US20150275039A1 - Application of a non-fluoro hydrophobic aqueous-based polyurethane resin dispersion - Google Patents
Application of a non-fluoro hydrophobic aqueous-based polyurethane resin dispersion Download PDFInfo
- Publication number
- US20150275039A1 US20150275039A1 US14/739,105 US201514739105A US2015275039A1 US 20150275039 A1 US20150275039 A1 US 20150275039A1 US 201514739105 A US201514739105 A US 201514739105A US 2015275039 A1 US2015275039 A1 US 2015275039A1
- Authority
- US
- United States
- Prior art keywords
- cross
- groups
- dispersion
- aqueous
- linking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000006185 dispersion Substances 0.000 title abstract description 68
- 230000002209 hydrophobic effect Effects 0.000 title abstract description 49
- 125000001153 fluoro group Chemical group F* 0.000 title abstract description 25
- 229920005749 polyurethane resin Polymers 0.000 title description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 46
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 41
- 239000005871 repellent Substances 0.000 claims abstract description 39
- 238000004132 cross linking Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 229920003009 polyurethane dispersion Polymers 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 230000002940 repellent Effects 0.000 claims abstract description 15
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- HZBAVWLZSLOCFR-UHFFFAOYSA-N oxosilane Chemical compound [SiH2]=O HZBAVWLZSLOCFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 239000012948 isocyanate Substances 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 abstract description 114
- 229920005989 resin Polymers 0.000 abstract description 42
- 239000011347 resin Substances 0.000 abstract description 42
- 239000004744 fabric Substances 0.000 abstract description 35
- 230000008569 process Effects 0.000 abstract description 19
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 7
- 230000005923 long-lasting effect Effects 0.000 abstract description 5
- 150000007513 acids Chemical class 0.000 abstract description 3
- 239000000123 paper Substances 0.000 abstract description 2
- 150000003512 tertiary amines Chemical class 0.000 abstract description 2
- 239000002023 wood Substances 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000011521 glass Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 description 100
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 22
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 14
- 229920005862 polyol Polymers 0.000 description 12
- 150000003077 polyols Chemical class 0.000 description 11
- 239000000835 fiber Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 8
- 239000005642 Oleic acid Substances 0.000 description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 8
- 229920000909 polytetrahydrofuran Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 150000002191 fatty alcohols Chemical class 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000004970 Chain extender Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 4
- 0 C.C.C.C.C.C.C*NC(=O)OCOC(=O)N*NC(=O)OCC(C)(COC(=O)N*C)C(=O)O.CC.CC.CC(=O)O.CC([H]CO)(CO)C(=O)O.CC1(C)CC(OC#N)CC(C)(CN=C=O)C1.CCC1(C)CC(C)CC(C)(C)C1.CCCCCOC.CN=C=O.COC#N.P[U].[3H-12].[H]OCCCCO.[W]P[U] Chemical compound C.C.C.C.C.C.C*NC(=O)OCOC(=O)N*NC(=O)OCC(C)(COC(=O)N*C)C(=O)O.CC.CC.CC(=O)O.CC([H]CO)(CO)C(=O)O.CC1(C)CC(OC#N)CC(C)(CN=C=O)C1.CCC1(C)CC(C)CC(C)(C)C1.CCCCCOC.CN=C=O.COC#N.P[U].[3H-12].[H]OCCCCO.[W]P[U] 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 125000003010 ionic group Chemical group 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 3
- 229960003656 ricinoleic acid Drugs 0.000 description 3
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 125000004069 aziridinyl group Chemical group 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- YLOFUEIJJUSCOU-LYIPJUQKSA-P C.C.C.C.CC(=O)[O-].CC(=O)[O-].CCC(COC(=O)CCN1CC1)(COC(=O)CCN1CC1)COC(=O)CCN1CC1.CCCCCCCC/C=C\CCCCCCCC(=O)OCCNCCC(=O)OCC(CC)(COC(=O)CCNCCOC(C)=O)COC(=O)CCNCCOC(C)=O.CCCCCCCC/C=C\CCCCCCCC(=O)[O-].CC[NH+](CC)CC.CC[NH+](CC)CC.CC[NH+](CC)CC.CN.CN.CN.CN.CN.CN.CN.CN.[2H]SCP[W]P[U].[2H]SCP[W]P[U].[W]P[U].[W]P[U] Chemical compound C.C.C.C.CC(=O)[O-].CC(=O)[O-].CCC(COC(=O)CCN1CC1)(COC(=O)CCN1CC1)COC(=O)CCN1CC1.CCCCCCCC/C=C\CCCCCCCC(=O)OCCNCCC(=O)OCC(CC)(COC(=O)CCNCCOC(C)=O)COC(=O)CCNCCOC(C)=O.CCCCCCCC/C=C\CCCCCCCC(=O)[O-].CC[NH+](CC)CC.CC[NH+](CC)CC.CC[NH+](CC)CC.CN.CN.CN.CN.CN.CN.CN.CN.[2H]SCP[W]P[U].[2H]SCP[W]P[U].[W]P[U].[W]P[U] YLOFUEIJJUSCOU-LYIPJUQKSA-P 0.000 description 1
- GJDORADHQBLDBP-MZCXNYADSA-N C=C/C=C/NCOCCOCCO(CCC)(CCOCCOCN/C=C/C=C)CCOCCOC(=O)NC1=CC=CC=C1C.CC(C)(C1=CC=C(OCC(O)COC2=CC=C(C(C)(C)C3=CC=C(OCC4CO4)C=C3)C=C2)C=C1)C1=CC=C(OCC2CO2)C=C1.CC(COC(=O)CCN1CC1)OCC(C)OCC(C)OC(=O)CCN1CC1.CCC(COC(=O)CCN1CC1)(COC(=O)CCN1CC1)COC(=O)CCN1CC1.CN=C=O.O=C(CCN1CC1)OCCCCCCOC(=O)CCN1CC1.O=P(OCC1CO1)(OCC1CO1)OCC1CO1 Chemical compound C=C/C=C/NCOCCOCCO(CCC)(CCOCCOCN/C=C/C=C)CCOCCOC(=O)NC1=CC=CC=C1C.CC(C)(C1=CC=C(OCC(O)COC2=CC=C(C(C)(C)C3=CC=C(OCC4CO4)C=C3)C=C2)C=C1)C1=CC=C(OCC2CO2)C=C1.CC(COC(=O)CCN1CC1)OCC(C)OCC(C)OC(=O)CCN1CC1.CCC(COC(=O)CCN1CC1)(COC(=O)CCN1CC1)COC(=O)CCN1CC1.CN=C=O.O=C(CCN1CC1)OCCCCCCOC(=O)CCN1CC1.O=P(OCC1CO1)(OCC1CO1)OCC1CO1 GJDORADHQBLDBP-MZCXNYADSA-N 0.000 description 1
- DJVYPJITRLXGQV-WVLDIFRBSA-N CC.CC.CC(=O)O.CC(=O)O.CC(=O)O.CC(=O)[O-].CC([H]CO)(CO)C(=O)O.CC1(C)CC(OC#N)CC(C)(CN=C=O)C1.CC[NH+](CC)CC.CN.CN.CN=C=O.COC#N.C[Si](C)(OCO)O[Si](C)(C)O[Si](C)(C)OCO.[2H]P(I)I.[2H]SCPP[U].[2H]SCPP[U].[2H]SCPP[U].[2H]SCPP[U] Chemical compound CC.CC.CC(=O)O.CC(=O)O.CC(=O)O.CC(=O)[O-].CC([H]CO)(CO)C(=O)O.CC1(C)CC(OC#N)CC(C)(CN=C=O)C1.CC[NH+](CC)CC.CN.CN.CN=C=O.COC#N.C[Si](C)(OCO)O[Si](C)(C)O[Si](C)(C)OCO.[2H]P(I)I.[2H]SCPP[U].[2H]SCPP[U].[2H]SCPP[U].[2H]SCPP[U] DJVYPJITRLXGQV-WVLDIFRBSA-N 0.000 description 1
- DZXPQXAAWXPKGH-UHFFFAOYSA-N CCC(CO)(CO)CO.OCC(O)CO.OCCCC(O)CO.OCCN(CCO)CCO Chemical compound CCC(CO)(CO)CO.OCC(O)CO.OCCCC(O)CO.OCCN(CCO)CCO DZXPQXAAWXPKGH-UHFFFAOYSA-N 0.000 description 1
- IMYZYCNQZDBZBQ-UHFFFAOYSA-N CCCCCCCCC1OC1CCCCCCCC(=O)O Chemical compound CCCCCCCCC1OC1CCCCCCCC(=O)O IMYZYCNQZDBZBQ-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- CNNRPFQICPFDPO-UHFFFAOYSA-N octacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCO CNNRPFQICPFDPO-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229960001109 policosanol Drugs 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
Definitions
- the present invention relates to aqueous polyurethane (PU) dispersion, and its production method and use, especially a non-fluoro, hydrophobic aqueous PU dispersion, and its production method and use.
- PU polyurethane
- the fabric having a function of moisture permeation and sweat release which has been sold in market, uses the fabric which is fluoro-containing resin processed, i.e. fluoro-containing acrylic resin or PTFE (polytetrafluoroethylene) attached film.
- fluoro-containing resin processed i.e. fluoro-containing acrylic resin or PTFE (polytetrafluoroethylene) attached film.
- these materials already reach its limitation of water-repellent fabric in the aspect of resistance.
- no matter using fluoro containing resin or PTFE attached film as material for water-repellent treatment these materials all have C8-fluoro compounds, PFOA (perfluoro-octanoic acid) or PFOS (perfluoro-octanesulfonic acid) salt and the like. These compounds are certified causing carcinogenesis.
- the water repellent having C8-fluoro compounds is eliminated gradually, and will be prohibited from 2015.
- low carbon such as C6 or C4
- the usage of low carbon flour-containing compounds require a higher amount than C8-flour-compounds do. This situation is expected to cause an impact to environment, especially the accumulation in alive organism, and further may cause the defects for considering the damage of ecological environment of earth.
- the resin used in resin having flour-containing nowadays is acrylic-based resin mainly.
- this kind of resin cannot process the following cross-linking reaction.
- the processed products of resin having flour-content cannot maintain long-term efficacy of water repellent, and this is a problem which the fabric for treating water repellent needs to be dealt with.
- the method of attached film it is necessary for using specific extended PTFE film materials, specific dispensing glue and the facility for attaching film to carry out the process of attaching film for water-repellent fiber.
- it requires specific professional method to clean it and that would be another inconvenience.
- the water-repellent fabric in the market would have the following defects:
- the bad hand-feel Using the coating of water repellent having acrylic resin fluoro or PTFE attached film on the surface of fiber causes the stiff feeling when touching the fabric.
- the present invention selects non-fluoro compounds and non-toxic compounds having reactive functional groups individually, such as the compounds having hydrophobic property, like aliphatic compounds, i.e. aliphaltic long chain carbon-carbon bonding compounds, or PDMS (polydimethylsiloxane) and the like.
- aqueous polyurethane (PU) resin a “latent cross-linking (curing) agent” is added, and successfully develops “single-component cross-linking non-fluoro hydrophobic aqueous polyurethane (PU) dispersion”.
- PU resin would generate a cross-linking reaction with the latent cross-linking agent to increase the cross-linking density of this hydrophobic PU resin, and further to improve washing resistance and solvent resistance of hydrophobic polyurethane resin to reach a long-term hydrophobic (water-repellent) function.
- non-fluoro hydrophobic aqueous polyurethane dispersion having long-term water-repellent function of the present invention comply the requirements of energy saving and carbon dioxide reduction and is expected to replace the fluoro-containing water repellent which is going to be eliminated.
- the technical characteristics of the present invention mainly are selecting separately or mix-using a compound comprising alcohols, amines, acids, saturated or unsaturated (double-bonded or epoxidized) aliphatic acids which have reactive aliphatic long chain carbon-carbon bond, for instance, ricinoleic acid, fatty acid ester or oleic acid, or a hydrophobic compound, for instance, polydimethylsiloxane containing alcohol groups, amino groups or oxosilane groups, to react with ployiscyanate as reactive material of hydrophobic polyurethane (PU) resin.
- PU hydrophobic polyurethane
- adding compounds containing hydrophilic group such as COOH
- hydrophobic polyurethane resin has a long lasting hydrophobic (water-repellent) function. In the present specification, it would refer this kind of hydrophobic PU as “single-component cross-linking non-fluoro hydrophobic aqueous PU dispersion”.
- the “single-component cross-linking non-fluoro hydrophobic aqueous PU dispersion” of the present invention has reactive hydrophobic aqueous PU resin, which it can generate interpenetrating polymeric networks (IPN) by self-crosslink reaction to insert between fabric (such as longitudinal yarn and latitudinal yarn), wood, or the fiber of paper and form physical insertion or even chemical bonding under room temperature.
- IPN interpenetrating polymeric networks
- the cross-linking reaction of the components of this new invention can carry out under room temperature, and can use a single component or any mixing ratio of aliphatic long chain carbon-carbon bond or PDMS as a hydrophobic PU modified components, especially that the amount of hydrophobic groups requires less amount (5-10%) to reach the water-repellent efficacy.
- the non-fluoro hydrophobic PU dispersion of the present invention is coated on the surface of the fabrics by simple coating method (by a method of scraper, roller, impregnation, spray or screen printing and the like), and dried under room temperature to achieve the cross-linking long-term hydrophobic PU resin coating.
- the processed fabric maintains 85% of the original water-repellent efficacy after washed (after 50 washing cycles) in the test of static contact angle and dynamic sliding angle of water drops.
- the present invention provides a production method of non-fluoro hydrophobic aqueous dispersion comprising the following steps: selecting a compound comprising alcohols, amines, acids, saturated or unsaturated (double-bonded or epoxidized) aliphatic groups or polydimethylsiloxane (PDMS) comprising alcohol groups, amino groups, oxosilane groups to be reacted with 3-Isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate to obtain a PU prepolymer having NCO terminal group; after neutralizing, adding water to disperse the PU prepolymer to obtain an aqueous PU dispersion; and adding a cross-linking (curing) agent into the aqueous PU dispersion to obtain an ambient temperature self linking aqueous PU dispersion.
- PDMS polydimethylsiloxane
- the unsaturated aliphatic groups have functional groups of alcohol groups, amino groups, carboxyl groups or double bond.
- the average molecular weight of polydimethylsiloxane is 500-3000, and polydimethylsiloxane has reactive functional groups of alcohol groups, amino groups, carboxyl groups, epoxy groups, oxosilane groups or double bond.
- the aliphatic containing alcohol group is higher alcohols or diols having carbon numbers from 10 to 30.
- the aliphatic containing amino group is the compound having carbon number from 10 to 30.
- the aliphatic containing double bond is castor oil, palm oil, soybean oil or epoxidized soybean oil.
- the cross-linking agent is poly-aziridine cross-linking agent.
- the aqueous polyurethane dispersion which reacts the cross-linking agent comprises aliphatic of aliphatic acids having carbon number from 10 to 30.
- the polydimethylsiloxane group of the cross-linked aqueous polyurethane-dispersion is on the main chain or side chain of polyurethane resin.
- the present invention also provides a non-fluoro hydrophobic aqueous polyurethane dispersion, wherein the polyurethane dispersion obtained by the aforementioned production method.
- the polyurethane dispersion can be made into single-liquid form.
- the present invention further provides an use of water repellent applied a polyurethane dispersion, wherein the polyurethane dispersion obtained by the aforementioned production method or is the aforementioned polyurethane dispersion.
- the polyurethane dispersion is applied on an object which is going to be coated under pH value less than 7 to make the carboxylate reactive functional groups comprised react with a cross-linking agent to generate a ring-opening cross-linking reaction.
- the object which is going to be coated has hydroxyl groups, carboxylic acids, epoxy groups or amino groups.
- the silane groups comprised in the polyurethane dispersion reacts with hydroxyl groups or amino groups of the object which is going to be coated to form chemical bonding.
- the polyurethane dispersion can be coated on a surface of the object which is going to be coated by a method of scraper, roller, impregnation, spray or screen printing and the like.
- non-fluoro hydrophobic aqueous PU resin of the present invention By using the non-fluoro hydrophobic aqueous PU resin of the present invention, it can reach the following advantages and efficacy:
- a self-emulsified (having internal ionic groups) aqueous PU dispersion 1.
- the self-linking procedure for energy saving and carbon dioxide reduction which may be self cross-linked (under room-temperature dried or pH value being less than 7.0) provides the functions of washing resistance, solvent resistance and long lasting hydrophobic efficacy.
- PU resin may flexibly adjust the softness and density to provide long lasting hydrophobic (water-repellent) properties.
- hydrophobic molecular chain domain groups
- aliphatic long chain carbon-carbon bond aliphatics or fatty acids
- PDMS polydimethylsiloxane
- FIG. 1 displays a SEM micrograph of the fiber treated by aqueous PU dispersion containing aliphatic acids and PDMS which are mixed and reacted (unwashed);
- FIG. 2 displays a EDS of the fiber treated by aqueous PU dispersion containing aliphatic acids and PDMS which are mixed and reacted (unwashed);
- FIG. 3 displays a SEM micrograph of the fiber treated by aqueous PU dispersion containing aliphatic acids and PDMS which are mixed and reacted (after 40 washing cycles);
- FIG. 4 displays an EDS of the fiber treated by aqueous PU dispersion containing aliphatic acids and PDMS which are mixed and reacted (after 40 washing cycles) (still have silicon on the surface of fiber).
- hydrophobic aqueous PU dispersion and the application of water-repellent treatment thereof
- DMPA 2,2′-bis(hydroxymethyl) propionic acid
- PTMEG-2000 polytetramethylene ether glycol
- IPDI isophorone diisocyanate
- polyether polyol for instance, PPG or PTMEG
- polyisocyanate (IPDI) materials or diol compounds containing hydrophilic functional groups as internal emulsifier (for instance, dimethylol propanic acid, DMPA) and fatty alcohols (aliphatic long chain carbon-carbon bond alcohol compounds).
- DMPA dimethylol propanic acid
- fatty alcohols aliphatic long chain carbon-carbon bond alcohol compounds
- PPG or PTMEG polyether polyol
- IPDI polyisocyante
- DMPA internal emulsifier
- a long chain fatty acid containing PU prepolymer having isocyanate as terminal-ended group (with hydroxyl or epoxidized fatty acid involved in the reaction).
- This aliphatic PU prepolymer having isocyanate (NCO) as terminal-ended group and adding aliphatic acids (as stearic acid, oleic acid, epoxidized oleic acid or ricinoleic acid) alone or proper ratio separately in PU prepolymer.
- PPG or PTMEG polyether polyol
- IPDI polyisocyante
- DMPA internal emulsifier
- PDMS polydimethylsiloxane
- the details of the preparation scheme please refer to the following scheme 3.
- the fatty (alcohol or acid) or polydimethylsiloxane (PDMS)-containing aqueous PU dispersion is introduced carboxylic acid group (COOH) separately.
- carboxylic acid group COOH
- the ionic group carboxyl groups, COO—
- the ionic group is used as internal emulsifier to provide the stability of aqueous PU dispersion.
- the latent cross-linking agent containing aziridine functional groups (as TMPTA-AZ or CX-100) added into “single-liquid non-fluoro hydrophobic aqueous PU dispersion” would react with carboxyl groups in PU resin to process open-ring cross-linking reaction under room temperature being dried at ambient temperature. It would react with hydrophilic carboxyl groups and form hydrophobic amino ester bonding, and improve the cross-linking density of aqueous PU resin on drying. The water resistance, solvent resistance, mechanical strength and heat stability would be improved accordingly. Due to the aziridine functional groups contained in aqueous PU as a latent cross-linking agent having high pH value, aziridine can present in water dispersion stably.
- aqueous PU dispersion containing different amount of polydimethylsiloxane (PDMS) or aliphatic acid or fatty alcohol is coated by a simple method (scraper, roller, impregnation, spray or screen printing and the like) to process the treatment of water-repellent on the surface of fabric.
- PDMS polydimethylsiloxane
- aliphatic acid or fatty alcohol is coated by a simple method (scraper, roller, impregnation, spray or screen printing and the like) to process the treatment of water-repellent on the surface of fabric.
- the self-curing (cross-linking) reaction is carried out to form PU resin with interpenetrating networks (IPN) structure tightly and anchored between longitudinal yarn and latitudinal yarn of the fabric, so that it improve the durability of water washing of water-repellent resin treated fabric.
- IPN interpenetrating networks
- the present invention is clarified by preferable specific embodiments which are not used to limit the present invention.
- diol compounds containing hydrophilic functional groups as internal emulsifier such as ionic internal emulsifier and non-ionic internal emulsifier
- fatty alcohol of long chain carbon-carbon aliphatic alcohols compounds to process addition polymerization reaction by different formulating method.
- the aliphatic long chain carbon-carbon PU oligomer and prepolymer used isocyanate as terminal-ended groups are formed. Further neutralization by a tertiary amine deionized water and chain extender to process the steps of chain extension and water dispersion with mechanical agitation. It results in a formation of self-emulsified aliphatic carbon-carbon chain containing aqueous-based PU dispersions.
- polyurethane elastomers The property of polyurethane elastomers is due to the chain structure having flexibility and the structure of minor branching or partial net cross-linking Polyols with better flexibility are polyesters, polyethers, polyether-ester polyols or polyester-amide polyols and the like.
- Polyether Polyols (b) Polyether Polyols (PP):
- the common polyether polyols are as following: polyethylene glycols, polypropylene glycols, polytetramethylene glycols which have the average molecular weight ranging in 400-4000.
- the most common diisocyante is toluene diisocyanates (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4-methylene diphenyl diisocyanate (MDI) and the like.
- aromatic diisocyanates the main toluene diisocyanates in the market comprise: 80% of 2,4-toluene diisocyanates (TDI) and 20% of 2,6-toluene diisocyanates (TDI).
- TDI 2,4-toluene diisocyanates
- the activity of para-(4-) isocyanate functional groups is higher than ortho-(2-,6-) ones by 4 to 5 times. It benefits for producing selective isocyanate prepolymer.
- Triols Cross-Linking Agent Glycerol, Trimethylolpropane (TMP), 1,2,6-Hexanetriol, Triethanolamine (TEA) and the Like.
- DMPA Dimethylolpropanic Acid
- DMBA Dimethylolbutanoic Acid
- the aliphatic long chain carbon-carbon bond containing—PU oligomer and prepolymer is obtained from a process of the addition polymerization of polyols, polyisocyanates and ionic center (as an internal emulsifier, DMPA). Then proceed a process of neutralization with trialkylamine (e.g. triethylamine, TEA), and chain-extension with ethylenediamine during water dispersion.
- trialkylamine e.g. triethylamine, TEA
- TEA triethylamine
- the internal ionic center within PU resin that having stable micelles of PU particles formation that suspends in the aqueous PU dispersion.
- the latent PU cross-linking agent is added into the aqueous dispersion and it results in the formation of stable “cross-linking single-component aliphatic long chain carbon-carbon bond containing aqueous PU dispersion” (its pH value >8.0).
- the cross-linking reaction takes place during drying process at ambient temperature or the pH value drops below 7.0.
- This cross-linked PU resin owns the physical and chemical properties of water resistance, solvent resistance, mechanical strength and heat stability would be improved in large scale accordingly.
- This latent cross-linking agent (such as TMPTA-AZ) could be triggered the ring-opening reaction self-curing by lowering its pH value of resin system. It is a convenient (single component), energy saving (at ambient temperature) cross-linking reaction takes place immediately when the pH value of PU system lowers than 7.0.
- the common ambient temperature cross-linking agents are listed as following:
- DMPA 2,2′-bis(hydroxymethyl) propionic acid
- PTMEG-2000 polytetramethylene ether glycol
- T-12 0.1%(w/w) catalyst
- IPDI isophorone diisocyanate
- isocyanate functional groups having selective diisocyantes (polyisocyantes, IPDI)), triol (glycerol or trimethylolpropane, TMP) and long chain fatty alcohol compounds (fatty alcohol or higher alcohol), by using an excess amount of isocyanates (IPDI), and then adding minor catalyst, dibutyltin dilaurate (DBTDL) to accelerate the reaction being completed. It results in the formation of NCO-terminated aliphatic long chain carbon-carbon bond containing PU oligomer.
- IPDI polyisocyantes
- TMP trimethylolpropane
- DBTDL dibutyltin dilaurate
- polyether polyol e.g., PPG or PTMEG
- polyisocyanate (IPDI) materials or diol compounds containing hydrophilic functional groups as internal emulsifier (for instance, dimethylol propanic acid, DMPA) and fatty alcohols (aliphatic long chain carbon-carbon bond alcohol compounds).
- hydrophilic functional groups for instance, dimethylol propanic acid, DMPA
- fatty alcohols aliphatic long chain carbon-carbon bond alcohol compounds
- PDMS polydimethylsiloxane
- DMPA dimethylol propanic acid
- IPDI Isophorone diisocyanate
- PDMS-containing PU prepolymer having isocyanate as terminal groups.
- An aqueous mixture of de-ionized water of neutralizing agent (triethylamine, TEA) and chain-extender (ethylene diamine) is added into this PDMS-prepolymer slowly with agitation and “self-emulsified PDMS-containing aqueous PU dispersion” is obtained.
- neutralizing agent triethylamine, TEA
- chain-extender ethylene diamine
- the ratio of PDMS containing aqueous PU dispersion with oleic soap (oleic acid amine soap) (PDMS/oleic) with 2/1, 1/1 and 1/2, are selected and mixing separately.
- TMPTA-AZ a latent cross-linking agent (3 phr) is added into each mixture as latent cross-linking agent.
- Both PDMS and oleic acid are chemical bonded with hydrophobic PU resin.
- the dried cross-linking PDMS/oleic hybridized hydrophobic PU resin is shown as the following scheme 5.
- Example 5 diluting the cross-linking PDMS/oleic containing hybridized PU dispersion with de-ionized water to proper concentration (5-10% of solid). Then apply it on the surface of fabric to carry out the hydrophobic treatment. It is cross-linked and forming interpenetrating polymeric network (IPN) structures and anchored into fabric after drying. That improves the bonding strength between treated PU resin and fabric that improve washing durability and solvent resistance of hydrophobic treated fabrics.
- IPN interpenetrating polymeric network
- the PU resin of the present invention has no fluoro and the water repellent treatment with less energy requirement which comply with the non-toxic requirements and provision of components used in fabrics in the future to people nowadays.
- the present invention comparing to prior water repellent which uses fluoro compounds has superior efficacy.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a cross-linking non-fluoro hydrophobic aqueous polyurethane dispersion, which is produced by selecting a compound comprising alcohols, amines, acids, saturated or unsaturated (double-bonded or epoxidized) aliphatic long chain carbon-carbon groups or polydimethylsiloxane comprising alcohol groups, amines, oxosilane to be reacted with IPDI to obtain a PU prepolymer; adding a compound having tertiary amines to neutralize the carboxylic acid of PU prepolymer and adding water to disperse the PU prepolymer; and adding a ambient temperature cross-linking agent to obtain a cross-linking hydrophobic aqueous PU dispersion of the present invention. The hydrophobic aqueous-based PU resin has no fluorine which is friendly to the environment, and may further self cross-links on its applications on fabric, paper, wood, glass and metal surfaces, respectively on drying at ambient temperature which is energy saving process. Its cross-linking reaction of this hydrophobic PU system that will achieve a long-lasting water repellent surface treatment.
Description
- The present invention relates to aqueous polyurethane (PU) dispersion, and its production method and use, especially a non-fluoro, hydrophobic aqueous PU dispersion, and its production method and use.
- Nowadays, the public places importance on outdoor activities, sports and work out. Regarding the dressing while doing exercise, the requirements for a functional dress are light, convenient and comfortable. Hence, this kind of functional dressing becomes the main business of the development. Generally, an outdoor dressing for user to feel comfortable usually requires a water-repellent surface, i.e. its materials have hydrophobic properties, and a property for releasing the moisture from human body at the same time, i.e. the fabric having a breathable function (moisture permeation and sweat release). This kind of product is needed in the current market.
- The fabric having a function of moisture permeation and sweat release, which has been sold in market, uses the fabric which is fluoro-containing resin processed, i.e. fluoro-containing acrylic resin or PTFE (polytetrafluoroethylene) attached film. However, these materials already reach its limitation of water-repellent fabric in the aspect of resistance. In addition, no matter using fluoro containing resin or PTFE attached film as material for water-repellent treatment, these materials all have C8-fluoro compounds, PFOA (perfluoro-octanoic acid) or PFOS (perfluoro-octanesulfonic acid) salt and the like. These compounds are certified causing carcinogenesis. Hence, the water repellent having C8-fluoro compounds is eliminated gradually, and will be prohibited from 2015. Although there are low carbon (such as C6 or C4) flour-compounds used in market as flour-containing water repellent, in order to achieve to an expected water-repellent efficacy, the usage of low carbon flour-containing compounds require a higher amount than C8-flour-compounds do. This situation is expected to cause an impact to environment, especially the accumulation in alive organism, and further may cause the defects for considering the damage of ecological environment of earth.
- In addition, the resin used in resin having flour-containing nowadays is acrylic-based resin mainly. When applying it to the coating process, this kind of resin cannot process the following cross-linking reaction. Hence, the processed products of resin having flour-content cannot maintain long-term efficacy of water repellent, and this is a problem which the fabric for treating water repellent needs to be dealt with. However, if the method of attached film is carried out, it is necessary for using specific extended PTFE film materials, specific dispensing glue and the facility for attaching film to carry out the process of attaching film for water-repellent fiber. Regarding the cleaning in aspect of customers, it requires specific professional method to clean it and that would be another inconvenience.
- Generally, the water-repellent fabric in the market would have the following defects:
- 1. The bad hand-feel: Using the coating of water repellent having acrylic resin fluoro or PTFE attached film on the surface of fiber causes the stiff feeling when touching the fabric.
- 2. The poor washing durability: After the process of water-repellent coating, the known water-repellent fabric is only covered by the water repellent on its surface, instead of polymeric inter-penetrating networks (IPN) anchoring in fabric and forming between fabric yarns. Hence, after multiple times of use, it is easy to damage the fabric due to rubbing and washing, further to decrease the water-repellent function. The fabric has the durability decrease.
- 3. Poor Breathability: The processes material, such as water repellent, is covered on the surface of fabric by the coverage method. Due to overdose of resin coating on, the excess amount of resin plugs the fabric and decreases the original air permeability of fabric. The fabric has the defect on breathability.
- 4. The cost of protecting environment is too high: In the known knowledge, no matter using the method of coating or attached film, it requires a fluoro-containing polymer that can cause pollution loading, bio-toxicity and the accumulation in alive organism to environment. The fabric has the defect that cause damage to ecology of earth.
- To sum up, it is necessary to develop a water repellent having non-fluoro compounds which is valuable and the water repellent needs to be improved urgently.
- The present invention selects non-fluoro compounds and non-toxic compounds having reactive functional groups individually, such as the compounds having hydrophobic property, like aliphatic compounds, i.e. aliphaltic long chain carbon-carbon bonding compounds, or PDMS (polydimethylsiloxane) and the like. As the reactive materials of aqueous polyurethane (PU) resin, a “latent cross-linking (curing) agent” is added, and successfully develops “single-component cross-linking non-fluoro hydrophobic aqueous polyurethane (PU) dispersion”. When carrying out applying, i.e. while drying or the pH value of dispersion drops less than 7.0, PU resin would generate a cross-linking reaction with the latent cross-linking agent to increase the cross-linking density of this hydrophobic PU resin, and further to improve washing resistance and solvent resistance of hydrophobic polyurethane resin to reach a long-term hydrophobic (water-repellent) function.
- The non-fluoro hydrophobic aqueous polyurethane dispersion having long-term water-repellent function of the present invention comply the requirements of energy saving and carbon dioxide reduction and is expected to replace the fluoro-containing water repellent which is going to be eliminated.
- The technical characteristics of the present invention mainly are selecting separately or mix-using a compound comprising alcohols, amines, acids, saturated or unsaturated (double-bonded or epoxidized) aliphatic acids which have reactive aliphatic long chain carbon-carbon bond, for instance, ricinoleic acid, fatty acid ester or oleic acid, or a hydrophobic compound, for instance, polydimethylsiloxane containing alcohol groups, amino groups or oxosilane groups, to react with ployiscyanate as reactive material of hydrophobic polyurethane (PU) resin. In addition, in the material of PU resin, adding compounds containing hydrophilic group (such as COOH) to PU resin. After neutralizing, it would provide a self-emulsified hydrophilic ionic center for PU resin. While adding water to disperse the PU prepolymer, it would form “Self-emulsified Non-fluoro Hydrophobic Aqueous PU dispersion”. Further adding a suitable amount of cross-linking agent (such as TMPTA-AZ or CX-100) to form a stable “single-component cross-linking form” aqueous PU dispersion (its pH value maintaining 8.0 or higher belongs stable emulsion). While drying on application (or while the pH value is less than 7.0), i.e. when the ionic groups (COOH) in PU resin and the reactive functional groups (such as aziridine) of cross-linking (curing) agent under room-temperature and dry condition, it would generate a ring-opening cross-linking reaction to increase the cross-linking density in order to improve washing resistance and solvent resistance. The hydrophobic polyurethane resin has a long lasting hydrophobic (water-repellent) function. In the present specification, it would refer this kind of hydrophobic PU as “single-component cross-linking non-fluoro hydrophobic aqueous PU dispersion”.
- The “single-component cross-linking non-fluoro hydrophobic aqueous PU dispersion” of the present invention has reactive hydrophobic aqueous PU resin, which it can generate interpenetrating polymeric networks (IPN) by self-crosslink reaction to insert between fabric (such as longitudinal yarn and latitudinal yarn), wood, or the fiber of paper and form physical insertion or even chemical bonding under room temperature. The cross-linking reaction of the components of this new invention can carry out under room temperature, and can use a single component or any mixing ratio of aliphatic long chain carbon-carbon bond or PDMS as a hydrophobic PU modified components, especially that the amount of hydrophobic groups requires less amount (5-10%) to reach the water-repellent efficacy.
- The non-fluoro hydrophobic PU dispersion of the present invention is coated on the surface of the fabrics by simple coating method (by a method of scraper, roller, impregnation, spray or screen printing and the like), and dried under room temperature to achieve the cross-linking long-term hydrophobic PU resin coating. The processed fabric maintains 85% of the original water-repellent efficacy after washed (after 50 washing cycles) in the test of static contact angle and dynamic sliding angle of water drops.
- The present invention provides a production method of non-fluoro hydrophobic aqueous dispersion comprising the following steps: selecting a compound comprising alcohols, amines, acids, saturated or unsaturated (double-bonded or epoxidized) aliphatic groups or polydimethylsiloxane (PDMS) comprising alcohol groups, amino groups, oxosilane groups to be reacted with 3-Isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate to obtain a PU prepolymer having NCO terminal group; after neutralizing, adding water to disperse the PU prepolymer to obtain an aqueous PU dispersion; and adding a cross-linking (curing) agent into the aqueous PU dispersion to obtain an ambient temperature self linking aqueous PU dispersion.
- Preferably, the unsaturated aliphatic groups have functional groups of alcohol groups, amino groups, carboxyl groups or double bond.
- Preferably, the average molecular weight of polydimethylsiloxane is 500-3000, and polydimethylsiloxane has reactive functional groups of alcohol groups, amino groups, carboxyl groups, epoxy groups, oxosilane groups or double bond.
- Preferably, the aliphatic containing alcohol group is higher alcohols or diols having carbon numbers from 10 to 30.
- Preferably, the aliphatic containing amino group is the compound having carbon number from 10 to 30.
- Preferably, the aliphatic containing double bond is castor oil, palm oil, soybean oil or epoxidized soybean oil.
- Preferably, the cross-linking agent is poly-aziridine cross-linking agent.
- Preferably, the aqueous polyurethane dispersion which reacts the cross-linking agent comprises aliphatic of aliphatic acids having carbon number from 10 to 30.
- Preferably, the polydimethylsiloxane group of the cross-linked aqueous polyurethane-dispersion is on the main chain or side chain of polyurethane resin.
- The present invention also provides a non-fluoro hydrophobic aqueous polyurethane dispersion, wherein the polyurethane dispersion obtained by the aforementioned production method.
- Preferably, the polyurethane dispersion can be made into single-liquid form.
- The present invention further provides an use of water repellent applied a polyurethane dispersion, wherein the polyurethane dispersion obtained by the aforementioned production method or is the aforementioned polyurethane dispersion.
- Preferably, the polyurethane dispersion is applied on an object which is going to be coated under pH value less than 7 to make the carboxylate reactive functional groups comprised react with a cross-linking agent to generate a ring-opening cross-linking reaction.
- Preferably, the object which is going to be coated has hydroxyl groups, carboxylic acids, epoxy groups or amino groups.
- Preferably, the silane groups comprised in the polyurethane dispersion reacts with hydroxyl groups or amino groups of the object which is going to be coated to form chemical bonding.
- Preferably, the polyurethane dispersion can be coated on a surface of the object which is going to be coated by a method of scraper, roller, impregnation, spray or screen printing and the like.
- By using the non-fluoro hydrophobic aqueous PU resin of the present invention, it can reach the following advantages and efficacy:
- 1. A self-emulsified (having internal ionic groups) aqueous PU dispersion.
- 2. Being non-fluoro (non-toxic aliphatic long chain carbon-carbon bond compounds or polydimethylsiloxane) and hydrophobic.
- 3. The self-linking procedure for energy saving and carbon dioxide reduction which may be self cross-linked (under room-temperature dried or pH value being less than 7.0) provides the functions of washing resistance, solvent resistance and long lasting hydrophobic efficacy.
- 4. PU resin may flexibly adjust the softness and density to provide long lasting hydrophobic (water-repellent) properties.
- 5. Both of hydrophobic molecular chain domain (groups) aliphatic long chain carbon-carbon bond aliphatics (or fatty acids) and polydimethylsiloxane (PDMS) can be used alone and also can be used together (in different ratios) to achieve complementary hydrophobic properties.
-
FIG. 1 displays a SEM micrograph of the fiber treated by aqueous PU dispersion containing aliphatic acids and PDMS which are mixed and reacted (unwashed); -
FIG. 2 displays a EDS of the fiber treated by aqueous PU dispersion containing aliphatic acids and PDMS which are mixed and reacted (unwashed); -
FIG. 3 displays a SEM micrograph of the fiber treated by aqueous PU dispersion containing aliphatic acids and PDMS which are mixed and reacted (after 40 washing cycles); and -
FIG. 4 displays an EDS of the fiber treated by aqueous PU dispersion containing aliphatic acids and PDMS which are mixed and reacted (after 40 washing cycles) (still have silicon on the surface of fiber). - The present invention is described in details by the following embodiments and figures to clarify the production method for non-fluoro
- hydrophobic aqueous PU dispersion and the application of water-repellent treatment thereof
- (1) The Preparation of Isocyanate Terminated Polyurethane (PU) Prepolymer
- Taking 13.4 g of 2,2′-bis(hydroxymethyl) propionic acid (DMPA) and 200 g of polytetramethylene ether glycol (PTMEG-2000) separately and placing them into four-necked reaction tank, and heating to 140° C. to melt DMPA and stirring it with mechanical agitation evenly. Wait for the temperature drop to 50° C., adding 0.1%(w/w) reactive catalyst T-12 and 66.6 g of isophorone diisocyanate (IPDI) and keep reaction temperature below 86° C. with stirring until the reaction is completed (NCO % below the calculated value). After the reaction is completed, processing NCO titration to analyze the degree of reaction, as long as it reaches NCO % is less than 3% and remains at that value for one hour. Further using FT-IR to determine the presence of the NCO peak (near 2267 cm−1) in order to make sure that if the reaction is completed or not. The reaction scheme is as the aforementioned scheme 1.
- (2) The Preparation of “Self-Emulsified Aliphatic Long Chain Carbon-Carbon Bond Containing Aqueous PU Dispersion”
- Selecting polyether polyol (for instance, PPG or PTMEG), polyisocyanate (IPDI) materials, or diol compounds containing hydrophilic functional groups as internal emulsifier (for instance, dimethylol propanic acid, DMPA) and fatty alcohols (aliphatic long chain carbon-carbon bond alcohol compounds). A long chain carbon-carbon bond containing PU prepolymer having isocyanate as terminal groups (with fatty alcohols involved in the reaction). Determine the amount of NCO to confirm that the reaction is completed, and adding triethylamine to neutralize and adding deionized water and chain extender (such as ethylenediamine) to process the steps of chain extension and dispersion, and the self-emulsified aliphatic long chain carbon-carbon bond containing aqueous PU dispersion is obtained. In this aqueous PU dispersion, adding proper quantity cross-linking agent (TMPTA-AZ or CX100) and maintain the pH value of aqueous PU dispersion system greater than 8.0. The stable “self-emulsified aliphatic long chain carbon-carbon bond containing aqueous PU dispersion” is formed. The details of the preparation scheme please refer to the following scheme 2.
- (3) The Preparation of Room-Temperature Cross-Linked “Single-Liquid Non-Fluoro Hydrophobic Aliphatic Acid (Ester)-Contained Aqueous PU Dispersion”
- Selecting polyether polyol (PPG or PTMEG), polyisocyante (IPDI) materials, or diol compounds containing hydrophilic functional groups as internal emulsifier (DMPA) and high carbon-carbon aliphatic acid compounds to process PU resin. A long chain fatty acid containing PU prepolymer having isocyanate as terminal-ended group (with hydroxyl or epoxidized fatty acid involved in the reaction). This aliphatic PU prepolymer having isocyanate (NCO) as terminal-ended group, and adding aliphatic acids (as stearic acid, oleic acid, epoxidized oleic acid or ricinoleic acid) alone or proper ratio separately in PU prepolymer. Then adding triethylamine to neutralize and adding deionized water and chain extender (such as diethylamine) to process the steps of chain extension and dispersion (aliphatic fatty acid becomes soap after neutralization which have emulsified efficacy), and the self-emulsified aliphatic soap-containing aqueous-based PU dispersions is obtained. In this aqueous PU dispersion, adding proper quantity latent cross-linking agent (TMPTA-AZ or CX100) and maintain the pH value of aqueous PU dispersion more than 8.0. The stable “self-emulsified fatty acid-containing aqueous PU dispersion” is formed.
- (4) The Preparation of Room-Temperature Cross-Linked “Single-Liquid Non-Fluoro Hydrophobic Polydimethylsiloxane-Contained Aqueous PU Dispersion”
- Selecting polyether polyol (PPG or PTMEG), polyisocyante (IPDI) materials, or diol compounds containing hydrophilic functional groups as internal emulsifier (DMPA) and polydimethylsiloxane(PDMS)-containing diol are added to process PU resin. The PDMS-containing PU prepolymer having isocyanate as terminal-ended group, and then adding triethylamine to neutralize and adding deionized water and chain extender (such as diethylamine) to process the steps of chain extension and dispersion, and “self-emulsified polydimethylsiloxane-containing aqueous PU dispersion” is obtained. The details of the preparation scheme please refer to the following scheme 3.
- (5) The Room-Temperature Bridge Reaction of “Single-Liquid Non-Fluoro Hydrophobic Aqueous PU Dispersion”
- Regarding the “single-component hydrophobic aqueous PU dispersion” of the present invention, the fatty (alcohol or acid) or polydimethylsiloxane (PDMS)-containing aqueous PU dispersion is introduced carboxylic acid group (COOH) separately. After neutralization and dispersion by adding water under a high speed mechanical mixing, the ionic group (carboxyl groups, COO—) induced is used as internal emulsifier to provide the stability of aqueous PU dispersion. The latent cross-linking agent containing aziridine functional groups (as TMPTA-AZ or CX-100) added into “single-liquid non-fluoro hydrophobic aqueous PU dispersion” would react with carboxyl groups in PU resin to process open-ring cross-linking reaction under room temperature being dried at ambient temperature. It would react with hydrophilic carboxyl groups and form hydrophobic amino ester bonding, and improve the cross-linking density of aqueous PU resin on drying. The water resistance, solvent resistance, mechanical strength and heat stability would be improved accordingly. Due to the aziridine functional groups contained in aqueous PU as a latent cross-linking agent having high pH value, aziridine can present in water dispersion stably. When under low pH value (<7.0), aziridine would process open-ring reaction with carboxylic acid (COOH) in PU resin or process open-ring reaction itself under room temperature without heating or other energy (the radiation of UV). The details of the cross-linking (curing) reaction please refer to the following scheme 4.
- (6) The Treatment of Water-Repellent Coating
- The aqueous PU dispersion containing different amount of polydimethylsiloxane (PDMS) or aliphatic acid or fatty alcohol is coated by a simple method (scraper, roller, impregnation, spray or screen printing and the like) to process the treatment of water-repellent on the surface of fabric. Under the condition of room temperature, the self-curing (cross-linking) reaction is carried out to form PU resin with interpenetrating networks (IPN) structure tightly and anchored between longitudinal yarn and latitudinal yarn of the fabric, so that it improve the durability of water washing of water-repellent resin treated fabric. After the washing test of National Standard AATCC135-2004 to wash it for 40 cycles, it still remains 85% of the original water-repellent efficacy. This kind of water-repellent PU resin requires only small amount (5-15% solid contents) for coating to achieve water-repellent efficacy.
- The present invention is clarified by preferable specific embodiments which are not used to limit the present invention.
- The synthesis and preparation of self-emulsified aliphatic long chain carbon-carbon bond containing aqueous PU dispersions
- Using different polyols of polymer and polyisocyantes materials, diol compounds containing hydrophilic functional groups as internal emulsifier (such as ionic internal emulsifier and non-ionic internal emulsifier) and fatty alcohol of long chain carbon-carbon aliphatic alcohols compounds to process addition polymerization reaction by different formulating method. The aliphatic long chain carbon-carbon PU oligomer and prepolymer used isocyanate as terminal-ended groups are formed. Further neutralization by a tertiary amine deionized water and chain extender to process the steps of chain extension and water dispersion with mechanical agitation. It results in a formation of self-emulsified aliphatic carbon-carbon chain containing aqueous-based PU dispersions.
- The materials which are needed to synthesize self-emulsified aliphatic carbon-carbon chain containing aqueous-based PU dispersions are listed as following:
- The property of polyurethane elastomers is due to the chain structure having flexibility and the structure of minor branching or partial net cross-linking Polyols with better flexibility are polyesters, polyethers, polyether-ester polyols or polyester-amide polyols and the like.
-
- (b) Polyether Polyols (PP): The common polyether polyols are as following: polyethylene glycols, polypropylene glycols, polytetramethylene glycols which have the average molecular weight ranging in 400-4000.
- The most common diisocyante is toluene diisocyanates (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4-methylene diphenyl diisocyanate (MDI) and the like. In aromatic diisocyanates, the main toluene diisocyanates in the market comprise: 80% of 2,4-toluene diisocyanates (TDI) and 20% of 2,6-toluene diisocyanates (TDI). In the 2,4-toluene diisocyanates molecule, the activity of para-(4-) isocyanate functional groups is higher than ortho-(2-,6-) ones by 4 to 5 times. It benefits for producing selective isocyanate prepolymer.
- In addition, in aliphatic diisocyanates, two isocyanate functional groups in isophorone diisocyanate (IPDI) show different activity. Without the influence of catalyst, secondary isocyanate functional groups (2°-NCO) have higher reaction rate than the one of primary isocyanate functional groups (1°-NCO). Surprisingly, after adding minor tin catalyst, secondary isocyanate functional groups (2°-NCO) have higher reaction rate than the one of primary isocyanate functional groups (1°-NCO) by 11 to 15 times, which is a dominant advantage. Using the selective isocyanate functional groups in steps of producing polyurethane prepolymer, it benefits for easy operation in producing procedures and the isocyanate prepolymer generated is valuable.
-
- The aliphatic long chain carbon-carbon bond containing—PU oligomer and prepolymer is obtained from a process of the addition polymerization of polyols, polyisocyanates and ionic center (as an internal emulsifier, DMPA). Then proceed a process of neutralization with trialkylamine (e.g. triethylamine, TEA), and chain-extension with ethylenediamine during water dispersion. The internal ionic center within PU resin that having stable micelles of PU particles formation that suspends in the aqueous PU dispersion. The latent PU cross-linking agent is added into the aqueous dispersion and it results in the formation of stable “cross-linking single-component aliphatic long chain carbon-carbon bond containing aqueous PU dispersion” (its pH value >8.0). The cross-linking reaction takes place during drying process at ambient temperature or the pH value drops below 7.0.
- This cross-linked PU resin owns the physical and chemical properties of water resistance, solvent resistance, mechanical strength and heat stability would be improved in large scale accordingly. By improving the cross-linking density to enhance the polymeric network structure of PU resin. This latent cross-linking agent (such as TMPTA-AZ) could be triggered the ring-opening reaction self-curing by lowering its pH value of resin system. It is a convenient (single component), energy saving (at ambient temperature) cross-linking reaction takes place immediately when the pH value of PU system lowers than 7.0. The common ambient temperature cross-linking agents are listed as following:
- [1] Octanol, C8, [2] 1-Nonanol, C9, [3] 1-Decanol, C10, [4] Undecanol, C11, [5] Dodecanol, C12, [6] 1-Tetradecanol, C14, [7] Cetyl alcohol, C16, [8] Stearyl alcohol, C18, [9] Arachidyl alcohol, C20, [10] Docosanol, C22, [11] Octanosol, C28, [12] Triacontanol, C30, [13] Policosanol, Cn Aliphatic acids
[1] Oleic acid, C18, [2] Ricinoleic acid, C18, [3] 12-Hydroxystearic acid, C18), [4] epoxidized oleic acid, C18 - Taking 13.4 g of 2,2′-bis(hydroxymethyl) propionic acid (DMPA) and 200 g of polytetramethylene ether glycol (PTMEG-2000) separately and placing them into four-necked reaction tank, and heating to 140° C. to melt DMPA and stirring it with mechanical agitation evenly. Wait for the temperature drop to 80° C., adding 0.1%(w/w) catalyst (T-12) and 66.6 g of isophorone diisocyanate (IPDI) and keep reaction temperature below 86° C. with stirring until the reaction is completed (NCO % below the calculated value). After the reaction is completed, processing NCO titration to analyze the degree of reaction, as long as it reaches NCO % is less than 3% and remains at that value for one hour. Further using FT-IR to determine the presence of the NCO peak (near 2267 cm−1) in order to make sure that if the reaction is completed.
- Using isocyanate functional groups having selective diisocyantes (polyisocyantes, IPDI)), triol (glycerol or trimethylolpropane, TMP) and long chain fatty alcohol compounds (fatty alcohol or higher alcohol), by using an excess amount of isocyanates (IPDI), and then adding minor catalyst, dibutyltin dilaurate (DBTDL) to accelerate the reaction being completed. It results in the formation of NCO-terminated aliphatic long chain carbon-carbon bond containing PU oligomer.
- Selecting polyether polyol (e.g., PPG or PTMEG), polyisocyanate (IPDI) materials, or diol compounds containing hydrophilic functional groups as internal emulsifier (for instance, dimethylol propanic acid, DMPA) and fatty alcohols (aliphatic long chain carbon-carbon bond alcohol compounds). A long chain carbon-carbon bond containing PU prepolymer having isocyanate as terminal group (with fatty alcohols involved in the reaction). Determine the amount of NCO to confirm that the reaction is completed, and adding triethylamine to neutralize and adding deionized water with a chain extender (such as diethyleneamine) to process the steps of chain extension and dispersion, and the self-emulsified aliphatic-containing aqueous PU dispersions is obtained. In this aqueous PU dispersion, adding proper quantity latent cross-linking agent (TMPTA-AZ or CX100) and maintain the pH value (>8.0) of aqueous PU dispersion. The stable “single-component cross-linking aliphatic long chain carbon-carbon bond containing aqueous PU dispersion” is formed.
- Taking 180 g of polydimethylsiloxane (PDMS)diol (for instance, KF-6001) and 13.4 g of dimethylol propanic acid (DMPA, an internal ionic center) separately and placing them into four-necked reaction flask, and heating to 140° C. to melt DMPA under vacuum and with constant mechanical agitation for 4 hours. After cooling down to 50° C., then 0.2 g of catalyst (T-12) and 66.6 g of Isophorone diisocyanate (IPDI) are added into PDMS diol with agitation and keep the reaction temperature below 86° C. until the reaction is completed (NCO % below the calculated value). It results in a formation of PDMS-containing PU prepolymer having isocyanate as terminal groups. An aqueous mixture of de-ionized water of neutralizing agent (triethylamine, TEA) and chain-extender (ethylene diamine) is added into this PDMS-prepolymer slowly with agitation and “self-emulsified PDMS-containing aqueous PU dispersion” is obtained.
- The ratio of PDMS containing aqueous PU dispersion with oleic soap (oleic acid amine soap) (PDMS/oleic) with 2/1, 1/1 and 1/2, are selected and mixing separately. Then TMPTA-AZ, a latent cross-linking agent (3 phr) is added into each mixture as latent cross-linking agent. Each becomes “cross-linking PDMS/oleic containing hydridizied PU dispersions”. After drying at ambient temperature, it results in the formation of cross-linked PDMS/oleic containing hybridized PU resin. Both PDMS and oleic acid are chemical bonded with hydrophobic PU resin. The dried cross-linking PDMS/oleic hybridized hydrophobic PU resin is shown as the following scheme 5.
- Mixing PU/oleic acid mixed aqueous dispersion and aqueous PDMS-PU dispersion which are obtained from synthesis reaction by the ratio of 2:1, 1:1 and 1:2, and then adding TMPTA-AZ cross-linking agent. The dried cross-linking scheme is shown as the following scheme 5.
- Following Example 5, diluting the cross-linking PDMS/oleic containing hybridized PU dispersion with de-ionized water to proper concentration (5-10% of solid). Then apply it on the surface of fabric to carry out the hydrophobic treatment. It is cross-linked and forming interpenetrating polymeric network (IPN) structures and anchored into fabric after drying. That improves the bonding strength between treated PU resin and fabric that improve washing durability and solvent resistance of hydrophobic treated fabrics.
- Please refer to Table 1. Shown as the SEM micrographs (
FIG. 1 andFIG. 3 ) and EDS (FIG. 2 andFIG. 4 ), it proves that the treatment on the surface of fabric by the cross-linked PDMS/oleic containing hybridized PU resin of the present invention can maintain over 85% original hydrophobic property (water-repellent efficacy) after 40 washing cycles, furthermore, it is found that there are silicon of PDMS stays on the surface of fabric (EDS). -
TABLE 1 The hydrophobic property of the fiber surface treated by aqueous PU dispersion containing aliphatic acid and PDMS mixed (washed 40 times) PDMS/oleic ratio of hybridized PU resin 2/1 1/1 1/2 Water drop contact angle on 125.0 128.3 135.3 treated fabrics (°) Sliding angle of water drops (°) 18.8 17.8 17.8 on treated fabric surface Time for water drops stay on >60 >60 >60 treated fabrics (min)
To sum up the aforementioned description, the non-fluoro hydrophobic PDMS/oleic containing hybridized PU (polyurethane) resin of the present invention can have long lasting hydrophobic property after 40 washing cycles of treated fabrics. By cross-linking reaction to improve the cross-linking density of hydrophobic PDMS/oleic containing hybridized PU resin of the present invention, it has improved the property of washing durability (resistance) and solvent resistance. Besides, the PU resin of the present invention has no fluoro and the water repellent treatment with less energy requirement which comply with the non-toxic requirements and provision of components used in fabrics in the future to people nowadays. The present invention comparing to prior water repellent which uses fluoro compounds has superior efficacy.
Claims (5)
1. An use of water repellent applied an aqueous polyurethane dispersion, wherein the polyurethane dispersion obtained by the production method comprises the following steps:
selecting a compound comprising alcohols, amines, carboxylic acids, saturated or double-bonded or epoxidized aliphatic groups or polydimethylsiloxane comprising alcohol groups, amino groups, oxosilane to be reacted with polyisocyante to obtain a polyurethane prepolymer having isocynate (NCO) terminal group;
adding a compound having hydrophilic functional groups into the polyurethane prepolymer having isocyanate terminal groups, after neutralizing, adding water to disperse the polyurethane prepolymer to form an aqueous polyurethane dispersion; and
adding a room-temperature cross-linking agent into the aqueous polyurethane dispersion to obtain a self-crosslinked aqueous polyurethane dispersion.
2. The use according to claim 1 , wherein the polyurethane dispersion is applied on an object which is going to be coated under pH value less than 7 to make the carboxylate reactive functional groups comprised react with a cross-linking agent to generate an open ring cross-linking reaction.
3. The use according to claim 2 , wherein the object which is going to be coated has hydroxyl groups, carboxylic acids, epoxy groups or amino groups.
4. The use according to claim 3 , wherein the silane groups comprised in the polyurethane dispersion reacts with hydroxyl groups or amino groups of the object which is going to be coated to form chemical bonding.
5. The use according to claim 4 , wherein the polyurethane dispersion can be coated on a surface of the object which is going to be coated by a method of scraper, roller, impregnation, spray or screen printing and the like.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/739,105 US20150275039A1 (en) | 2013-09-23 | 2015-06-15 | Application of a non-fluoro hydrophobic aqueous-based polyurethane resin dispersion |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW102134071A TWI480299B (en) | 2013-09-23 | 2013-09-23 | Non-fluoro hydrophobic aqueous polyurethane resin dispersion, and production method and use thereof |
US14/144,534 US9688879B2 (en) | 2013-09-23 | 2013-12-30 | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof |
US14/739,105 US20150275039A1 (en) | 2013-09-23 | 2015-06-15 | Application of a non-fluoro hydrophobic aqueous-based polyurethane resin dispersion |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/144,534 Division US9688879B2 (en) | 2013-09-23 | 2013-12-30 | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
US20150275039A1 true US20150275039A1 (en) | 2015-10-01 |
Family
ID=52691181
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/144,534 Active US9688879B2 (en) | 2013-09-23 | 2013-12-30 | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof |
US14/739,078 Abandoned US20150275038A1 (en) | 2013-09-23 | 2015-06-15 | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion |
US14/739,105 Abandoned US20150275039A1 (en) | 2013-09-23 | 2015-06-15 | Application of a non-fluoro hydrophobic aqueous-based polyurethane resin dispersion |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/144,534 Active US9688879B2 (en) | 2013-09-23 | 2013-12-30 | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof |
US14/739,078 Abandoned US20150275038A1 (en) | 2013-09-23 | 2015-06-15 | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion |
Country Status (2)
Country | Link |
---|---|
US (3) | US9688879B2 (en) |
TW (1) | TWI480299B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3263614A1 (en) | 2016-06-30 | 2018-01-03 | Henkel AG & Co. KGaA | Waterborne hybrid polyurethane/polysiloxane dispersions |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI480299B (en) * | 2013-09-23 | 2015-04-11 | Univ Tamkang | Non-fluoro hydrophobic aqueous polyurethane resin dispersion, and production method and use thereof |
US11292920B2 (en) | 2015-06-10 | 2022-04-05 | Ppg Industries Ohio, Inc. | Water repellant surface treatment for aircraft transparencies and methods of treating aircraft transparencies |
WO2017022504A1 (en) | 2015-07-31 | 2017-02-09 | 株式会社村田製作所 | Electronic component and method for producing same |
WO2018052644A1 (en) * | 2016-09-19 | 2018-03-22 | Dow Corning Corporation | Polyurethane-polyorganosiloxane copolymer and method for its preparation |
US11672768B2 (en) * | 2016-09-19 | 2023-06-13 | Dow Silicones Corporation | Skin contact adhesive and methods for its preparation and use |
US20210177726A1 (en) | 2017-02-15 | 2021-06-17 | Dow Silicones Corporation | Personal care compositions including a polyurethane - polyorganosiloxane copolymer |
CN107936216B (en) * | 2017-11-30 | 2021-02-09 | 黎明化工研究设计院有限责任公司 | Organic silicon modified isocyanate prepolymer for solvent-free synthetic leather and preparation method thereof |
US11802204B2 (en) | 2018-08-10 | 2023-10-31 | Board Of Trustees Of Michigan State University | Thermoset omniphobic compositions with improved barrier properties, related articles, and related methods |
TWI694093B (en) * | 2019-01-18 | 2020-05-21 | 福盈科技化學股份有限公司 | Method of preparing polyurethane-acrylic hybrid fluorine-free water repellent and its application |
CN111254719B (en) * | 2020-01-16 | 2022-09-09 | 上海汇得科技股份有限公司 | Fluoride-free water repellent agent for polyurethane synthetic leather and preparation method thereof |
CN111944117A (en) * | 2020-08-28 | 2020-11-17 | 陕西科技大学 | Amino silicone oil modified waterborne polyurethane and preparation method thereof |
CN112280004B (en) * | 2020-10-21 | 2022-01-28 | 江苏海洋大学 | Blocked polyurethane prepolymer and preparation method thereof |
CN112281493A (en) * | 2020-11-16 | 2021-01-29 | 五邑大学 | Fluoride-free waterproof finishing agent and preparation method thereof |
CN113214731A (en) * | 2021-04-26 | 2021-08-06 | 中科院广州化灌工程有限公司 | Durable plant oil-based anti-graffiti easy-to-clean coating and preparation method and application thereof |
CN113087868B (en) * | 2021-05-19 | 2022-09-30 | 上海矽璃材料科技有限公司 | Solvent-free carboxyl organic silicon polyurethane resin copolymer and preparation method thereof |
CN113845683A (en) * | 2021-08-11 | 2021-12-28 | 界首市旭升塑胶制品有限公司 | Automatically cleaning plastic rain shoes with super amphiphobic coating |
CN114133533B (en) * | 2021-12-17 | 2023-08-11 | 广东科鼎功能材料有限公司 | Water-based polyurethane adhesive and preparation method thereof |
CN114751828B (en) * | 2022-04-20 | 2023-08-29 | 江苏恒力化纤股份有限公司 | Hydroxyl-terminated oleate, environment-friendly hydrophobic polyurethane and preparation method and application thereof |
CN115216982B (en) * | 2022-08-15 | 2024-03-08 | 喻盛 | Digital direct spraying method for water-based paint in natural drying baking-free procedure |
CN116836364A (en) * | 2023-07-18 | 2023-10-03 | 佛山市三水嘉得邦化工有限公司 | Preparation process of organosilicon modified aqueous polyurethane adhesive |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5354807A (en) * | 1992-01-24 | 1994-10-11 | H. B. Fuller Licensing & Financing, Inc. | Anionic water dispersed polyurethane polymer for improved coatings and adhesives |
US20060258801A1 (en) * | 2003-09-09 | 2006-11-16 | Emilio Martin | Aqueous polymer compositions |
US20150086713A1 (en) * | 2013-09-23 | 2015-03-26 | Tamkang University | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4301053A (en) * | 1980-01-29 | 1981-11-17 | General Electric Company | Polyurethane resin coating composition |
JP3089623B2 (en) * | 1992-12-25 | 2000-09-18 | 日本ポリウレタン工業株式会社 | Self-emulsifying polyisocyanate composition, aqueous coating composition and aqueous adhesive composition |
TW502043B (en) * | 1999-08-09 | 2002-09-11 | Chinese Petroleum Corp | Process for preparing self-emulsified aqueous epoxy resin dispersion, single-pack double curable aqueous resin composition comprising the same and single-pack curable composition of aqueous hybrid resin comprising the same |
US6613859B2 (en) * | 2001-01-17 | 2003-09-02 | A. Andrew Shores | Silicone and ionically modified urethane oligomer |
DE10216896A1 (en) * | 2002-04-17 | 2003-11-13 | Goldschmidt Ag Th | Aqueous polysiloxane-polyurethane dispersion, its production and use in coating materials |
TW591047B (en) * | 2002-11-19 | 2004-06-11 | Chung Shan Inst Of Science | Process for preparing poly(urea-urethane) |
WO2005005504A1 (en) * | 2003-07-14 | 2005-01-20 | Cytec Surface Specialties, S.A. | Waterbone self-crosslinkable polyurethane dispersions and polyurethane: acrylic hybrid dispersions |
EP1858947B1 (en) * | 2005-03-17 | 2009-12-02 | DSM IP Assets B.V. | Aqueous polyurethane compositions |
US20070066709A1 (en) * | 2005-09-20 | 2007-03-22 | Tamkang University | Manufacturing method for ambient temperature self-curable system of water borne-based polymeric ink |
US7368174B2 (en) * | 2005-12-14 | 2008-05-06 | Lord Corporation | Aqueous dispersion coating composition having noise and/or friction abatement properties |
JP5463612B2 (en) * | 2006-09-28 | 2014-04-09 | 横浜ゴム株式会社 | Urethane emulsion |
TWI362394B (en) * | 2007-02-12 | 2012-04-21 | Univ Tamkang | Preparing method for reactive hydrophilic polyurethane resins and their applications at ambient temperature |
TWI401349B (en) * | 2008-10-14 | 2013-07-11 | Univ Tamkang | Long-lasting water-repellent textile treatment process using crosslinking pdms-containing pu |
US9617453B2 (en) * | 2009-12-14 | 2017-04-11 | Air Products And Chemicals, Inc. | Solvent free aqueous polyurethane dispersions and methods of making and using the same |
NZ606787A (en) * | 2010-10-06 | 2014-11-28 | Novartis Ag | Water-processable silicone-containing prepolymers and uses thereof |
TW201217469A (en) * | 2010-10-28 | 2012-05-01 | Chou Tai Chang | Ambient-temperature self-curable and fluorine containing aqueous-based polyurethane (PU) dispersion and manufacturing method of the same and its coated film applications |
-
2013
- 2013-09-23 TW TW102134071A patent/TWI480299B/en not_active IP Right Cessation
- 2013-12-30 US US14/144,534 patent/US9688879B2/en active Active
-
2015
- 2015-06-15 US US14/739,078 patent/US20150275038A1/en not_active Abandoned
- 2015-06-15 US US14/739,105 patent/US20150275039A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5354807A (en) * | 1992-01-24 | 1994-10-11 | H. B. Fuller Licensing & Financing, Inc. | Anionic water dispersed polyurethane polymer for improved coatings and adhesives |
US20060258801A1 (en) * | 2003-09-09 | 2006-11-16 | Emilio Martin | Aqueous polymer compositions |
US20150086713A1 (en) * | 2013-09-23 | 2015-03-26 | Tamkang University | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3263614A1 (en) | 2016-06-30 | 2018-01-03 | Henkel AG & Co. KGaA | Waterborne hybrid polyurethane/polysiloxane dispersions |
WO2018001654A1 (en) | 2016-06-30 | 2018-01-04 | Henkel Ag & Co. Kgaa | Waterborne hybrid polyurethane/polysiloxane dispersions |
Also Published As
Publication number | Publication date |
---|---|
TWI480299B (en) | 2015-04-11 |
US20150275038A1 (en) | 2015-10-01 |
TW201512236A (en) | 2015-04-01 |
US20150086713A1 (en) | 2015-03-26 |
US9688879B2 (en) | 2017-06-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9688879B2 (en) | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof | |
KR101776539B1 (en) | Leather-like sheet | |
CN102112510B (en) | Anionic polyurethane aqueous dispersions | |
US11976212B2 (en) | Polyols, polyurethane dispersions, and uses thereof | |
JP3972234B2 (en) | Aqueous urethane resin composition for porous formation | |
JP5768043B2 (en) | Polyurethane resin aqueous dispersion, nonporous film, moisture-permeable waterproof fabric, and method for producing the same | |
KR20180018682A (en) | Process for the production of solidification products | |
JP3174371B2 (en) | Water-dispersible, electrolyte-stable polyetherester-modified polyurethane ionomers, their preparation and their use in mixtures with polymers containing perfluoroalkyl groups | |
KR100812635B1 (en) | Dispersion polycarbonate polyurethane resin | |
JP5413703B1 (en) | Urethane resin composition, leather-like sheet and laminate | |
JP3975716B2 (en) | Aqueous resin composition for forming fiber laminate skin layer and artificial leather using the same | |
CN105603758B (en) | A kind of elastic force moving fabric | |
JP4679311B2 (en) | Nonporous membrane-type moisture-permeable and waterproof adhesive composition and method for producing moisture-permeable and waterproof fabric | |
JP2020105445A (en) | Aqueous polyurethane resin, method for manufacturing the same, aqueous polyurethane resin composition and leather material | |
JP4510518B2 (en) | Ultrafine fiber composition and method for producing the same | |
WO2021132657A1 (en) | Moisture-permeable waterproof fabric | |
TWI623596B (en) | Fluorine-free water repellent and its preparation method | |
CN109689718A (en) | Chemically-resistant PUD and method for the non-woven synthetic leather application of microfibre | |
JP5469545B2 (en) | Natural leather products with excellent oleic acid resistance | |
KR100606983B1 (en) | Manufacturing method of ionic polyols containing metal sulfoisophthalate in the main chain and Composition for water-dispersible polyurethane elastomer based on the ionic polyols | |
CN105671968B (en) | A kind of protective fabric | |
JP6877665B1 (en) | Antiviral agent composition and antiviral fabric, antiviral polyurethane sheet and antiviral polyvinyl chloride sheet treated with the composition. | |
JP7009675B1 (en) | Water repellent composition, kit, water repellent fiber product and its manufacturing method | |
JPH0663181B2 (en) | Binder for pigment printing | |
JP2004115941A (en) | Method for treating fiber raw material and base material obtained by the treating method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |