Effects 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
- D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4291—Olefin series
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
Definitions
- microfibers are produced with a limited number of fiber-grade synthetic polymers such as PE, PP, PET, and PLA.
- the limited number of options for fiber-grade polymers is due to a set of stringent requirements for fiber melt spinning.
- biopolymers such as starch, although thermoplastic starch is widely used in blends of polyolefin or PLA for breathable, stretchable, or packaging film applications.
- thermoplastic modified starch can be added to fiber-grade polyolefins.
- the resulting fibers such as those in U.S. Pat. No. 6,623,854 to Bond, cannot be spun without the fibers breaking, except at very low speeds, which is inefficient, costly, and inappropriate for commercial production.
- TPMS thermoplastic modified starch
- meltblown-grade polyolefins cannot be spun into fiber individually using staple fiber spinning equipment because their melt-flow indexes (MFIs) are insufficient.
- MFIs melt-flow indexes
- U.S. Pat. No. 8,470,222 B2 to Shi et al. describes a biodegradable fiber spun from blends of modified aliphatic-aromatic polyester and TPMS.
- the reason to modify aliphatic-aromatic polyester via alcoholysis is because thermoplastic starch alone cannot be spun into fibers due to its unfavorable rheological characteristics.
- the modified aliphatic-aromatic polyester can alter rheological profile of thermoplastic starch suitable for fiber melt spinning.
- polyester resins are expensive relative to polyolefins and alcoholysis through reactive extrusion can involve the use of undesirable chemical reagents.
- the disclosure described herein directly blends meltblown-grade polyolefins and thermoplastic modified starch for wet-laid microfiber spinning.
- the results demonstrate an unexpected success to spin fibers from blends of meltblown-grade polyolefin and thermoplastic starch.
- conventional fiber-grade polyolefin containing TPMS cannot be realistically spun into fibers.
- the present disclosure describes novel fiber compositions using meltblown polyolefins and thermoplastic modified starch to create miscible blends for wet-laid microfiber spinning via conventional polymer processing equipment.
- This disclosure addresses the use of a low-cost starch biopolymer together with a commodity meltblown-grade polyolefin for wet-laid microfiber production.
- Successful inclusion of thermoplastic starch in meltblown-grade polyethylene or polypropylene for wet-laid microfiber spinning creates opportunities in 1) cost reduction when it is used in bath/facial tissue or towel manufacturing, and in 2) increased use of bio-based renewable material content, all of which is consistent with sustainability objectives.
- synthetic microfibers are made in a conventional fiber spinning process (not a meltblown process) from a blend of meltblown-grade polyolefin(s) and thermoplastic modified starch (TPMS). These blends can be made with or without a compatibilizer, such as maleic anhydride grafted polymers or polar-group grafted polymeric additives or coupling agents.
- TPMS thermoplastic modified starch
- the wet-laid microfiber can be in any cross-sectional configurations such as monofilament, side-by side, island-in-the sea, or sheath-core structures.
- the fibers can be cut into staple fibers or used as a continuous fiber without cutting. For tissue applications, the fibers are cut into lengths less than 5 mm, with a normal range of 1 to 3 mm long.
- spun microfibers include a blend of 70 wt. % to 90 wt. % meltblown-grade polyolefin and 10 wt. % to 30 wt. % thermoplastic starch, wherein the microfibers are suitable for use in a wet-laid process.
- a method for producing spun microfibers includes producing a blend of 70 wt. %-90 wt. % meltblown-grade polyolefin with 10 wt. % to 30 wt. % thermoplastic modified starch (TPMS) derived from native starch; and spinning the blend into microfibers in a fiber spinning process, wherein the microfibers are suitable for use in a wet-laid process.
- TPMS thermoplastic modified starch
- a method for producing an absorbent product includes producing a blend of 70 wt. %-90 wt. % meltblown-grade polyolefin with 10 wt. % to 30 wt. % thermoplastic modified starch (TPMS), wherein the blend prior to spinning has a melt flow index greater than 150; spinning the blend into microfibers in a fiber spinning process; cutting the microfibers into staple fibers; and incorporating the staple fibers into a wet-laid process for making a nonwoven web.
- TPMS thermoplastic modified starch
- FIG. 1 graphically illustrates Differential Scanning calorimeter (DSC) thermograms (2nd heat) of PP/TPMS blend samples;
- FIG. 2 graphically illustrates the effect of composition (Wt % TPMS) on melt temperature of PP/TPMS blends
- FIG. 3 graphically illustrates the effect of composition (Wt % TPMS) on melt enthalpy of PP/TPMS blends.
- absorbent article and “absorbent product” refer herein to an article that can be placed against or in proximity to the body (i.e., contiguous with the body) of the wearer to absorb and contain various liquid, solid, and semi-solid exudates discharged from the body.
- absorbent articles as described herein, are intended to be discarded after a limited period of use instead of being laundered or otherwise restored for reuse.
- the present disclosure is applicable to various disposable absorbent articles, including, but not limited to, diapers, training pants, youth pants, swim pants, feminine hygiene products, including, but not limited to, menstrual pads, incontinence products, medical garments, surgical pads and bandages, other personal care or health care garments, and the like without departing from the scope of the present disclosure.
- the term can also include bath tissue, facial tissue, toweling, and the like.
- carded web refers herein to a web containing natural or synthetic staple fibers typically having fiber lengths less than about 100 mm. Bales of staple fibers can undergo an opening process to separate the fibers that are then sent to a carding process that separates and combs the fibers to align them in the machine direction after which the fibers are deposited onto a moving wire for further processing. Such webs are usually subjected to some type of bonding process such as thermal bonding using heat and/or pressure. In addition to or in lieu thereof, the fibers can be subject to adhesive processes to bind the fibers together such as by the use of powder adhesives.
- the carded web can be subjected to fluid entangling, such as hydroentangling, to further intertwine the fibers and thereby improve the integrity of the carded web.
- Carded webs, due to the fiber alignment in the machine direction, once bonded, will typically have more machine direction strength than cross machine direction strength.
- hydrophilic refers herein to fibers or the surfaces of fibers that are wetted by aqueous liquids in contact with the fibers.
- the degree of wetting of the materials can, in turn, be described in terms of the contact angles and the surface tensions of the liquids and materials involved.
- Equipment and techniques suitable for measuring the wettability of particular fiber materials or blends of fiber materials can be provided by Cahn SFA-222 Surface Force Analyzer System, or a substantially equivalent system. When measured with this system, fibers having contact angles less than 90 degrees are designated “wettable” or hydrophilic, and fibers having contact angles greater than 90 degrees are designated “nonwettable” or hydrophobic.
- meltblown refers herein to fibers formed by extruding a molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into converging high velocity heated gas (e.g., air) streams that attenuate the filaments of molten thermoplastic material to reduce their diameter, which can be a microfiber diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface to form a web of randomly dispersed meltblown fibers.
- heated gas e.g., air
- nonwoven refers herein to materials and webs of material that are formed without the aid of a textile weaving or knitting process.
- the materials and webs of materials can have a structure of individual fibers, filaments, or threads (collectively referred to as “fibers”) that can be interlaid, but not in an identifiable manner as in a knitted fabric.
- Nonwoven materials or webs can be formed from many processes such as, but not limited to, meltblowing processes, spunbonding processes, carded web processes, etc.
- pliable refers herein to materials that are compliant and that will readily conform to the general shape and contours of the wearer's body.
- spunbond refers herein to small diameter fibers that are formed by extruding molten thermoplastic material as filaments from a plurality of fine capillaries of a spinnerette having a circular or other configuration, with the diameter of the extruded filaments then being rapidly reduced by a conventional process such as, for example, eductive drawing, and processes that described in U.S. Pat. No. 4,340,563 to Appel et al., U.S. Pat. No. 3,692,618 to Dorschner et al., U.S. Pat. No. 3,802,817 to Matsuki et al., U.S. Pat. Nos. 3,338,992 and 3,341,394 to Kinney, U.S. Pat.
- Spunbond fibers are generally continuous and often have average deniers larger than about 0.3, and in an aspect, between about 0.6, 5 and 10 and about 15, 20 and 40. Spunbond fibers are generally not tacky when they are deposited on a collecting surface.
- thermoplastic refers herein to a polymeric material that becomes pliable or moldable above a specific temperature and returns to a solid state upon cooling.
- meltblown-grade polyolefin refers to a polyolefin characterized by an extremely high melt flow rate homopolymer resin.
- the melt flow rate of a meltblown-grade polyolefin can range from 200 to 1550 g/10 min under standard testing conditions (ISO 1133-1). Meltblown-grade polyolefins can also have a narrow molecular weight distribution.
- microfiber refers to a fiber (including staple fibers and filaments) with a linear mass density less than 1 dtex, where dtex is an abbreviation of decitex, the mass in grams per 10,000 meters.
- a method of producing wet-laid microfibers using spunbond TPMS and meltblown-grade polymers is disclosed herein.
- This disclosure addresses the use of a low-cost starch biopolymer together with a low-cost commodity meltblown-grade polyolefin for wet-laid microfiber production.
- Successful inclusion of thermoplastic starch in meltblown-grade polyethylene or polypropylene for wet-laid microfiber spinning creates opportunities for cost reduction when used in bath/facial tissue or towel manufacturing, and in increased use of bio-based renewable material content, all of which are consistent with sustainability objectives.
- NBSK northern bleached softwood Kraft
- Products such as tissue, towels, and industrial wipers are responsible for a significant portion of virgin NBSK consumption.
- NBSK can be the most expensive fiber among a company's spend on commodity pulps annually.
- the initiative described herein generally NBSK replacement using a low-cost wet-laid microfiber, is a timely initiative to support corporate sustainability.
- the fibers described herein can also be used in any other suitable nonwoven process including the production of bonded carded webs.
- the present disclosure employs a thermoplastic starch.
- Starch is a natural polymer composed of amylose and amylopectin.
- Amylose is essentially a linear polymer having a molecular weight in the range of 100,000-500,000, whereas amylopectin is a highly branched polymer having a molecular weight of up to several million.
- typical sources includes seeds of cereal grains, such as corn, waxy corn, wheat, sorghum, rice, and waxy rice; tubers, such as potatoes; roots, such as tapioca (i.e., cassava and manioc), sweet potato, and arrowroot; and the pith of the sago palm.
- any natural (unmodified) and/or modified starch may be employed in the present invention.
- Modified starches for instance, are often employed that have been chemically modified by typical processes known in the art (e.g., esterification, etherification, oxidation, acid hydrolysis, enzymatic hydrolysis, etc.).
- Starch ethers and/or esters may be particularly desirable, such as hydroxyalkyl starches, carboxymethyl starches, etc.
- the hydroxyalkyl group of hydroxylalkyl starches may contain, for instance, 2 to 10 carbon atoms, in some embodiments from 2 to 6 carbon atoms, and in some embodiments, from 2 to 4 carbon atoms.
- hydroxyalkyl starches such as hydroxyethyl starch, hydroxypropyl starch, hydroxybutyl starch, and derivatives thereof.
- Starch esters may be prepared using a wide variety of anhydrides (e.g., acetic, propionic, butyric, and so forth), organic acids, acid chlorides, or other esterification reagents. The degree of esterification may vary as desired, such as from 1 to 3 ester groups per glucosidic unit of the starch.
- the starch may contain different percentages of amylose and amylopectin, different size starch granules and different polymeric weights for amylose and amylopectin.
- High amylose starches contain greater than about 50% by weight amylose and low amylose starches contain less than about 50% by weight amylose.
- low amylose starches having an amylose content of from about 10% to about 40% by weight, and in some embodiments, from about 15% to about 35% by weight are particularly suitable for use in the present invention. Examples of such low amylose starches include corn starch and potato starch, both of which have an amylose content of approximately 20% by weight.
- Such low amylose starches typically have a number average molecular weight (“Mn”) ranging from about 50,000 to about 1,000,000 grams per mole, in some embodiments from about 75,000 to about 800,000 grams per mole, and in some embodiments, from about 100,000 to about 600,000 grams per mole, as well as a weight average molecular weight (“Mw”) ranging from about 5,000,000 to about 25,000,000 grams per mole, in some embodiments from about 5,500,000 to about 15,000,000 grams per mole, and in some embodiments, from about 6,000,000 to about 12,000,000 grams per mole.
- Mw/Mn The ratio of the weight average molecular weight to the number average molecular weight
- the polydispersity index may range from about 20 to about 100.
- a plasticizer is also employed in the thermoplastic starch to help render the starch melt-processible.
- Starches for instance, normally exist in the form of granules that have a coating or outer membrane that encapsulates the more water-soluble amylose and amylopectin chains within the interior of the granule. When heated, plasticizers may soften and penetrate the outer membrane and cause the inner starch chains to absorb water and swell. This swelling will, at some point, cause the outer shell to rupture and result in an irreversible destructurization of the starch granule.
- the starch polymer chains containing amylose and amylopectin polymers which are initially compressed within the granules, will stretch out and form a generally disordered intermingling of polymer chains. Upon resolidification, however, the chains may reorient themselves to form crystalline or amorphous solids having varying strengths depending on the orientation of the starch polymer chains. Because the starch is thus capable of melting and resolidifying at certain temperatures, it is generally considered a “thermoplastic starch.”
- Suitable plasticizers may include, for instance, polyhydric alcohol plasticizers, such as sugars (e.g., glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose, and erythrose), sugar alcohols (e.g., erythritol, xylitol, malitol, mannitol, and sorbitol), polyols (e.g., ethylene glycol, glycerol, propylene glycol, dipropylene glycol, butylene glycol, and hexane triol), etc.
- sugars e.g., glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose, and erythrose
- sugar alcohols e.g., erythrito
- Suitable are hydrogen bond forming organic compounds which do not have hydroxyl group including urea and urea derivatives; anhydrides of sugar alcohols such as sorbitan; animal proteins such as gelatin; vegetable proteins such as sunflower protein, soybean proteins, cotton seed proteins; and mixtures thereof.
- Other suitable plasticizers may include phthalate esters, dimethyl and diethylsuccinate and related esters, glycerol triacetate, glycerol mono and diacetates, glycerol mono, di, and tripropionates, butanoates, stearates, lactic acid esters, citric acid esters, adipic acid esters, stearic acid esters, oleic acid esters, and other acid esters.
- Aliphatic acids may also be used, such as copolymers of ethylene and acrylic acid, polyethylene grafted with maleic acid, polybutadiene-co-acrylic acid, polybutadiene-co-maleic acid, polypropylene-co-acrylic acid, polypropylene-co-maleic acid, and other hydrocarbon based acids.
- a low molecular weight plasticizer is preferred, such as less than about 20,000 g/mol, preferably less than about 5,000 g/mol and more preferably less than about 1,000 g/mol.
- the relative amount of starches and plasticizers employed in the thermoplastic starch may vary depending on a variety of factors, such as the desired molecular weight, the type of starch, the affinity of the plasticizer for the starch, etc. Typically, however, starches constitute from about 30 wt. % to about 95 wt. %, in some embodiments from about 40 wt. % to about 90 wt. %, and in some embodiments, from about 50 wt. % to about 85 wt. % of the thermoplastic starch. Likewise, plasticizers typically constitute from about 5 wt. % to about 55 wt. %, in some embodiments from about 10 wt. % to about 45 wt.
- thermoplastic composition %, and in some embodiments, from about 15 wt. % to about 35 wt. % of the thermoplastic composition.
- weight of starch referenced herein includes any bound water that naturally occurs in the starch before mixing it with other components to form the thermoplastic starch. Starches, for instance, typically have a bound water content of about 5% to 16% by weight of the starch.
- thermoplastic starch Additional information with respect to the processing and use of thermoplastic starch can be found in U.S. Pat. No. 8,470,222 to Shi et al., which is incorporated herein by reference to the extent it does not conflict herewith.
- Conventional synthetic microfibers are made in a conventional fiber spinning process (not a meltblown process) from conventional fiber-grade polymer.
- the process described herein substitutes a blend of less expensive meltblown-grade polyolefin(s) and a low-cost thermoplastic modified starch (TPMS).
- TPMS thermoplastic modified starch
- These blends can be made with or without a compatibilizer, such as maleic anhydride grafted polymers or polar-group grafted polymeric additives or coupling agents.
- the wet-laid microfiber described herein can be in any cross-sectional configurations such as monofilament, side-by side, island-in-the sea, or sheath-core structures.
- the fibers can be cut into staple fibers or used as a continuous fiber without cutting. For tissue applications, the fibers are cut into lengths less than 5 mm, with a normal range of 1 mm to 3 mm long.
- TPMS TPMS
- meltblown-grade polyolefins are not able to be spun into fiber on their own because their MFIs are either too low (TPMS) or too high (meltblown-grade polyolefins) to produce fibers.
- microfibers produced herein can be optionally surface treated with a surfactant for use in a wet-laid process. These microfibers, with or without surfactant treatment, can be used in tissue/towel substrates, absorbent articles, and in any other suitable application.
- the present disclosure relates to microfiber material compositions and methods for thermoplastic starch extrusion converting, compounding, and wet-laid microfiber fabrication for tissue and towel applications.
- meltblown-grade polyolefin and TPMS can be blended with or without any compatibilizer, including but not limited to, maleic anhydride grafted polymers or polar-group grafted polymeric additives or coupling agents for successful fiber spinning.
- compatibilizer including but not limited to, maleic anhydride grafted polymers or polar-group grafted polymeric additives or coupling agents for successful fiber spinning.
- Experimental data indicates these blends can be spun into a fiber, which is then surface treated using a selected surfactant to create a wet-laid fiber for papermaking.
- the microfiber surface can be treated by surfactants such as SF-19 during microfiber spinning or a surfactant could be compounded into the fiber blends outlined in U.S. Pat. No. 5,759,926 to Pike et al.
- Hydroxypropylated corn starch GLUCOSOL 800
- GLUCOSOL 800 Hydroxypropylated corn starch
- GPC weight-averaged molecular weight
- the modified starch has a bulk density of 0.64 g/cm 3 , its particle sizes pass 98% min through 140 Mesh, and it is supplied as off-white powders.
- METOCENE MF650X metallocene polypropylene homopolymer purchased from Lyondellbasell (Carrollton, Tex.), has a specific density of 0.91 g/cm 3 and a melt flow index (230° C./2.16 kg) of 1200 g/10 min.
- DNDA-1082 linear low density polyethylene purchased from the Dow Chemical Company (Midland, Mich.), has a specific density is 0.94 g/cm 3 and a melt flow index (190° C./2.16 kg) of 160 g/10 min.
- PPH 3762 polypropylene homopolymer and PPH M3766 metallocene isostatic polypropylene were purchased from Total Petrochemicals (Houston, Tex.).
- the specific density and melt flow index for PPH 3762 are 0.91 g/cm 3 and 18 g/10 min (190° C./2.16 kg) and those for PPH M3766 are 0.90 g/cm 3 and 23 g/10 min (190° C./2.16 kg).
- PLA 6201 D fiber-grade polylactic acid was purchased from NatureWorks (Minnetonka, Minn.), with a specific density of 1.24 g/cm 3 and a melt flow index (190° C./2.16 kg) of 15 to 30 g/10 min.
- FUSABOND E528 anhydride-modified polyethylene and FUSABOND 353 chemically-modified polypropylene copolymer are used as compatibilizers, purchased from DuPont (Wilmington, Del.).
- INFUSE 9807 high-performance olefin block copolymer is purchased from the Dow Chemical Company (Midland, Mich.). It has a density of 0.87 g/cm 3 and a melt flow index of 15 g/10 min (190° C. and 2.16 kg).
- Masil SF-19 is a surfactant used to make a fiber surface hydrophilic. It was purchased from Lubrizol Inc. (Spartanburg, S.C.).
- a K-TRON feeder (K-Tron America, Pitman, N.J.) was used to feed the starch material into a ZSK-30 extruder (Werner and Pfleidere Corporation, Ramsey, N.J.).
- the ZSK-30 extruder is a co-rotating, twin screw extruder.
- the extruder diameter is 30 mm with the length of the screws up to 1328 mm.
- the extruder has 14 barrels, numbered consecutively 1-14 from the feed hopper to the die.
- the first barrel (#1) received the modified starch at 15 lbs./hr. when the extruder was heated to the temperature profile as shown in Table 1 and the screw was set to rotate at 170 rpm.
- Glycerin as a plasticizer was pumped into barrel #2 using an Eldex pump from Eldex Laboratories, Inc. (Napa, Calif.). The vent was opened at the end of the extruder to release moisture.
- the die used to convert starch to thermoplastic starch has 3 openings of 5 mm in diameter that were separated by 3 mm. The thermoplastic starch strands were cooled on a conveyer belt and then pelletized.
- Example 2 The following examples were made similarly to those of Example 1 with the exception that no glycerin was needed. All processing conditions such as temperatures, screw speed, etc. from Example 2 to Example 10 are listed in Table 2 below.
- Example 2 20 10 90* 160 99 118 141 155 161 145 144 167 20-25 46-51
- Example 4 20 30 70* 160 99 118 141 155 161 145 144 167 20-25 61-70
- Example 5 20 25 75* 160 100 121 140 155 160 145 145 164 20-25 58-64
- Example 6 20 10 90 160 100 120 140 155 160 147 145 162 10-20 61-66
- Example 7 20 20 80 160 100 120 140 155 160 147 145 162 18-20 71-78
- Example 9 Example 8 @ 50% 50* 160 100 120 140 155 160 147 145 162 20-23 40-43
- Example 10 20 10
- Examples 2 to 5 were blends created using TPMS made from Example 1 and meltblown-grade polypropylene with a compatibilizer.
- Examples 6 to 7 were blends created using TPMS made from Example 1 and meltblown-grade polypropylene without any compatibilizer.
- Example 8 was a blend created using TPMS made from Example 1 and meltblown-grade polyethylene with a compatibilizer.
- Example 9 was a blend created by compounding Example 8 and the meltblown-grade PP using 5% INFUSE 9807 high-performance olefin block copolymer as a compatibilizer for polyolefin resins.
- Examples 10 is a blend created using non-meltblown-grade polypropylene (PPH M3766) and TPMS with a compatibilizer.
- melt flow rate is the weight of a polymer (in grams) forced through an extrusion rheometer orifice (0.0825-inch diameter) when subjected to a load of 2160 grams in 10 minutes, typically at 190° C. or 230° C. Unless otherwise indicated, the melt flow rate was measured in accordance with ASTM Test Method D1239 with a melt indexer (Tinius Olsen, Willow Grove, Pa.). The melt flow indexes for all 10 examples were measured and are listed in Table 3. The melt flow index value for TPMS is close to be negligible. In comparison to the neat meltblown-grade polypropylene, the melt flow index values for the blends containing TPMS are significantly lower.
- Example 8 is the blend using meltblown-grade polyethylene and TPMS (70/30); its melt flow index value is also significantly lower relative to the neat meltblown-grade polyethylene.
- DSC Differential Scanning calorimeter
- a fiber spinning line (Davis Standard Corporation, Pawcatuck, Conn.), which consists of two extruders, a quench chamber, and a godet with a maximal speed of 3000 meters per minute was used for melt fiber spinning.
- the spinning line had the capacity to make monofilament, side-by-side, and sheath core fibers.
- the spinning die plate used for the monofilament fiber samples presented in this disclosure was a 16-hole plate with each hole having a diameter of 0.4 mm. Only one extruder was used. Table 4 outlines the fiber spinning processing conditions and corresponding sample codes.
- Example 11 was a sheath core fiber, where the core material was from Example 9 and the sheath material is PLA 6201 D fiber-grade polylactic acid at a ratio of (90/10).
- Tenacity values were expressed in terms of gram-force per denier.
- the denier is the mass in grams per 9000 meters of fiber. Peak elongation (% strain at break), peak stress, and peak load were also measured.
- Fiber mechanical properties were determined for the blends at 300 and 500 meters per minute drawing speeds. The properties of fibers spun at 700 m/min were not tested. The results are tabulated in Table 5.
- the blends containing no FUSABOND compatibilizer shown in Examples 6 and 7 can be spun into fibers but fiber elongation is relatively low.
- Example 10 can be spun into fiber only at 300 m/min; at 500 m/min the fiber could not be spun for tenacity testing.
- the fiber diameters varied but were mostly about 30 to 40 microns, depending on fiber drawing speed. The fiber peak stress improved as fiber drawing speed is increased.
- meltblown-grade polyolefins are commonly used to make meltblown webs for nonwoven applications.
- the prior art does not teach how to compound meltblown-grade polyolefin with thermoplastic modified starch for short-cut wet-laid microfibers in tissue or towel applications. Fibers were surprisingly able to be spun from the novel blends described herein. These new wet-laid microfiber compositions and fabrication processes produced results not previously thought possible.
- spun microfibers include a blend of 70 wt. % to 90 wt. % meltblown-grade polyolefin and 10 wt. % to 30 wt. % thermoplastic starch, wherein the microfibers are suitable for use in a wet-laid process.
- a second particular aspect includes the first particular aspect, wherein the blend prior to spinning has a melt flow index greater than 150.
- a third particular aspect includes the first and/or second aspect, wherein the microfibers are staple fibers.
- a fourth particular aspect includes one or more of aspects 1-3, further including a surfactant treatment.
- a fifth particular aspect includes one or more of aspects 1-4, the blend further including a compatibilizer.
- a sixth particular aspect includes one or more of aspects 1-5, wherein the meltblown-grade polyolefin is polypropylene.
- a seventh particular aspect includes one or more of aspects 1-6, wherein the meltblown-grade polyolefin is polyethylene.
- An eighth particular aspect includes one or more of aspects 1-7, wherein the starch is a native starch derived from cereal grains such as corn, waxy corn, wheat, sorghum, rice, and waxy rice; tubers such as potatoes; roots such as tapioca, sweet potato, and arrowroot; or the pith of the sago palm.
- the starch is a native starch derived from cereal grains such as corn, waxy corn, wheat, sorghum, rice, and waxy rice; tubers such as potatoes; roots such as tapioca, sweet potato, and arrowroot; or the pith of the sago palm.
- a ninth particular aspect includes one or more of aspects 1-8, wherein native starch has been modified to become thermoplastic modified starch (TPMS).
- TPMS thermoplastic modified starch
- a method for producing spun microfibers includes producing a blend of 70 wt. %-90 wt. % meltblown-grade polyolefin with 10 wt. % to 30 wt. % thermoplastic modified starch (TPMS) derived from native starch; and spinning the blend into microfibers in a fiber spinning process, wherein the microfibers are suitable for use in a wet-laid process.
- TPMS thermoplastic modified starch
- An eleventh particular aspect includes the tenth particular aspect, wherein the blend prior to spinning has a melt flow index greater than 150.
- a twelfth particular aspect includes the eleventh and/or tenth aspect, further including cutting the microfibers into staple fibers.
- a thirteenth particular aspect includes one or more of aspects 10-12, further including applying a surfactant treatment to the microfibers.
- a fourteenth particular aspect includes one or more of aspects 10-13, wherein the blend further includes a compatibilizer.
- a fifteenth particular aspect includes one or more of aspects 10-14, wherein the meltblown-grade polyolefin is polypropylene.
- a sixteenth particular aspect includes one or more of aspects 10-15, wherein the meltblown-grade polyolefin is polyethylene.
- a seventeenth particular aspect includes one or more of aspects 10-16, wherein the native starch is derived from cereal grains such as corn, waxy corn, wheat, sorghum, rice, and waxy rice; tubers such as potatoes; roots such as tapioca, sweet potato, and arrowroot; or the pith of the sago palm.
- the native starch is derived from cereal grains such as corn, waxy corn, wheat, sorghum, rice, and waxy rice; tubers such as potatoes; roots such as tapioca, sweet potato, and arrowroot; or the pith of the sago palm.
- a method for producing an absorbent product includes producing a blend of 70 wt. %-90 wt. % meltblown-grade polyolefin with 10 wt. % to 30 wt. % thermoplastic modified starch (TPMS), wherein the blend prior to spinning has a melt flow index greater than 150; spinning the blend into microfibers in a fiber spinning process; cutting the microfibers into staple fibers; and incorporating the staple fibers into a wet-laid process for making a nonwoven web.
- TPMS thermoplastic modified starch
- a nineteenth particular aspect includes the eighteenth particular aspect, further including converting the nonwoven web into an absorbent product.
- a twentieth particular aspect includes the eighteenth and/or nineteenth aspects, wherein the absorbent product is a tissue product.
- any ranges of values set forth in this disclosure contemplate all values within the range and are to be construed as support for claims reciting any sub-ranges having endpoints that are whole number values within the specified range in question.
- a disclosure of a range of from 1 to 5 shall be considered to support claims to any of the following ranges: 1 to 5; 1 to 4; 1 to 3; 1 to 2; 2 to 5; 2 to 4; 2 to 3; 3 to 5; 3 to 4; and 4 to 5.
Abstract
Description
- Current wet-laid microfibers are produced with a limited number of fiber-grade synthetic polymers such as PE, PP, PET, and PLA. The limited number of options for fiber-grade polymers is due to a set of stringent requirements for fiber melt spinning. There are no wet-laid microfibers containing biopolymers such as starch, although thermoplastic starch is widely used in blends of polyolefin or PLA for breathable, stretchable, or packaging film applications.
- In an attempt to increase sustainability, thermoplastic modified starch (TPMS) can be added to fiber-grade polyolefins. The resulting fibers, however, such as those in U.S. Pat. No. 6,623,854 to Bond, cannot be spun without the fibers breaking, except at very low speeds, which is inefficient, costly, and inappropriate for commercial production. Using TPMS with standard fiber spinning grades of polyolefins does not allow commercial scale speeds. Further, TPMS and meltblown-grade polyolefins cannot be spun into fiber individually using staple fiber spinning equipment because their melt-flow indexes (MFIs) are insufficient. TPMS has an MFI that is too low, whereas meltblown-grade polyolefins have an MFI that is too high.
- U.S. Pat. No. 8,470,222 B2 to Shi et al. describes a biodegradable fiber spun from blends of modified aliphatic-aromatic polyester and TPMS. The reason to modify aliphatic-aromatic polyester via alcoholysis is because thermoplastic starch alone cannot be spun into fibers due to its unfavorable rheological characteristics. The modified aliphatic-aromatic polyester can alter rheological profile of thermoplastic starch suitable for fiber melt spinning. However, polyester resins are expensive relative to polyolefins and alcoholysis through reactive extrusion can involve the use of undesirable chemical reagents. The disclosure described herein directly blends meltblown-grade polyolefins and thermoplastic modified starch for wet-laid microfiber spinning. The results demonstrate an unexpected success to spin fibers from blends of meltblown-grade polyolefin and thermoplastic starch. Conversely, as described above, conventional fiber-grade polyolefin containing TPMS cannot be realistically spun into fibers.
- It is well known that few renewable materials by themselves are suitable for fiber spinning. Attempts to date have dealt with improving processability for renewable materials such as starch in their respective blends for fiber spinning. Different processing aids were added into fiber blends. However, there is no direct use of meltblown synthetic polymers in their blends.
- The present disclosure describes novel fiber compositions using meltblown polyolefins and thermoplastic modified starch to create miscible blends for wet-laid microfiber spinning via conventional polymer processing equipment.
- This disclosure addresses the use of a low-cost starch biopolymer together with a commodity meltblown-grade polyolefin for wet-laid microfiber production. Successful inclusion of thermoplastic starch in meltblown-grade polyethylene or polypropylene for wet-laid microfiber spinning creates opportunities in 1) cost reduction when it is used in bath/facial tissue or towel manufacturing, and in 2) increased use of bio-based renewable material content, all of which is consistent with sustainability objectives.
- More specifically, synthetic microfibers are made in a conventional fiber spinning process (not a meltblown process) from a blend of meltblown-grade polyolefin(s) and thermoplastic modified starch (TPMS). These blends can be made with or without a compatibilizer, such as maleic anhydride grafted polymers or polar-group grafted polymeric additives or coupling agents. The wet-laid microfiber can be in any cross-sectional configurations such as monofilament, side-by side, island-in-the sea, or sheath-core structures. The fibers can be cut into staple fibers or used as a continuous fiber without cutting. For tissue applications, the fibers are cut into lengths less than 5 mm, with a normal range of 1 to 3 mm long.
- In one aspect, spun microfibers include a blend of 70 wt. % to 90 wt. % meltblown-grade polyolefin and 10 wt. % to 30 wt. % thermoplastic starch, wherein the microfibers are suitable for use in a wet-laid process.
- In another aspect, a method for producing spun microfibers includes producing a blend of 70 wt. %-90 wt. % meltblown-grade polyolefin with 10 wt. % to 30 wt. % thermoplastic modified starch (TPMS) derived from native starch; and spinning the blend into microfibers in a fiber spinning process, wherein the microfibers are suitable for use in a wet-laid process.
- In still another aspect, a method for producing an absorbent product includes producing a blend of 70 wt. %-90 wt. % meltblown-grade polyolefin with 10 wt. % to 30 wt. % thermoplastic modified starch (TPMS), wherein the blend prior to spinning has a melt flow index greater than 150; spinning the blend into microfibers in a fiber spinning process; cutting the microfibers into staple fibers; and incorporating the staple fibers into a wet-laid process for making a nonwoven web.
- The foregoing and other features and aspects of the present disclosure and the manner of attaining them will become more apparent, and the disclosure itself will be better understood by reference to the following description, appended claims and accompanying drawings, where:
-
FIG. 1 graphically illustrates Differential Scanning calorimeter (DSC) thermograms (2nd heat) of PP/TPMS blend samples; -
FIG. 2 graphically illustrates the effect of composition (Wt % TPMS) on melt temperature of PP/TPMS blends; and -
FIG. 3 graphically illustrates the effect of composition (Wt % TPMS) on melt enthalpy of PP/TPMS blends. - Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present disclosure. The drawings are representational and are not necessarily drawn to scale. Certain proportions thereof might be exaggerated, while others might be minimized.
- The terms “absorbent article” and “absorbent product” refer herein to an article that can be placed against or in proximity to the body (i.e., contiguous with the body) of the wearer to absorb and contain various liquid, solid, and semi-solid exudates discharged from the body. Such absorbent articles, as described herein, are intended to be discarded after a limited period of use instead of being laundered or otherwise restored for reuse. It is to be understood that the present disclosure is applicable to various disposable absorbent articles, including, but not limited to, diapers, training pants, youth pants, swim pants, feminine hygiene products, including, but not limited to, menstrual pads, incontinence products, medical garments, surgical pads and bandages, other personal care or health care garments, and the like without departing from the scope of the present disclosure. The term can also include bath tissue, facial tissue, toweling, and the like.
- The term “carded web” refers herein to a web containing natural or synthetic staple fibers typically having fiber lengths less than about 100 mm. Bales of staple fibers can undergo an opening process to separate the fibers that are then sent to a carding process that separates and combs the fibers to align them in the machine direction after which the fibers are deposited onto a moving wire for further processing. Such webs are usually subjected to some type of bonding process such as thermal bonding using heat and/or pressure. In addition to or in lieu thereof, the fibers can be subject to adhesive processes to bind the fibers together such as by the use of powder adhesives. The carded web can be subjected to fluid entangling, such as hydroentangling, to further intertwine the fibers and thereby improve the integrity of the carded web. Carded webs, due to the fiber alignment in the machine direction, once bonded, will typically have more machine direction strength than cross machine direction strength.
- The term “hydrophilic” refers herein to fibers or the surfaces of fibers that are wetted by aqueous liquids in contact with the fibers. The degree of wetting of the materials can, in turn, be described in terms of the contact angles and the surface tensions of the liquids and materials involved. Equipment and techniques suitable for measuring the wettability of particular fiber materials or blends of fiber materials can be provided by Cahn SFA-222 Surface Force Analyzer System, or a substantially equivalent system. When measured with this system, fibers having contact angles less than 90 degrees are designated “wettable” or hydrophilic, and fibers having contact angles greater than 90 degrees are designated “nonwettable” or hydrophobic.
- The term “meltblown” refers herein to fibers formed by extruding a molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into converging high velocity heated gas (e.g., air) streams that attenuate the filaments of molten thermoplastic material to reduce their diameter, which can be a microfiber diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface to form a web of randomly dispersed meltblown fibers. Such a process is disclosed, for example, in U.S. Pat. No. 3,849,241 to Butin et al., which is incorporated herein by reference. Meltblown fibers are microfibers that can be continuous or discontinuous, are generally smaller than about 0.6 denier, and can be tacky and self-bonding when deposited onto a collecting surface.
- The term “nonwoven” refers herein to materials and webs of material that are formed without the aid of a textile weaving or knitting process. The materials and webs of materials can have a structure of individual fibers, filaments, or threads (collectively referred to as “fibers”) that can be interlaid, but not in an identifiable manner as in a knitted fabric. Nonwoven materials or webs can be formed from many processes such as, but not limited to, meltblowing processes, spunbonding processes, carded web processes, etc.
- The term “pliable” refers herein to materials that are compliant and that will readily conform to the general shape and contours of the wearer's body.
- The term “spunbond” refers herein to small diameter fibers that are formed by extruding molten thermoplastic material as filaments from a plurality of fine capillaries of a spinnerette having a circular or other configuration, with the diameter of the extruded filaments then being rapidly reduced by a conventional process such as, for example, eductive drawing, and processes that described in U.S. Pat. No. 4,340,563 to Appel et al., U.S. Pat. No. 3,692,618 to Dorschner et al., U.S. Pat. No. 3,802,817 to Matsuki et al., U.S. Pat. Nos. 3,338,992 and 3,341,394 to Kinney, U.S. Pat. No. 3,502,763 to Hartmann, U.S. Pat. No. 3,502,538 to Peterson, and U.S. Pat. No. 3,542,615 to Dobo et al., each of which is incorporated herein in its entirety by reference. Spunbond fibers are generally continuous and often have average deniers larger than about 0.3, and in an aspect, between about 0.6, 5 and 10 and about 15, 20 and 40. Spunbond fibers are generally not tacky when they are deposited on a collecting surface.
- The term “thermoplastic” refers herein to a polymeric material that becomes pliable or moldable above a specific temperature and returns to a solid state upon cooling.
- The term “meltblown-grade polyolefin” refers to a polyolefin characterized by an extremely high melt flow rate homopolymer resin. The melt flow rate of a meltblown-grade polyolefin can range from 200 to 1550 g/10 min under standard testing conditions (ISO 1133-1). Meltblown-grade polyolefins can also have a narrow molecular weight distribution.
- The term “microfiber” refers to a fiber (including staple fibers and filaments) with a linear mass density less than 1 dtex, where dtex is an abbreviation of decitex, the mass in grams per 10,000 meters.
- Generally, a method of producing wet-laid microfibers using spunbond TPMS and meltblown-grade polymers is disclosed herein. This disclosure addresses the use of a low-cost starch biopolymer together with a low-cost commodity meltblown-grade polyolefin for wet-laid microfiber production. Successful inclusion of thermoplastic starch in meltblown-grade polyethylene or polypropylene for wet-laid microfiber spinning creates opportunities for cost reduction when used in bath/facial tissue or towel manufacturing, and in increased use of bio-based renewable material content, all of which are consistent with sustainability objectives.
- Many companies wish to reduce their forest fiber footprints. A key component in achieving this goal can be to transfer a significant portion of wood fiber sourced from natural forests to alternative, renewable sources. In certain cases, this goal calls for a reduction in northern bleached softwood Kraft (NBSK) pulp. Products such as tissue, towels, and industrial wipers are responsible for a significant portion of virgin NBSK consumption. NBSK can be the most expensive fiber among a company's spend on commodity pulps annually. There are also uncertainties with respect to long softwood fiber supply and fluctuations in NBSK prices. The initiative described herein, generally NBSK replacement using a low-cost wet-laid microfiber, is a timely initiative to support corporate sustainability. The fibers described herein can also be used in any other suitable nonwoven process including the production of bonded carded webs.
- The present disclosure employs a thermoplastic starch. Starch is a natural polymer composed of amylose and amylopectin. Amylose is essentially a linear polymer having a molecular weight in the range of 100,000-500,000, whereas amylopectin is a highly branched polymer having a molecular weight of up to several million. Although starch is produced in many plants, typical sources includes seeds of cereal grains, such as corn, waxy corn, wheat, sorghum, rice, and waxy rice; tubers, such as potatoes; roots, such as tapioca (i.e., cassava and manioc), sweet potato, and arrowroot; and the pith of the sago palm. Broadly speaking, any natural (unmodified) and/or modified starch may be employed in the present invention. Modified starches, for instance, are often employed that have been chemically modified by typical processes known in the art (e.g., esterification, etherification, oxidation, acid hydrolysis, enzymatic hydrolysis, etc.). Starch ethers and/or esters may be particularly desirable, such as hydroxyalkyl starches, carboxymethyl starches, etc. The hydroxyalkyl group of hydroxylalkyl starches may contain, for instance, 2 to 10 carbon atoms, in some embodiments from 2 to 6 carbon atoms, and in some embodiments, from 2 to 4 carbon atoms. Representative hydroxyalkyl starches such as hydroxyethyl starch, hydroxypropyl starch, hydroxybutyl starch, and derivatives thereof. Starch esters, for instance, may be prepared using a wide variety of anhydrides (e.g., acetic, propionic, butyric, and so forth), organic acids, acid chlorides, or other esterification reagents. The degree of esterification may vary as desired, such as from 1 to 3 ester groups per glucosidic unit of the starch.
- Regardless of whether it is in a native or modified form, the starch may contain different percentages of amylose and amylopectin, different size starch granules and different polymeric weights for amylose and amylopectin. High amylose starches contain greater than about 50% by weight amylose and low amylose starches contain less than about 50% by weight amylose. Although not required, low amylose starches having an amylose content of from about 10% to about 40% by weight, and in some embodiments, from about 15% to about 35% by weight, are particularly suitable for use in the present invention. Examples of such low amylose starches include corn starch and potato starch, both of which have an amylose content of approximately 20% by weight. Such low amylose starches typically have a number average molecular weight (“Mn”) ranging from about 50,000 to about 1,000,000 grams per mole, in some embodiments from about 75,000 to about 800,000 grams per mole, and in some embodiments, from about 100,000 to about 600,000 grams per mole, as well as a weight average molecular weight (“Mw”) ranging from about 5,000,000 to about 25,000,000 grams per mole, in some embodiments from about 5,500,000 to about 15,000,000 grams per mole, and in some embodiments, from about 6,000,000 to about 12,000,000 grams per mole. The ratio of the weight average molecular weight to the number average molecular weight (“Mw/Mn”), i.e., the “polydispersity index”, is also relatively high. For example, the polydispersity index may range from about 20 to about 100.
- A plasticizer is also employed in the thermoplastic starch to help render the starch melt-processible. Starches, for instance, normally exist in the form of granules that have a coating or outer membrane that encapsulates the more water-soluble amylose and amylopectin chains within the interior of the granule. When heated, plasticizers may soften and penetrate the outer membrane and cause the inner starch chains to absorb water and swell. This swelling will, at some point, cause the outer shell to rupture and result in an irreversible destructurization of the starch granule. Once destructurized, the starch polymer chains containing amylose and amylopectin polymers, which are initially compressed within the granules, will stretch out and form a generally disordered intermingling of polymer chains. Upon resolidification, however, the chains may reorient themselves to form crystalline or amorphous solids having varying strengths depending on the orientation of the starch polymer chains. Because the starch is thus capable of melting and resolidifying at certain temperatures, it is generally considered a “thermoplastic starch.”
- Suitable plasticizers may include, for instance, polyhydric alcohol plasticizers, such as sugars (e.g., glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose, and erythrose), sugar alcohols (e.g., erythritol, xylitol, malitol, mannitol, and sorbitol), polyols (e.g., ethylene glycol, glycerol, propylene glycol, dipropylene glycol, butylene glycol, and hexane triol), etc. Also suitable are hydrogen bond forming organic compounds which do not have hydroxyl group, including urea and urea derivatives; anhydrides of sugar alcohols such as sorbitan; animal proteins such as gelatin; vegetable proteins such as sunflower protein, soybean proteins, cotton seed proteins; and mixtures thereof. Other suitable plasticizers may include phthalate esters, dimethyl and diethylsuccinate and related esters, glycerol triacetate, glycerol mono and diacetates, glycerol mono, di, and tripropionates, butanoates, stearates, lactic acid esters, citric acid esters, adipic acid esters, stearic acid esters, oleic acid esters, and other acid esters. Aliphatic acids may also be used, such as copolymers of ethylene and acrylic acid, polyethylene grafted with maleic acid, polybutadiene-co-acrylic acid, polybutadiene-co-maleic acid, polypropylene-co-acrylic acid, polypropylene-co-maleic acid, and other hydrocarbon based acids. A low molecular weight plasticizer is preferred, such as less than about 20,000 g/mol, preferably less than about 5,000 g/mol and more preferably less than about 1,000 g/mol.
- The relative amount of starches and plasticizers employed in the thermoplastic starch may vary depending on a variety of factors, such as the desired molecular weight, the type of starch, the affinity of the plasticizer for the starch, etc. Typically, however, starches constitute from about 30 wt. % to about 95 wt. %, in some embodiments from about 40 wt. % to about 90 wt. %, and in some embodiments, from about 50 wt. % to about 85 wt. % of the thermoplastic starch. Likewise, plasticizers typically constitute from about 5 wt. % to about 55 wt. %, in some embodiments from about 10 wt. % to about 45 wt. %, and in some embodiments, from about 15 wt. % to about 35 wt. % of the thermoplastic composition. It should be understood that the weight of starch referenced herein includes any bound water that naturally occurs in the starch before mixing it with other components to form the thermoplastic starch. Starches, for instance, typically have a bound water content of about 5% to 16% by weight of the starch.
- Additional information with respect to the processing and use of thermoplastic starch can be found in U.S. Pat. No. 8,470,222 to Shi et al., which is incorporated herein by reference to the extent it does not conflict herewith.
- Conventional synthetic microfibers are made in a conventional fiber spinning process (not a meltblown process) from conventional fiber-grade polymer. The process described herein substitutes a blend of less expensive meltblown-grade polyolefin(s) and a low-cost thermoplastic modified starch (TPMS). These blends can be made with or without a compatibilizer, such as maleic anhydride grafted polymers or polar-group grafted polymeric additives or coupling agents. The wet-laid microfiber described herein can be in any cross-sectional configurations such as monofilament, side-by side, island-in-the sea, or sheath-core structures. The fibers can be cut into staple fibers or used as a continuous fiber without cutting. For tissue applications, the fibers are cut into lengths less than 5 mm, with a normal range of 1 mm to 3 mm long.
- If TPMS is added to fiber-grade polyolefins in a conventional fiber-spinning process, fibers cannot be spun without the fibers breaking except at very low speeds. Further, TPMS and meltblown-grade polyolefins are not able to be spun into fiber on their own because their MFIs are either too low (TPMS) or too high (meltblown-grade polyolefins) to produce fibers.
- The microfibers produced herein can be optionally surface treated with a surfactant for use in a wet-laid process. These microfibers, with or without surfactant treatment, can be used in tissue/towel substrates, absorbent articles, and in any other suitable application.
- The present disclosure relates to microfiber material compositions and methods for thermoplastic starch extrusion converting, compounding, and wet-laid microfiber fabrication for tissue and towel applications. Examples containing meltblown-grade polyolefin and TPMS can be blended with or without any compatibilizer, including but not limited to, maleic anhydride grafted polymers or polar-group grafted polymeric additives or coupling agents for successful fiber spinning. Experimental data indicates these blends can be spun into a fiber, which is then surface treated using a selected surfactant to create a wet-laid fiber for papermaking.
- To be hydrophilic or wettable for tissue or towel applications, the microfiber surface can be treated by surfactants such as SF-19 during microfiber spinning or a surfactant could be compounded into the fiber blends outlined in U.S. Pat. No. 5,759,926 to Pike et al.
- The following is provided for exemplary purposes to facilitate understanding of the disclosure and should not be construed to limit the disclosure to the examples. Other formulations and substrates can be used within this disclosure and the claims presented below.
- Materials
- Hydroxypropylated corn starch, GLUCOSOL 800, was purchased from Chemstar (Minneapolis, Minn.) with a weight-averaged molecular weight, determined by GPC, of 2,900,000 and a polydispersity estimated at 28. The modified starch has a bulk density of 0.64 g/cm3, its particle sizes pass 98% min through 140 Mesh, and it is supplied as off-white powders.
- METOCENE MF650X metallocene polypropylene homopolymer, purchased from Lyondellbasell (Carrollton, Tex.), has a specific density of 0.91 g/cm3 and a melt flow index (230° C./2.16 kg) of 1200 g/10 min.
- DNDA-1082 linear low density polyethylene, purchased from the Dow Chemical Company (Midland, Mich.), has a specific density is 0.94 g/cm3 and a melt flow index (190° C./2.16 kg) of 160 g/10 min.
- PPH 3762 polypropylene homopolymer and PPH M3766 metallocene isostatic polypropylene were purchased from Total Petrochemicals (Houston, Tex.). The specific density and melt flow index for PPH 3762 are 0.91 g/cm3 and 18 g/10 min (190° C./2.16 kg) and those for PPH M3766 are 0.90 g/cm3 and 23 g/10 min (190° C./2.16 kg).
- PLA 6201 D fiber-grade polylactic acid was purchased from NatureWorks (Minnetonka, Minn.), with a specific density of 1.24 g/cm3 and a melt flow index (190° C./2.16 kg) of 15 to 30 g/10 min.
- FUSABOND E528 anhydride-modified polyethylene and FUSABOND 353 chemically-modified polypropylene copolymer are used as compatibilizers, purchased from DuPont (Wilmington, Del.).
- INFUSE 9807 high-performance olefin block copolymer is purchased from the Dow Chemical Company (Midland, Mich.). It has a density of 0.87 g/cm3 and a melt flow index of 15 g/10 min (190° C. and 2.16 kg).
- Masil SF-19 is a surfactant used to make a fiber surface hydrophilic. It was purchased from Lubrizol Inc. (Spartanburg, S.C.).
- Material Processing
- A K-TRON feeder (K-Tron America, Pitman, N.J.) was used to feed the starch material into a ZSK-30 extruder (Werner and Pfleidere Corporation, Ramsey, N.J.). The ZSK-30 extruder is a co-rotating, twin screw extruder. The extruder diameter is 30 mm with the length of the screws up to 1328 mm. The extruder has 14 barrels, numbered consecutively 1-14 from the feed hopper to the die. The first barrel (#1) received the modified starch at 15 lbs./hr. when the extruder was heated to the temperature profile as shown in Table 1 and the screw was set to rotate at 170 rpm. Glycerin as a plasticizer was pumped into
barrel # 2 using an Eldex pump from Eldex Laboratories, Inc. (Napa, Calif.). The vent was opened at the end of the extruder to release moisture. The die used to convert starch to thermoplastic starch has 3 openings of 5 mm in diameter that were separated by 3 mm. The thermoplastic starch strands were cooled on a conveyer belt and then pelletized. -
TABLE 1 Processing Conditions for Making TPMS on ZSK-30 Material Feeding Extruder Sample Rate Modified Glycerin Speed Extruder Temperature Profile (° C.) Pmelt Torque No. (lb/hr) Starch (%) (rpm) T1 T2 T3 T4 T5 T6 T7 Tmelt (psi) (%) Example 1 15 75 25 170 80 105 137 150 145 142 140 155 60-70 50-60 - The following examples were made similarly to those of Example 1 with the exception that no glycerin was needed. All processing conditions such as temperatures, screw speed, etc. from Example 2 to Example 10 are listed in Table 2 below.
-
TABLE 2 Processing Conditions for Compounding TPMS with Polyolef ins on ZSK-30 Resin Non- Feeding DNDA MF650X Meltblown Extruder Rate TPMS 1082 PE PP PPH Speed Extruder Temperature Profile (° C.) Pmelt Torque Sample No. (lb/hr) (%) (%) (%) (%) (rpm) T1 T2 T3 T4 T5 T6 T7 Tmelt (psi) (%) Example 2 20 10 90* 160 99 118 141 155 161 145 144 167 20-25 46-51 Example 3 20 20 80* 160 99 118 141 155 161 145 144 167 20-25 63-68 Example 4 20 30 70* 160 99 118 141 155 161 145 144 167 20-25 61-70 Example 5 20 25 75* 160 100 121 140 155 160 145 145 164 20-25 58-64 Example 6 20 10 90 160 100 120 140 155 160 147 145 162 10-20 61-66 Example 7 20 20 80 160 100 120 140 155 160 147 145 162 18-20 71-78 Example 8 20 30 70** 160 100 120 140 155 160 147 145 162 18-22 60-65 Example 9 20 Example 8 @ 50% 50* 160 100 120 140 155 160 147 145 162 20-23 40-43 Example 10 20 10 (M3766) 90* 160 140 150 160 160 160 160 164 191 120-125 64-66 *FUSABOND 353 chemically-modified polypropylene copolymer used at about 1%. **FUSABOND E528 anhydride-modified polyethylene used at about 1%. - Examples 2 to 5 were blends created using TPMS made from Example 1 and meltblown-grade polypropylene with a compatibilizer.
- Examples 6 to 7 were blends created using TPMS made from Example 1 and meltblown-grade polypropylene without any compatibilizer.
- Example 8 was a blend created using TPMS made from Example 1 and meltblown-grade polyethylene with a compatibilizer.
- Example 9 was a blend created by compounding Example 8 and the meltblown-grade PP using 5% INFUSE 9807 high-performance olefin block copolymer as a compatibilizer for polyolefin resins.
- Examples 10 is a blend created using non-meltblown-grade polypropylene (PPH M3766) and TPMS with a compatibilizer.
- Thermal Properties
- The melt flow rate (MFR) is the weight of a polymer (in grams) forced through an extrusion rheometer orifice (0.0825-inch diameter) when subjected to a load of 2160 grams in 10 minutes, typically at 190° C. or 230° C. Unless otherwise indicated, the melt flow rate was measured in accordance with ASTM Test Method D1239 with a melt indexer (Tinius Olsen, Willow Grove, Pa.). The melt flow indexes for all 10 examples were measured and are listed in Table 3. The melt flow index value for TPMS is close to be negligible. In comparison to the neat meltblown-grade polypropylene, the melt flow index values for the blends containing TPMS are significantly lower. Example 8 is the blend using meltblown-grade polyethylene and TPMS (70/30); its melt flow index value is also significantly lower relative to the neat meltblown-grade polyethylene.
-
TABLE 3 Fiber Blend Melt Flow Index (in g/10 min) Example 1 2 3 4 5 6 7 8 9 10 MFI <0.5 646 499 375 412 609 478 60 200 13 - A Differential Scanning calorimeter (DSC) analysis was carried out to understand the thermal properties of the resin samples. Pellet samples were analyzed using a TA Instruments Q200 Differential Scanning calorimeter. A DSC thermogram for a sample (approximately 5 mg) in a sealed aluminum pan was recorded in the temperature range of 50° C. to 200 QC under a dynamic nitrogen atmosphere using a heating/cooling rate of 10° C./min. Universal analysis NT software provided by TA Instruments was used for analyzing data.
- DSC thermograms (2nd heat) for blends of PP with TPMS amounts ranging from 10% to 20% to 30% (resin samples made from Examples 2, 3, and 4) are compared in
FIG. 1 . As shown inFIG. 2 , the melting temperatures for all blends are around 154° C., which is the melting temperature of neat meltblown-grade polypropylene. The results show that the melt temperature does not vary significantly with increasing TPMS content. The melt enthalpy, however, which is displayed inFIG. 3 , decreased from 99 J/g (the neat meltblown-grade polypropylene) to about 75 J/g for the PP/TPMS (70/30) blend, indicating a decrease in crystallinity. - Fiber Spinning
- A fiber spinning line (Davis Standard Corporation, Pawcatuck, Conn.), which consists of two extruders, a quench chamber, and a godet with a maximal speed of 3000 meters per minute was used for melt fiber spinning. The spinning line had the capacity to make monofilament, side-by-side, and sheath core fibers. The spinning die plate used for the monofilament fiber samples presented in this disclosure was a 16-hole plate with each hole having a diameter of 0.4 mm. Only one extruder was used. Table 4 outlines the fiber spinning processing conditions and corresponding sample codes.
-
TABLE 4 Fiber Spinning Parameters Extruders for Sample 11 Sample No. Examples 2 to 4 Examples 6 to 7 Example 10 Sheath Core Extruder Zone 7 (° C.) 175 160 210 200 180 Zone 6 (° C.) 175 160 210 200 180 Zone 5 (° C.) 165 160 174 200 180 Zone 4 (° C.) 170 160 210 200 180 Zone 3 (° C.) 170 150 210 195 180 Zone 2 (° C.) 170 150 200 195 175 Zone 1 (° C.) 153 140 165 195 175 Ext 1 Melt 90 65 1145 650 790 Outlet Pressure (psi) Spinning Spin Beam 180 160 190 195 Temp and (° C.) Speed Godet Speed 700, 500, 300 700, 500, 300 300 700, 500, 300 (m/min) Misc. Ext 1 Melt 6.6 9 14.6 2 18 Pump (rpm) Pack Type Monofilament Monofilament Monofilament Sheath/Core - Example 11 was a sheath core fiber, where the core material was from Example 9 and the sheath material is PLA 6201 D fiber-grade polylactic acid at a ratio of (90/10).
- Fiber Properties
- Individual fiber specimens were shortened (i.e., cut with scissors) to 38 mm in length and placed separately on a black velvet cloth. 10 to 15 fiber specimens were collected in this manner. The fiber specimens were then mounted in a substantially straight condition on a rectangular paper frame having external dimensions of 51 mm×51 mm and internal dimensions of 25 mm×25 mm. The ends of each fiber specimen were operatively attached to the frame by carefully securing the fiber ends to the sides of the frame with adhesive tape. Each fiber specimen was then measured for its external, cross-fiber dimension employing a conventional laboratory microscope that was properly calibrated and set at 40× magnification. This cross-fiber dimension was recorded as the diameter of the individual fiber specimen. The frame helped to mount the ends of the sample fiber specimens in the upper and lower grips of a constant rate of extension type tensile tester,
MTS SYNERGY 200 tensile tester from MTS Systems Corporation (Eden Prairie, Mich.). - Tenacity values were expressed in terms of gram-force per denier. The denier is the mass in grams per 9000 meters of fiber. Peak elongation (% strain at break), peak stress, and peak load were also measured.
- Fiber mechanical properties were determined for the blends at 300 and 500 meters per minute drawing speeds. The properties of fibers spun at 700 m/min were not tested. The results are tabulated in Table 5.
-
TABLE 5 Fiber Mechanical Properties Fiber Drawing Peak Peak Speed Load Stress Elongation Denier Example No. Blend Ratio (m/min) (gf) (MPa) (%) Tenacity (gf) Example 2 PP/TPMS (90/10) 300 3.6 30.7 132 0.37 9.3 500 2.5 37.0 277 0.47 5.4 Example 3 PP/TPMS (80/20) 300 3.8 33.4 693 0.42 8.9 500 2.5 39.6 655 0.50 5.2 Example 4 PP/TPMS (70/30) 300 3.4 27.1 581 0.34 10.2 500 2.0 41.6 472 0.52 3.9 Example 6 PP/TPMS (90/10) 300 2.0 27.6 188 0.35 6.0 500 2.1 44.1 235 0.56 4.0 Example 7 PP/TPMS (80/20) 300 1.9 27.2 164 0.34 6.9 500 1.8 35.8 199 0.46 5.1 Example 10 PP3766/TPMS (90/10) 300 11.9 102 667 1.28 9.3 500 N/A N/A N/A N/A N/A Example 12 PLA/Example 9 (10/90) 300 8.7 37.5 233 0.47 21.3 500 5.4 48.8 197 0.61 9.9 - As indicated, fiber elongation improved with an increasing amount of the modified thermoplastic starch in Examples 3 and 4 relative to Example 2. The blends containing no FUSABOND compatibilizer shown in Examples 6 and 7 can be spun into fibers but fiber elongation is relatively low. Example 10 can be spun into fiber only at 300 m/min; at 500 m/min the fiber could not be spun for tenacity testing. The fiber diameters varied but were mostly about 30 to 40 microns, depending on fiber drawing speed. The fiber peak stress improved as fiber drawing speed is increased.
- Meltblown-grade polyolefins are commonly used to make meltblown webs for nonwoven applications. The prior art does not teach how to compound meltblown-grade polyolefin with thermoplastic modified starch for short-cut wet-laid microfibers in tissue or towel applications. Fibers were surprisingly able to be spun from the novel blends described herein. These new wet-laid microfiber compositions and fabrication processes produced results not previously thought possible.
- In a first particular aspect, spun microfibers include a blend of 70 wt. % to 90 wt. % meltblown-grade polyolefin and 10 wt. % to 30 wt. % thermoplastic starch, wherein the microfibers are suitable for use in a wet-laid process.
- A second particular aspect includes the first particular aspect, wherein the blend prior to spinning has a melt flow index greater than 150.
- A third particular aspect includes the first and/or second aspect, wherein the microfibers are staple fibers.
- A fourth particular aspect includes one or more of aspects 1-3, further including a surfactant treatment.
- A fifth particular aspect includes one or more of aspects 1-4, the blend further including a compatibilizer.
- A sixth particular aspect includes one or more of aspects 1-5, wherein the meltblown-grade polyolefin is polypropylene.
- A seventh particular aspect includes one or more of aspects 1-6, wherein the meltblown-grade polyolefin is polyethylene.
- An eighth particular aspect includes one or more of aspects 1-7, wherein the starch is a native starch derived from cereal grains such as corn, waxy corn, wheat, sorghum, rice, and waxy rice; tubers such as potatoes; roots such as tapioca, sweet potato, and arrowroot; or the pith of the sago palm.
- A ninth particular aspect includes one or more of aspects 1-8, wherein native starch has been modified to become thermoplastic modified starch (TPMS).
- In a tenth aspect, a method for producing spun microfibers includes producing a blend of 70 wt. %-90 wt. % meltblown-grade polyolefin with 10 wt. % to 30 wt. % thermoplastic modified starch (TPMS) derived from native starch; and spinning the blend into microfibers in a fiber spinning process, wherein the microfibers are suitable for use in a wet-laid process.
- An eleventh particular aspect includes the tenth particular aspect, wherein the blend prior to spinning has a melt flow index greater than 150.
- A twelfth particular aspect includes the eleventh and/or tenth aspect, further including cutting the microfibers into staple fibers.
- A thirteenth particular aspect includes one or more of aspects 10-12, further including applying a surfactant treatment to the microfibers.
- A fourteenth particular aspect includes one or more of aspects 10-13, wherein the blend further includes a compatibilizer.
- A fifteenth particular aspect includes one or more of aspects 10-14, wherein the meltblown-grade polyolefin is polypropylene.
- A sixteenth particular aspect includes one or more of aspects 10-15, wherein the meltblown-grade polyolefin is polyethylene.
- A seventeenth particular aspect includes one or more of aspects 10-16, wherein the native starch is derived from cereal grains such as corn, waxy corn, wheat, sorghum, rice, and waxy rice; tubers such as potatoes; roots such as tapioca, sweet potato, and arrowroot; or the pith of the sago palm.
- In an eighteenth particular aspect, a method for producing an absorbent product includes producing a blend of 70 wt. %-90 wt. % meltblown-grade polyolefin with 10 wt. % to 30 wt. % thermoplastic modified starch (TPMS), wherein the blend prior to spinning has a melt flow index greater than 150; spinning the blend into microfibers in a fiber spinning process; cutting the microfibers into staple fibers; and incorporating the staple fibers into a wet-laid process for making a nonwoven web.
- A nineteenth particular aspect includes the eighteenth particular aspect, further including converting the nonwoven web into an absorbent product.
- A twentieth particular aspect includes the eighteenth and/or nineteenth aspects, wherein the absorbent product is a tissue product.
- In the interests of brevity and conciseness, any ranges of values set forth in this disclosure contemplate all values within the range and are to be construed as support for claims reciting any sub-ranges having endpoints that are whole number values within the specified range in question. By way of hypothetical example, a disclosure of a range of from 1 to 5 shall be considered to support claims to any of the following ranges: 1 to 5; 1 to 4; 1 to 3; 1 to 2; 2 to 5; 2 to 4; 2 to 3; 3 to 5; 3 to 4; and 4 to 5.
- The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.”
- All documents cited in the Detailed Description are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present disclosure. To the extent that any meaning or definition of a term in this written document conflicts with any meaning or definition of the term in a document incorporated by references, the meaning or definition assigned to the term in this written document shall govern.
- While particular aspects of the present disclosure have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the disclosure. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this disclosure.
Claims (20)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2016/067131 WO2018111299A1 (en) | 2016-12-16 | 2016-12-16 | Wet-laid microfibers including polyolefin and thermoplastic starch |
Publications (1)
Publication Number | Publication Date |
---|---|
US20190330770A1 true US20190330770A1 (en) | 2019-10-31 |
Family
ID=62558965
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/467,516 Pending US20190330770A1 (en) | 2016-12-16 | 2016-12-16 | Wet-laid microfibers including polyolefin and thermoplastic starch |
Country Status (2)
Country | Link |
---|---|
US (1) | US20190330770A1 (en) |
WO (1) | WO2018111299A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11359088B2 (en) | 2015-06-30 | 2022-06-14 | BiologiQ, Inc. | Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material |
US11674018B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics |
US11674014B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Blending of small particle starch powder with synthetic polymers for increased strength and other properties |
US11807741B2 (en) | 2015-06-30 | 2023-11-07 | BiologiQ, Inc. | Articles formed with renewable green plastic materials and starch-based polymeric materials lending increased biodegradability |
US11840623B2 (en) | 2015-06-30 | 2023-12-12 | BiologiQ, Inc. | Methods for lending biodegradability to non-biodegradable polyolefin and nylon materials |
US11879058B2 (en) | 2015-06-30 | 2024-01-23 | Biologiq, Inc | Yarn materials and fibers including starch-based polymeric materials |
US11926940B2 (en) | 2015-06-30 | 2024-03-12 | BiologiQ, Inc. | Spunbond nonwoven materials and fibers including starch-based polymeric materials |
US11926929B2 (en) | 2015-06-30 | 2024-03-12 | Biologiq, Inc | Melt blown nonwoven materials and fibers including starch-based polymeric materials |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112411011A (en) * | 2020-10-28 | 2021-02-26 | 杨莉莉 | Method for twin-spinning non-woven fabric |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090305592A1 (en) * | 2008-06-06 | 2009-12-10 | Kimberly-Clark Worldwide, Inc. | Fibers Formed from a Blend of a Modified Aliphatic-Aromatic Copolyester and Thermoplastic Starch |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0393276A (en) * | 1989-09-05 | 1991-04-18 | Toshiba Micro Electron Kk | Semiconductor storage device and manufacture thereof |
US20020168518A1 (en) * | 2001-05-10 | 2002-11-14 | The Procter & Gamble Company | Fibers comprising starch and polymers |
US20070082982A1 (en) * | 2005-10-11 | 2007-04-12 | The Procter & Gamble Company | Water stable compositions and articles comprising starch and methods of making the same |
JP5237751B2 (en) * | 2008-10-20 | 2013-07-17 | 三井化学株式会社 | Starch resin composition with good spinnability |
CN103147227A (en) * | 2013-03-04 | 2013-06-12 | 武汉华丽生物材料有限公司 | Bio-based non-woven fabrics and preparation method thereof |
-
2016
- 2016-12-16 WO PCT/US2016/067131 patent/WO2018111299A1/en active Application Filing
- 2016-12-16 US US16/467,516 patent/US20190330770A1/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090305592A1 (en) * | 2008-06-06 | 2009-12-10 | Kimberly-Clark Worldwide, Inc. | Fibers Formed from a Blend of a Modified Aliphatic-Aromatic Copolyester and Thermoplastic Starch |
Non-Patent Citations (1)
Title |
---|
Metocene MF650X, LyondellBasell, April 19, 2016—obtained from Wayback Machine (Year: 2016) * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11359088B2 (en) | 2015-06-30 | 2022-06-14 | BiologiQ, Inc. | Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material |
US11674018B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics |
US11674014B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Blending of small particle starch powder with synthetic polymers for increased strength and other properties |
US11807741B2 (en) | 2015-06-30 | 2023-11-07 | BiologiQ, Inc. | Articles formed with renewable green plastic materials and starch-based polymeric materials lending increased biodegradability |
US11840623B2 (en) | 2015-06-30 | 2023-12-12 | BiologiQ, Inc. | Methods for lending biodegradability to non-biodegradable polyolefin and nylon materials |
US11879058B2 (en) | 2015-06-30 | 2024-01-23 | Biologiq, Inc | Yarn materials and fibers including starch-based polymeric materials |
US11926940B2 (en) | 2015-06-30 | 2024-03-12 | BiologiQ, Inc. | Spunbond nonwoven materials and fibers including starch-based polymeric materials |
US11926929B2 (en) | 2015-06-30 | 2024-03-12 | Biologiq, Inc | Melt blown nonwoven materials and fibers including starch-based polymeric materials |
Also Published As
Publication number | Publication date |
---|---|
WO2018111299A1 (en) | 2018-06-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20190330770A1 (en) | Wet-laid microfibers including polyolefin and thermoplastic starch | |
JP3786817B2 (en) | Absorbent flexible structure containing starch fibers | |
AU2008290287B2 (en) | Biodegradable water-sensitive films | |
US7998888B2 (en) | Thermoplastic starch for use in melt-extruded substrates | |
EP1934389B1 (en) | Water stable fibers and articles comprising starch, and methods of making the same | |
US9056967B2 (en) | Water-sensitive biodegradable film | |
EP2794215B1 (en) | Method for forming a thermoplastic composition that contains a plasticized starch polymer | |
AU2012356190A1 (en) | Method for forming a thermoplastic composition that contains a renewable biopolymer | |
KR20160019109A (en) | Absorbent article containing a nonwoven web formed from porous polyolefin fibers | |
AU2012356192A1 (en) | Multi-layered film containing a biopolymer | |
US11879058B2 (en) | Yarn materials and fibers including starch-based polymeric materials | |
US10060052B2 (en) | Fibrous elements comprising an acrylamide-based copolymer and fibrous structures employing same | |
AU2013282910A1 (en) | Biodegradable and flushable multi-layered film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |