US20170030010A1 - Water repellent, soil resistant, fluorine-free compositions - Google Patents
Water repellent, soil resistant, fluorine-free compositions Download PDFInfo
- Publication number
- US20170030010A1 US20170030010A1 US15/302,905 US201515302905A US2017030010A1 US 20170030010 A1 US20170030010 A1 US 20170030010A1 US 201515302905 A US201515302905 A US 201515302905A US 2017030010 A1 US2017030010 A1 US 2017030010A1
- Authority
- US
- United States
- Prior art keywords
- composition
- fiber protection
- component
- protection composition
- fiber
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 148
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000002689 soil Substances 0.000 title claims abstract description 54
- 239000005871 repellent Substances 0.000 title claims abstract description 22
- 230000002940 repellent Effects 0.000 title claims abstract description 21
- 239000004753 textile Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000000835 fiber Substances 0.000 claims description 81
- -1 volchonskoite Substances 0.000 claims description 57
- 229920006243 acrylic copolymer Polymers 0.000 claims description 24
- 239000002105 nanoparticle Substances 0.000 claims description 21
- 239000007921 spray Substances 0.000 claims description 21
- 238000011282 treatment Methods 0.000 claims description 21
- 239000004927 clay Substances 0.000 claims description 17
- 239000006260 foam Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 229910052898 antigorite Inorganic materials 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052626 biotite Inorganic materials 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052620 chrysotile Inorganic materials 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001649 dickite Inorganic materials 0.000 claims description 3
- OUGJKAQEYOUGKG-UHFFFAOYSA-N ethyl 2-methylidenebutanoate Chemical compound CCOC(=O)C(=C)CC OUGJKAQEYOUGKG-UHFFFAOYSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000271 hectorite Inorganic materials 0.000 claims description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 3
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910000273 nontronite Inorganic materials 0.000 claims description 3
- 229910001737 paragonite Inorganic materials 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 3
- 229910000275 saponite Inorganic materials 0.000 claims description 3
- 229910000276 sauconite Inorganic materials 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 claims description 3
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical group [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 238000007756 gravure coating Methods 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims 2
- 229920002994 synthetic fiber Polymers 0.000 abstract description 5
- 238000009877 rendering Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 30
- 239000000126 substance Substances 0.000 description 27
- 229920001577 copolymer Polymers 0.000 description 20
- 239000004744 fabric Substances 0.000 description 20
- 229940094522 laponite Drugs 0.000 description 20
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 20
- 238000012360 testing method Methods 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 14
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229930195729 fatty acid Natural products 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 150000004665 fatty acids Chemical class 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000000523 sample Substances 0.000 description 11
- 239000012530 fluid Substances 0.000 description 10
- 239000007859 condensation product Substances 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 239000004902 Softening Agent Substances 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000004088 foaming agent Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 241000894007 species Species 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- 241000408710 Hansa Species 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 230000000699 topical effect Effects 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 238000003809 water extraction Methods 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229940057950 sodium laureth sulfate Drugs 0.000 description 3
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- CEZCCHQBSQPRMU-UHFFFAOYSA-L chembl174821 Chemical compound [Na+].[Na+].COC1=CC(S([O-])(=O)=O)=C(C)C=C1N=NC1=C(O)C=CC2=CC(S([O-])(=O)=O)=CC=C12 CEZCCHQBSQPRMU-UHFFFAOYSA-L 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- GWBBVOVXJZATQQ-UHFFFAOYSA-L etidronate disodium Chemical compound [Na+].[Na+].OP(=O)([O-])C(O)(C)P(O)([O-])=O GWBBVOVXJZATQQ-UHFFFAOYSA-L 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229940039717 lanolin Drugs 0.000 description 2
- 235000019388 lanolin Nutrition 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000012192 staining solution Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 206010064063 CHARGE syndrome Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 102100038215 Chromodomain-helicase-DNA-binding protein 7 Human genes 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 240000002989 Euphorbia neriifolia Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920006309 Invista Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 201000009916 Postpartum depression Diseases 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical class [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- GEPGFAGMWQJLTK-UHFFFAOYSA-N hydroxymethyl-bis(2-prop-2-enoyloxyethyl)azanium;methyl sulfate Chemical compound COS([O-])(=O)=O.C=CC(=O)OCC[NH+](CO)CCOC(=O)C=C GEPGFAGMWQJLTK-UHFFFAOYSA-N 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- YDNLNVZZTACNJX-UHFFFAOYSA-N isocyanatomethylbenzene Chemical class O=C=NCC1=CC=CC=C1 YDNLNVZZTACNJX-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical class CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- 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
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- 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
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/08—Processes in which the treating agent is applied in powder or granular form
Definitions
- the present invention pertains to fluorine-free compositions rendering textile articles, such as carpets and other textile floor coverings made from synthetic fibres or natural fibres water repellent, soil resistant and stain resistant.
- the invention pertains additionally to a method for treating textile articles and for treated textile articles being water repellent, soil resistant and stain resistant, especially carpets.
- U.S. Pat. No. 6,824,854 discloses a carpet treated with a soil resistant agent comprising a dispersion of polyfluoro organic compounds having at least one urea, urethane or ester linkage in combination with an anionic surfactant.
- the ratio of polyfluoro compound to surfactant is thereby from about 0.075:1.0 to about 5:1.
- U.S. Pat. No. 4,264,484 relates to a carpet which is soil resistant and stain resistant and which has been treated with a composition comprising a liquid containing a water-insoluble polymer derived from ethylenically unsaturated monomer free of nonvinylic fluorine having one major transition temperature higher than about 25° C. and a water insoluble fluoroaliphatic radical- and aliphatic chlorine-containing ester having a major transition temperature higher than about 25° C.
- EP-A 2 205 688 discloses a method of treating substrates with fluorinated water-soluble (meth)acrylate copolymers which do impart water repellancy, soil resistance and stain resistance to the treated substrates thereby
- EP-A 2 222 734 describes a copolymer and a method for treatment of fibrous substrates with such copolymer to render them soil resistant and to impart minimal water repellency.
- the copolymer is prepared by polymerization of methacrylic acid with certain fluorinated alkylated benzyl isocyanates having straight chain or branched perfluoroalkyl groups.
- EP-A 1 368 525 describes a composition and its use for treating textiles, fibres and fabric substrates, whereby desirable properties like water repellency and durability are enhanced.
- Said composition is a quite complex mixture of various components such as a compound having an epoxy functionality, a compound having an alkoxy functionality, a crosslinking component selected from specific compounds and a catalyst comprising metal salts of mineral acids, e.g. zinc chloride, magnesium chloride, metal soaps and anhydrides.
- a condensation product is formed that is suitable to impart the desired properties to textiles when the compounds having the particular functionalities and the crosslinking component is reacted with the catalyst and cured.
- WO 2013 059387 A1, WO 2013 059395 A1, WO 2013 059400 A1, and WO 2013 059416 A1 describe non-fluorinated soil resist compositions featuring various combinations of surfactant, stain resist, and optional inorganic oxide species.
- the preferred soil resistant species are given as including polymethylmethacrylate, methyl methacrylate/ethyl methacrylate copolymer, an alkali metal salt of a hydrolysed styrene/maleic anhydride copolymer or of a hydrolyzed styrene/maleic anhydride/cumene terpolymer, an ammonium salt of a styrene/maleic anhydride copolymer or of a hydrolyzed styrene/maleic anhydride/cumene terpolymer, amorphous silicon dioxide, colloidal silica, and amorphous silica.
- the related art fails to disclose a carpet or a textile floor covering treated with fluorine-free chemical compositions providing durable soil resistance and water repellency, and a carpet or textile floor covering free of fluorine and having these high quality properties.
- compositions that reliably impart durable surface protection to textile flooring substrates against the detrimental influences of water and soil.
- Such compositions should be easy to manufacture and easy to apply to textiles of synthetic or natural origin, while at the same time imparting a comparable protection as with fluorine containing chemicals as they are currently available on the market.
- reliable water repellency should be provided to carpets and textile floor coverings by treatment with such new compositions.
- the present invention pertains to a fluorine-free fiber protectant Composition X1 comprising:
- Another object of the invention is a fluorine-free fiber protectant Composition X2 comprising components A, B, C and:
- compositions effective under this disclosure are effective and include only B, C and D to yield a third composition, Composition X3. And some compositions include only A and D, to yield a fourth composition, Composition X4.
- Another object of the invention is an article of manufacture, especially a carpet or a textile floor covering, which is treated with the composition as defined hereinbefore by e.g. spray application or foam application, whereby the article is rendered water repellent and soil resistant.
- Another object of the invention is a method for the fluorine-free treatment of textiles or fibres of synthetic or natural origin with a composition as defined herein in an effective amount to render the textiles or fibers water repellent, soil resistant, and soft.
- Another object of the invention is a kit providing one or more of Compositions X1, X2, X3 or X4 in separate containers, that are then be mixed and/or used at a place of carpet manufacture.
- Fluorochemicals are used as topical protectant ingredients in many industrial applications, including carpets and textiles industries. As topical protectants, certain fluorochemicals impart desirable water repellency, oil repellency and soil repellency attributes to substrates as surface coatings.
- certain fluorochemicals such as long chain polymeric perfluorocarbon species, have been shown to be precursors to undesirably bio-persistent species, such as perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonic acids (PFSAs). Examples of long chain polymeric perfluorocarbon species are those having C8, C10 or C10 perfluorinated side chains.
- Water repellency refers to the degree to which a substrate repels water and water/isopropanol mixtures and is determined using a similar method to that for oil repellency.
- compositions in this disclosure are free of fluorine-containing ingredients.
- the compositions X1, X2 and X3 comprise two or more of components A, B, C and D, and the application rates of one or more of X1, X2 or X3 onto the carpet or textile floor covering may be adjusted to achieve maximum water and soil repellency benefit. Such performance benefits are, at the same time, economically advantageous.
- Typical nanoparticulate silicate clays useful in the invention as component A include those described in U.S. Patent Application Publication No. 2011/0311757 to Iverson et al., which is incorporated herein by reference. These nanoparticulate silicate clays can be selected from the group consisting of smectites, kaolins, illites, chlorites, attapulgites, and combinations thereof.
- More specific examples include montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volkonskoite, vermiculite, kaolinite, dickite, antigorite, anauxite, indellite, chrysotile, bravaisite, muscovite, paragonite, biotite, corrensite, penninite, donbassite, sudoite, pennine, sepiolite, palygorskyte, and combinations thereof.
- the nanoparticulate silicate component, A may be natural or synthetic.
- the nanoparticulate silicate component includes synthetic hectorite. Regardless of whether the clay nanoparticle is natural or synthetic, the clay nanoparticle component may be present in an amount from about 0.9 to about 24 volume parts of the combined composition X1. Typically, the clay nanoparticle is present in an amount of about 7 to about 14 parts by volume of the composition X1.
- suitable nanoparticulate silicates are those commercially available from BYK Additives GmbH under the brand name Laponite®. These include Laponite® RID, Laponite® RDS, Laponite® JS, Laponite® SL25, and Laponite® S482.
- Laponite® SL-25 is a basic (pH 8-10), 21.5-25 wt % solids aqueous dispersion.
- the nanoparticulate silicate found in Laponite® SL25 has an average particle size of from about 20 nm to about 90 nm, and a surface area of from about 120 m 2 /g to about 500 m 2 /g;
- Typical acrylic polymer components for use in the present disclosure as component B include those anionic or non-ionic, fluorine-free, water-dispersed acrylics that are known to act as binding agents, wherein the mixture including the acrylic copolymer binding agent (“binder”) forms a transparent or largely transparent coating.
- the acrylic copolymer binder is self-crosslinking.
- the water-based non-fluorinated acrylic copolymer provides a certain degree of durable water repellency to the treated carpets and fibers.
- Binding agents useful according to this disclosure include any non-fluorinated emulsifiable acrylic polymer or copolymer suitable for use as a coating ingredient for soft surfaces, such as textiles, yarn, fabric, carpets, rugs, mats, or hard surfaces, such as vinyl tile, stone masonry, ceramic tile, and hardwood flooring. Many examples of such acrylic co-polymers can be utilized as component B in the compositions described by this disclosure.
- Acrylic-based copolymers having at least one of acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylate, methyl ethacrylate, ethyl ethacrylate, propyl ethacrylate, butyl ethacrylate, acrylic acid, and ethylene monomers, and combinations and blends thereof, are suitable candidates for use according to this disclosure.
- the acrylic-based copolymers can be non-ionic, or anionic, but the preferred acrylic-based copolymers in this disclosure have a net anionic charge association. Further, preferred components are those anionic acrylic-based copolymers that are self-crosslinking, and can thus crosslink by application of thermal and/or photoinitiated stimuli. Numerous non-fluorinated, emulsified acrylic copolymers suitable as component B are commercially available, such as the self-crosslinking families of RHOPLEXTM and PRIMALTM emulsions, manufactured by Rohm and Haas Company.
- PRIMALTM ECO-36 (Rohm and Haas), which is an anionic, self-crosslinking acrylic based copolymer that can be applied on a substrate as a 46.5-47.5 wt % solids aqueous emulsion.
- PRIMALTM ECO-16 self-crosslinking, non-ionic, methyl methacrylate—ethyl acrylate copolymer
- PRIMALTM ECO-8 self-crosslinking, nonionic
- MMA/EA copolymers corresponding polymer products from other manufacturers may also be used.
- Another possible water-based acrylic copolymer may be ethylene acrylic acid copolymer (EAA). These dispersion polymers are also known under various tradenames. For example TECSEAL E-799/45 (Trub Emulsions Chemie), an ethylene-acrylic acid dispersion (solids content 45%, Tg 4° C.), may be used. Still another possible water-based acrylic copolymer class may be styrene-acrylic copolymers.
- Acrylic copolymers of different types with differing mechanical properties may be blended with each other to achieve the desired final properties of the treated fiber.
- the advantages of the acrylic copolymers can be summarized as
- Typical textile softening agents for use in the present disclosure as component D include those that are known to act as textile softening agents, wherein the mixture including the textile softening agent provides a smoother handle to the textile.
- Textile softening agents can act to improve the sewability of threads, or the softness or more pleasing tactile sensation of carpets and knitted fabrics.
- Textile softening agents can act to enhance lubricity when used to treat yarns, fabrics, textiles, carpets, and the like. Suitable examples of such agents are described by Rudat in U.S. Patent Appl. No.
- 2008 0287020 as being aminosilicones or aminosiloxanes, oils of various types, polyalkylene glycols, polyalkylene waxes, partially-oxidized polyalkylene waxes, lanolin and lanolin derivatives, fatty acids, fatty acid esters, oxidized or functionalized polyolefins, and stearates. Rudat describes the use of aminosiloxanes as efficacious when combined with fluorochemicals and silsesquioxane-containing sols.
- U.S. Patent Appl. No. 2008 0287020 is incorporated herein by reference.
- Polysiloxane compounds such as amino functional polydimethylsiloxane; fatty acid condensation products, such as condensation products of hydrated tallow with 2-[2-aminoethyl)-amino]ethanol; and acetate salt (CAS No. 68425-52-5) or acryl compounds such as bis [acryloxyethyl]-hydroxymethyl ammonium methyl sulfate (CAS No. 93334-15-7) are suitable in principle as softeners.
- a softener from the above mentioned compounds or a mixture of them can be included in the composition according to the invention. Suitable softeners have been described previously by Baumann in EP 1,746,199 B1.
- Such textile and carpeting softeners are commercially available, and examples of suitable products are Finistrol® AFN (fatty acid condensation product) of Thor, Speyer, Germany, and Megasoft® JET-LF of Huntsman Textile Effects, Langweid am Lech, Germany; Perrustol® CCA 500 (fatty acid condensation product) of Rudolf GmbH & Co. KG, Geretsried, Germany; Raniesoft® TS 20 (fatty acid condensation product) of Ranie Chemie, Wiehl, Germany; Softycon N (fatty acid condensation product) Textilcolor AG, Sevelen, Switzerland; Tubingal® OHS of CHT R.
- Finistrol® AFN fatty acid condensation product
- Thor Speyer, Germany
- Megasoft® JET-LF Huntsman Textile Effects, Langweid am Lech, Germany
- Perrustol® CCA 500 fatty acid condensation product
- Raniesoft® TS 20 fatty acid condensation product of Ranie Chemie, Wiehl, Germany
- Softycon N
- the fiber treatment compositions disclosed herein are improvements over PFCA and PFSA fiber treatment technology.
- the aqueous compositions can be utilized directly, only with the addition of water of dilution. Further, the application process is environmentally friendly, resulting only in release of water vapor and negligent amounts of nonhazardous cosolvent vapors (dispersion aids) when the substrate is dried.
- Nanoparticles as a general class of chemical molecules, are known to extend the soiling protection properties provided by fluorine containing chemicals. As disclosed in U.S. patent application No. 2011/0311757 A1, herein incorporated by reference, nanoparticle treatments have been used previously as a fluorine extender for anti-soiling purposes.
- WO2013/116486 herein incorporated by reference, teaches nanoparticles shown to have anti-soiling properties when used in conjunction with non-fluorinated chemicals having water repellent properties. The nanoparticles disclosed in WO2013/116486 demonstrate efficacy of non-fluorochemical treatments to produce a softer hand fiber, while retaining desirable soil-resistant attributes.
- a soil repellent fiber comprising a fluorine-free surface treatment comprising at least one clay nanoparticle component and at least one acrylic copolymer component.
- the clay nanoparticle can refer to particles substantially comprising minerals of the following geological classes: smectites, kaolins, chlorites, and attapulgites.
- These classes include specific clays such as montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volchonskoite, vermiculite, kaolinite, dickite, antigorite, anauxite, indellite, chrysotile, bravaisite, suscovite, paragonite, biotite, corrensite, penninite, donbassite, sudoite, pennine, sepiolite, and polygorskyte.
- specific clays such as montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volchonskoite, vermiculite, kaolinite, dickite, antigorite, anauxite, indellite, chrysotile, bravaisite, suscovit
- the clay nanoparticles can be either synthetic or natural, including synthetic hectorite, and Laponite® from BYK Additive GmbH, Moosburg/Germany.
- the Laponite® clay nanoparticles can be Laponite® RD, Laponite® RDS, Laponite® JS, Laponite® S482 and Laponite® SL25.
- the concentrates according to the disclosure typically contain stabilizing additives.
- Preferred concentrates according to the disclosure cany contain surfactant or emulsifier species.
- surfactants suitable for the present disclosure are any of the anionic or non-ionic surfactants commonly used in formulating chemicals, such as triethanolamine, water-soluble salts of alkylbenzene sulfonates such as the isopropylamine salt of a C 14 -alkyl benzene sulfonic acid, and/or a C 14 fatty alcohol sulfate, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alpha-olefin sulfonates and sulfosuccinates, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alky
- non-surfactant emulsifier species are diethylene glycol monobutyl ether (butyl diglycol) and ethylene glycol monohexyl ether (hexyl glycol). Glycols and glycol ethers are particularly preferred emulsifiers.
- the preferred emulsifiers ensure the textile softening constituents are kept as a finely divided emulsion in water.
- the choice of non-ionic emulsifiers is advantageous as they act to inhibit unwanted foaming during application, and they contribute to uniform treatment on the substrate surface. Should foaming be desired for application, a foaming agent can be provided.
- Other stabilizing additives include peptizing agents.
- Peptizing agents improve dispersability of nanoparticulates in a dispersion medium such as water.
- examples of peptizing agents suitable for this disclosure are disodium etidronate, sodium carbonates, sodium metaphosphates, sodium polyacrylates, and sodium hydroxide.
- Disodium etidronate is an especially preferred peptizing agent.
- compositions X1, X2, X3 or X4 as fiber, yarn, fabric, textile and carpet treatments for durable water repellency and soiling protection.
- topical application of composition X1 in an amount from about 500 ppm to about 5,000 ppm nanoparticulate silicate can result in the desired end use performance of durable water repellency and soil resistance.
- Compositions X3 and X4 can be applied simultaneously and can also result in the desired end use performance of durable water repellency and soil resistance. This is a significant discovery because it eliminates the need for additional economic costs, processing steps and equipment and environmental concerns involved with the use of fiourochemicals or other water repellant technologies, such as microcrystalline waxes.
- Topical compositions X1, X2, X3 and X4 can be applied by many different methods, such as gravure coating, silk screen printing, roll coating, size press coating, spray bar application, rotary spray applicator, bath application, or foam wet processing methods.
- the compositions can be diluted prior to application. Suitable dilutents include those known in the art.
- the diluent is water.
- the acidity of the formulation may be adjusted.
- the pH may be adjusted to be between 5 and 10. In another nonlimiting embodiment, the pH may be adjusted to be between 5.5 and 6.5.
- the topical compositions X1, X2, X3, and X4 that on drying and evaporation of the water, form a coating on the substrate.
- Suitable substrates may be textile, yarn, fiber, fabric or carpeting. Examples of preferred methods of application in this disclosure are spray bar application and rotary spray applicator.
- Rotary applicator systems such the WEKO-FLOW with WEKO-SIGMA liquid application system, manufactured by Weitmann & Konrad GmbH & Co. KG of Leinfelden-Echterdingen, Germany are suitable.
- rotary applicator systems such as The Wave and The IQ Spray Application Systems, manufactured by Consultex Systems of Spartanburg, S.C., USA are suitable for application of compositions of this disclosure.
- Spray bar applicator systems, or spray manifold systems, are well known in the trade, and any such system is suitable for applying the compositions described herein.
- wt. % active solids the approximate amount, in terms of weight percent, of the active component in the formulated material.
- Formulated it is meant that, for example, one or more of the active components A, B, or C, are provided as complex water-borne mixtures, in combination with such chemical adjuncts as surfactants, co-solvents, emulsifying agents, peptizing agents, or dispersing agents, for example.
- the anionic acrylic-based copolymer, B can therefore be provided as a water-borne formulation having certain adjuncts present, and, separately, the textile softening agent, C, can be provided as a water-borne product having certain adjuncts present, and in this form B and C can, for example, be combined and mixed with A and D.
- Nanoparticulate A multidimensional particle in which one of its dimensions is less than 100 nm in length.
- owf “on weight of fiber.”
- the amount of solids of fiber protectant applied after evaporation of solvent.
- the value of solids applied owf is typically expressed as a percentage of the mass of fiber present in the article.
- fluid ppv parts per volume of a formulated (fluid-based) composition component.
- Soil repellency and dry soil resistance Terms used herein interchangeably to describe the ability to prevent dry soils from sticking to a fiber.
- the dry soil may be dirt tracked in by foot traffic.
- tpi twists per inch.
- WPU Weight Pick-up
- compositions X1, X2, X3 and X4 which are suitable for the present invention:
- composition X1 Composition X1:
- composition X1 Exemplary ranges for ingredients in Composition X1.
- the parts per volume refer to ranges of approx. wt. %, active component Identifier ingredient fluid ppv A Laponitee ® SL25 21.5-25 4-96 B Primal TM ECO-36 46.5-47.5 3-50 C Water, any balance auxiliary stabilizers Total 100
- active component Identifier ingredient fluid ppv A Laponitee ® SL25 21.5-25 4-96 B Primal TM ECO-36 46.5-47.5 3-50 C Water, any balance auxiliary stabilizers Total 100
- component Identifier fluid ppv A Laponite ® SL25 75 B Primal TM ECO-36 20 C Water, any 5 auxiliary stabilizers Total 100
- composition X2 Composition X2:
- component Identifier active ingredient fluid ppv A Laponite ® SL25 21.5-25 4-90 B Primal TM ECO-36 46.5-47.5 3-40 D Tubingal OHS 37 2-30 C Water, any balance auxiliary stabilizers Total 100
- component Identifier fluid ppv A Laponite ® SL25 80.0 B Primal TM ECO-36 10.0 D Tubingal OHS 5.0 C Water, any balance auxiliary stabilizers Total 100
- composition X3 is a composition having the following properties:
- composition X4
- Soil repellency refers to the ability of a fibrous substrate to resist the adhesion of dry soils.
