WO2024037987A1 - Extruded polyvinyl alcohol fibres and fibrous products - Google Patents
Extruded polyvinyl alcohol fibres and fibrous products Download PDFInfo
- Publication number
- WO2024037987A1 WO2024037987A1 PCT/EP2023/072322 EP2023072322W WO2024037987A1 WO 2024037987 A1 WO2024037987 A1 WO 2024037987A1 EP 2023072322 W EP2023072322 W EP 2023072322W WO 2024037987 A1 WO2024037987 A1 WO 2024037987A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fibres
- polyvinyl alcohol
- molten
- hydrolysis
- butanediol
- Prior art date
Links
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 130
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 121
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 230000007062 hydrolysis Effects 0.000 claims abstract description 43
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 39
- 229920001519 homopolymer Polymers 0.000 claims abstract description 26
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims abstract description 10
- 235000010234 sodium benzoate Nutrition 0.000 claims abstract description 10
- 239000004299 sodium benzoate Substances 0.000 claims abstract description 10
- 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 claims abstract description 8
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims abstract description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000013773 glyceryl triacetate Nutrition 0.000 claims abstract description 7
- 239000001087 glyceryl triacetate Substances 0.000 claims abstract description 7
- 229960002622 triacetin Drugs 0.000 claims abstract description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 5
- SAMYCKUDTNLASP-UHFFFAOYSA-N hexane-2,2-diol Chemical compound CCCCC(C)(O)O SAMYCKUDTNLASP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims abstract description 4
- AGNTUZCMJBTHOG-UHFFFAOYSA-N 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)CO AGNTUZCMJBTHOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 4
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims abstract description 4
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims abstract description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 4
- 235000013539 calcium stearate Nutrition 0.000 claims abstract description 4
- 239000008116 calcium stearate Substances 0.000 claims abstract description 4
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000010355 mannitol Nutrition 0.000 claims abstract description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940096992 potassium oleate Drugs 0.000 claims abstract description 4
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims abstract description 4
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000008117 stearic acid Substances 0.000 claims abstract description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 3
- RVKPQXGYBPTWPT-UHFFFAOYSA-N 3-methylhexane-2,2-diol Chemical compound CCCC(C)C(C)(O)O RVKPQXGYBPTWPT-UHFFFAOYSA-N 0.000 claims abstract description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 3
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims abstract description 3
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229930091371 Fructose Natural products 0.000 claims abstract description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 3
- 239000005715 Fructose Substances 0.000 claims abstract description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 3
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims abstract description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 3
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims abstract description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims abstract description 3
- 150000002148 esters Chemical class 0.000 claims abstract description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 3
- 229940068886 polyethylene glycol 300 Drugs 0.000 claims abstract description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims abstract description 3
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 3
- 235000013772 propylene glycol Nutrition 0.000 claims abstract description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000835 fiber Substances 0.000 claims description 24
- 229920000433 Lyocell Polymers 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 8
- 239000004626 polylactic acid Substances 0.000 claims description 7
- 238000009960 carding Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 3
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims 5
- 229920003043 Cellulose fiber Polymers 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 13
- YVHAOWGRHCPODY-UHFFFAOYSA-N 3,3-dimethylbutane-1,2-diol Chemical compound CC(C)(C)C(O)CO YVHAOWGRHCPODY-UHFFFAOYSA-N 0.000 abstract 1
- XPFCZYUVICHKDS-UHFFFAOYSA-N 3-methylbutane-1,3-diol Chemical compound CC(C)(O)CCO XPFCZYUVICHKDS-UHFFFAOYSA-N 0.000 abstract 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 109
- 229920000642 polymer Polymers 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000004744 fabric Substances 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229940059574 pentaerithrityl Drugs 0.000 description 6
- 229920002689 polyvinyl acetate Polymers 0.000 description 5
- 239000011118 polyvinyl acetate Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 229920000297 Rayon Polymers 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- -1 for example Polymers 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
-
- 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
-
- 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
- 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
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/007—Addition polymers
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
- D04H3/03—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments at random
- D04H3/033—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments at random reorientation immediately after yarn or filament formation
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
- D04H3/105—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by needling
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
- D04H3/11—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by fluid jet
-
- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/12—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with filaments or yarns secured together by chemical or thermo-activatable bonding agents, e.g. adhesives, applied or incorporated in liquid or solid form
-
- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/14—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding
Definitions
- This invention relates to polyvinyl alcohol fibres, methods of making polyvinyl alcohol fibres and products manufactured from polyvinyl alcohol fibres.
- the invention relates particularly but not exclusively to products comprising extruded polyvinyl alcohol fibres, methods of making extruded polyvinyl alcohol fibres and products incorporating such fibres.
- Polyvinyl alcohol has many advantages in comparison to polymers which are traditionally used for manufacture of non-woven fibre products. Polyvinyl alcohol is soluble in water, particularly when heated, facilitating reclamation, recycling and environmental degradation.
- Polyvinyl alcohol is manufactured by hydrolysis of homopolymer or co-polymers of polyvinyl acetate.
- Polyvinyl alcohol manufactured by partial or complete hydrolysis of homopolymeric polyvinyl acetate is referred to as homopolymeric polyvinyl alcohol.
- the degree of hydrolysis determines the properties of the resultant polymer.
- Co-polymeric polyvinyl alcohols or homopolymeric polyvinyl alcohol with a low degree (LD) of hydrolysis are easy to process but have inferior mechanical and chemical properties.
- Homopolymeric polyvinyl alcohol with a high degree (HD) of hydrolysis, for example 85% or greater, has superior properties but is not processable without degradation under conditions using apparatus employed for manufacture of polyolefin non-woven fibres.
- Polyvinyl alcohol is soluble in water and fibres have traditionally been made by solution spinning methods using polyvinyl alcohol with a low degree (LD) of hydrolysis.
- WO2017/046361 discloses a method for manufacture of processable polyvinyl alcohol having a degree of hydrolysis of 98% or greater.
- W02022/008521 discloses a method for manufacture of processable polyvinyl alcohol having a degree of hydrolysis in the range of 93% to 98% or more.
- W02022/008516 discloses a method for manufacture of plasticised polyvinyl alcohol having a degree of hydrolysis of 93 wt% to 98 wt% or more.
- a method of manufacture of polyvinyl alcohol fibres comprises the steps of: providing a polyvinyl alcohol composition comprising homopolymeric polyvinyl alcohol having a degree of hydrolysis of 88 wt% to 98 wt% or greater; and a weight average molecular weight in the range from 14,000 to 36,000; a plasticiser selected from the group consisting of: diglycerol, triglycerol, fructose, ribose, xylose, D-mannitol, triacetin, pentaerythritol, dipentaerythritol, methyl pentanediol, 1,2-propanediol, 1,4-butanediol, 2-hydroxy-l,3-propanediol, 3-methyl-l,3-butanediol, 3,3- dimethyl-l,2-butanediol, polyethylene glycol 300, polyethylene glycol 400,
- the degree of hydrolysis may be 95 wt% to 98 wt%, for example 93 wt% to 95 wt%.
- the molecular weight of the homopolymeric polyvinyl alcohol may be in the range from 14,000 to 35,000.
- Molecular weights in this specification are weight average molecular weights and are measured using conventional liquid chromatographic techniques.
- the composition may be melted at a temperature from 220°C to 240°C, for example 220°C to 230°C.
- the polyvinyl alcohol composition of this invention may have a melt flow index (MFI) of 30 to 80g/10min, for example 50 to 75g/10min, for example 70 to 75g/10min. Melt flow indices referred to in this specification are determined at 230°C using a weight of 10kg by conventional techniques.
- the polyvinyl alcohol composition of this invention is stable at the temperature at which it is melted and extruded.
- Polyvinyl alcohol, not containing a plasticiser and stabiliser as disclosed herein, particularly the homopolymer having a high degree of hydrolysis, may be liable to decompose at the temperatures required for melting and extrusion processing.
- Advantageous polyvinyl alcohol fibres of this invention are capable of being processed on a commercial scale, using conventional fibre processing apparatus.
- Polyvinyl alcohol according to this invention can be processed into filaments or fibres. These may be converted by crimping and cutting into staple fibres suitable for carding, wet laying and air laying to form a range of non-woven products.
- Advantageous polyvinyl alcohol fibres of this invention are capable of being processed on a commercial scale, for example using apparatus running at 4,500 m.min’ 1
- the stabilised polyvinyl alcohol polymers used in this invention may be manufactured in accordance with W02022/008516 and W02022/008521, the disclosures of which are incorporated into this specification by reference for all purposes.
- the polyvinyl alcohol composition may be made by a method comprising the steps of: introducing into a mixing reactor a polyvinyl alcohol polymer comprising homopolymeric polyvinyl alcohol or a blend thereof having a degree of hydrolysis in the range of 88 wt% to 98 wt% or more; wherein the mixing reactor comprises a blending chamber having a primary inlet, a primary outlet and at least two inter-engaging components extending between the primary inlet and primary outlet, the components being arranged to apply a shearing force to the polymer while the polymer is conveyed by the components from the inlet through a reaction zone to the outlet; one or more secondary inlets located downstream from the primary inlet for introducing reactants comprising a processing aid, a plasticiser and a reactive stabiliser to the chamber to form a reaction mixture; wherein the plasticiser is selected from the group disclosed above wherein the reactive stabiliser is selected from the group consisting of: sodium stearate, potassium oleate, sodium benzoate, calcium ste
- a reactive mixing apparatus typically an extruder in accordance with this invention allows the processing aid and plasticiser to be reacted with the polyvinyl alcohol or blend thereof, without decomposition of the polymer followed by removal of all or most of the processing aid from the secondary outlet to give plasticised polyvinyl alcohol or a blend thereof.
- a reactive stabiliser may result in an advantageous reduction in the extent of degradation during melt processing. This allows homopolymeric polyvinyl alcohol having a high degree of hydrolysis, for example 88 wt% or higher to be processed to form fibres or pellets from which fibres may be formed by extrusion.
- the reactive stabiliser may be used in an amount of about 0.1 wt% to about 5 wt%, for example about 0.1 wt% to about 3 wt%, for example 0.1 wt% to about 1.5 wt%, for example from about 0.2 wt% to about 0.5 wt%, for example about 0.25 wt%.
- the reactive stabilisers of this invention may decrease the extent of degradation of the polymer during processing.
- Homopolymeric polyvinyl alcohol has been difficult to process due to degradation at the high temperatures required.
- the liability of degradation has led to use of polyvinyl alcohol co-polymers with a consequent loss of engineering properties. This can be seen by UV spectral analysis of the amount of conjugation present in the polymer. Sodium benzoate has been found to be particularly effective.
- Homopolymeric polyvinyl alcohol is manufactured by hydrolysis of homopolymeric polyvinyl acetate, the degree of hydrolysis being 93wt% or more in embodiments of this invention.
- Polyvinyl alcohol co-polymers made by hydrolysis of polyvinyl acetate copolymers have inferior properties compared to homopolymeric polyvinyl alcohol.
- Homopolymeric polyvinyl alcohol may exhibit advantageous properties.
- Polyvinyl alcohol polymers of this invention may have high tensile strength and flexibility.
- the polyvinyl alcohol may be manufactured by hydrolysis of homopolymeric polyvinyl acetate, wherein the extent of hydrolysis is in the range from 88 wt% up to 98 wt%, for example 93 wt% to less than 98 wt%, for example 93 wt% to 97 wt%, for example 93 wt% to 95 wt%.
- a blend of two or more polyvinyl alcohol polymers may be employed, for example a blend of two polyvinyl alcohol polymers with a relatively high molecular weight and a relatively low molecular weight respectively.
- a blend of polyvinyl alcohols with the same molecular weight and different degrees of hydrolysis can be combined. Blending different polyvinyl alcohol grades together enables the properties of the resultant polymer to be enhanced, for example melt strength.
- a blend of two polyvinyl alcohol polymers with a molecular weight in the range 22,000 to 38,000 a first polymer having a low degree of hydrolysis and a second polymer having a high degree of hydrolysis may be blended in a ratio of 40:60 to 60:40, for example about 50:50 by weight.
- the blends of different molecular weight polymers employed are selected in accordance with the physical properties required in the finished product. This may require different molecular weight materials being used. Use of more than two different molecular weight polymers may be advantageous. The use of a single molecular weight polymer is not precluded.
- a blend may allow control of the viscosity of the polymer. Selection of a stabiliser in accordance with the present invention allows use of blends of a desired viscosity without a loss of other properties. Alternatively, use of a blend may permit use of polyvinyl alcohol with one or more stabilisers while maintaining viscosity or other properties to permit manufacture of pellets or films.
- the processing aid is preferably water.
- the processing aid may comprise a mixture of water and one or more hydroxyl compounds with a boiling point less than the boiling point or melting point of the plasticiser. Use of water is preferred for cost and environmental reasons.
- Two or more plasticisers may be employed.
- a binary mixture may be preferred.
- the plasticiser may be selected from the group consisting of: diglycerol, triglycerol, xylose, D-mannitol, triacetin, dipentaerythritol, 1,4-butanediol, 3,3- dimethyl-l,2-butanediol, and caprolactam.
- the total amount of plasticiser in the formulation may be from about 15 wt% to about 30 wt%.
- Polymer compositions and fibres of the present invention may not include any or any substantial amount of a water soluble salt, oil, wax or ethylene homopolymer or copolymer.
- the method of this invention provides many advantages.
- the method allows formation of thermally processable polyvinyl alcohol which can be used to create economical fibres that are highly functional while eliminating plastic pollution.
- Polyvinyl alcohol is water-soluble, non-toxic to the environment and inherently biodegradable.
- Hydrophilic polymers for example, polyvinyl alcohol degrade environmentally faster than hydrophobic polymers and do not show bioaccumulation.
- Thermoplastic polyvinyl alcohol can be mechanically recycled into pellets for repeated use.
- Fibres of this invention may have an advantageous smaller diameter. Fibres having a smaller diameter have a greater surface area which may be advantageous for air filtration, for example in face masks. Finer fibres may also be softer in texture. Furthermore, finer fibres may also have an increased rate of biodegradation after use.
- a non-woven product comprising thermally processable homopolymeric polyvinyl alcohol fibres having a degree of hydrolysis of 88 wt% or greater made in accordance with the first aspect of the present invention.
- a non-woven fibre product comprising homopolymeric polyvinyl alcohol fibres having a degree of hydrolysis of 88 wt% or greater.
- a non-woven product is defined by ISO9092 as an engineered fibrous assembly, primarily planar, which has been given a designed level of structural integrity by physical and/or chemical means, excluding weaving, knitting or paper making.
- Homopolymeric polyvinyl alcohol fibres of this invention provide many advantages in comparison to previously available polyvinyl alcohol containing fibres.
- the fibres of this invention and products made from these fibres exhibit improved tensile strength, barrier properties, water solubility and biodegradability.
- Homopolymeric polyvinyl alcohol fibres may unexpectedly exhibit all of these properties.
- copolymers have only been able to compromise and provide one or more of these properties at the expense of other properties.
- the fibres and products of the present invention have a desirable monomaterial structure which does not suffer from this disadvantage.
- Non-woven products comprising polyvinyl alcohol fibres of this invention in combination with fibres of cellulose pulp, viscose and mixtures thereof have excellent flushability, for example in accordance with UK Water Fine to Flush WIZ 4-02-06.
- Wet wipes manufactured from non-woven fibres of this invention exhibit excellent dry and wet tensile strength.
- Fibres of this invention may be made by extrusion of filaments of the melted polyvinyl alcohol polymer through a spinneret having small holes, for example 0.25mm in diameter.
- the extruded filaments may be drawn using godet rollers rotating at different speeds to form a multi filament tow.
- the multifilament tow may be crimped by heating followed by shaping with toothed or fluted rollers and cutting with rotary blades to provide fibres of desired length. Use of specific fibre lengths may confer compatibility with various non-woven fibre processing techniques.
- An extrusion temperature of 200°C to 250°C may be employed, preferably 210°C to 247°C.
- the number of filaments in a fibre may be in the range 24 to 72, dependent on the equipment used. Use of fibre comprising a bundle of 50 to 72 filaments may be advantageous to improve cohesion of the bundle of filaments during drawing and may allow for a higher drawing ratio.
- the larger number of filaments allows the tension applied during the drawing process to be distributed between the larger number of filaments.
- the rotational speed of the first godet roller may be 200 to 310mpm (m/min). Use of a godet 1 speed greater than 300 mpm may increase the frequency of melt breaks. An optimum speed for godet 1 may be about 295mpm.
- the rotational speed of the godet 5 roller may be 350 to 1665 mpm.
- the rotational speeds of godets 2 to 4 may have intermediate values. A higher drawing ratio may be achieved using 72 filaments resulting a finer fibre of 3 dtex or greater at a godet 5 speed of 500 rpm or higher.
- a metering pump speed may be employed. Use of a metering pump may improve stability of the process. A reduced residence time may reduce the risk of thermal degradation of the polymer.
- a spin finish may be applied to the filaments before the fibre passes to the godet rollers.
- a non-aqueous spin finish oil may be employed; for example, Tallopol DT, Tallopon Biocone or Vystat.
- a spin finish content of 0.4 wt% to 4.7 wt% may be used at a spin finish pump speed of 4 to 15 rpm.
- a minimum of 0.4 wt% of spin finish may be employed to provide sufficient cohesion between the filaments for drawing and winding.
- Fibres in accordance with this invention may be laid to form non-woven layers or webs by various methods, including: carding, air laying or wet laying.
- the fibres in a web may be bonded by a method selected from: hydroentanglement, needle punching, chemical or adhesive bonding and thermal bonding.
- fibre bundles are separated and individualised using carding wires to produce an orientated fibre network structure.
- Crimped polyvinyl alcohol fibres may be employed.
- the opened polyvinyl alcohol fibres may be dried, for example at 130°C for 10 minutes prior to carding to improve uniformity of the resultant web. In exemplary embodiments, drying is not necessary.
- thermally processable fibres of this invention allows manufacture on a commercial scale.
- a blend of polyvinyl alcohol (PVOH) fibres with sustainable fibres may be employed, for example the sustainable fibres may be selected from: lyocell, polylactic acid (PLA), poly hydroxy alkanoates and mixtures thereof.
- PVA polylactic acid
- a blending ratio of polyvinyl alcohol dyocell of 70:30 wt% to 90: 10 wt%, preferably 80:20 wt% or a ratio of polyvinyl alcohokPLA of 70:30 wt% to 90: 10 wt%, preferably 80:20 wt% may be employed.
- the carded web may have an areal density of 60 to 40gm' 2 , for example about
- 100% polyvinyl alcohol and 80:20 wt% polyvinyl alcohol dyocell carded webs may be needlepunched at 9mm penetration depth, hydroentangled at 30 bar or chemically bonded using, for example, ethylene vinyl acetate (EVA) binder.
- EVA ethylene vinyl acetate
- Through air bonding in which hot air is forced through the web, for example by convection, may be employed to melt an adhesive to avoid producing excessive compression.
- 80:20 wt% polyvinyl alcohokPLA carded webs may be through air bonded at 120°C for 2 minutes.
- Air laying methods may be employed, in which a turbulent air stream is used to produce an isotropic fibre network.
- crimped polyvinyl alcohol fibres may be cut to a length of 5mm and blended with pulp fibres (approximately 2mm) Georgia Pacific (GP) cellulose.
- pulp fibres approximately 2mm
- GP Georgia Pacific
- Ratios of polyvinyl alcohokcellulose of 80:20 wt% to 20:80 wt% for example about 50:50 wt% may be employed.
- the areal density may be about 50 gm' 2 , dependent on the application, for example single or multiple use applications.
- the polyvinyl alcohol fibres may be dried, for example at 130°C for 10 minutes, to improve separation. In exemplary embodiments, drying is not necessary.
- the airlaid webs may be hydroentangled and then dried.
- Fibres of this invention have the advantage that the polyvinyl alcohol fibrecontaining webs may be converted into hydroentangled airlaid non-woven fabrics having a high strength.
- the fibres, particularly comprising warm water soluble polyvinyl alcohol, were found to partially dissolve during the hydroentanglement process resulting in strong but stiff fabrics.
- a wetlaying process may be used to form non-woven fabrics with hot water-soluble polyvinyl alcohol fibres. In this process the polyvinyl alcohol fibres are dispersed in water and transferred onto a foraminous conveyor through which the water is removed to deposit a web of fibres.
- the fibres may be cut to a suitable length, for example 5mm and blended with pulp fibres, for example Sodra Black, at ratios of polyvinyl alcohokpulp of 50:50 wt% to 20:80 wt%.
- Lyocell fibres (1.4 dtex/5mm) may be blended at ratios of polyvinyl alcohokpulp of 50:50 wt% to 20:80 wt%.
- the areal density may be about 60gm' 2 . This density may be employed for manufacture of flushable wipes.
- the wetlaid webs may be hydroentangled and dried at 100°C for 30 seconds.
- the tensile strength was compared with commercial products.
- a blend of polyvinyl alcohol:pulp:lyocell in a ratio of 40:40:20 wt% exhibited a relatively high tensile strength of 11 to 13N, typically about 12N.
- Hydroentangled wetlaid fabrics of this invention incorporating pulp have relatively good tensile strength.
- Pulp fibres have typically high liquid absorption capacity. After hydroentanglement, the wetlaid web remains saturated resulting in partial dissolution of the polyvinyl alcohol fibres during the drying stage.
- the polyvinyl alcohol fibres act as a binder alongside formed hydrogen bonds between the pulp fibres.
- the increase in specific energy during hydroentanglement may increase the dry tensile strength of the fabrics incorporating lyocell fibres.
- Figure 1 is a diagrammatic view of fibre extruding apparatus in accordance with this invention.
- polyvinyl alcohol homopolymer compositions may be employed.
- PVOH degree of hydrolysis 98%; low viscosity 35.97%
- PVOH degree of hydrolysis 89%; low viscosity 35.97%
- PVOH degree of hydrolysis 98%; low viscosity 35.87%
- PVOH degree of hydrolysis 98%; low viscosity 25.20%
- PVOH degree of hydrolysis 98%; low viscosity 5.20%
- FIG. 1 illustrates apparatus for extrusion of polyvinyl alcohol fibres in accordance with the present invention.
- a feed hopper (1) supplies pellets of the polyvinyl alcohol composition to an extruder (2).
- the molten polymer is delivered from the extruder to a melt pump (3) which meters the polymer to a spin pack (4).
- the spin pack spins a fibre (10) through a quenching chamber (5) supplied with cooling air by a fan (11).
- a spin finish applicator (6) applies a coating to the fibre (10).
- the fibre is then delivered by roller (7) to a series of godet rollers (8) which produce drawn fibres.
- the fibres are then collected on a winder (9).
- Example 1 Multifilament polyvinyl alcohol fibres were extruded using the following parameters.
- the fibres were crimped using an IR heater temperature 220°C, speed 1.4 m/min, indented roller temperature 100°C and throughput rate 17 g/h.
- the following properties were observed using polyvinyl alcohol (PVOH) and polylactic acid (PLA).
- the properties of wetlaid hydroentangled PVOH webs were as follows. In further embodiments, the properties of wetlaid hydroentangled PVOH webs were as follows.
- the tensile strength of webs comprising polyvinyl alcohol/pulp blends were compared with commercial flushable wipes.
- the tensile strength was compared with lotion saturated wipes.
- the commercial wipes were squeezed by hand to remove excess lotion.
- the excess lotion was used to saturate the polyvinyl alcohol products of the present invention at a pick up of 200 wt% to 300 wt%.
- the increase in the specific energy had a positive impact on the wet tensile strength of the wetlaid hydroentangled fabrics with an increase of approximately 100 to 170%.
- the dispersibility of the wetlaid hydroentangled fabrics decreased with increased specific energy (30 bars x 2 / 50 bars x 4).
- the fibres were more interlocked promoting fibre roping.
- the wetlaid webs hydroentangled at high specific energy showed fragments size ⁇ 4cm which is one of the alternative requirements to pass the dispersibility in the sewer system.
- the PVOH fibres were successfully converted into wetlaid hydroentangled fabrics.
- the fabrics incorporating pulp fibres showed good dry and wet tensile strength and dispersibility, while the incorporation of lyocell fibres promoted the wet tensile strength but decreased the dispersibility of the hydroentangled wetlaid fabrics.
- the commercial flushable wipes passed the dispersibility in the drainline test with more than 50 wt% passing through a 12.5mm screen.
- hydroentangled wetlaid non-woven polyvinyl alcohol/pulp fabrics were compared with commercial flushable wipes.
- the commercial flushable wipes showed low dispersibility with less than 60 wt% passing through a 5.6mm sieve.
- the hydroentangled wetlaid fabrics incorporating 20 wt% polyvinyl alcohol fibre and 80 wt% pulp exhibited excellent results with 90 wt% passing through a 5.6mm screen.
- Webs comprising polyvinyl alcohol, pulp and viscose/lyocell exhibited better dispersibility performance in comparison to commercial flushable wipes.
- PVOH fibres in hydroentangled wetlaid fabrics incorporating pulp fibres improved the dry tensile strength. Incorporation of viscose or lyocell fibres improved the wet strength of the fabrics. A superior combination of wet strength and dispersibility performance was achieved using 40 wt% polyvinyl alcohol, 40 wt% pulp and 20 wt% viscose fibres.
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Abstract
A method of manufacture of a nonwoven product comprising polyvinyl alcohol fibres, the method comprising the steps of: providing a polyvinyl alcohol composition comprising homopolymeric polyvinyl alcohol having a degree of hydrolysis of 88% to 98% or greater; and a molecular weight in the range from 22,000 to 38,000; a plasticiser selected from the group consisting of: diglycerol, triglycerol, fructose, ribose, xylose, D-mannitol, triacetin, pentaerythritol, dipentaerythritol, methyl pentanediol, 1,2-propanediol, 1,4-butanediol, 2-hydroxy-1,3-propanediol, 3-methyl-1,3-butanediol, 3,3- dimethyl-1,2-butanediol, polyethylene glycol 300, polyethylene glycol 400, alkoxylated polyethylene glycol, caprolactam, tricyclic trimethylolpropane formal, rosin esters, erucamide, and mixtures thereof; and a stabilizer selected from the group consisting of: sodium stearate, potassium oleate, sodium benzoate, calcium stearate, stearic acid, dimethyl pentane diol, propionic acid and mixtures thereof; melting the composition at a temperature from 190°C to 250°C; extruding the melted composition to form an extrudate; forming the extrudate into molten fibres; drawing the molten fibres to form individual molten fibres or bundles of molten fibres; and allowing the molten fibres to solidify to form solid fibres or bundles of solid fibres.
Description
EXTRUDED POLYVINYL ALCOHOL FIBRES AND FIBROUS PRODUCTS
This invention relates to polyvinyl alcohol fibres, methods of making polyvinyl alcohol fibres and products manufactured from polyvinyl alcohol fibres. The invention relates particularly but not exclusively to products comprising extruded polyvinyl alcohol fibres, methods of making extruded polyvinyl alcohol fibres and products incorporating such fibres.
Polyvinyl alcohol has many advantages in comparison to polymers which are traditionally used for manufacture of non-woven fibre products. Polyvinyl alcohol is soluble in water, particularly when heated, facilitating reclamation, recycling and environmental degradation.
Polyvinyl alcohol is manufactured by hydrolysis of homopolymer or co-polymers of polyvinyl acetate. Polyvinyl alcohol manufactured by partial or complete hydrolysis of homopolymeric polyvinyl acetate is referred to as homopolymeric polyvinyl alcohol. The degree of hydrolysis determines the properties of the resultant polymer. Co-polymeric polyvinyl alcohols or homopolymeric polyvinyl alcohol with a low degree (LD) of hydrolysis are easy to process but have inferior mechanical and chemical properties. Homopolymeric polyvinyl alcohol with a high degree (HD) of hydrolysis, for example 85% or greater, has superior properties but is not processable without degradation under conditions using apparatus employed for manufacture of polyolefin non-woven fibres.
Polyvinyl alcohol is soluble in water and fibres have traditionally been made by solution spinning methods using polyvinyl alcohol with a low degree (LD) of hydrolysis.
In order to enhance water resistance, thermal e.g. hot drawing and chemical e.g. acetylation steps have been required.
WO2017/046361 discloses a method for manufacture of processable polyvinyl alcohol having a degree of hydrolysis of 98% or greater.
W02022/008521 discloses a method for manufacture of processable polyvinyl alcohol having a degree of hydrolysis in the range of 93% to 98% or more.
W02022/008516 discloses a method for manufacture of plasticised polyvinyl alcohol having a degree of hydrolysis of 93 wt% to 98 wt% or more.
According to a first aspect of the present invention, a method of manufacture of polyvinyl alcohol fibres comprises the steps of: providing a polyvinyl alcohol composition comprising homopolymeric polyvinyl alcohol having a degree of hydrolysis of 88 wt% to 98 wt% or greater; and a weight average molecular weight in the range from 14,000 to 36,000; a plasticiser selected from the group consisting of: diglycerol, triglycerol, fructose, ribose, xylose, D-mannitol, triacetin, pentaerythritol, dipentaerythritol, methyl pentanediol, 1,2-propanediol, 1,4-butanediol, 2-hydroxy-l,3-propanediol, 3-methyl-l,3-butanediol, 3,3- dimethyl-l,2-butanediol, polyethylene glycol 300, polyethylene glycol 400, alkoxylated polyethylene glycol, caprolactam, tricyclic trimethylolpropane formal, rosin esters, erucamide, and mixtures thereof; and a stabilizer selected from the group consisting of: sodium stearate, potassium oleate, sodium benzoate, calcium stearate, stearic acid, dimethyl pentane diol, propionic acid and mixtures thereof; melting the composition at a temperature from 190°C to 250°C; extruding the melted composition to form an extrudate; forming the extrudate into molten fibres; drawing the molten fibres to form individual molten fibres or bundles of molten fibres; and allowing the molten fibres to solidify to form solid fibres or bundles of solid fibres.
The degree of hydrolysis may be 95 wt% to 98 wt%, for example 93 wt% to 95 wt%.
In embodiments, the molecular weight of the homopolymeric polyvinyl alcohol may be in the range from 14,000 to 35,000.
Molecular weights in this specification are weight average molecular weights and are measured using conventional liquid chromatographic techniques.
In embodiments, the composition may be melted at a temperature from 220°C to 240°C, for example 220°C to 230°C.
The polyvinyl alcohol composition of this invention may have a melt flow index (MFI) of 30 to 80g/10min, for example 50 to 75g/10min, for example 70 to 75g/10min. Melt flow indices referred to in this specification are determined at 230°C using a weight of 10kg by conventional techniques.
The polyvinyl alcohol composition of this invention is stable at the temperature at which it is melted and extruded. Polyvinyl alcohol, not containing a plasticiser and stabiliser as disclosed herein, particularly the homopolymer having a high degree of hydrolysis, may be liable to decompose at the temperatures required for melting and extrusion processing.
Advantageous polyvinyl alcohol fibres of this invention are capable of being processed on a commercial scale, using conventional fibre processing apparatus.
Polyvinyl alcohol according to this invention can be processed into filaments or fibres. These may be converted by crimping and cutting into staple fibres suitable for carding, wet laying and air laying to form a range of non-woven products.
Advantageous polyvinyl alcohol fibres of this invention are capable of being processed on a commercial scale, for example using apparatus running at 4,500 m.min’1
The stabilised polyvinyl alcohol polymers used in this invention may be manufactured in accordance with W02022/008516 and W02022/008521, the disclosures of which are incorporated into this specification by reference for all purposes.
The polyvinyl alcohol composition may be made by a method comprising the steps of: introducing into a mixing reactor a polyvinyl alcohol polymer comprising homopolymeric polyvinyl alcohol or a blend thereof having a degree of hydrolysis in the range of 88 wt% to 98 wt% or more; wherein the mixing reactor comprises a blending chamber having a primary inlet, a primary outlet and at least two inter-engaging components extending between the primary inlet and primary outlet, the components being arranged to apply a shearing force to the polymer while the polymer is conveyed by the components from the inlet through a reaction zone to the outlet;
one or more secondary inlets located downstream from the primary inlet for introducing reactants comprising a processing aid, a plasticiser and a reactive stabiliser to the chamber to form a reaction mixture; wherein the plasticiser is selected from the group disclosed above wherein the reactive stabiliser is selected from the group consisting of: sodium stearate, potassium oleate, sodium benzoate, calcium stearate, stearic acid, dimethyl propionic acid, and mixtures thereof; wherein the blending chamber comprises a plurality of heated regions arranged so that the mixture is subjected to a temperature profile whereby the temperature increases from the inlet to the outlet; a secondary outlet located between the reaction zone and primary outlet arranged to allow removal of processing aid from the chamber; reacting the processing agent, plasticiser and polymer in the reaction zone to form plasticised polymer; and allowing the plasticised polymer to pass from the primary outlet.
Use of a reactive mixing apparatus, typically an extruder in accordance with this invention allows the processing aid and plasticiser to be reacted with the polyvinyl alcohol or blend thereof, without decomposition of the polymer followed by removal of all or most of the processing aid from the secondary outlet to give plasticised polyvinyl alcohol or a blend thereof.
Use of a reactive stabiliser may result in an advantageous reduction in the extent of degradation during melt processing. This allows homopolymeric polyvinyl alcohol having a high degree of hydrolysis, for example 88 wt% or higher to be processed to form fibres or pellets from which fibres may be formed by extrusion.
The reactive stabiliser may be used in an amount of about 0.1 wt% to about 5 wt%, for example about 0.1 wt% to about 3 wt%, for example 0.1 wt% to about 1.5 wt%, for example from about 0.2 wt% to about 0.5 wt%, for example about 0.25 wt%.
The reactive stabilisers of this invention may decrease the extent of degradation of the polymer during processing. Homopolymeric polyvinyl alcohol has been difficult to process due to degradation at the high temperatures required. The liability of degradation
has led to use of polyvinyl alcohol co-polymers with a consequent loss of engineering properties. This can be seen by UV spectral analysis of the amount of conjugation present in the polymer. Sodium benzoate has been found to be particularly effective.
Use of homopolymeric polyvinyl alcohol is particularly advantageous.
Homopolymeric polyvinyl alcohol is manufactured by hydrolysis of homopolymeric polyvinyl acetate, the degree of hydrolysis being 93wt% or more in embodiments of this invention. Polyvinyl alcohol co-polymers made by hydrolysis of polyvinyl acetate copolymers have inferior properties compared to homopolymeric polyvinyl alcohol.
Homopolymeric polyvinyl alcohol may exhibit advantageous properties.
Polyvinyl alcohol polymers of this invention may have high tensile strength and flexibility.
The polyvinyl alcohol may be manufactured by hydrolysis of homopolymeric polyvinyl acetate, wherein the extent of hydrolysis is in the range from 88 wt% up to 98 wt%, for example 93 wt% to less than 98 wt%, for example 93 wt% to 97 wt%, for example 93 wt% to 95 wt%.
A blend of two or more polyvinyl alcohol polymers may be employed, for example a blend of two polyvinyl alcohol polymers with a relatively high molecular weight and a relatively low molecular weight respectively.
A blend of polyvinyl alcohols with the same molecular weight and different degrees of hydrolysis can be combined. Blending different polyvinyl alcohol grades together enables the properties of the resultant polymer to be enhanced, for example melt strength.
For fibre production a blend of two polyvinyl alcohol polymers with a molecular weight in the range 22,000 to 38,000, a first polymer having a low degree of hydrolysis and a second polymer having a high degree of hydrolysis may be blended in a ratio of 40:60 to 60:40, for example about 50:50 by weight.
The blends of different molecular weight polymers employed are selected in accordance with the physical properties required in the finished product. This may require different molecular weight materials being used. Use of more than two different molecular weight polymers may be advantageous. The use of a single molecular weight polymer is not precluded.
Use of a blend may allow control of the viscosity of the polymer. Selection of a stabiliser in accordance with the present invention allows use of blends of a desired viscosity without a loss of other properties. Alternatively, use of a blend may permit use of polyvinyl alcohol with one or more stabilisers while maintaining viscosity or other properties to permit manufacture of pellets or films.
The processing aid is preferably water. Alternatively, the processing aid may comprise a mixture of water and one or more hydroxyl compounds with a boiling point less than the boiling point or melting point of the plasticiser. Use of water is preferred for cost and environmental reasons.
Two or more plasticisers may be employed.
When a mixture of plasticisers is employed, a binary mixture may be preferred.
In an embodiment, the plasticiser may be selected from the group consisting of: diglycerol, triglycerol, xylose, D-mannitol, triacetin, dipentaerythritol, 1,4-butanediol, 3,3- dimethyl-l,2-butanediol, and caprolactam.
The total amount of plasticiser in the formulation may be from about 15 wt% to about 30 wt%.
Polymer compositions and fibres of the present invention may not include any or any substantial amount of a water soluble salt, oil, wax or ethylene homopolymer or copolymer.
The method of this invention provides many advantages. The method allows formation of thermally processable polyvinyl alcohol which can be used to create economical fibres that are highly functional while eliminating plastic pollution. Polyvinyl
alcohol is water-soluble, non-toxic to the environment and inherently biodegradable. Hydrophilic polymers, for example, polyvinyl alcohol degrade environmentally faster than hydrophobic polymers and do not show bioaccumulation. Thermoplastic polyvinyl alcohol can be mechanically recycled into pellets for repeated use.
Fibres of this invention may have an advantageous smaller diameter. Fibres having a smaller diameter have a greater surface area which may be advantageous for air filtration, for example in face masks. Finer fibres may also be softer in texture. Furthermore, finer fibres may also have an increased rate of biodegradation after use.
According to a second aspect of the present invention there is provided a non-woven product comprising thermally processable homopolymeric polyvinyl alcohol fibres having a degree of hydrolysis of 88 wt% or greater made in accordance with the first aspect of the present invention.
According to a third aspect of the present invention, there is provided a non-woven fibre product comprising homopolymeric polyvinyl alcohol fibres having a degree of hydrolysis of 88 wt% or greater.
A non-woven product is defined by ISO9092 as an engineered fibrous assembly, primarily planar, which has been given a designed level of structural integrity by physical and/or chemical means, excluding weaving, knitting or paper making.
Homopolymeric polyvinyl alcohol fibres of this invention provide many advantages in comparison to previously available polyvinyl alcohol containing fibres. The fibres of this invention and products made from these fibres exhibit improved tensile strength, barrier properties, water solubility and biodegradability. Homopolymeric polyvinyl alcohol fibres may unexpectedly exhibit all of these properties. In comparison, copolymers have only been able to compromise and provide one or more of these properties at the expense of other properties. The fibres and products of the present invention have a desirable monomaterial structure which does not suffer from this disadvantage.
Non-woven products comprising polyvinyl alcohol fibres of this invention in combination with fibres of cellulose pulp, viscose and mixtures thereof have excellent
flushability, for example in accordance with UK Water Fine to Flush WIZ 4-02-06. Wet wipes manufactured from non-woven fibres of this invention exhibit excellent dry and wet tensile strength.
Fibres of this invention may be made by extrusion of filaments of the melted polyvinyl alcohol polymer through a spinneret having small holes, for example 0.25mm in diameter. The extruded filaments may be drawn using godet rollers rotating at different speeds to form a multi filament tow. The multifilament tow may be crimped by heating followed by shaping with toothed or fluted rollers and cutting with rotary blades to provide fibres of desired length. Use of specific fibre lengths may confer compatibility with various non-woven fibre processing techniques.
The following extrusion and drawing conditions may be employed.
An extrusion temperature of 200°C to 250°C may be employed, preferably 210°C to 247°C.
The number of filaments in a fibre may be in the range 24 to 72, dependent on the equipment used. Use of fibre comprising a bundle of 50 to 72 filaments may be advantageous to improve cohesion of the bundle of filaments during drawing and may allow for a higher drawing ratio. The larger number of filaments allows the tension applied during the drawing process to be distributed between the larger number of filaments.
The rotational speed of the first godet roller (godet 1) may be 200 to 310mpm (m/min). Use of a godet 1 speed greater than 300 mpm may increase the frequency of melt breaks. An optimum speed for godet 1 may be about 295mpm. The rotational speed of the godet 5 roller may be 350 to 1665 mpm. The rotational speeds of godets 2 to 4 may have intermediate values. A higher drawing ratio may be achieved using 72 filaments resulting a finer fibre of 3 dtex or greater at a godet 5 speed of 500 rpm or higher.
A metering pump speed may be employed. Use of a metering pump may improve stability of the process. A reduced residence time may reduce the risk of thermal degradation of the polymer.
A spin finish may be applied to the filaments before the fibre passes to the godet rollers. A non-aqueous spin finish oil may be employed; for example, Tallopol DT, Tallopon Biocone or Vystat. A spin finish content of 0.4 wt% to 4.7 wt% may be used at a spin finish pump speed of 4 to 15 rpm.
A minimum of 0.4 wt% of spin finish may be employed to provide sufficient cohesion between the filaments for drawing and winding.
Fibres in accordance with this invention may be laid to form non-woven layers or webs by various methods, including: carding, air laying or wet laying. The fibres in a web may be bonded by a method selected from: hydroentanglement, needle punching, chemical or adhesive bonding and thermal bonding.
In a carding method, fibre bundles are separated and individualised using carding wires to produce an orientated fibre network structure. Crimped polyvinyl alcohol fibres may be employed.
The opened polyvinyl alcohol fibres may be dried, for example at 130°C for 10 minutes prior to carding to improve uniformity of the resultant web. In exemplary embodiments, drying is not necessary.
Use of the thermally processable fibres of this invention allows manufacture on a commercial scale.
A blend of polyvinyl alcohol (PVOH) fibres with sustainable fibres may be employed, for example the sustainable fibres may be selected from: lyocell, polylactic acid (PLA), poly hydroxy alkanoates and mixtures thereof.
A blending ratio of polyvinyl alcohol dyocell of 70:30 wt% to 90: 10 wt%, preferably 80:20 wt% or a ratio of polyvinyl alcohokPLA of 70:30 wt% to 90: 10 wt%, preferably 80:20 wt% may be employed.
The carded web may have an areal density of 60 to 40gm'2, for example about
50gm'2.
In an embodiment, 100% polyvinyl alcohol and 80:20 wt% polyvinyl alcohol dyocell carded webs may be needlepunched at 9mm penetration depth, hydroentangled at 30 bar or chemically bonded using, for example, ethylene vinyl acetate (EVA) binder.
Through air bonding in which hot air is forced through the web, for example by convection, may be employed to melt an adhesive to avoid producing excessive compression.
80:20 wt% polyvinyl alcohokPLA carded webs may be through air bonded at 120°C for 2 minutes.
Air laying methods may be employed, in which a turbulent air stream is used to produce an isotropic fibre network.
In an embodiment, crimped polyvinyl alcohol fibres may be cut to a length of 5mm and blended with pulp fibres (approximately 2mm) Georgia Pacific (GP) cellulose.
Ratios of polyvinyl alcohokcellulose of 80:20 wt% to 20:80 wt% for example about 50:50 wt% may be employed.
The areal density may be about 50 gm'2, dependent on the application, for example single or multiple use applications.
The polyvinyl alcohol fibres may be dried, for example at 130°C for 10 minutes, to improve separation. In exemplary embodiments, drying is not necessary.
The airlaid webs may be hydroentangled and then dried.
Fibres of this invention have the advantage that the polyvinyl alcohol fibrecontaining webs may be converted into hydroentangled airlaid non-woven fabrics having a high strength. The fibres, particularly comprising warm water soluble polyvinyl alcohol, were found to partially dissolve during the hydroentanglement process resulting in strong but stiff fabrics.
A wetlaying process may be used to form non-woven fabrics with hot water-soluble polyvinyl alcohol fibres. In this process the polyvinyl alcohol fibres are dispersed in water and transferred onto a foraminous conveyor through which the water is removed to deposit a web of fibres.
In embodiments, the fibres may be cut to a suitable length, for example 5mm and blended with pulp fibres, for example Sodra Black, at ratios of polyvinyl alcohokpulp of 50:50 wt% to 20:80 wt%.
Lyocell fibres (1.4 dtex/5mm) may be blended at ratios of polyvinyl alcohokpulp of 50:50 wt% to 20:80 wt%.
The areal density may be about 60gm'2. This density may be employed for manufacture of flushable wipes.
The wetlaid webs may be hydroentangled and dried at 100°C for 30 seconds.
The tensile strength was compared with commercial products. A blend of polyvinyl alcohol:pulp:lyocell in a ratio of 40:40:20 wt% exhibited a relatively high tensile strength of 11 to 13N, typically about 12N.
Hydroentangled wetlaid fabrics of this invention incorporating pulp have relatively good tensile strength. Pulp fibres have typically high liquid absorption capacity. After hydroentanglement, the wetlaid web remains saturated resulting in partial dissolution of the polyvinyl alcohol fibres during the drying stage. The polyvinyl alcohol fibres act as a binder alongside formed hydrogen bonds between the pulp fibres.
The increase in specific energy during hydroentanglement may increase the dry tensile strength of the fabrics incorporating lyocell fibres.
Percentages and other quantities referred to in this specification are by weight unless stated otherwise and are selected from any ranges quoted to total 100%.
The invention is further described by means of example but not in any limitative sense, with reference to the accompanying drawing of which:
Figure 1 is a diagrammatic view of fibre extruding apparatus in accordance with this invention.
In embodiments of the present invention the following polyvinyl alcohol homopolymer compositions may be employed.
Polymer composition A
PVOH; degree of hydrolysis 98%; low viscosity 35.97%
PVOH; degree of hydrolysis 89%; low viscosity 35.97%
Trimethylol propane 14.37%
Sodium benzoate 0.21%
Glycerol 4.29%
Water 9.20%
Polymer composition B
PVOH; degree of hydrolysis 99%; high viscosity 7.193%
PVOH; degree of hydrolysis 98%; low viscosity 64.737%
Trimethylol propane 14.37%
Sodium benzoate 0.21
Glycerol 4.29%
Water 9.20%
Polymer composition C
PVOH; degree of hydrolysis 98%; low viscosity 35.87%
PVOH; degree of hydrolysis 89%; low viscosity 35.87%
Di-pentaery thritol 6.21%
Triacetin 12.41%
Sodium benzoate 0.25%
Water 9.39%
Polymer composition D
PVOH; degree of hydrolysis 98%; low viscosity 22.61%
PVOH; degree of hydrolysis 97%; medium viscosity 52.76%
Di-pentaerythritol 4.99%
Sodium benzoate 0.25%
Triacetin 10.00%
Water 9.39%
Polymer composition E
PVOH; degree of hydrolysis 98%; low viscosity 25.20%
PVOH; degree of hydrolysis 98%; low viscosity 5.20%
PVOH; degree of hydrolysis 89%; low viscosity 25.21%
Di-pentaerythritol 5.00%
Triacetin 10.00%
Water 9.39%
Polymer composition F
PVOH; degree of hydrolysis 98%; low viscosity 27.33%
PVOH; degree of hydrolysis 98%; low viscosity 27.33%
PVOH; degree of hydrolysis 89%; low viscosity 27.33%
Di-pentaerythritol 8.00%
Methyl pentanediol 5.50%
Glycerol 4.50%
Polymer composition G
PVOH; degree of hydrolysis 98%; low viscosity 72.45%
PVOH; degree of hydrolysis 99%; high viscosity 9.20%
Di Pentaerythritol 7.95%
Methyl pentanediol 5.63%
Glycerol 4.50%
Sodium benzoate 0.27%
Figure 1 illustrates apparatus for extrusion of polyvinyl alcohol fibres in accordance with the present invention. A feed hopper (1) supplies pellets of the polyvinyl alcohol
composition to an extruder (2). The molten polymer is delivered from the extruder to a melt pump (3) which meters the polymer to a spin pack (4). The spin pack spins a fibre (10) through a quenching chamber (5) supplied with cooling air by a fan (11). A spin finish applicator (6) applies a coating to the fibre (10). The fibre is then delivered by roller (7) to a series of godet rollers (8) which produce drawn fibres. The fibres are then collected on a winder (9).
The fibres were crimped using an IR heater temperature 220°C, speed 1.4 m/min, indented roller temperature 100°C and throughput rate 17 g/h.
The following properties were observed using polyvinyl alcohol (PVOH) and polylactic acid (PLA).
The properties of wetlaid hydroentangled PVOH webs were as follows.
In further embodiments, the properties of wetlaid hydroentangled PVOH webs were as follows.
Example 2
The tensile strength of webs comprising polyvinyl alcohol/pulp blends were compared with commercial flushable wipes.
The tensile strength was compared with lotion saturated wipes. The commercial wipes were squeezed by hand to remove excess lotion. The excess lotion was used to saturate the polyvinyl alcohol products of the present invention at a pick up of 200 wt% to 300 wt%.
The wetlaid webs hydroentangled at high specific energy (30 bars x 2 / bars x 4) exhibited higher wet tensile strength compared to the benchmark flushable wipes and the wetlaid webs hydroentangled at low specific energy (30 bars x 2 / 50 bars x 2). The increase in the specific energy had a positive impact on the wet tensile strength of the wetlaid hydroentangled fabrics with an increase of approximately 100 to 170%.
There was no significant differences in the wet strength between the 50:50 PVOH:Lyocell and 80:20 PVOH:Lyocell fabrics hydroentangled at the high specific energy (p>0.05).
Example 3
The dispersibility in the drain line of polyvinyl alcohol/pulp blends was compared with commercial flushable wipes.
Tests were carried out to determine dispersibility in a sewer system. Commercial wipes showed low dispersibility with less than 60% passing a 5.6mm screen.
The PVOH wetlaid fabrics hydroentangled at low specific energy (30 bars x 2 / 50 bars x 2) showed relatively good dispersibility with > 70 wt% passing the 5.6mm screen. The decrease in lyocell fibre length from 5mm to 3mm had a positive impact on dispersibility.
The dispersibility of the wetlaid hydroentangled fabrics decreased with increased specific energy (30 bars x 2 / 50 bars x 4). The fibres were more interlocked promoting fibre roping.
After the dispersibility test, the wetlaid webs hydroentangled at high specific energy showed fragments size < 4cm which is one of the alternative requirements to pass the dispersibility in the sewer system.
The PVOH fibres were successfully converted into wetlaid hydroentangled fabrics. The fabrics incorporating pulp fibres showed good dry and wet tensile strength and dispersibility, while the incorporation of lyocell fibres promoted the wet tensile strength but decreased the dispersibility of the hydroentangled wetlaid fabrics.
The commercial flushable wipes passed the dispersibility in the drainline test with more than 50 wt% passing through a 12.5mm screen.
The wetlaid hydroentangled polyvinyl alcohol-containing webs exhibited excellent results with more than 80 wt% passing through a 12.5 mm screen.
Example 4
The hydroentangled wetlaid non-woven polyvinyl alcohol/pulp fabrics were compared with commercial flushable wipes.
The commercial flushable wipes showed low dispersibility with less than 60 wt% passing through a 5.6mm sieve. The hydroentangled wetlaid fabrics incorporating 20 wt% polyvinyl alcohol fibre and 80 wt% pulp exhibited excellent results with 90 wt% passing through a 5.6mm screen.
Webs comprising polyvinyl alcohol, pulp and viscose/lyocell exhibited better dispersibility performance in comparison to commercial flushable wipes.
Use of PVOH fibres in hydroentangled wetlaid fabrics incorporating pulp fibres improved the dry tensile strength. Incorporation of viscose or lyocell fibres improved the wet strength of the fabrics. A superior combination of wet strength and dispersibility performance was achieved using 40 wt% polyvinyl alcohol, 40 wt% pulp and 20 wt% viscose fibres.
Example 5
The results show that the formulation can be drawn to a higher ratio to form finer fibres with a thickness of 2 dtex. A greater melt strength was achieved.
Claims
1. A method of manufacture of a nonwoven product comprising polyvinyl alcohol fibres, the method comprising the steps of: providing a polyvinyl alcohol composition comprising homopolymeric polyvinyl alcohol having a degree of hydrolysis of 88% to 98% or greater; and a molecular weight in the range from 22,000 to 38,000; a plasticiser selected from the group consisting of: diglycerol, triglycerol, fructose, ribose, xylose, D-mannitol, triacetin, pentaerythritol, dipentaerythritol, methyl pentanediol, 1,2-propanediol, 1,4-butanediol, 2-hydroxy-l,3-propanediol, 3-methyl-l,3-butanediol, 3,3- dimethyl-l,2-butanediol, polyethylene glycol 300, polyethylene glycol 400, alkoxylated polyethylene glycol, caprolactam, tricyclic trimethylolpropane formal, rosin esters, erucamide, and mixtures thereof; and a stabilizer selected from the group consisting of: sodium stearate, potassium oleate, sodium benzoate, calcium stearate, stearic acid, dimethyl pentane diol, propionic acid and mixtures thereof; melting the composition at a temperature from 190°C to 250°C; extruding the melted composition to form an extrudate; forming the extrudate into molten fibres; drawing the molten fibres to form individual molten fibres or bundles of molten fibres; and allowing the molten fibres to solidify to form solid fibres or bundles of solid fibres.
2. A method as claimed in any preceding claim including the step of forming fibres into a non-woven web by a method selected from: carding, airlaying and wetlaying.
3. A method as claimed in claim 2, wherein the fibres are dried and then carded.
4. A method as claimed in claim 2 or 3, wherein fibres in the non-woven web are bonded by a method selected from hydroentanglement, needlepunching, chemical bonding or thermal bonding.
5. A method as claimed in any preceding claim, including the step of blending the polyvinyl alcohol fibres with sustainable fibres.
6. A method as claimed in claim 5, wherein the sustainable fibres are selected from the group consisting of: lyocell, polylactic acid, polyhydroxy alkanoates, cellulose pulp and mixtures thereof.
7. A method as claimed in claim 6, wherein polyvinyl alcohol fibres and lyocell fibres are blended in a ratio of polyvinyl alcohol: lyocell in the range 70:30 to 90:10 wt%, preferably 80:20 wt%.
8. A method as claimed in claim 7, wherein polyvinyl alcohol fibres and polylactic acid fibres are blended in a ratio of polyvinyl alcohol: polylactic acid in the range 70:30 to 90:10 wt%.
9. A method as claimed in claim 8, wherein the ratio of polyvinyl alcohol: polylactic acid is in the range 80:20 wt%.
10. A method as claimed in any of claim 3, wherein the carded web has an areal density of 60 to 40 gm'2.
11. A method as claimed in any of claim 10, wherein the carded web has an areal density of 50 gm'2.
12. A non-woven fibre product made in accordance with the method of any of claims 1 to 11.
13. A non-woven fibre product as claimed in claim 12, wherein the product is a wipe.
14. A non-woven fibre product comprising fibres of homopolymeric polyvinyl alcohol having a degree of hydrolysis of 88% or greater.
15. A non-woven fibre product as claimed in claim 14 further comprising sustainable cellulose fibres.
16. A non-woven fibre product as claimed in claim 15, wherein the sustainable fibres are selected from: lyocell, polylactic acid, polyhydroxy alkanoates and mixtures thereof.
Applications Claiming Priority (2)
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EP22190330.5A EP4321665A1 (en) | 2022-08-13 | 2022-08-13 | Extruded polyvinyl alcohol fibres and fibrous products |
EP22190330.5 | 2022-08-13 |
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WO2024037987A1 true WO2024037987A1 (en) | 2024-02-22 |
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PCT/EP2023/072322 WO2024037987A1 (en) | 2022-08-13 | 2023-08-11 | Extruded polyvinyl alcohol fibres and fibrous products |
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EP (2) | EP4321665A1 (en) |
TW (1) | TW202424296A (en) |
WO (1) | WO2024037987A1 (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1199190A (en) * | 1966-11-14 | 1970-07-15 | Du Pont | Absorbent Non-Woven Fabrics |
US3997489A (en) * | 1974-11-25 | 1976-12-14 | E. I. Du Pont De Nemours And Company | Melt extrudable polyvinyl alcohol compositions |
WO2017046361A1 (en) | 2015-09-18 | 2017-03-23 | Aquapak Polymers Limited | Process and apparatus for manufacture of processable polyvinyl alcohol |
US20170369693A1 (en) * | 2013-03-25 | 2017-12-28 | Peter Morris Research And Development Limited | Water-soluble polymer and polymer internal lubricant |
WO2021067474A1 (en) * | 2019-09-30 | 2021-04-08 | Monosol, Llc | Nonwoven water-soluble composite structure |
WO2022008521A1 (en) | 2020-07-06 | 2022-01-13 | Aquapak Polymers Limited | Process for manufacture of plasticised homopolymeric polyvinyl alcohol and plasticised polyvinyl alcohol polymer obtained therefrom |
US20220228305A1 (en) * | 2019-04-24 | 2022-07-21 | Monosol, Llc | Nonwoven water dispersible article for unit dose packaging |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2023531767A (en) * | 2020-06-27 | 2023-07-25 | モノソル リミテッド ライアビリティ カンパニー | Bathing experience molded product enclosed in film and manufacturing method |
-
2022
- 2022-08-13 EP EP22190330.5A patent/EP4321665A1/en not_active Withdrawn
-
2023
- 2023-08-11 TW TW112130377A patent/TW202424296A/en unknown
- 2023-08-11 WO PCT/EP2023/072322 patent/WO2024037987A1/en unknown
- 2023-08-11 EP EP23191132.2A patent/EP4321666A1/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1199190A (en) * | 1966-11-14 | 1970-07-15 | Du Pont | Absorbent Non-Woven Fabrics |
US3997489A (en) * | 1974-11-25 | 1976-12-14 | E. I. Du Pont De Nemours And Company | Melt extrudable polyvinyl alcohol compositions |
US20170369693A1 (en) * | 2013-03-25 | 2017-12-28 | Peter Morris Research And Development Limited | Water-soluble polymer and polymer internal lubricant |
WO2017046361A1 (en) | 2015-09-18 | 2017-03-23 | Aquapak Polymers Limited | Process and apparatus for manufacture of processable polyvinyl alcohol |
US20220228305A1 (en) * | 2019-04-24 | 2022-07-21 | Monosol, Llc | Nonwoven water dispersible article for unit dose packaging |
WO2021067474A1 (en) * | 2019-09-30 | 2021-04-08 | Monosol, Llc | Nonwoven water-soluble composite structure |
WO2022008521A1 (en) | 2020-07-06 | 2022-01-13 | Aquapak Polymers Limited | Process for manufacture of plasticised homopolymeric polyvinyl alcohol and plasticised polyvinyl alcohol polymer obtained therefrom |
WO2022008516A1 (en) | 2020-07-06 | 2022-01-13 | Aquapak Polymers Limited | Method for manufacture of a plasticised polyvinyl alcohol mixture |
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EP4321665A1 (en) | 2024-02-14 |
EP4321666A1 (en) | 2024-02-14 |
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