- the tests performed to evaluate soiling performance levels generally involve applying standardized, non-liquid-containing dry soil compositions to a fibrous substrate, and further subjecting the substrate to a moving load to simulate wear or trafficking.
- the soiled substrate is subsequently subjected to a controlled soil removal process, such as by vacuum cleaner. These tests may also involve water extraction.
- the substrate is then compared to a control sample, or a standard of established value.
- Composition X1 is the combination of A, B, and C at a range of incorporation indicated in Table 1.
- a suitable range of application of X1 onto an area of carpet fiber substrate is 0.1%-8% owf.
- Application of X1 at less than 0.1% owf is ineffective for durable soil and water repellency, and application of X1 at greater than 8% owf is understood to understood to not be economical under current market conditions, or practical as would be considered using the preferred methods of application in industry.
- a more preferable range of application of X1 on a fiber substrate such as carpet is 0.3%-2.5% owf.
- Composition X2 is the combination of all four of A, B, C, and D, at a range of incorporation indicated in Table 2.
- a suitable range of application of X2 onto an area of carpet fiber substrate is 0.1%-8% owf.
- a more preferable range of application of X2 on a fiber substrate such as carpet is 0.4%-2.5% owf.
- Composition X3 is the combination of B, C, and D at a range of incorporation indicated in Table 3.
- a suitable range of application of X3 onto an area of carpet fiber substrate is 0.1%-6% owf.
- Application of X3 at less than 0.1% owf is ineffective for softness improvement, and application of X3 at greater than 6% owf is understood to have a detrimental effect on the soil resistance of the substrate.
- a more preferable range of application of X3 on a fiber substrate such as carpet is 0.3%-2.0% owf.
- Composition X4 is the combination of A, and C at a range of incorporation indicated in Table 4.
- a suitable range of application of X4 onto an area of carpet fiber substrate is 0.1%-8% owf.
- Application of X4 at less than 0.3% owf is ineffective for soil resistance, while application of X4 at greater than 8% owf is understood to not be economical under current market conditions, or practical as would be considered using the preferred methods of application in industry.
- a more preferable range of application of X4 on a fiber substrate such as carpet is 0.5%-4.0% owf.
- Compositions X1, X2, X3, or X4 are prepared by one or more of mixing, agitating, sonicating, or physically blending the individual chemistries A, B, D, in their requisite proportions, in diluent C.
- compositions X1, X2, X3, or X4 are prepared by taking each of A, B, D, and dispersing, emulsifying, sonicating, dissolving, or agitating each in diluent C, prior to combining the components by one or more of: mixing, agitating, sonicating, or physically blending the individual chemistries A, B, D, in their requisite proportions, in diluent C.
- a Composition X1 is applied to yarns, fibers, textiles, fabrics or carpets.
- the disclosed nanoparticle clays, A, acrylic-based copolymers, B, and aqueous diluent, C, are combined, in one pot, to yield a composition, X1, that is a surprisingly stable complex liquid mixture and is effective for durable water and soil repellency for fibers.
- Composition X1 is thereafter suitable for transport to a manufacturing facility, where it can optionally be diluted with water, then applied onto yarns, fibers, textiles, fabrics or carpets.
- a Composition X2 is applied to yarns, fibers, textiles, fabrics or carpets.
- the disclosed nanoparticle clays, A, acrylic-based copolymers, B, aqueous diluent, C, and textile softening agents, D, are combined, in one pot, to yield a composition, X2, that is a surprisingly stable complex liquid mixture and is effective for durable water and soil repellency for fibers, with additional softness benefit.
- Composition X2 is thereafter suitable for transport to a manufacturing facility, where it can optionally be diluted with water, then applied onto yarns, fibers, textiles, fabrics or carpets.
- compositions X1, X2, X3 and X4 are sequentially applied to yarns, fibers, textiles, fabrics or carpets.
- compositions X1, X2, X3 and X4 are applied simultaneously to yarns, fibers, textiles, fabrics or carpets.
- compositions X1, X2, X3, and X4 of the present disclosure find particular utility in systems that apply liquids under low- or no-foam conditions.
- Application methods wherein no- or low-foam compositions are desired include spray bar and rotary spray liquid applicator methods.
- any foaming agent used in the trade is suitable to add in order may be employed for applying to apply one or more of a Composition X1, X2, X3 or X4 as a foam.
- foaming agents suitable for use include, but are not limited to alkyl amine oxides, for example Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland), C 12 to C 18 coconut fatty acid alkyl dimethyl amine oxides, available from Clariant, sodium alpha olefin sulphonates (e.g. Hansanyl® OS, Hansa Group AG, Germany) and sodium laureth sulfate (e.g.
- foaming agents suitable for use include, but are not limited to alkyl amine oxides, for example Laviron 118 SK (Puicra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland), C 12 to C 18 coconut fatty acid alkyl dimethyl amine oxides, available from Clariant, sodium alpha olefin sulphonates (e.g. Hansanyl® OS, Hansa Group AG, Germany) and sodium laureth sulfate (e.g. Hansanol® NS 242 conc, Hansa Group AG, Germany).
- alkyl amine oxides for example Laviron 118 SK (Puicra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland)
- C 12 to C 18 coconut fatty acid alkyl dimethyl amine oxides available from Clariant
- sodium alpha olefin sulphonates e.g. Hansanyl® OS, Hansa Group AG, Germany
- compositions X1, X2, X3 and X4 are transported to manufacturers, diluted accordingly, and applied individually to yarns, fibers, textiles, fabrics or carpets.
- the acidity of Compositions X1, X2, X3, or X4 is adjusted to be between pH 5.0 and pH 10, prior to application to yarns, fibers, textiles, fabrics or carpets.
- a preferable pH is between pH 5.5 and pH 6.5.
- compositions X1, X2, X3 and X4 are transported to manufacturers together as a kit, or chemical package. In this aspect they are diluted accordingly, and then co-applied to yarns, fibers, textiles, fabrics or carpets.
- compositions X1, X2, X3 and X4 are transported to manufacturers together as a kit, or chemical package. In this aspect they are combined at the manufacturing site, diluted accordingly, and the resulting liquor is applied onto yarns, fibers, textiles, fabrics or carpets.
- the fluorine-free fiber protection compositions included herein may additionally contain one or more stain-block chemistries, in order to combine soil protection and water repellency with suitable stain protection. If a stain-blocker is used, it is preferred to also add a dispersing agent in order to support better application of the composition in aqueous form.
- Anti-stain components for use in the disclosed stain blocker compositions have a component bearing an acidic moiety which associates with polymer amine end groups and protects them from staining by acidic dye stains.
- the general category of chemicals suitable to the process of the instant invention can comprise any chemical that blocks positively charged dye sites.
- Stain blockers are available in various forms such as syntans, sulfonated novolacs, sulfonated aromatic aldehyde condensation products (SACs) and/or reaction phenolics, olefins, products of formaldehyde, phenolics, substituted thiophenolics, sulfones, substituted sulfones, polymers or copolymers of branched olefins, cyclic olefins, sulfonated olefins, acrylates, methacrylates, maleic dianyhydride, and organosulfonic acids.
- SACs sulfonated aromatic aldehyde condensation products
- the stain blocker is typically water soluble and generally penetrates the fiber while the anti-soil, usually a fluorochemical, is a non-water soluble dispersion that coats the surface of fiber.
- stain blockers include, but are not limited to: phenol formaldehyde polymers or copolymers such as CEASESTAIN and STAINAWAY (from American Emulsions Company, Inc., Dalton, Ga.), MESITOL (from Bayer Corporation, Rock Hill, N.C.), ERIONAL (from Ciba Corporation, Greensboro, N.C.), INTRATEX (from Crompton & Knowles Colors, Inc., Charlotte, N.C.), STAINKLEER (from Dyetech, Inc., Dalton, Ga.), LANOSTAIN (from Lenmar Chemical Corporation, Dalton, Ga.), and SR-300, SR-400, and SR-500 (from E. I.
- SCOTCHGARD FX series carpet protectors from 3M Company, St. Paul, Minn.
- sulfonated fatty acids from Rockland React-Rite, Inc., Rockmart, Ga.
- ARROSHIELDTM stain resist product line ArrowStar LLC, Dalton, Ga., U.S.
- I-Protect® 2126 IVISTA S. a
- Stain-blockers are usually ionic in nature and can be equally well applied in both discontinuous and continuous application in the carpet manufacturing process. In the continuous application, the carpet runs through the usual dyeing and printing stages, whereas in the discontinuous application various separate baths are used.
- the procedure to apply the stain-blocker to the textile can be in two steps or in a single application step.
- the stain-blocker application is followed by a treatment with one or more of X1, X2 or X3.
- stain-block chemistry is applied and one or more of X1, X2 or X3 are applied simultaneously, using foam application process technology such as is practiced in the trade.
- a dosage rate of 3.0 to 7.0% aqueous liquor on weight of fiber is recommended for the stain blocker.
- a separate treatment bath for the stain-blocking is used after the carpet dyeing process.
- the carpet is treated for a time period of from 20 to 30 minutes at a temperature of from 70 to 75° C.
- the pH-value depends on the type of stain-blocker and should be held between 2.5 and 7.0.
- the carpet runs through the usual dyeing and printing stages.
- the stain-blocker is applied through a suitable application mechanism such as a dip trough, waterfall applicator or fluidyer.
- the stain block liquor should be applied at or around 60° C. ⁇ 10° C., although the process will also work at colder temperatures.
- the stain-blocker is fixed in the steamer with a steaming time of 60 to 90 seconds.
- the carpet is then washed, vacuumed and dried.
- a soil resistant and water repellent application with one or more of components X1, X2, or X3 follows the stain-blocker, in the same process.
- Suitable dispersing agents for this purpose include, but are not limited to, fatty alcohol polyglycolethers (e.g. Sera® Sperse M-DEW; DyStar Textilmaschine GmbH & Co.) and alkyl aryl aminethoxylate (e.g. Avolan® IW liquid, Tanatex® Chemicals, The Netherlands), both of which are nonionic in nature.
- fatty alcohol polyglycolethers e.g. Sera® Sperse M-DEW; DyStar Textilmaschine GmbH & Co.
- alkyl aryl aminethoxylate e.g. Avolan® IW liquid, Tanatex® Chemicals, The Netherlands
- the textile fibers for the substrate, the carpet or the floor covering which is subjected to treatment with the compositions of the invention is of synthetic or natural origin.
- Suitable synthetic textiles are made from polymer bases such as polyamide like polyamide 6.6, which is known as poly(hexamethylene adipamide), or polyamide 6, which is known as poly(caprolactam), or polyesters like poly(ethylene terephthalate) and poly(propylene terephthalate), or poly(propylene), or mixtures or blends of one or more of such suitable polymer bases.
- Suitable textiles of natural origin are fibres made from wool or cotton.
- Soil resistant and water repellent chemicals are usually applied as the last step in carpet finishing, after application of stain resist chemistry, and prior to drying or backing. Soil resistant and water repellent chemicals may be applied to the carpet via spray application or foam application, which is known in the art. Following dilution of as-received formulated products, industry-recommended rates for application are from 1.0 wt % to 1.6 wt % on weight of carpet fiber (corresponding to 500 ppm to 800 ppm elemental fluorine content). However, application ranges for the fluorine-free fiber protection compositions useful for purpose of this disclosure are usually from 0.25 to 3.5 wt %.
- Spray application is the easiest method of applying soil resistant and water repellent chemicals.
- a spray facility may be installed in front of a dryer after coloration or in front of a latex backing oven.
- a suction hood should be installed above the spray bar.
- An aqueous solution of the composition is pumped through spray nozzles, installed above the running carpet, onto the carpet pile. For better distribution/penetration into the pile the solution should be applied to moistened carpet fiber.
- an aqueous liquor of the composition is pumped into a tank where it is metered for application by a spinning rotary plate. The rotary plate acts to apply microscopic droplets of the aqueous composition in uniform fashion onto the moving fiber, yarn, fabric, textile or carpet substrate.
- Foam application is the most advanced method for the treatment of carpets with soil resistant and water repellent chemicals. By using this minimum moisture application system, highly concentrated liquors in a foam state are applied to carpets running past. A further advantage of the foam application method is its improved penetration. Foam application facilities can be installed in front of a dryer or a latex backing oven. In case of insufficient foam stability a foaming agent can be added advantageously. These foaming agents are formulated in such a way that they decompose under common drying temperatures and do not negatively impact the performance of the soil resistant and water repellent chemicals.
- Suitable foaming agents include, but are not limited to alkyl amine oxides, for example Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland), C 12 to C 18 coconut fatty acid alkyl dimethyl amine oxides, available from Clariant, sodium alpha olefin sulphonates (e.g. Hansanyl® OS, Hansa Group AG, Germany) and sodium laureth sulfate (e.g. Hansanol® NS 242 conc, Hansa Group AG, Germany).
- alkyl amine oxides for example Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland)
- C 12 to C 18 coconut fatty acid alkyl dimethyl amine oxides available from Clariant
- sodium alpha olefin sulphonates e.g. Hansanyl® OS, Hansa Group AG, Germany
- sodium laureth sulfate
- carpet samples are mounted on the interior of a drum, and chrome alloy steel balls, nylon polymer pellets, and a standard dry soil are added.
- the soil used is AATCC 122/123 standard soil:
- the test simulates initial soiling by dirty shoe soles (represented by the polymer pellets) in that the soil acts on both the carpet, and on the polymer pellets. 1.000 revolutions in a drum.
- This test determines a finished carpet's resistance to wetting by aqueous liquids. Drops of water-alcohol mixtures of varying surface tensions are placed on the fabric and the extent of surface wetting is determined visually. If after 10 seconds, four out of the five drops are still visible as spherical to hemispherical, the carpet is given a passing rating and the test is repeated with a higher rating number liquid.
- the repellency rating of the sample is the highest rating number liquid used to pass the repellency test. Carpets with a rating of 4 or higher have good anti-soiling properties. Without anti-soil treatment, most nylon carpets have a rating of 1 for water repellency.
- Acid dye stain resistance is evaluated using a procedure modified from the American Association of Textile Chemists and Colorists (AATCC) Method 175-2003, “Stain Resistance: Pile Floor Coverings.” 9 wt % of aqueous staining solution is prepared, according to the manufacturer's directions, by mixing cherry-flavored KOOL-AID® powder (Kraft/General Foods, White Plains, N.Y., a powdered drink mix containing, inter alia, FD&C Red No. 40). A carpet sample (4 ⁇ 6-inch) is placed on a flat non-absorbent surface. A hollow plastic 2-inch (5.1 cm) diameter cup is placed tightly over the carpet sample.
- AATCC American Association of Textile Chemists and Colorists
- KOOL-AID® staining solution Twenty ml of the KOOL-AID® staining solution is poured into the cup and the solution is allowed to absorb completely into the carpet sample. The cup is removed and the stained carpet sample is allowed to sit undisturbed for 24 hours. Following incubation, the stained sample is rinsed thoroughly under cold tap water, excess water is removed by centrifugation, and the sample is dried in air. The carpet sample was visually inspected and rated for staining according to the FD&C Red No. 40 Stain Scale described in AATCC Method 175-2003. Stain resistance is measured using a 1-10 scale. An undetectable test staining is accorded a value of 10.
- the carpet test sample is not pre-cleaned and is placed flat on a smooth, horizontal surface.
- the cleaning solution is added into the tank of the spray-extraction unit, whereas cleaning is accomplished by moving the cleaning head over the carpet's surface.
- Samples are cleaned over a maximum time period of 2 minutes or until the stain is completely removed (less than 2 min).
- Example 1 was performed to demonstrate the soiling performance and water repellency of a Composition X2.
- the application liquor was applied manually in the lab using a hand-held spray device to a standard velour carpet dyed “baby blue” made from nylon 6,6, and having a fibre weight of 600 g/m 2 .
- the chemical application was followed by a curing process in a laboratory oven at 130° C. for about 15 minutes. As can be seen in Table 5 the combination exceeds/meets the test requirements.
- Example 2 was performed to demonstrate the soiling performance and water repellency of a carpet treated by co-application of a Composition X3 and X4.
- the application liquor was applied using a WEKO application system onto a carpet tile, light grey in colour and having pile weight 400 g/m 2 , followed by a curing process in an oven at 130° C. for about 8 minutes. As can be seen in Table 6, the treatment exceeds/meets the test requirements.
- Example 3a ISO WR 2.0% X2 original sample 3.25 2-3 After 1 cycle HWE 3.25 2
- Example 3b ISO WR 0.35% X3, original sample 3 2 2.0% X4 After 1 cycle HWE 3 2
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Paints Or Removers (AREA)
Abstract
Description
- The present invention pertains to fluorine-free compositions rendering textile articles, such as carpets and other textile floor coverings made from synthetic fibres or natural fibres water repellent, soil resistant and stain resistant. The invention pertains additionally to a method for treating textile articles and for treated textile articles being water repellent, soil resistant and stain resistant, especially carpets.
- Generally, it was known to use fluorine containing chemicals and compositions to impart a variety of valuable properties to textile fibres of synthetic or natural origin, especially to protect carpets and other textile floor coverings from wetting and soiling.
- U.S. Pat. No. 6,824,854 discloses a carpet treated with a soil resistant agent comprising a dispersion of polyfluoro organic compounds having at least one urea, urethane or ester linkage in combination with an anionic surfactant. The ratio of polyfluoro compound to surfactant is thereby from about 0.075:1.0 to about 5:1.
- U.S. Pat. No. 4,264,484 relates to a carpet which is soil resistant and stain resistant and which has been treated with a composition comprising a liquid containing a water-insoluble polymer derived from ethylenically unsaturated monomer free of nonvinylic fluorine having one major transition temperature higher than about 25° C. and a water insoluble fluoroaliphatic radical- and aliphatic chlorine-containing ester having a major transition temperature higher than about 25° C.
- EP-A 2 205 688 discloses a method of treating substrates with fluorinated water-soluble (meth)acrylate copolymers which do impart water repellancy, soil resistance and stain resistance to the treated substrates thereby
- EP-A 2 222 734 describes a copolymer and a method for treatment of fibrous substrates with such copolymer to render them soil resistant and to impart minimal water repellency. The copolymer is prepared by polymerization of methacrylic acid with certain fluorinated alkylated benzyl isocyanates having straight chain or branched perfluoroalkyl groups.
- It has also been known, to impart fluorine-free water repellency to textiles and fabrics.
- EP-A 1 368 525 describes a composition and its use for treating textiles, fibres and fabric substrates, whereby desirable properties like water repellency and durability are enhanced. Said composition is a quite complex mixture of various components such as a compound having an epoxy functionality, a compound having an alkoxy functionality, a crosslinking component selected from specific compounds and a catalyst comprising metal salts of mineral acids, e.g. zinc chloride, magnesium chloride, metal soaps and anhydrides. A condensation product is formed that is suitable to impart the desired properties to textiles when the compounds having the particular functionalities and the crosslinking component is reacted with the catalyst and cured.
- WO 2013 059387 A1, WO 2013 059395 A1, WO 2013 059400 A1, and WO 2013 059416 A1 describe non-fluorinated soil resist compositions featuring various combinations of surfactant, stain resist, and optional inorganic oxide species. The preferred soil resistant species are given as including polymethylmethacrylate, methyl methacrylate/ethyl methacrylate copolymer, an alkali metal salt of a hydrolysed styrene/maleic anhydride copolymer or of a hydrolyzed styrene/maleic anhydride/cumene terpolymer, an ammonium salt of a styrene/maleic anhydride copolymer or of a hydrolyzed styrene/maleic anhydride/cumene terpolymer, amorphous silicon dioxide, colloidal silica, and amorphous silica.
- However, the related art fails to disclose a carpet or a textile floor covering treated with fluorine-free chemical compositions providing durable soil resistance and water repellency, and a carpet or textile floor covering free of fluorine and having these high quality properties.
- Moreover, there is an increasing interest in the carpet and textile floor covering industry to replace the presently used C6-fluorochemicals with fluorine-free soil resistant and water repellent products. Eco labels such as “Blue Angel,” which is awarded by RAL gGmbH, St. Augustin, Germany and others are continuously reinforcing this trend.
- Thus, it was an object of the present disclosure to provide fluorine-free compositions that reliably impart durable surface protection to textile flooring substrates against the detrimental influences of water and soil. Such compositions should be easy to manufacture and easy to apply to textiles of synthetic or natural origin, while at the same time imparting a comparable protection as with fluorine containing chemicals as they are currently available on the market. In addition, reliable water repellency should be provided to carpets and textile floor coverings by treatment with such new compositions.
- The present invention, therefore, pertains to a fluorine-free fiber protectant Composition X1 comprising:
-
- A) A nanoparticulate silicate clay (also referred to as a clay nanoparticle);
- B) An anionic acrylic-based copolymer binding agent;
- C) water
whereby the mixing ratio is from 0.8 to 24 volume parts for A, from 1.3 to 23.8 volume parts for B, and the balance is C. Composition X1 is useful for applications such as natural or synthetic fiber protection. Furthermore, following evaporation of water, the fibers treated with composition X1 display improved water and soil repellency characteristics useful as substitutes for, and replacements of, the fluorinated fiber protectant compositions currently applied.
- Another object of the invention is a fluorine-free fiber protectant Composition X2 comprising components A, B, C and:
-
- D) A textile softening agent;
whereby the mixing ratio is from 0.9 to 22.5 volume parts for A, from 1.3 to 19 volume parts for B, from 0.7 to 11 volume parts D, and the balance is C. Composition X2 is also useful for applications such as natural or synthetic fiber protection.
- D) A textile softening agent;
- Additionally, other compositions effective under this disclosure are effective and include only B, C and D to yield a third composition, Composition X3. And some compositions include only A and D, to yield a fourth composition, Composition X4.
- Another object of the invention is an article of manufacture, especially a carpet or a textile floor covering, which is treated with the composition as defined hereinbefore by e.g. spray application or foam application, whereby the article is rendered water repellent and soil resistant.
- Another object of the invention is a method for the fluorine-free treatment of textiles or fibres of synthetic or natural origin with a composition as defined herein in an effective amount to render the textiles or fibers water repellent, soil resistant, and soft.
- Another object of the invention is a kit providing one or more of Compositions X1, X2, X3 or X4 in separate containers, that are then be mixed and/or used at a place of carpet manufacture.
- Fluorochemicals are used as topical protectant ingredients in many industrial applications, including carpets and textiles industries. As topical protectants, certain fluorochemicals impart desirable water repellency, oil repellency and soil repellency attributes to substrates as surface coatings. However, certain fluorochemicals, such as long chain polymeric perfluorocarbon species, have been shown to be precursors to undesirably bio-persistent species, such as perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonic acids (PFSAs). Examples of long chain polymeric perfluorocarbon species are those having C8, C10 or C10 perfluorinated side chains. There is a desire to reduce the overall usage of fluorochemicals in the carpets and textiles industries, for environmental and also for cost reasons. Thus, it can be understood that durable water- and soil-repellent fibers that contain a reduced amount of fluorochemicals are in demand. Recent trends in this field have been towards the adoption of emulsified, shorter chain perfluorinated polymer ingredients to apply onto fibers, carpets, fabrics and the like. Examples of shorter chain perfluorinated polymers are those having C4 and/or C6 side-chains. A salient review on this topic is provided by Wang, Cousins, Scheringer and Hungerbuehler in Environmental International. [“Fluorinated alternatives to long-chain perfluoroalkyl carboxylic acids (PFCSs), perfluoroalkane sulfonic acids (PFSAs) and their potential precursors,” Environmental International, 60, 242-248 (2013)] However, a more impactful solution to the problem is to eliminate fluorochemical-containing treatments, and instead use non-fluorinated compositions that impart the desired water- and soil-repellant performance attributes. Eco labels such as “Blue Angel,” which is awarded by RAL gGmbH, St. Augustin, Germany and others are continuously reinforcing this trend.
- There is a need in the carpets and textiles industries for solutions to provide durable water repellency and soil repellency attributes to fibrous substrates without the use of long chain polymeric perfluorocarbon species. Water repellency refers to the degree to which a substrate repels water and water/isopropanol mixtures and is determined using a similar method to that for oil repellency.
- Unlike currently applied soil resistant or water repellent chemicals, the compositions in this disclosure are free of fluorine-containing ingredients. The compositions X1, X2 and X3 comprise two or more of components A, B, C and D, and the application rates of one or more of X1, X2 or X3 onto the carpet or textile floor covering may be adjusted to achieve maximum water and soil repellency benefit. Such performance benefits are, at the same time, economically advantageous.
- Typical nanoparticulate silicate clays useful in the invention as component A include those described in U.S. Patent Application Publication No. 2011/0311757 to Iverson et al., which is incorporated herein by reference. These nanoparticulate silicate clays can be selected from the group consisting of smectites, kaolins, illites, chlorites, attapulgites, and combinations thereof. More specific examples include montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volkonskoite, vermiculite, kaolinite, dickite, antigorite, anauxite, indellite, chrysotile, bravaisite, muscovite, paragonite, biotite, corrensite, penninite, donbassite, sudoite, pennine, sepiolite, palygorskyte, and combinations thereof.
- The nanoparticulate silicate component, A, may be natural or synthetic. In one aspect the nanoparticulate silicate component includes synthetic hectorite. Regardless of whether the clay nanoparticle is natural or synthetic, the clay nanoparticle component may be present in an amount from about 0.9 to about 24 volume parts of the combined composition X1. Typically, the clay nanoparticle is present in an amount of about 7 to about 14 parts by volume of the composition X1. Examples of suitable nanoparticulate silicates are those commercially available from BYK Additives GmbH under the brand name Laponite®. These include Laponite® RID, Laponite® RDS, Laponite® JS, Laponite® SL25, and Laponite® S482. Laponite® SL-25 is a basic (pH 8-10), 21.5-25 wt % solids aqueous dispersion. The nanoparticulate silicate found in Laponite® SL25 has an average particle size of from about 20 nm to about 90 nm, and a surface area of from about 120 m2/g to about 500 m2/g;
- Typical acrylic polymer components for use in the present disclosure as component B include those anionic or non-ionic, fluorine-free, water-dispersed acrylics that are known to act as binding agents, wherein the mixture including the acrylic copolymer binding agent (“binder”) forms a transparent or largely transparent coating. In some instances, the acrylic copolymer binder is self-crosslinking. When used according to the present disclosure, the water-based non-fluorinated acrylic copolymer provides a certain degree of durable water repellency to the treated carpets and fibers.
- Binding agents useful according to this disclosure include any non-fluorinated emulsifiable acrylic polymer or copolymer suitable for use as a coating ingredient for soft surfaces, such as textiles, yarn, fabric, carpets, rugs, mats, or hard surfaces, such as vinyl tile, stone masonry, ceramic tile, and hardwood flooring. Many examples of such acrylic co-polymers can be utilized as component B in the compositions described by this disclosure. Acrylic-based copolymers having at least one of acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylate, methyl ethacrylate, ethyl ethacrylate, propyl ethacrylate, butyl ethacrylate, acrylic acid, and ethylene monomers, and combinations and blends thereof, are suitable candidates for use according to this disclosure. The acrylic-based copolymers can be non-ionic, or anionic, but the preferred acrylic-based copolymers in this disclosure have a net anionic charge association. Further, preferred components are those anionic acrylic-based copolymers that are self-crosslinking, and can thus crosslink by application of thermal and/or photoinitiated stimuli. Numerous non-fluorinated, emulsified acrylic copolymers suitable as component B are commercially available, such as the self-crosslinking families of RHOPLEX™ and PRIMAL™ emulsions, manufactured by Rohm and Haas Company. One preferred binding agent is PRIMAL™ ECO-36 (Rohm and Haas), which is an anionic, self-crosslinking acrylic based copolymer that can be applied on a substrate as a 46.5-47.5 wt % solids aqueous emulsion. Depending on process requirements, PRIMAL™ ECO-16 (self-crosslinking, non-ionic, methyl methacrylate—ethyl acrylate copolymer) and PRIMAL™ ECO-8 (self-crosslinking, nonionic) may also be used. As MMA/EA copolymers, corresponding polymer products from other manufacturers may also be used.
- Another possible water-based acrylic copolymer may be ethylene acrylic acid copolymer (EAA). These dispersion polymers are also known under various tradenames. For example TECSEAL E-799/45 (Trub Emulsions Chemie), an ethylene-acrylic acid dispersion (solids content 45%, Tg 4° C.), may be used. Still another possible water-based acrylic copolymer class may be styrene-acrylic copolymers.
- It must be understood that the invention is not limited to the use of substances identified by certain tradenames, but other substance with similar properties for the purpose and effects of the invention may be used.
- Acrylic copolymers of different types with differing mechanical properties may be blended with each other to achieve the desired final properties of the treated fiber. The advantages of the acrylic copolymers can be summarized as
-
- transparency,
- heat-curability,
- adhesivity or durability, and
- water repellency on fiber or carpet.
- Typical textile softening agents for use in the present disclosure as component D, include those that are known to act as textile softening agents, wherein the mixture including the textile softening agent provides a smoother handle to the textile. Textile softening agents can act to improve the sewability of threads, or the softness or more pleasing tactile sensation of carpets and knitted fabrics. Textile softening agents can act to enhance lubricity when used to treat yarns, fabrics, textiles, carpets, and the like. Suitable examples of such agents are described by Rudat in U.S. Patent Appl. No. 2008 0287020 as being aminosilicones or aminosiloxanes, oils of various types, polyalkylene glycols, polyalkylene waxes, partially-oxidized polyalkylene waxes, lanolin and lanolin derivatives, fatty acids, fatty acid esters, oxidized or functionalized polyolefins, and stearates. Rudat describes the use of aminosiloxanes as efficacious when combined with fluorochemicals and silsesquioxane-containing sols. U.S. Patent Appl. No. 2008 0287020 is incorporated herein by reference. Polysiloxane compounds, such as amino functional polydimethylsiloxane; fatty acid condensation products, such as condensation products of hydrated tallow with 2-[2-aminoethyl)-amino]ethanol; and acetate salt (CAS No. 68425-52-5) or acryl compounds such as bis [acryloxyethyl]-hydroxymethyl ammonium methyl sulfate (CAS No. 93334-15-7) are suitable in principle as softeners. A softener from the above mentioned compounds or a mixture of them can be included in the composition according to the invention. Suitable softeners have been described previously by Baumann in EP 1,746,199 B1. Such textile and carpeting softeners are commercially available, and examples of suitable products are Finistrol® AFN (fatty acid condensation product) of Thor, Speyer, Germany, and Megasoft® JET-LF of Huntsman Textile Effects, Langweid am Lech, Germany; Perrustol® CCA 500 (fatty acid condensation product) of Rudolf GmbH & Co. KG, Geretsried, Germany; Raniesoft® TS 20 (fatty acid condensation product) of Ranie Chemie, Wiehl, Germany; Softycon N (fatty acid condensation product) Textilcolor AG, Sevelen, Switzerland; Tubingal® OHS of CHT R. Beitlich GmbH, Tübingen, Germany; and Cefasoft NI (fatty acid condensation product) of Zschimmer & Schwarz Mohsdorf GmbH & Co. KG, Mohsdorf, Germany. EP 1,746,199 is incorporated herein by reference.
- In general, the fiber treatment compositions disclosed herein are improvements over PFCA and PFSA fiber treatment technology. The aqueous compositions can be utilized directly, only with the addition of water of dilution. Further, the application process is environmentally friendly, resulting only in release of water vapor and negligent amounts of nonhazardous cosolvent vapors (dispersion aids) when the substrate is dried.
- Nanoparticles, as a general class of chemical molecules, are known to extend the soiling protection properties provided by fluorine containing chemicals. As disclosed in U.S. patent application No. 2011/0311757 A1, herein incorporated by reference, nanoparticle treatments have been used previously as a fluorine extender for anti-soiling purposes. WO2013/116486, herein incorporated by reference, teaches nanoparticles shown to have anti-soiling properties when used in conjunction with non-fluorinated chemicals having water repellent properties. The nanoparticles disclosed in WO2013/116486 demonstrate efficacy of non-fluorochemical treatments to produce a softer hand fiber, while retaining desirable soil-resistant attributes.
- A soil repellent fiber is disclosed comprising a fluorine-free surface treatment comprising at least one clay nanoparticle component and at least one acrylic copolymer component. The clay nanoparticle can refer to particles substantially comprising minerals of the following geological classes: smectites, kaolins, chlorites, and attapulgites. These classes include specific clays such as montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volchonskoite, vermiculite, kaolinite, dickite, antigorite, anauxite, indellite, chrysotile, bravaisite, suscovite, paragonite, biotite, corrensite, penninite, donbassite, sudoite, pennine, sepiolite, and polygorskyte. The clay nanoparticles can be either synthetic or natural, including synthetic hectorite, and Laponite® from BYK Additive GmbH, Moosburg/Germany. The Laponite® clay nanoparticles can be Laponite® RD, Laponite® RDS, Laponite® JS, Laponite® S482 and Laponite® SL25.
- The concentrates according to the disclosure typically contain stabilizing additives. Preferred concentrates according to the disclosure cany contain surfactant or emulsifier species. Examples of surfactants suitable for the present disclosure are any of the anionic or non-ionic surfactants commonly used in formulating chemicals, such as triethanolamine, water-soluble salts of alkylbenzene sulfonates such as the isopropylamine salt of a C14-alkyl benzene sulfonic acid, and/or a C14 fatty alcohol sulfate, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alpha-olefin sulfonates and sulfosuccinates, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, the water-soluble salts or esters of alpha-sulfonated fatty acids containing from about 6 to about 20 carbon atoms in the fatty acid group and from about 1 to about 10 carbon atoms in the ester group, and the like. Examples of preferred non-surfactant emulsifier species are diethylene glycol monobutyl ether (butyl diglycol) and ethylene glycol monohexyl ether (hexyl glycol). Glycols and glycol ethers are particularly preferred emulsifiers. The preferred emulsifiers ensure the textile softening constituents are kept as a finely divided emulsion in water. The choice of non-ionic emulsifiers is advantageous as they act to inhibit unwanted foaming during application, and they contribute to uniform treatment on the substrate surface. Should foaming be desired for application, a foaming agent can be provided. Other stabilizing additives include peptizing agents. Peptizing agents improve dispersability of nanoparticulates in a dispersion medium such as water. Examples of peptizing agents suitable for this disclosure are disodium etidronate, sodium carbonates, sodium metaphosphates, sodium polyacrylates, and sodium hydroxide. Disodium etidronate is an especially preferred peptizing agent.
- However, the prior art fails to disclose the combinations of one or more of Compositions X1, X2, X3 or X4 as fiber, yarn, fabric, textile and carpet treatments for durable water repellency and soiling protection. The applicant has surprisingly found that topical application of composition X1 in an amount from about 500 ppm to about 5,000 ppm nanoparticulate silicate can result in the desired end use performance of durable water repellency and soil resistance. In another aspect of the present disclosure, Compositions X3 and X4 can be applied simultaneously and can also result in the desired end use performance of durable water repellency and soil resistance. This is a significant discovery because it eliminates the need for additional economic costs, processing steps and equipment and environmental concerns involved with the use of fiourochemicals or other water repellant technologies, such as microcrystalline waxes.
- Topical compositions X1, X2, X3 and X4 can be applied by many different methods, such as gravure coating, silk screen printing, roll coating, size press coating, spray bar application, rotary spray applicator, bath application, or foam wet processing methods. In one nonlimiting embodiment, the compositions can be diluted prior to application. Suitable dilutents include those known in the art. In one nonlimiting embodiment, the diluent is water. In another nonlimiting embodiment, the acidity of the formulation may be adjusted. In one nonlimiting embodiment, the pH may be adjusted to be between 5 and 10. In another nonlimiting embodiment, the pH may be adjusted to be between 5.5 and 6.5. Upon drying the treated substrate and evaporation of the water, the topical compositions X1, X2, X3, and X4 that on drying and evaporation of the water, form a coating on the substrate. Suitable substrates may be textile, yarn, fiber, fabric or carpeting. Examples of preferred methods of application in this disclosure are spray bar application and rotary spray applicator. Rotary applicator systems such the WEKO-FLOW with WEKO-SIGMA liquid application system, manufactured by Weitmann & Konrad GmbH & Co. KG of Leinfelden-Echterdingen, Germany are suitable. Similarly, rotary applicator systems such as The Wave and The IQ Spray Application Systems, manufactured by Consultex Systems of Spartanburg, S.C., USA are suitable for application of compositions of this disclosure. Spray bar applicator systems, or spray manifold systems, are well known in the trade, and any such system is suitable for applying the compositions described herein.
- While mostly familiar to those versed in the art, the following definitions are provided in the interest of clarity.
- approx. wt. % active solids: the approximate amount, in terms of weight percent, of the active component in the formulated material.
Formulated: For the purpose of this disclosure, by “formulated” it is meant that, for example, one or more of the active components A, B, or C, are provided as complex water-borne mixtures, in combination with such chemical adjuncts as surfactants, co-solvents, emulsifying agents, peptizing agents, or dispersing agents, for example. The anionic acrylic-based copolymer, B, can therefore be provided as a water-borne formulation having certain adjuncts present, and, separately, the textile softening agent, C, can be provided as a water-borne product having certain adjuncts present, and in this form B and C can, for example, be combined and mixed with A and D.
Nanoparticulate: A multidimensional particle in which one of its dimensions is less than 100 nm in length.
owf: “on weight of fiber.” The amount of solids of fiber protectant applied after evaporation of solvent. The value of solids applied owf is typically expressed as a percentage of the mass of fiber present in the article.
fluid ppv: parts per volume of a formulated (fluid-based) composition component.
Soil repellency and dry soil resistance: Terms used herein interchangeably to describe the ability to prevent dry soils from sticking to a fiber. For example, the dry soil may be dirt tracked in by foot traffic.
tpi: twists per inch.
WPU (Wet Pick-up): The amount of solution weight that was applied to the fiber before drying off the solvent. - The invention will be described in more detail with the help of following examples that do not restrict the scope of the invention. Further, it should be understood that the recipes in this disclosure reflect specific use rates for components added as part of a discrete example recipe, but these recipes should not be construed to be limited for the purpose of this disclosure as not encompassing a range of similarly effective use rates for the indicated recipe components. For example, if component B is listed as being used in a composition at 10.0 ppv, it should be understood that B can also be used in the composition at 5, 7, 9, 11, 13, and 15 ppv.
- The following are examples of mixtures of compositions X1, X2, X3 and X4 which are suitable for the present invention:
-
-
TABLE 1 Exemplary ranges for ingredients in Composition X1. The parts per volume refer to ranges of approx. wt. %, active component Identifier ingredient fluid ppv A Laponitee ® SL25 21.5-25 4-96 B Primal ™ ECO-36 46.5-47.5 3-50 C Water, any balance auxiliary stabilizers Total 100 An example recipe for Composition X1. component Identifier fluid ppv A Laponite ® SL25 75 B Primal ™ ECO-36 20 C Water, any 5 auxiliary stabilizers Total 100 -
-
TABLE 2 Exemplary ranges for ingredients in Composition X2. approx. wt. %, component Identifier active ingredient fluid ppv A Laponite ® SL25 21.5-25 4-90 B Primal ™ ECO-36 46.5-47.5 3-40 D Tubingal OHS 37 2-30 C Water, any balance auxiliary stabilizers Total 100 An example recipe for Composition X2. component Identifier fluid ppv A Laponite ® SL25 80.0 B Primal ™ ECO-36 10.0 D Tubingal OHS 5.0 C Water, any balance auxiliary stabilizers Total 100 -
-
TABLE 3 Exemplary ranges for ingredients in Composition X2. approx. wt. %, component Identifier active ingredient fluid ppv B Primal ™ ECO-36 46.5-47.5 5-80 D Tubingal OHS 37 5-40 C Water, any Balance balance auxiliary stabilizers Total 100 An example recipe for Composition X3. component Identifier fluid ppv B Primal ™ ECO-36 62.5 D Tubingal OHS 37.5 C Water, any Balance auxiliary stabilizers Total 100 -
-
TABLE 4 Exemplary ranges for ingredients in Composition X4. approx. wt. %, component Identifier active ingredient fluid ppv A Laponite ® SL-25 21.5-25 40-100 C Water, any Balance balance auxiliary stabilizers Total 100 An example recipe for Composition X4. component Identifier fluid ppv A Laponite ®SL-25 95 C Water, any 5 auxiliary stabilizers Total 100 - Soil repellency refers to the ability of a fibrous substrate to resist the adhesion of dry soils. The tests performed to evaluate soiling performance levels generally involve applying standardized, non-liquid-containing dry soil compositions to a fibrous substrate, and further subjecting the substrate to a moving load to simulate wear or trafficking. The soiled substrate is subsequently subjected to a controlled soil removal process, such as by vacuum cleaner. These tests may also involve water extraction. The substrate is then compared to a control sample, or a standard of established value.
- Composition X1 is the combination of A, B, and C at a range of incorporation indicated in Table 1. A suitable range of application of X1 onto an area of carpet fiber substrate is 0.1%-8% owf. Application of X1 at less than 0.1% owf is ineffective for durable soil and water repellency, and application of X1 at greater than 8% owf is understood to understood to not be economical under current market conditions, or practical as would be considered using the preferred methods of application in industry. A more preferable range of application of X1 on a fiber substrate such as carpet is 0.3%-2.5% owf.
- Composition X2 is the combination of all four of A, B, C, and D, at a range of incorporation indicated in Table 2. A suitable range of application of X2 onto an area of carpet fiber substrate is 0.1%-8% owf. A more preferable range of application of X2 on a fiber substrate such as carpet is 0.4%-2.5% owf.
- Composition X3 is the combination of B, C, and D at a range of incorporation indicated in Table 3. A suitable range of application of X3 onto an area of carpet fiber substrate is 0.1%-6% owf. Application of X3 at less than 0.1% owf is ineffective for softness improvement, and application of X3 at greater than 6% owf is understood to have a detrimental effect on the soil resistance of the substrate. A more preferable range of application of X3 on a fiber substrate such as carpet is 0.3%-2.0% owf.
- Composition X4 is the combination of A, and C at a range of incorporation indicated in Table 4. A suitable range of application of X4 onto an area of carpet fiber substrate is 0.1%-8% owf. Application of X4 at less than 0.3% owf is ineffective for soil resistance, while application of X4 at greater than 8% owf is understood to not be economical under current market conditions, or practical as would be considered using the preferred methods of application in industry. A more preferable range of application of X4 on a fiber substrate such as carpet is 0.5%-4.0% owf.
- In one aspect, Compositions X1, X2, X3, or X4 are prepared by one or more of mixing, agitating, sonicating, or physically blending the individual chemistries A, B, D, in their requisite proportions, in diluent C.
- In another aspect, Compositions X1, X2, X3, or X4 are prepared by taking each of A, B, D, and dispersing, emulsifying, sonicating, dissolving, or agitating each in diluent C, prior to combining the components by one or more of: mixing, agitating, sonicating, or physically blending the individual chemistries A, B, D, in their requisite proportions, in diluent C.
- In yet another aspect, a Composition X1 is applied to yarns, fibers, textiles, fabrics or carpets. The disclosed nanoparticle clays, A, acrylic-based copolymers, B, and aqueous diluent, C, are combined, in one pot, to yield a composition, X1, that is a surprisingly stable complex liquid mixture and is effective for durable water and soil repellency for fibers. Composition X1 is thereafter suitable for transport to a manufacturing facility, where it can optionally be diluted with water, then applied onto yarns, fibers, textiles, fabrics or carpets.
- In another aspect, a Composition X2 is applied to yarns, fibers, textiles, fabrics or carpets. The disclosed nanoparticle clays, A, acrylic-based copolymers, B, aqueous diluent, C, and textile softening agents, D, are combined, in one pot, to yield a composition, X2, that is a surprisingly stable complex liquid mixture and is effective for durable water and soil repellency for fibers, with additional softness benefit. Composition X2 is thereafter suitable for transport to a manufacturing facility, where it can optionally be diluted with water, then applied onto yarns, fibers, textiles, fabrics or carpets.
- In yet another aspect, one or more of Compositions X1, X2, X3 and X4 are sequentially applied to yarns, fibers, textiles, fabrics or carpets.
- In still another aspect, one or more of Compositions X1, X2, X3 and X4 are applied simultaneously to yarns, fibers, textiles, fabrics or carpets.
- In another aspect, as any foam produced by agitating X1, X2, X3 or X4 is short-lived, compositions X1, X2, X3, and X4 of the present disclosure find particular utility in systems that apply liquids under low- or no-foam conditions. Application methods wherein no- or low-foam compositions are desired include spray bar and rotary spray liquid applicator methods.
- In yet another aspect of the disclosure, should foam application prove necessary, then any foaming agent used in the trade is suitable to add in order may be employed for applying to apply one or more of a Composition X1, X2, X3 or X4 as a foam. Examples of foaming agents suitable for use include, but are not limited to alkyl amine oxides, for example Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland), C12 to C18 coconut fatty acid alkyl dimethyl amine oxides, available from Clariant, sodium alpha olefin sulphonates (e.g. Hansanyl® OS, Hansa Group AG, Germany) and sodium laureth sulfate (e.g. Hansanol® NS 242 conc, Hansa Group AG, Germany). However, should foam application prove necessary, any of standard foaming agents used in the trade are suitable. Examples of foaming agents suitable for use include, but are not limited to alkyl amine oxides, for example Laviron 118 SK (Puicra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland), C12 to C18 coconut fatty acid alkyl dimethyl amine oxides, available from Clariant, sodium alpha olefin sulphonates (e.g. Hansanyl® OS, Hansa Group AG, Germany) and sodium laureth sulfate (e.g. Hansanol® NS 242 conc, Hansa Group AG, Germany).
- In another aspect, one or more of Compositions X1, X2, X3 and X4 are transported to manufacturers, diluted accordingly, and applied individually to yarns, fibers, textiles, fabrics or carpets.
- In another aspect, the acidity of Compositions X1, X2, X3, or X4 is adjusted to be between pH 5.0 and pH 10, prior to application to yarns, fibers, textiles, fabrics or carpets. A preferable pH is between pH 5.5 and pH 6.5.
- In yet another aspect, one or more of Compositions X1, X2, X3 and X4 are transported to manufacturers together as a kit, or chemical package. In this aspect they are diluted accordingly, and then co-applied to yarns, fibers, textiles, fabrics or carpets.
- In still another aspect, one or more of Compositions X1, X2, X3 and X4 are transported to manufacturers together as a kit, or chemical package. In this aspect they are combined at the manufacturing site, diluted accordingly, and the resulting liquor is applied onto yarns, fibers, textiles, fabrics or carpets.
- The fluorine-free fiber protection compositions included herein may additionally contain one or more stain-block chemistries, in order to combine soil protection and water repellency with suitable stain protection. If a stain-blocker is used, it is preferred to also add a dispersing agent in order to support better application of the composition in aqueous form. Anti-stain components for use in the disclosed stain blocker compositions have a component bearing an acidic moiety which associates with polymer amine end groups and protects them from staining by acidic dye stains. The general category of chemicals suitable to the process of the instant invention can comprise any chemical that blocks positively charged dye sites. Stain blockers are available in various forms such as syntans, sulfonated novolacs, sulfonated aromatic aldehyde condensation products (SACs) and/or reaction phenolics, olefins, products of formaldehyde, phenolics, substituted thiophenolics, sulfones, substituted sulfones, polymers or copolymers of branched olefins, cyclic olefins, sulfonated olefins, acrylates, methacrylates, maleic dianyhydride, and organosulfonic acids. They are usually made by reacting formaldehyde, phenol, polymethacrylic acid, maleic dianyhydride, and sulfonic acid depending on specific chemistry. Further, the stain blocker is typically water soluble and generally penetrates the fiber while the anti-soil, usually a fluorochemical, is a non-water soluble dispersion that coats the surface of fiber.
- Examples of stain blockers include, but are not limited to: phenol formaldehyde polymers or copolymers such as CEASESTAIN and STAINAWAY (from American Emulsions Company, Inc., Dalton, Ga.), MESITOL (from Bayer Corporation, Rock Hill, N.C.), ERIONAL (from Ciba Corporation, Greensboro, N.C.), INTRATEX (from Crompton & Knowles Colors, Inc., Charlotte, N.C.), STAINKLEER (from Dyetech, Inc., Dalton, Ga.), LANOSTAIN (from Lenmar Chemical Corporation, Dalton, Ga.), and SR-300, SR-400, and SR-500 (from E. I. du Pont de Nemours and Company, Wilmington, Del.); polymers of methacrylic acid such as the SCOTCHGARD FX series carpet protectors (from 3M Company, St. Paul, Minn.); sulfonated fatty acids from Rockland React-Rite, Inc., Rockmart, Ga.); the ARROSHIELD™ stain resist product line (ArrowStar LLC, Dalton, Ga., U.S.), I-Protect® 2126 (INVISTA S. a r. l., Germany) and the Ultraguard SB-700 stain resist product line (Tri-Tex, Canada).
- Stain-blockers are usually ionic in nature and can be equally well applied in both discontinuous and continuous application in the carpet manufacturing process. In the continuous application, the carpet runs through the usual dyeing and printing stages, whereas in the discontinuous application various separate baths are used.
- The procedure to apply the stain-blocker to the textile, e.g. a rug, can be in two steps or in a single application step. In the two step procedure the stain-blocker application is followed by a treatment with one or more of X1, X2 or X3. In the single step application, in which a co-application system is used, stain-block chemistry is applied and one or more of X1, X2 or X3 are applied simultaneously, using foam application process technology such as is practiced in the trade.
- A dosage rate of 3.0 to 7.0% aqueous liquor on weight of fiber is recommended for the stain blocker. In the case of discontinuous application a separate treatment bath for the stain-blocking is used after the carpet dyeing process. The carpet is treated for a time period of from 20 to 30 minutes at a temperature of from 70 to 75° C. The pH-value depends on the type of stain-blocker and should be held between 2.5 and 7.0. In the case of continuous application, the carpet runs through the usual dyeing and printing stages. The stain-blocker is applied through a suitable application mechanism such as a dip trough, waterfall applicator or fluidyer. The stain block liquor should be applied at or around 60° C.±10° C., although the process will also work at colder temperatures. The stain-blocker is fixed in the steamer with a steaming time of 60 to 90 seconds. The carpet is then washed, vacuumed and dried. Ideally, a soil resistant and water repellent application with one or more of components X1, X2, or X3 follows the stain-blocker, in the same process.
- Suitable dispersing agents for this purpose include, but are not limited to, fatty alcohol polyglycolethers (e.g. Sera® Sperse M-DEW; DyStar Textilfarben GmbH & Co.) and alkyl aryl aminethoxylate (e.g. Avolan® IW liquid, Tanatex® Chemicals, The Netherlands), both of which are nonionic in nature.
- As mentioned already before, the textile fibers for the substrate, the carpet or the floor covering which is subjected to treatment with the compositions of the invention is of synthetic or natural origin. Suitable synthetic textiles are made from polymer bases such as polyamide like polyamide 6.6, which is known as poly(hexamethylene adipamide), or polyamide 6, which is known as poly(caprolactam), or polyesters like poly(ethylene terephthalate) and poly(propylene terephthalate), or poly(propylene), or mixtures or blends of one or more of such suitable polymer bases. Suitable textiles of natural origin are fibres made from wool or cotton.
- Soil resistant and water repellent chemicals are usually applied as the last step in carpet finishing, after application of stain resist chemistry, and prior to drying or backing. Soil resistant and water repellent chemicals may be applied to the carpet via spray application or foam application, which is known in the art. Following dilution of as-received formulated products, industry-recommended rates for application are from 1.0 wt % to 1.6 wt % on weight of carpet fiber (corresponding to 500 ppm to 800 ppm elemental fluorine content). However, application ranges for the fluorine-free fiber protection compositions useful for purpose of this disclosure are usually from 0.25 to 3.5 wt %.
- Spray application is the easiest method of applying soil resistant and water repellent chemicals. A spray facility may be installed in front of a dryer after coloration or in front of a latex backing oven. In order to prevent spray spreading, a suction hood should be installed above the spray bar. An aqueous solution of the composition is pumped through spray nozzles, installed above the running carpet, onto the carpet pile. For better distribution/penetration into the pile the solution should be applied to moistened carpet fiber. Alternatively, an aqueous liquor of the composition is pumped into a tank where it is metered for application by a spinning rotary plate. The rotary plate acts to apply microscopic droplets of the aqueous composition in uniform fashion onto the moving fiber, yarn, fabric, textile or carpet substrate.
- Foam application is the most advanced method for the treatment of carpets with soil resistant and water repellent chemicals. By using this minimum moisture application system, highly concentrated liquors in a foam state are applied to carpets running past. A further advantage of the foam application method is its improved penetration. Foam application facilities can be installed in front of a dryer or a latex backing oven. In case of insufficient foam stability a foaming agent can be added advantageously. These foaming agents are formulated in such a way that they decompose under common drying temperatures and do not negatively impact the performance of the soil resistant and water repellent chemicals.
- Suitable foaming agents include, but are not limited to alkyl amine oxides, for example Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland), C12 to C18 coconut fatty acid alkyl dimethyl amine oxides, available from Clariant, sodium alpha olefin sulphonates (e.g. Hansanyl® OS, Hansa Group AG, Germany) and sodium laureth sulfate (e.g. Hansanol® NS 242 conc, Hansa Group AG, Germany).
- Both spray application and foam application require a subsequent drying process. Raising the carpet pile face to a temperature of 110 to 130° C. during the drying process is important to allow the soil resistant and water repellent chemicals to completely bond onto the fibre.
- The following working examples are useful to illustrate more specifically the instant invention.
- For the determination of the results of the invention, the following test methods have been applied:
- Carpet samples are mounted on the interior of a drum, and chrome alloy steel balls, nylon polymer pellets, and a standard dry soil are added. The soil used is AATCC 122/123 standard soil:
-
- 38 wt.-% Peat moss (dark)
- 17 wt.-% Portland cement
- 17 wt.-% Kaolin clay
- 17 wt.-% Silica (200 mesh)
- 1.75 wt.-% Carbon black (lamp or furnace black)
- 0.50 wt.-% Red iron oxide
- 8.75 wt.-% Mineral oil (medicinal grade)
- After the drum is loaded it is sealed and the rotated for 1,000 revolutions, followed by vacuuming. The test simulates initial soiling by dirty shoe soles (represented by the polymer pellets) in that the soil acts on both the carpet, and on the polymer pellets. 1.000 revolutions in a drum. The carpets are then evaluated according to a gray scale: level 1=, strong soiling, level 5=no soiling. Target=2.5 or higher.
- The test is later abbreviated as: “ISO”
- This test (adapted from AATCC method 193) determines a finished carpet's resistance to wetting by aqueous liquids. Drops of water-alcohol mixtures of varying surface tensions are placed on the fabric and the extent of surface wetting is determined visually. If after 10 seconds, four out of the five drops are still visible as spherical to hemispherical, the carpet is given a passing rating and the test is repeated with a higher rating number liquid. The repellency rating of the sample is the highest rating number liquid used to pass the repellency test. Carpets with a rating of 4 or higher have good anti-soiling properties. Without anti-soil treatment, most nylon carpets have a rating of 1 for water repellency.
- The test is later abbreviated as: “WR”.
- The following liquids were used for water repellency tests:
-
Rating Liquid Composition Number % Isopropanol % Water 1 2 98 2 5 95 3 10 90 4 20 80 5 30 70 6 40 60 - Acid dye stain resistance is evaluated using a procedure modified from the American Association of Textile Chemists and Colorists (AATCC) Method 175-2003, “Stain Resistance: Pile Floor Coverings.” 9 wt % of aqueous staining solution is prepared, according to the manufacturer's directions, by mixing cherry-flavored KOOL-AID® powder (Kraft/General Foods, White Plains, N.Y., a powdered drink mix containing, inter alia, FD&C Red No. 40). A carpet sample (4×6-inch) is placed on a flat non-absorbent surface. A hollow plastic 2-inch (5.1 cm) diameter cup is placed tightly over the carpet sample. Twenty ml of the KOOL-AID® staining solution is poured into the cup and the solution is allowed to absorb completely into the carpet sample. The cup is removed and the stained carpet sample is allowed to sit undisturbed for 24 hours. Following incubation, the stained sample is rinsed thoroughly under cold tap water, excess water is removed by centrifugation, and the sample is dried in air. The carpet sample was visually inspected and rated for staining according to the FD&C Red No. 40 Stain Scale described in AATCC Method 175-2003. Stain resistance is measured using a 1-10 scale. An undetectable test staining is accorded a value of 10.
- The carpet test sample is not pre-cleaned and is placed flat on a smooth, horizontal surface. The cleaning solution of 1.0% Sapur® Duo (available at Ecolab®, pH=7) is used to do the hot water extraction with a Kaercher spray-extraction cleaner. The cleaning solution is added into the tank of the spray-extraction unit, whereas cleaning is accomplished by moving the cleaning head over the carpet's surface. Samples are cleaned over a maximum time period of 2 minutes or until the stain is completely removed (less than 2 min). The cleaned samples are air dried and rated as follows: 5.0=complete removal, 4.0=very good removal (>75%), 3.0=good removal (>50%), 2.0=fair removal (<50%) and 1.0=poor removal (<25%).
- Example 1 was performed to demonstrate the soiling performance and water repellency of a Composition X2. The application liquor was applied manually in the lab using a hand-held spray device to a standard velour carpet dyed “baby blue” made from nylon 6,6, and having a fibre weight of 600 g/m2. The chemical application was followed by a curing process in a laboratory oven at 130° C. for about 15 minutes.
As can be seen in Table 5 the combination exceeds/meets the test requirements. -
TABLE 5 Amount owl ISO WR 1.6% X2 3 2 2.0% X2 3.25 2-3 2.5% X2 3.25 2-3 Untreated Carpet 1.75 to 2.0 0
Example 2 was performed to demonstrate the soiling performance and water repellency of a carpet treated by co-application of a Composition X3 and X4. The application liquor was applied using a WEKO application system onto a carpet tile, light grey in colour and having pile weight 400 g/m2, followed by a curing process in an oven at 130° C. for about 8 minutes.
As can be seen in Table 6, the treatment exceeds/meets the test requirements. -
TABLE 6 ISO WR 0.35% X3 3 2-3 2.0% X4
Example 3 was performed to demonstrate the durability after hot water extraction (HWE) of carpets treated thusly: -
- a.) manually in the lab using a hand-held spray device to apply the given liquor noted in Table 7 to a standard velour carpet, 600 g/m2, color “babyblue,” followed by a curing process in a lab oven at 130° C. for about 15 minutes, and
- b.) using the WEKO application system to apply the liquor noted in Table 7 onto a carpet tile, light grey in colour, and having a pile weight of 400 g/m2, followed by a curing process in an oven at 130° C. for about 8 minutes.
-
TABLE 7 Example 3a ISO WR 2.0% X2 original sample 3.25 2-3 After 1 cycle HWE 3.25 2 Example 3b ISO WR 0.35% X3, original sample 3 2 2.0% X4 After 1 cycle HWE 3 2
Claims (37)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14164089.6 | 2014-04-09 | ||
EP14164089 | 2014-04-09 | ||
PCT/US2015/024926 WO2015157419A1 (en) | 2014-04-09 | 2015-04-08 | Water repellent, soil resistant, fluorine-free compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
US20170030010A1 true US20170030010A1 (en) | 2017-02-02 |
Family
ID=50440603
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/302,905 Abandoned US20170030010A1 (en) | 2014-04-09 | 2015-04-08 | Water repellent, soil resistant, fluorine-free compositions |
Country Status (11)
Country | Link |
---|---|
US (1) | US20170030010A1 (en) |
EP (1) | EP3129544B1 (en) |
JP (1) | JP6783144B2 (en) |
CN (1) | CN106460309A (en) |
AU (1) | AU2015243869B2 (en) |
CA (1) | CA2944196A1 (en) |
DK (1) | DK3129544T3 (en) |
ES (1) | ES2716080T3 (en) |
MX (1) | MX2016013188A (en) |
TR (1) | TR201900969T4 (en) |
WO (1) | WO2015157419A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180095586A1 (en) * | 2016-10-05 | 2018-04-05 | Hyundai Motor Company | Method and apparatus for controlling vehicular user interface under driving condition |
WO2019090333A1 (en) | 2017-11-06 | 2019-05-09 | Gpcp Ip Holdings Llc | Formulation for cleaning hard surfaces |
US10288543B2 (en) * | 2016-01-16 | 2019-05-14 | Columbia Insurance Company | Methods for determining moisture permeability in textiles |
US10662263B2 (en) * | 2014-10-01 | 2020-05-26 | Jowat Se | Aqueous coagulatable polymer dispersion and use thereof as an adhesive |
US11564429B2 (en) | 2019-05-24 | 2023-01-31 | Southern Mills, Inc. | Flame resistant finished fabrics exhibiting water repellency and methods for making the same |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3464710B1 (en) | 2016-05-24 | 2020-05-13 | INVISTA Textiles (U.K.) Limited | Compositions for the treatment of articles, and articles treated thereform |
CN114075785B (en) * | 2020-08-11 | 2023-08-18 | 鲁泰纺织股份有限公司 | Finishing method for improving non-ironing property and hand feeling of pure cotton plain weave yarn-dyed fabric |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0247371A (en) * | 1988-08-08 | 1990-02-16 | Kiyoueishiya Yushi Kagaku Kogyo Kk | Silicone-based softening agent composition for textile |
JPH05132864A (en) * | 1991-11-14 | 1993-05-28 | Kao Corp | Softening and finishing agent for clothes |
US20040025262A1 (en) * | 2000-12-05 | 2004-02-12 | Christoph Hamers | Reagent-modified particulate polymers for treatment of the surface of textile and non-textile materials |
US20070048344A1 (en) * | 2005-08-31 | 2007-03-01 | Ali Yahiaoui | Antimicrobial composition |
US20090165216A1 (en) * | 2000-08-25 | 2009-07-02 | Eric Aubay | Composition based on nanoparticles or a nanolatex of polymers for fabric care |
US20110311757A1 (en) * | 2009-12-10 | 2011-12-22 | Invista North America S.A.R.I. | Soil repellency aqueous dispersions, soil repellant soft articles, and methods of making the same |
US20120015575A1 (en) * | 2009-03-28 | 2012-01-19 | Huntsman Textile Effects (Germany) Gmbh | Flourine-Free Aqueous Dispersion for Treating Textile Fabrics |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS551393B2 (en) * | 1973-11-19 | 1980-01-14 | ||
JPS6461576A (en) * | 1987-08-27 | 1989-03-08 | Lion Corp | Gloss preventing composition |
JP2000034671A (en) * | 1998-07-17 | 2000-02-02 | Teijin Ltd | Deodorant fibrous structure |
US20050204477A1 (en) * | 2004-03-22 | 2005-09-22 | Casella Victor M | Fabric treatment for stain release |
AU2004285579B2 (en) * | 2003-10-30 | 2011-02-10 | Nano Met-Zero, Inc. | Composite materials comprising metal-loaded nanoparticles |
FR2895398B1 (en) * | 2005-12-23 | 2008-03-28 | Saint Gobain Vetrotex | GLASS YARN COATED WITH AN ENSIMAGE COMPRISING NANOPARTICLES. |
JP2007270378A (en) * | 2006-03-31 | 2007-10-18 | Daikin Ind Ltd | Water-repellent, oil-repellent, and dirt-removed textile products and their processing methods |
EP2146953A4 (en) * | 2007-05-18 | 2014-03-12 | Invista Tech Sarl | PROCESS AND COMPOSITION FOR TREATING FIBROUS SUBSTRATES |
JP5398051B2 (en) * | 2008-06-23 | 2014-01-29 | 花王株式会社 | Detergent composition |
CN101429727B (en) * | 2008-12-22 | 2010-12-08 | 四川大学 | Two-component acrylic polymer/montmorillonite nanocomposite textile size and preparation method thereof |
EP2638204A2 (en) * | 2010-11-12 | 2013-09-18 | Invista Technologies S.à.r.l. | Aqueous dispersion of dye, stain-blocker, and fluorochemical and its use in the manufacture of carpet |
US20130102215A1 (en) * | 2011-10-19 | 2013-04-25 | E I Du Pont De Nemours And Company | Nonfluorinated soil resist and repellency compositions |
IN2014MN01670A (en) * | 2012-01-31 | 2015-05-29 | Invista Technologies Srl |
-
2015
- 2015-04-08 CN CN201580031002.XA patent/CN106460309A/en active Pending
- 2015-04-08 AU AU2015243869A patent/AU2015243869B2/en not_active Ceased
- 2015-04-08 JP JP2016561338A patent/JP6783144B2/en not_active Expired - Fee Related
- 2015-04-08 CA CA2944196A patent/CA2944196A1/en not_active Abandoned
- 2015-04-08 WO PCT/US2015/024926 patent/WO2015157419A1/en active Application Filing
- 2015-04-08 MX MX2016013188A patent/MX2016013188A/en unknown
- 2015-04-08 DK DK15777478.7T patent/DK3129544T3/en active
- 2015-04-08 US US15/302,905 patent/US20170030010A1/en not_active Abandoned
- 2015-04-08 EP EP15777478.7A patent/EP3129544B1/en not_active Not-in-force
- 2015-04-08 TR TR2019/00969T patent/TR201900969T4/en unknown
- 2015-04-08 ES ES15777478T patent/ES2716080T3/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0247371A (en) * | 1988-08-08 | 1990-02-16 | Kiyoueishiya Yushi Kagaku Kogyo Kk | Silicone-based softening agent composition for textile |
JPH05132864A (en) * | 1991-11-14 | 1993-05-28 | Kao Corp | Softening and finishing agent for clothes |
US20090165216A1 (en) * | 2000-08-25 | 2009-07-02 | Eric Aubay | Composition based on nanoparticles or a nanolatex of polymers for fabric care |
US20040025262A1 (en) * | 2000-12-05 | 2004-02-12 | Christoph Hamers | Reagent-modified particulate polymers for treatment of the surface of textile and non-textile materials |
US20070048344A1 (en) * | 2005-08-31 | 2007-03-01 | Ali Yahiaoui | Antimicrobial composition |
US20120015575A1 (en) * | 2009-03-28 | 2012-01-19 | Huntsman Textile Effects (Germany) Gmbh | Flourine-Free Aqueous Dispersion for Treating Textile Fabrics |
US20110311757A1 (en) * | 2009-12-10 | 2011-12-22 | Invista North America S.A.R.I. | Soil repellency aqueous dispersions, soil repellant soft articles, and methods of making the same |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10662263B2 (en) * | 2014-10-01 | 2020-05-26 | Jowat Se | Aqueous coagulatable polymer dispersion and use thereof as an adhesive |
US10288543B2 (en) * | 2016-01-16 | 2019-05-14 | Columbia Insurance Company | Methods for determining moisture permeability in textiles |
US20180095586A1 (en) * | 2016-10-05 | 2018-04-05 | Hyundai Motor Company | Method and apparatus for controlling vehicular user interface under driving condition |
WO2019090333A1 (en) | 2017-11-06 | 2019-05-09 | Gpcp Ip Holdings Llc | Formulation for cleaning hard surfaces |
US11564429B2 (en) | 2019-05-24 | 2023-01-31 | Southern Mills, Inc. | Flame resistant finished fabrics exhibiting water repellency and methods for making the same |
US11571032B2 (en) | 2019-05-24 | 2023-02-07 | Southern Mills, Inc. | Flame resistant finished fabrics exhibiting water repellency and methods for making the same |
US12029269B2 (en) | 2019-05-24 | 2024-07-09 | Southern Mills, Inc. | Flame resistant finished fabrics exhibiting water repellency and methods for making the same |
Also Published As
Publication number | Publication date |
---|---|
EP3129544A1 (en) | 2017-02-15 |
EP3129544A4 (en) | 2018-01-24 |
AU2015243869A1 (en) | 2016-10-27 |
TR201900969T4 (en) | 2019-02-21 |
CN106460309A (en) | 2017-02-22 |
EP3129544B1 (en) | 2019-01-09 |
CA2944196A1 (en) | 2015-10-15 |
WO2015157419A1 (en) | 2015-10-15 |
AU2015243869B2 (en) | 2019-11-28 |
JP2017519117A (en) | 2017-07-13 |
MX2016013188A (en) | 2017-01-16 |
JP6783144B2 (en) | 2020-11-11 |
ES2716080T3 (en) | 2019-06-10 |
DK3129544T3 (en) | 2019-03-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2015243869B2 (en) | Water repellent, soil resistant, fluorine-free compositions | |
US10072378B2 (en) | Water repellent, soil resistant, fluorine-free compositions | |
US11359099B2 (en) | Hydrophobic extenders in fluorinated surface effect coatings | |
JP2008542567A (en) | Textile base material with layered finish structure | |
WO1996038622A1 (en) | Improved aqueous anti-soiling composition | |
US11459485B2 (en) | Non-fluorinated coating and finish agents | |
EP3464710B1 (en) | Compositions for the treatment of articles, and articles treated thereform | |
US20130101782A1 (en) | Nonfluorinated soil and stain resist compositions | |
US20090110870A1 (en) | Soil resist additive | |
WO2013059416A1 (en) | Nonfluorinated soil resist compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: INVISTA NORTH AMERICA S.A.R.L., DELAWARE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BAUMANN, MARKUS;REEL/FRAME:046018/0281 Effective date: 20180502 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: ADVISORY ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE AFTER FINAL ACTION FORWARDED TO EXAMINER |
|
AS | Assignment |
Owner name: INVISTA NORTH AMERICA, LLC, DELAWARE Free format text: CHANGE OF NAME;ASSIGNOR:INVISTA NORTH AMERICA S.A.R.L.;REEL/FRAME:054765/0645 Effective date: 20201001 |
|
AS | Assignment |
Owner name: INV PERFORMANCE SURFACES, LLC, DELAWARE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:INVISTA NORTH AMERICA, LLC;REEL/FRAME:054914/0854 Effective date: 20201001 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |