WO1996030584A1 - Aqueous oil and water repellent compositions - Google Patents
Aqueous oil and water repellent compositions Download PDFInfo
- Publication number
- WO1996030584A1 WO1996030584A1 PCT/US1995/003949 US9503949W WO9630584A1 WO 1996030584 A1 WO1996030584 A1 WO 1996030584A1 US 9503949 W US9503949 W US 9503949W WO 9630584 A1 WO9630584 A1 WO 9630584A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- acrylate
- fluorochemical
- group
- carbon atoms
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 226
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 230000002940 repellent Effects 0.000 title abstract description 11
- 239000005871 repellent Substances 0.000 title abstract description 11
- -1 adipate ester Chemical class 0.000 claims abstract description 89
- 239000000758 substrate Substances 0.000 claims abstract description 81
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 61
- 229920002635 polyurethane Polymers 0.000 claims abstract description 53
- 239000004814 polyurethane Substances 0.000 claims abstract description 53
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 19
- 125000002091 cationic group Chemical group 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 16
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 14
- 150000001412 amines Chemical group 0.000 claims abstract description 11
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 47
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 26
- 150000003254 radicals Chemical class 0.000 claims description 26
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 239000012948 isocyanate Substances 0.000 claims description 19
- 150000002513 isocyanates Chemical class 0.000 claims description 18
- 125000005647 linker group Chemical group 0.000 claims description 18
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 13
- 150000002148 esters Chemical group 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 9
- 150000001350 alkyl halides Chemical class 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 125000002837 carbocyclic group Chemical group 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical group CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 claims description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004386 diacrylate group Chemical group 0.000 claims description 5
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 150000004662 dithiols Chemical class 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 claims description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 3
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 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
- 229920001897 terpolymer Polymers 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims 2
- 239000004744 fabric Substances 0.000 abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 57
- 238000003756 stirring Methods 0.000 description 47
- 239000007787 solid Substances 0.000 description 36
- 235000019441 ethanol Nutrition 0.000 description 33
- 239000003921 oil Substances 0.000 description 29
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- 239000000243 solution Substances 0.000 description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 27
- 238000012360 testing method Methods 0.000 description 24
- 239000000839 emulsion Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 15
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 15
- 239000000443 aerosol Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 229940093499 ethyl acetate Drugs 0.000 description 9
- 235000019439 ethyl acetate Nutrition 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 238000010998 test method Methods 0.000 description 9
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005065 mining Methods 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000003380 propellant Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 2
- KNIUHBNRWZGIQQ-UHFFFAOYSA-N 7-diethoxyphosphinothioyloxy-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 KNIUHBNRWZGIQQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- GFHFQMHRBGDUAI-UHFFFAOYSA-N CCOC(C(C)=C)=O.Br Chemical compound CCOC(C(C)=C)=O.Br GFHFQMHRBGDUAI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000003842 bromide salts Chemical class 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000006162 fluoroaliphatic group Chemical group 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001012 protector Effects 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- QYOXLKAKUAASNA-UHFFFAOYSA-N 1-bromodocosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCBr QYOXLKAKUAASNA-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JTKQRCUKXQPXMZ-UHFFFAOYSA-N 2-cyano-2-[(2-cyano-1-sulfopropan-2-yl)diazenyl]propane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)(C#N)N=NC(C)(CS(O)(=O)=O)C#N JTKQRCUKXQPXMZ-UHFFFAOYSA-N 0.000 description 1
- SFHMWAZVMCDSRD-UHFFFAOYSA-N C(C=C)(=O)OC(C(N(S(=O)(=O)C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)CCCC)(F)F)(F)F Chemical compound C(C=C)(=O)OC(C(N(S(=O)(=O)C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)CCCC)(F)F)(F)F SFHMWAZVMCDSRD-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PHHYFYQZNZBGRC-UHFFFAOYSA-N [1,1,2,2-tetrafluoro-2-[1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctylsulfonyl(methyl)amino]ethyl] prop-2-enoate Chemical compound C=CC(=O)OC(F)(F)C(F)(F)N(C)S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PHHYFYQZNZBGRC-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 1
- 125000005518 carboxamido group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- AJBINAIYBRKSGF-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;octadecyl prop-2-enoate Chemical compound CCOC(=O)C(C)=C.CCCCCCCCCCCCCCCCCCOC(=O)C=C AJBINAIYBRKSGF-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 239000002759 woven fabric Substances 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
- 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
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
Definitions
- This invention relates to oil and water repellent compositions for the treatment of fabrics and other fiber containing substrates at ambient conditions, to the treated substrates and to methods of treating those substrates.
- fluorochemicals have generally required the inclusion of significant amounts of organic solvents which may be undesirable.
- organic solvents which may be undesirable.
- fluorochemical compositions e.g., those which do not include significant organic solvents
- fluorochemical compositions While more acceptable, has been less than satisfactory because such aqueous compositions have generally required the performance of additional steps in the application of the composition to a substrate, such as the application of heat to the treated substrate.
- certain known tests are employed to measure the degree to which a substrate effectively repels water and oil under different conditions.
- the present invention provides fluorochemical compositions suitable for application on a variety of fiber-containing substrates such as fabrics and textile fibers comprising cotton, nylon, polyester, polyolefin, acrylic, acetate, leather or blends thereof and materials such as apparel, upholstery and carpet to impart a broad range of oil and water repellent properties.
- the compositions of the invention are water based formulations which may be applied to substrates and dried without thermal treatment, i.e., at ambient conditions.
- Applicants have found that a class of fluorochemical acrylate polymers having a polymerizable cationic emulsifier incorporated with the polymer can be blended with polyurethane containing blends to provide a class of fabric protective compositions which exhibit improved oil and water repellency.
- the invention provides a composition for treating fiber-containing substrates to impart improved oil and water repellency thereto, the composition comprising: (a) A polyalkoxylated polyurethane having pendant perfluoroalkyl groups, said polyalkoxylated polyurethane comprising the reaction product of an aliphatic or aromatic tri- or higher order isocyanate, a fluorinated alcohol, amine, or mercaptan, and a poly(oxyalkylene) diol or dithiol; and
- a fluorochemical acrylate polymer comprising the reaction product of a fluorinated acrylate or methacrylate monomer, at least one alkyl acrylate or methacrylate monomer, and a polymerizable cationic emulsifier comprising a quaternary amine surfactant.
- compositions preferably also include (c) an alkylene glycol fluoro acrylate polymer comprising the reaction product of a fluorinated acrylate or methacrylate monomer, polyalkylene glycol acrylate or methacrylate, and polyalkylene glycol diacrylate or dimethacrylate.
- a fluorochemical adipate ester can be included in the compositions of the invention. The above components are blended together within the composition at a weight ratio of (a):(b), or (a)+(c):(b), or (a)+(c)+(d):(b) from 25: 1 to 1 :25 and more preferably, at a 1 : 1 weight ratio.
- the fluorochemical acrylate polymers can be represented by the general formula:
- R f is a fluoroaliphatic radical
- Q is an organic linking group
- R b and R b are the same or different and are selected from the group
- R d , R d ', R d ", R d '" can be the same or different and are selected from the group consisting of H or -CH 3 ,
- R a , R a ', R a " can be the same or different and are selected from the group consisting of an alkyl group having from 1 to 18 carbon atoms, R c is a saturated aliphatic (linear or branched) or cyclic alkyl, or a
- cyclic and aliphatic alkyls having at least 1 and generally from 4 to 30 carbon atoms, and preferably from 8 to 20 carbon atoms;
- Z is an anion selected from the group consisting of chloride, bromide, iodide, sulfonate, alkyl sulfonate, phosphate, and mixtures thereof; n 1 , n 2 , and n 3 are numbers which may independently range from 10 to 70, and
- n 4 is a number which is at least 1 and generally is within the range from 1 to 6.
- compositions of the invention are aqueous emulsions which include only minor amounts of organic solvent.
- the compositions may include pH modifiers and corrosion inhibitors.
- the aqueous compositions of the invention can be provided in aerosol form with the inclusion of an appropriate aerosol propellant such as isobutane, for example.
- Gland conditions means at prevailing room temperature and humidity without additional thermal treatment and/or drying equipment.
- Fiber-containing substrate or “substrate” means fabrics, textile fibers or filaments, fabrics made into finished products made from cotton polyester, polyolefin, nylon, acrylic, acetate, leather and blends of the foregoing as well as finished garments, upholstered furniture and carpet.
- Polymerizable emulsifier means a class of quaternized organic salts which serve simultaneously as monomeric reactants and as stabilizing agents in emulsion polymerization. Unless indicated otherwise, “stabilizing agent”, “emulsifier” and “surfactant” are identical in meaning and are used interchangeably. In describing acrylate and methacrylate compounds, the term “(meth)acrylate” is intended to indicate both acrylate as well as methacrylate as equally plausible species.
- the invention provides a method for treating substrates to provide oil and water repellency comprising treating a substrate with the composition of the invention and drying the treated substrate.
- the invention also provides substrates having oil and water repellency when treated with the composition of the invention.
- the fluorochemical compositions of the present invention are water based blends and can be applied to a variety of substrates at ambient conditions to provide a broad range of oil and water repellency properties, as described below.
- the individual components in the compositions are discussed and described separately, as indicated.
- compositions of the invention may include an alkylene glycol fluorochemical acrylate polymer (or "alkylene glycol fluoro acrylate”) comprising the reaction product of a fluorinated acrylate or methacrylate monomer, polyalkylene glycol acrylate or methacrylate monomer and polyalkylene glycol diacrylate or dimethacrylate monomer.
- alkylene glycol fluoro acrylates are included within the more preferred embodiments of the invention to enhance the stability of the composition in the presence of minor amounts of coalescent solvents and especially in the presence of corrosion inhibitors added to the composition when formulating an aerosol blend.
- the alkylene glycol fluoro acrylates also aid in the wetting of a substrate with the compositions of the invention.
- Fluoro acrylate polymers useful in the present invention are disclosed, for example, in U.S. Pat. Nos. 5,350,795 (Smith et al.), 3,787,351 (Olson) and 4,795,793 (Amimoto et al.), all of which are incorporated herein by reference.
- the preferred alkylene glycol fluoro acrylates have randomly arranged repeating units represented as
- R f is a fluoroaliphatic radical
- R 3 is H or CH 3
- R 4 is an alkylene group having 2 to 4 carbon atoms
- Q is an organic linking group and x is an integer of at least 5, generally 10 to 75 and can be as high as 100.
- the fluoroaliphatic group ( R f ) is a stable, inert, nonpolar, preferably saturated monovalent moiety which is both oleophobic and hydrophobic.
- the alkylene glycol fluoro acrylate preferably comprises from 2 to about 25 R f groups and preferably comprises about 5 percent to about 30 percent, and more preferably about 8 percent to about 20 percent fluorine by weight based on the total weight of the oligomer, with the fluorine being essentially in the Regroups.
- R f preferably contains at least about 3 carbon atoms, more preferably 3 to about 25 carbon atoms, and most preferably about 6 to about 12 carbon atoms.
- R f can contain straight chain, branched chain, or cyclic fluorinated alkyl groups or combinations thereof or combinations thereof with straight chain, branched chain, or cyclic alkyl groups.
- R f is preferably free of polymerizable olefinic unsaturation and can optionally contain linking heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen. It is preferred that each R f contain about 40% to about 78% fluorine by weight, more preferably about 50% to about 78% fluorine by weight.
- the terminal portion of the Regroup contains a fully fluorinated terminal group.
- This terminal group preferably contains at least 7 fluorine atoms, i.e., CF 3 CF 2 CF 2 -, (CF 3 ) 2 CF-, -CF 2 SF 5 , or the like.
- R f are the perfluorinated aliphatic groups, i.e., those of the formula C n F 2n+1.
- the fluoroaliphatic group, R f is linked to the ester group by a linking group designated Q.
- Linking group Q can be a covalent bond, a heteroatom, e.g., O or S, or an organic moiety.
- Q is an organic moiety containing 1 to about 20 carbon atoms, and optionally containing oxygen, nitrogen-, or sulfur-containing groups or a combination thereof, and preferably free of functional groups (e.g., polymerizable olefinic double bonds, thiols, easily abstracted hydrogen atoms such as cumyl hydrogens, and other such functionality known to those skilled in the art) that substantially interfere with free-radical polymerization.
- linking group Q examples include straight chain, branched chain, or cyclic alkylene, arylene, aralkylene, oxy, oxo, thio, sulfonyl, sulfinyl, imino, sulfonamido, carboxamido, carbonyloxy, urethanylene, ureylene, and combinations thereof such as sulfonamidoalkylene.
- Preferred linking groups Q can be selected according to ease of preparation and commercial availability. Below is a partial representative list of suitable organic Q groups.
- each k is independently an integer from 1 to about 20
- g is an integer from 0 to about 10
- h is an integer from 1 to about 20
- R' is hydrogen, phenyl, or alkyl of 1 to about 4 carbon atoms
- R" is alkyl of 1 to about 20 carbon atoms.
- Q is preferably alkylene or sulfonamido, or sulfonamidoalkylene.
- R 4 is an alkylene group having 2 to
- the oxyalkylene units in the poly(oxyalkylene) may be the same, as in poly(oxypropylene), or may be a mixture, as in a straight or branched chain or randomly distributed oxyethylene and oxypropylene units or as in a straight or branched chain of blocks of oxyethylene units and blocks of
- the poly(oxyalkylene) chain can be interrupted by or include one or more catenary linkages, though it is preferred that such linkages be free of reactive functional groups containing active hydrogen atoms, providing such linkages do not substantially alter the solubility-imparting character of the poly(oxyalkylene) chain.
- active hydrogen atom as used in this application means a hydrogen atom (other than an amido hydrogen atom) which leads to chain transfer or chain termination during free radical polymerization.
- the catenary linkages have three or more valences, they provide a means for obtaining a branched chain of oxyalkylene units.
- the poly(oxyalkylene) radicals in the oligomers can be the same or different, and they can be pendant. It is also preferred that the molecular weight of the poly(oxyalkylene) radical be between about 500 and 5000 or higher, i.e., 100,000 or more, more preferably 2000 to 4000, in order to obtain a desired solubility.
- the alkylene glycol fluoro acrylate polymers can be prepared, or example, by free radical initiated copolymerization of a fluoroaliphatic radical-containing acrylate with a poly(oxyalkylene) monoacrylate, diacrylate or mixtures thereof.
- the molecular weight of the alkylene glycol fluoro acrylate polymer can be controlled by adjusting the concentration and activity of the initiator, concentration of monomers, and temperature, and by chain-transfer agents, such as thiols, e.g., n-octyl mercaptan.
- Fluoroaliphatic acrylates such as those described in the above preparation, are known in the art (e.g., see U.S. Pat. Nos.
- poly(oxyalkylene) acrylates used in the above preparation, and other acrylates useful for such purposes can be prepared from commercially available hydroxy and alkoxy poly(oxyalkylene) materials, such as those sold under the trade designations "PLURONIC” (available from BASF Corp. of Parsipanny, New Jersey), "CARBOWAX” and “TRITON” (available from Union Carbide Corp), by reacting such hydroxy materials in a known manner with acrylic acid, methacrylic acid, acryloyl chloride, or acrylic anhydride.
- PLURONIC available from BASF Corp. of Parsipanny, New Jersey
- CARBOWAX CARBOWAX
- TRITON available from Union Carbide Corp
- unsaturated monomers suitable for the preparation of the polymers of this invention for example by copolymerizing with corresponding poly(oxyalkylene)-containing, thermally ethylenically unsaturated comonomers, are known in the art (e.g., see U.S. Pat. Nos. 2,592,069, 2,995,542, 3,078,245, 3,081,274, 3,291,843 and 3,325,163, and the ethylenically unsaturated materials suitable for providing fluoroaliphatic radical-containing structural units disclosed in U.S. Pat. No.
- alkylene glycol fluorochemical acrylate polymers may also optionally contain units derived from other monomers such as alkyl acrylates, vinylidene chloride, and n-methylol acrylamide.
- a preferred polyethoxylated alkylene glycol fluoro acrylate is a
- compositions according to the present invention will include a
- polyurethane polyalkoxylated polyurethane
- polyurethane preferably having pendant perfluoroalkyl groups and comprising the reaction product of an aliphatic tri- or higher order isocyanate, a fluorinated alcohol, amine or mercaptan, and a poly(oxyalkylene) diol or dithiol.
- the urethanes useful in the compositions of the invention are commensurate in scope with those disclosed in the aforementioned U.S. Pat No. 5,350,795 (Smith et al.) and are represented by the formula:
- R f is a fluoroaliphatic radical
- R h is a non-fluorinated hydrocarbon radical
- Q is an organic linking group
- A is a residue of a tri- or higher order isocyanate, i.e., the residue being that portion of the tri- or higher order isocyanate minus the reacted—NCO groups,
- R 1 ) y is a poly(oxyalkylene) moiety, R 1 being an oxyalkylene group with 2 to 6 carbon atoms or a cyclic ether or ester moiety having 2 to 6 carbon atoms and y is a number of about 10 to 50,
- X is O, S or a linking group terminating in O or S, (e.g.,—CH 2 CH 2 O)
- R 2 is a residue of a tri- or higher order isocyanate, two of the isocyanate groups of the tri- or higher order isocyanate forming the depicted urethane groups and the other isocyanate groups reacted to form pendant—QR f or—QR h groups
- s is a number of at least 1 and can be 3 or higher
- z is zero or a number of up to about 4,
- s + z is a number of about 4 or higher
- t is a number of at least about 10, preferably 15 to 35.
- the polyalkoxylated polyurethanes have a weight average molecular weight of at least about 40,000, preferably about 65.000 to 250,000.
- the polyalkoxylated polyurethanes depicted above there are a plurality of R f radicals which can be the same or different. This also applies to a plurality of Q, A, R 1 and R 2 groups.
- the polyalkoxylated polyurethanes will contain about 5 to 40 weight percent, preferably about 10 to 30 weight percent, of carbon-bonded fluorine. If the fluorine content is less than about 10 weight percent, impractical large amounts of the polymer will generally be required, while fluorine contents greater than about 35 weight percent generally result in polymers which have too low a solubility to be efficiently used in the compositions of the invention.
- the non-fluorinated hydrocarbon group R h is optionally included within the polyurethanes depicted above.
- z is zero (e.g., the polyurethane includes no R h groups).
- R h can be a straight chain, branched chain, or cyclic alkyl.
- R h is preferably free of polymerizable olefinic unsaturation and can optionally contain catenary heteroatoms such as oxygen divalent or hexavalent sulfur, or nitrogen.
- the non-fluorinated hydrocarbon group can optionally contain epoxide or aziridine functionalities.
- the non-fluorinated hydrocarbon group contains about 1 to 36 carbon atoms, more preferably 10 to 24 carbon atoms.
- R 1 y , R 1 is an oxyalkylene group having 2 to 4 carbon atoms, such as -OCH 2 CH 2 -, -OCH 2 CH 2 CH 2 -, -OCH(CH 3 )CH 2 -, and -OCH(CH 3 )CH(CH 3 )-,
- the oxyalkylene units in the poly(oxyalkylene) may be the same, as in poly(oxypropylene), or they may be different such as in a mixture of straight or branched chain or randomly distributed oxyethylene and oxypropylene units or as in a straight or branched chain of blocks of oxyethylene units and blocks of oxypropylene units.
- the poly(oxyalkylene) chain can be interrupted by or include one or more catenary linkages which may have three or more valences to provide a means for obtaining a branched chain or oxyalkylene units.
- the molecular weight of the poly(oxyalkylene) radical can be about 750 to 2000, preferably about 900 to 1750.
- R 2 which is a residue of a tri- or higher order isocyanate, can be formed from such isocyanate compounds as polyaromatic polyisocyanate ("Papi”) such as that available under the trade designation “VORANATE” M220 (available from Dow Chemical Co. of Midland, Michigan) or "DESMODUR" N-100,
- the fluoroaliphatic radical-containing oxyalkylene urethanes used in this invention can be prepared in a known manner such as by condensation
- fluorochemical urethanes can be included in the compositions of the invention, as known by those skilled in the art. Further descriptions of useful fluorochemical oxyalkylenes can be found in U.S. Pat. No. 3,787,351 and U.S. Pat. No. 4,289,892, for example. Fluorochemical Acrylate Polymers with Polymerizable Emulsifier
- compositions of the invention further include fluorochemical acrylate polymers having copolymerizable surfactants incorporated therein.
- the fluorochemical acrylate polymers comprise the polymerized reaction product of a fluorinated (meth)acrylate monomer; at least one alkyl (meth)acrylate monomer; and a polymerizable cationic emulsifier comprising a quaternary amine surfactant.
- a preferred fluorochemical acrylate polymer is represented by the general formula
- R f is a fluoroaliphatic radical, as above,
- Q is an organic linking group, as above,
- R b and R b ' are the same or different and are selected from the group
- R d , R d ', R d ", R d “' can be the same or different and are selected from the group consisting of H or -CH 3 ,
- R a , R a ', R a " can be the same or different and are selected from the group consisting of an alkyl group having from 1 to 18 carbon atoms,
- R c is a saturated aliphatic (linear or branched) or cyclic alkyl, or a
- n 1 , n 2 , and n 3 are numbers which may independently range from 10 to 70, and
- n 4 is a number which is at least 1 and generally is within the range from 1 to 6.
- R d , R d ', R d ", R d '" can be the same or different and are selected from the group consisting of H or -CH 3 , so that the acrylate and the methacrylate species are equally plausible for use as monomers in the above fluorochemical acrylate polymers.
- Suitable fluorinated (meth)acrylate monomers useful in the invention are those selected from the group consisting of N-methyl perfluoro octylsulfonamidoethyl (meth)acrylate, N-ethyl perfluoro
- the fluorinated (meth)acrylate monomer is N-methyl perfluoro octylsulfonamidoethyl acrylate.
- the fluorinated (meth)acrylate monomer comprises from about 15 to about 40 mole percent, and, more preferably, between 20 and 30 mole percent of the total polymerizable species present in the final copolymer.
- the fluorochemical acrylate polymer is made with at least one alkyl
- alkyl (meth)acrylate monomer Preferably, two alkyl (meth)acrylate monomers are used in the preparation of the above polymer.
- Suitable alkyl (meth)acrylate monomers are alkyl esters of acrylic or methacrylic acid wherein the alkyl groups, R a or R a ', are independently selected from the group of C 1 to C 18 alky Is which may be linear, branched, cyclic or polycyclic, within the above parameters.
- Preferred alkyl (meth)acrylates are selected from the group consisting of methylacrylate, ethylacrylate, butylacrylate, hexylacrylate, isooctylacrylate, isodecylacrylate, octadecylacrylate ethylmethacrylate, butylmethacrylate, cyclohexylmethacrylate and mixtures thereof. More preferably, the alkyl (meth)acrylate monomers comprise an alkyl acrylate and an alkyl methacrylate and, most preferably are n-butyl acrylate and n-butyl methacrylate.
- the polymerizable cationic emulsifier comprises a quaternary amine surfactant capable of entering into free radical polymerization reactions with one or more of the monomers used to synthesize the fluorochemical acrylate polymer.
- the emulsifiers contain at least one carbon-carbon double bond situated so that the double bond is capable of entering into free radical
- polymerization reactions e.g., the double bond is not stearically or electronically hindered.
- the copolymerizable cationic emulsifiers are quaternary ammonium salts of of alkyl acrylates of the general formula
- R a ", R b , R b ', R c , R d '", and Z, are as described above.
- the cationic copolymerizable emulsifier comprises the reaction product of N,N-dimethylaminoethyl methacrylate and an alkyl halide having a carbon chain length from about 4 to about 30 carbon atoms and, more preferably, from about 8 to about 20 carbon atoms.
- a preferred alkyl halide is hexadecylbromide because of its commercial availability as well as its ease of use in making emulsified polymers.
- Other quaternary salts of the above formula are described in U.S. Letters Patent Nos. 3,780,092; 3,928,423; 3,936,492 and
- the cationic copolymerizable emulsifier preferably comprises from about 0.5 percent to about 10 percent based on the total weight of the other monomers present in the fluorochemical acrylate polymer, and most preferably, from about 2 to about 6 percent.
- the quaternary ammonium salt can be prepared first by reacting N,N-dimethylaminoethyl methacrylate and an alkyl halide according to the General Preparative Procedure A herein.
- the emulsifier and the other monomers are then emulsion polymerized.
- Water, the fluorinated monomer(s) the alkyl (meth)acrylate monomer(s) and the surfactant are homogenized in a known manner at elevated temperatures (e.g., 55 to 70 °C).
- the emulsion is treated with a suitable water soluble free-radical initiator under a nitrogen blanket.
- the initiator is preferably added to the emulsion to provide a concentration of initiator of between about 0.05% to 2% and preferably 0.1 to 0.5% by weight based on the total weight of the monomers in the emulsion.
- concentration of initiator of between about 0.05% to 2% and preferably 0.1 to 0.5% by weight based on the total weight of the monomers in the emulsion.
- Suitable initiators include 2,2'-azobis-(2-cyanopropane-1-sulfonate), 2,2'-azobis-(2-amidinopropane)dihydrochloride, ⁇ , ⁇ -azobis-butyramidinium chloride, and azobis-(N,N'-dimethylene isobutyramidine) and its salts with strong acids and mixtures thereof.
- a preferred water soluble initiator is 2,2'-azobis-(2-amidinopropane)dihydrochloride, available under the trade designation "V-50" from Wako Chemicals USA, Inc. of Richmond, Virginia.
- V-50 is 2,2'-azobis-(2-amidinopropane)dihydrochloride
- the resulting polymeric emulsion may be diluted with water prior to blending the polymer with the other components in the compositions of the invention, as is further described below.
- fluorochemical esters may be included within the compositions of the invention.
- the esters useful in the compositions of the invention are commensurate in scope with those disclosed in the aforementioned U.S. Pat No. 5,350,795. These esters may be included within the compositions to help maintain a high level of repellency for the treated fabric after the fabric is abraded, for example.
- the treated substrates may experience somewhat diminished repellency after being subjected to conditions of abrasion, but the compositions are still useful in the treatment of substrates, as described herein.
- Fluorochemical esters useful in the present invention can be formed by reacting a perfluoroalkyl aliphatic alcohol or mixture of alcohols with mono- or polycarboxylic acids which can contain other
- a particularly preferred fluorochemical ester is the fluorochemical adipate ester which represented by the formula
- the fluorochemical adipate ester can be prepared by reacting a precursor fluoroaliphatic radical- and chlorine-containing alcohol with adipic acid.
- a most preferred ester is represented by the formula
- a method of preparing the alcohol precursors is by reaction of
- epichlorohydrin with a fluoroaliphatic radical-containing alcohol.
- fluoroaliphatic radical-containing alcohol Readily available alcohols which can be used in this preparation are those corresponding to the formula
- R f and Q are as defined above,
- R 5 is hydrogen or a lower alkyl
- R 6 is hydrogen, lower alkyl, or aryl of 6 to 12 carbons and R 5 and R 6 can be connected together to form a cyclic structure, aromatic or cycloaliphatic, including the hydroxyl-bearing carbon atom.
- fluoroaliphatic radical-containing alcohols When the fluoroaliphatic radical-containing alcohols are reacted with epichlorohydrin to form the corresponding fluoroaliphatic alcohols, the latter can correspond to the formula
- R f , Q, R 1 and R 2 are as defined above and p is an integer from 1 to 5.
- fluoroaliphatic radical- and chlorine-containing alcohols are those disclosed, for example, in U.S. Pat. No. 4,043,823 (Loudas) and U.S. Pat. No. 4,289,892 (Soch).
- compositions of the invention comprise a blend of the above described ingredients and the preparation of such blends is set forth in detail in the General Preparative Procedures and in the Examples herein.
- the compositions of the present invention comprise a blend of first and second major components wherein the first major component comprises polyalkoxylated polyurethane, preferably with polyalkylene glycol fluorochemical acrylate copolymer and, optionally including a fluorochemical adipate ester, all as described above.
- the second major component comprises fluorochemical acrylate polymer with the polymerizable cationic emulsifier, also as described above.
- the polyurethane in aqueous emulsion, can be used alone and may be prepared following the General
- Preparative Procedure B herein e.g., about 15% solids
- the alkylene glycol fluoro acrylate may be prepared according to the General Preparative Procedure C, allowing for changes in the monomers and the substituent groups according to the parameters set forth above.
- the alkylene glycol fluoro acrylate is blended with the polyurethane to provide a weight ratio of polyurethane:alkylene glycol fluoro acrylate of about 3:2.
- the polyurethane, the alkylene glycol fluoro acrylate and the ester are blended in deionized water, stirred to promote thorough mixing and excess solvent is stripped from the mixture to give a blend which is preferably from about 5% to about 20% solids in water and more preferably between 10% and 16%.
- the polyurethane is present within the first component at a weight percent of between about 50% and 90% and most preferably about 50%.
- the alkylene glycol fluoro acrylate may be present at a weight percent of 10% to 50% and most preferably about 33%.
- the optional adipate ester is generally present at a weight percent of 10% to 20% and most preferably about 17%.
- the fluorochemical acrylate polymer is made as an aqueous emulsion and generally following the General Preparative Procedure A while allowing for changes of the monomers and the substituent groups according to the general parameters set forth herein.
- the two major components are blended in deionized water to achieve a preferred solids content of about 3 percent by weight and a solids weight ratio between the two components ranging from about 25 : 1 and 1 :25 and more preferably from 9: 1 to 1 :9. Most preferably, the two major components are blended to achieve a solids weight ratio of about 1 :1 in the finished composition.
- coalescing solvents are then added along with minor amounts of other solvent (e.g., alcohol) to increase fabric wetting, improve the stability of the composition and reduce the likelihood of residue formation on the treated substrate.
- Aerosol propellants such as isobutane and the like are used in packaging the compositions in aerosol form.
- known corrosion inhibitors are preferably included within such aerosol products to prevent corrosion within the steel cans normally used to package such products.
- Suitable coalescing solvents include the alkylene glycol ethers such as dipropylene glycol mono n-butyl ether, propylene glycol mono methyl ether, dipropylene glycol mono n-propyl ether, esters thereof and mixtures of the foregoing. Assuming a preferred solids concentration in the composition of about 3%, The coalescing solvents are present within the composition at a total weight percentage from about 2% to 10% and preferably about 4%. A small amount of an of an alkylol such as ethyl alcohol or isopropanol may be added to as an additional solvent as an aid to the stability of the composition and to prevent freezing.
- alkylene glycol ethers such as dipropylene glycol mono n-butyl ether, propylene glycol mono methyl ether, dipropylene glycol mono n-propyl ether, esters thereof and mixtures of the foregoing. Assuming a preferred solids concentration in the composition of about 3%,
- the alcohol is present at a weight percent in the finished composition of between about 0.5% and 3% and most preferably 1%.
- suitable solvents and their relative concentrations within the composition is within the skill of those practicing in the field.
- Suitable corrosion inhibitors include morpholine, ammonium hydroxide (30%), sodium nitrite, alkyl amines and combinations thereof.
- the concentrations of corrosion inhibitors is typically less than 1% by weight and most preferably is between about 0.5% and 1.0%, assuming a solids concentration in the composition of about 3%.
- a fast-breaking foam composition can be formulated with the addition of pH modifiers to the aerosol formulation mentioned above.
- a foam product may be desirable to enable the user of the composition to easily see where a treatment has been applied to thereby avoid over application of the composition as well as increased drying times.
- Anti-soiling agents may also be added to the compositions of the invention.
- Such agents are defined as materials which are solid, non-tacky water soluble or water dispersible and which, upon drying of the composition, are capable of rendering the substrate non-tacky and resistant to soiling.
- the inclusion of the anti-soiling agents within the compositions of the invention is optional.
- compositions described herein may be applied to a wide variety of fiber-containing substrates.
- substrates include textile fibers (or filaments) and fabrics, (including fabrics made into finished products) made from cotton, polyester, polyolefin, nylon, acrylic, acetate or blends thereof, as well as leather, finished garments, upholstered furniture and installed carpet.
- Individual fibers or filaments can be treated with the compositions of the invention as well as aggregate forms of such filaments or fibers (e.g., yarn, tow, web as well as woven or knit fabric).
- These substrates can be treated with the compositions of the invention by applying the compositions thereto using known techniques customarily used in applying fluorochemicals to fibers and fabrics.
- compositions can be applied to finished products such as apparel and upholstered furniture without the need for thermal curing and will provide excellent oil and water repellency without the inclusion of significant amounts of organic solvents.
- Suitable application techniques for applying these compositions include, for example, spraying, brushing, immersion or foaming.
- the amount of the compositions applied to the substrate is typically about 0.5 to 6 weight % solids and, more preferably, 1 to 4 weight % solids based on the weight of the fiber or fabric.
- treated substrates are tested for oil and water repellency according to the following test methods.
- the oil repellency of treated substrates is measured by the American Association of Textile Chemists and Colorists (AATCC) Test Method No.
- the abraded oil repellency test also provides a relative value of the substrates' oily stain resistance.
- the treated substrate is first placed on an ATTCC Crockmeter (as used in AATCC Test Method 8-1985 and commercially available from Atlas Electric Devices Co. of Chicago, Illinois) and subjected to 20 cycles of rubbing abrasion using a 1.6 centimeter disk of grade 600 abrasive paper (available under the trade designation "Wetordry Tri-M-ite" from Minnesota Mining and Manufacturing Company of St. Paul, Minnesota).
- the test substrate is treated in the same manner as in the oil repellency test described above using the same test oils. In general, an oil repellency of 4 or greater is desirable.
- the water/alcohol drop repellency test tests the ability of the substrate to repel various blends of water and isopropyl alcohol. Test drops of the liquid solutions are progressively applied to the treated substrate and, after 30 seconds, if the applied solution does not soak into the substrate, the solution is wicked or wiped away with a paper tissue and the surface of the substrate is observed for surface wetting. Eleven blends of water and alcohol are used (see table 2, below) with 100% water being the easiest to repel and 100% isopropyl alcohol being the most difficult.
- the treated substrate is given a number value corresponding to the solution having the highest concentration of isopropyl alcohol which the treated substrate was able to repel without observed wetting. For example, a substrate is given a value of 4 if it is able to repel the solution of 60% water and 40% isopropyl alcohol.
- the water spray test follows AATCC Test Method 22.
- the treated substrate is rated for water repellency as determined by the pattern of surface wetting described in table 3 below.
- the treated substrate is held taut within a 15-centimeter diameter ring at a 45° angle.
- 250 milliliters of water at a temperature of 27°C ( ⁇ 1°C) is dropped onto the substrate from a distance of 15.2 centimeters above the center of the substrate.
- the substrate is tapped lightly to remove excess water and is rated in a manner consistent with that shown in table 3.
- a higher number indicates better water repellency and, in general, a number of 65 or higher is desirable.
- the wet-through rating is performed on a treated substrate immediately following the water spray test, described above.
- the treated substrate which was rated in the above water spray test is immediately turned over and the back side of the substrate is visually observed and is touched by the observer to determine whether water has seeped through.
- a wet-through value from 1 to 6 is then given to the treated substrate, depending on the degree of "wetness.”
- a value of " 1 " signifies the back of the substrate is thoroughly wet, while a value of "6" indicates the substrate is completely dry.
- a composite repellency rating is tabulated for each composition on each substrate by summing the values obtained in each of the above test methods with the exception that the rating obtained in the water spray test is first divided by 10.
- the maximum composite repellency rating possible is 42.
- Fluorochemical Acrylate Polymer With Polymerizable Cationic Emulsifier A reaction vessel fitted with a condenser, a mechanical stirer, and a thermometer is charged with 9.0 grams of N,N-dimethylaminoethyl methacrylate (available from Aldrich Chemicals of Milwaukee, Wisconsin), 0.036 grams of butylated hydroxy toluene (BHT) (Aldrich Chemicals ), 18.8 grams acetone and 17.5 grams 1-bromohexadecane (Aldrich Chemicals) The mixture is heated at 75°C (165°-170° F) until the unreacted amine is below 0.05%, as determined by gas chromatography.
- N,N-dimethylaminoethyl methacrylate available from Aldrich Chemicals of Milwaukee, Wisconsin
- BHT butylated hydroxy toluene
- acetone 18.8 grams
- 1-bromohexadecane Aldrich Chemicals
- reaction solution is then cooled and the formation of a precipitate is observed.
- ethylacetate Aldrich Chemicals
- ethylacetate Aldrich Chemicals
- 16°C 16° F
- a white solid (2-(dimethyl hexadecylamino) ethylmethacrylate bromide) precipitates from the solution and the solid is filtered and washed twice with cold ethyl acetate and is dried in a vacuum oven at 50° C for 8 hours.
- the emulsion is transferred to a 16 ounce (0.47 liter) amber bottle and is treated with 0.06 grams of a free radical initiator, 2,2'-azobis-(2-amidinopropane)dihydrochloride ("V-50" from Wako Chemicals USA, Inc.), and nitrogen is bubbled through the emulsion for 1 minute.
- V-50 2,2'-azobis-(2-amidinopropane)dihydrochloride
- the bottle is capped and kept at 60°C while mixing at about 50 rpm in a launderometer for 5 hours.
- the resulting latex (about 30% solids) is cooled, filtered and is then ready for use in the formulations below.
- polyurethane solution is added to a 1-liter, 3-necked flask equipped with a mechanical stirrer, dropping funnel, thermometer and a heating mantle and heated to 65° C.
- Distilled water 510 grams heated to 65° C is slowly added with vigorous stirring. The resulting mixture is stirred for 10 minutes and ethyl acetate is removed by vacuum stripping to provide a translucent dispersion of about 15% solids.
- a poly (oxyalkalene) acrylate solution is first prepared by adding 120 grams toluene, 90 grams of a difunctional block-polymer with terminal hydroxyl groups (available under the trade designation "PLURONIC" 44 from BASF
- thermometer and a reflux condenser are added 184.6 grams of the polyurethane reaction mixture (in ethyl acetate and before adding water), as in General
- Preparative Procedure B 178.7 grams of acrylate copolymer made according to General Preparative Procedure C, 36 grams fluorochemical adipate ester made according to General Preparative Procedure D, 125 grams ethyl acetate and 960 grams deionized water. The resulting mixture is vigorously stirred for 1 hour while be heated to 65° - 70° C. Solvent is removed by vacuum stripping and about 750 grams of water is added as necessary to make a stable dispersion of about 12% solids.
- composition was made as in Example 1, except that 0.5 grams of the fluorochemical acrylate polymer, 23.8 grams of a blend made according to the above Procedure E and 71.2 grams deionized water were used to formulate a blend having a weight ratio of the fluorochemical acrylate polymer: [polyurethane + polyalkylene glycol fluorochemical acrylate copolymer + adipate ester] of about 1 :19.
- composition was made as in Example 1, except that 1.0 grams of the fluorochemical acrylate polymer, 22.5 grams of a blend made according to the above Procedure E and 72 grams deionized water were used to formulate a blend having a weight ratio of the fluorochemical acrylate polymer: [polyurethane + polyalkylene glycol fluorochemical acrylate copolymer + adipate ester] of about 1 :9.
- Example 4 Another composition was made as in Example 1, except that 9.0 grams of the fluorochemical acrylate polymer, 2.5 grams of a blend made according to the above Procedure E and 84 grams deionized water were used to formulate a blend having a weight ratio of the fluorochemical acrylate polymer:[polyurethane + polyalkylene glycol fluorochemical acrylate copolymer + adipate ester] of about 9:1.
- Example 2 Another composition was made as in Example 1, except that 9.5 grams of the fluorochemical acrylate polymer, 1.25 grams of a blend made according to the above Procedure E and 84.75 grams deionized water were used to formulate a blend having a weight ratio of the fluorochemical acrylate polymer: [polyurethane + polyalkylene glycol fluorochemical acrylate copolymer + adipate ester] of about 19:1.
- Example 2 Another composition was made as in Example 1, except that 1.7 grams of the fluorochemical acrylate polymer, 4.2 grams of a blend made according to the above Procedure E and 89.6 grams deionized water were used to formulate a blend comprising about 1% solids.
- the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester] was about 1 :1.
- Example 8 Another composition was made as in Example 1 , except that 10 grams of the fluorochemical acrylate polymer, 25 grams of a blend made according to the above Procedure E and 60.5 grams deionized water were used to formulate a blend comprising about 6% solids.
- the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester] was about 1 :1.
- a fluorochemical acrylate polymer was made according to the above Procedure A except that the bromide salt monomer was substituted with 3.12 grams of a 75% solids solution of 2-(trimethyl-amino)ethylmethacrylate chloride salt in water. 78.0 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer and 12.5 grams of a blend made according to the above Procedure E were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer:
- polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester was about 1 :1.
- a fluorochemical acrylate polymer was made according to the above
- Procedure A except that bromodocosane replaced the bromohexadecane to make 2-(dimethyldocosaneamino)ethylmethacrylate bromide salt.
- 78.0 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer and 12.5 grams of a blend made according to the above Procedure E were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring.
- the resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester] was about 1 :1.
- Example 10 A fluorochemical acrylate polymer was made according to the above Procedure A except that the butyl acrylate and butyl methacrylate were substituted with 23.26 grams of methyl acrylate. As in Example 1, 78.0 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer and 12.5 grams of a blend made according to the above Procedure E were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring.
- the resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester] was about 1 :1.
- a fluorochemical acrylate polymer was made according to the above Procedure A except that the butyl acrylate and butyl methacrylate were substituted with 23.26 grams of octadecyl acrylate.
- 78.0 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer and 12.5 grams of a blend made according to the above Procedure E were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring.
- the resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester] was about 1 :1.
- a fluorochemical acrylate polymer was made according to the above Procedure A except that the butyl acrylate and butyl methacrylate were substituted with 23.26 grams of methyl acrylate. 81.7 grams deionized water, 6.7 grams of the fluorochemical acrylate polymer and 7.1 grams of a polyurethane/acrylate polymer blend made according to the above Procedure F were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer] was about 2: 1.
- Example 16 Another composition was prepared as in Example 13 except that 81.7 grams deionized water, 6.7 grams of the fluorochemical acrylate polymer made according to the above Procedure A and 7.1 grams of a polyurethane/acrylate polymer blend made according to the above Procedure F were used.
- the resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer] was about 2:1
- a polyurethane polymer was prepared according to the above Procedure B except that a propylene oxide, ethylene oxide copolymer available under the trade designation "Pluronic” L62 (from BASF Corporation of Parsippany, New Jersey) was used in place of the ethylene glycol ("Carbowax" 1450).
- a propylene oxide, ethylene oxide copolymer available under the trade designation "Pluronic” L62 from BASF Corporation of Parsippany, New Jersey
- ethylene glycol Carbowax 1450
- a polyurethane polymer was prepared according to the above Procedure B except that the "Desmodur"N100 triisocyanate was replaced with “Desmodur” N3300 triisocyanate and the "Carbowax” 1450 ethylene glycol was replaced with “Carbowax” 400 ethylene glycol.
- 80.5 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer made according to the above Procedure A and 10 grams of the polyurethane were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring.
- the resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate
- polymer:polyurethane was about 1 :1.
- a composition was formulated as in Example 1 except that 72.5 grams of deionized water was used and the glycol ethers and the alcohol of Example 1 were substituted with 10 grams dipropylene glycol mono-n-propyl ether.
- Example 1 99.45 grams of a composition prepared according to Example 1 was formulated as an aerosol with 0.2 grams morpholine, 0.2 grams sodium nitrite and 0.15 grams ammonium hydroxide solution (30% in water) with stirring. The liquid was packaged in an aerosol can and 5.0 to 5.5 grams of isobutane was added as a propellant.
- Comparative Example E The commercial product was an aerosol version of a fabric protector available under the trade designation "ScotchGard" from
- compositions of the above Examples and the Comparative Examples were tested on different substrates according to the above Test Procedures. All substrates were prepared by hand-spraying 20.3cm by 22.9cm areas with the compositions. Care was taken to apply an even coverage of each composition used so that the dried add-on weight was about 2-3% of the weight of the dried fabric. The treated substrates were dried overnight at ambient conditions prior to testing.
- the fabric substrates employed in the testing are identified as follows:
- Fabric A is a bleached and washed polyester/cotton blend (65% polyester/35% cotton) commercially available under the style no. 7436 from Testfabrics, Inc. of Middlerex, New Jersey.
- Fabric B is a cotton sateen (100% cotton) weave which is desized and bleached available under the style no. 428 from Testfabrics, Inc
- Fabric C is an untreated, unfinished green rayon velvet upholstery fabric available from Collins & Aikman, Decorative Fabrics Division of Roxboro, North Carolina.
- Fabric D is a polypropylene velvet upholstery fabric available under the style no.62521 from Joan Fabrics of Lowell, Massachusetts.
- Fabric E is a woven upholstery fabric comprising 48% olefin/18% rayon/34% polyester available under the style no. 9352 from Chromatex of West Hazelton, Pa.
- compositions of the invention as compared with the compositions of the invention
- Table 4 shows the compositions of the present invention include a broader range of protective properties than the compositions of the Comparative Examples. Also, aerosol stability is typical for compositions of the invention.
- Example 1 The data for the fabric treated with the compostion of Example 1 set forth in Table 4, for example, demonstrates better abraded oil resistance than the fabric treated with the composition of Comparative A. Also, the composition of Example 1 provides aerosol stability which is not provided by the Comparative A
- Examples 8-1 1 represent inventive compositions made from monomers different than those used in the formulation of Example 1.
- Comparative E represents a solvent based formulation.
- the data demonstrates that the compositions of the invention provide oil and water repellency which is at least as effective as that provided by such a solvent based formulation (e.g.. compare Comparative E with Example 1).
- Example 12-18 demonstrate the effeciveness of inventive compositions comprising variations of components, consistent with the above description.
- Example 19 and Comparative Examples E and F Data was collected for Fabrics A, B, C, D and E and is set forth in Table 6 below.
- Example 19 The above data demonstrates the superior protective abilities of the inventive composition of Example 19 when compared with the water-based aerosol formulations of Comparative Example F, especially for Fabrics A, D and E, as reflected in the composite scores.
- the water based aerosol of Example 19 gave at least comparable performance for the solvent based composition of Comparative Example E overall, with improved performance over Comparative E noted on Fabric D.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Oil and water repellent compositions for the treatment of fiber containing substrates such as fabric and the like, substrates treated with these compositions and methods for the treatment of substrates are described. The compositions of the invention comprise (a) a polyalkoxylated polyurethane and (b) a fluorochemical acrylate polymer comprising the polymerized reaction product of a fluorinated acrylate or methacrylate monomer, at least one alkyl acrylate or methacrylate monomer and a polymerizable cationic emulsifier comprising a quaternary amine surfactant. Additionally, (c) a polyalkylene glycol fluorochemical acrylate copolymer and (d) a fluorochemical adipate ester can also be included within the compositions. The above components are blended together within the composition at a weight ratios of (a):(b), or (a)+(c):(b), or (a)+(c)+(d):(b) of from 19:1 to 1:19 and preferably about 1:1. The compositions may be applied to a variety of fiber containing substrates to achieve a broad range of oil and water repellent properties.
Description
AQUEOUS OIL AND WATER REPELLENT COMPOSITIONS
This invention relates to oil and water repellent compositions for the treatment of fabrics and other fiber containing substrates at ambient conditions, to the treated substrates and to methods of treating those substrates. Background of the Invention
Substrates such as woven fabrics, carpeting, upholstery and the like become soiled and stained when used, requiring frequent and repeated cleaning. Various chemical compositions have been proposed for the protection of such substrates against water and oil based soils and/or stains, and the patent literature describes many such compositions. United States Patent No. 5,350,795 to Smith et al., for example, includes a partial listing and discussion of the patent literature relating to fluorochemical compositions for the treatment of textiles and the like. As the literature indicates, fluorochemical compounds have been used successfully in the treatment of various substrates to render them more resistant to staining and, therefore, easier to clean.
Even though fluorochemicals have found fairly widespread use,
fluorochemicals have generally required the inclusion of significant amounts of organic solvents which may be undesirable. The use of water based
fluorochemical compositions (e.g., those which do not include significant organic solvents), while more acceptable, has been less than satisfactory because such aqueous compositions have generally required the performance of additional steps in the application of the composition to a substrate, such as the application of heat to the treated substrate. In light of the foregoing, it is desirable to provide oil and water repellent fluorochemical compositions which do not require a significant amount of organic solvent and which can be applied to a substrate and dried at ambient conditions to impart oil and water repellency.
In the evaluation of the oil and water repellent properties of treated substrates, certain known tests are employed to measure the degree to which a substrate effectively repels water and oil under different conditions. For any given composition, identical tests are performed on a number of different substrates (e.g., different fabric types) to fully assess the degree to which the composition is effective in protecting specific materials. As a result of such assessments, it is known that while some fluorochemical compositions will provide favorable or at least acceptable test results according to some of the aforementioned tests, the art has generally failed to provide a composition which is substantially free of organic solvents and which provides an improved range of oil and water repellent properties. Therefore, it is desirable to provide a composition suitable for the treatment of fiber-containing substrates which can be formulated and applied without significant amounts of organic solvents to provide a range of improved oil and water repellent properties at ambient conditions (e.g., the composition can be applied at room temperature without additional thermal treatment).
Summary Of The Invention
The present invention provides fluorochemical compositions suitable for application on a variety of fiber-containing substrates such as fabrics and textile fibers comprising cotton, nylon, polyester, polyolefin, acrylic, acetate, leather or blends thereof and materials such as apparel, upholstery and carpet to impart a broad range of oil and water repellent properties. The compositions of the invention are water based formulations which may be applied to substrates and dried without thermal treatment, i.e., at ambient conditions. Applicants have found that a class of fluorochemical acrylate polymers having a polymerizable cationic emulsifier incorporated with the polymer can be blended with polyurethane containing blends to provide a class of fabric protective compositions which exhibit improved oil and water repellency.
In one aspect, the invention provides a composition for treating fiber-containing substrates to impart improved oil and water repellency thereto, the composition comprising:
(a) A polyalkoxylated polyurethane having pendant perfluoroalkyl groups, said polyalkoxylated polyurethane comprising the reaction product of an aliphatic or aromatic tri- or higher order isocyanate, a fluorinated alcohol, amine, or mercaptan, and a poly(oxyalkylene) diol or dithiol; and
(b) A fluorochemical acrylate polymer comprising the reaction product of a fluorinated acrylate or methacrylate monomer, at least one alkyl acrylate or methacrylate monomer, and a polymerizable cationic emulsifier comprising a quaternary amine surfactant.
The compositions preferably also include (c) an alkylene glycol fluoro acrylate polymer comprising the reaction product of a fluorinated acrylate or methacrylate monomer, polyalkylene glycol acrylate or methacrylate, and polyalkylene glycol diacrylate or dimethacrylate. Optionally, (d) a fluorochemical adipate ester can be included in the compositions of the invention. The above components are blended together within the composition at a weight ratio of (a):(b), or (a)+(c):(b), or (a)+(c)+(d):(b) from 25: 1 to 1 :25 and more preferably, at a 1 : 1 weight ratio.
The fluorochemical acrylate polymers can be represented by the general formula:
Rf is a fluoroaliphatic radical,
Q is an organic linking group,
Rb and Rb are the same or different and are selected from the group
consisting of H and linear or branched hydrocarbons having from 1 to 4 carbon atoms or together forming a carbocyclic ring of from about 3 to about 12 members, and mixtures thereof, Rd, Rd', Rd", Rd'" can be the same or different and are selected from the group consisting of H or -CH3,
Ra, Ra', Ra" can be the same or different and are selected from the group consisting of an alkyl group having from 1 to 18 carbon atoms, Rc is a saturated aliphatic (linear or branched) or cyclic alkyl, or a
combination of cyclic and aliphatic alkyls having at least 1 and generally from 4 to 30 carbon atoms, and preferably from 8 to 20 carbon atoms;
Z is an anion selected from the group consisting of chloride, bromide, iodide, sulfonate, alkyl sulfonate, phosphate, and mixtures thereof; n1, n2, and n3 are numbers which may independently range from 10 to 70, and
n4 is a number which is at least 1 and generally is within the range from 1 to 6.
Preferably, the compositions of the invention are aqueous emulsions which include only minor amounts of organic solvent. In addition to the above listed ingredients, the compositions may include pH modifiers and corrosion inhibitors. The aqueous compositions of the invention can be provided in aerosol form with the inclusion of an appropriate aerosol propellant such as isobutane, for example.
In the description of the invention, certain terms are used which will be understood to have the meanings defined herein. "Ambient conditions" means at prevailing room temperature and humidity without additional thermal treatment
and/or drying equipment. "Fiber-containing substrate" or "substrate" means fabrics, textile fibers or filaments, fabrics made into finished products made from cotton polyester, polyolefin, nylon, acrylic, acetate, leather and blends of the foregoing as well as finished garments, upholstered furniture and carpet.
"Polymerizable emulsifier" means a class of quaternized organic salts which serve simultaneously as monomeric reactants and as stabilizing agents in emulsion polymerization. Unless indicated otherwise, "stabilizing agent", "emulsifier" and "surfactant" are identical in meaning and are used interchangeably. In describing acrylate and methacrylate compounds, the term "(meth)acrylate" is intended to indicate both acrylate as well as methacrylate as equally plausible species.
In another aspect, the invention provides a method for treating substrates to provide oil and water repellency comprising treating a substrate with the composition of the invention and drying the treated substrate. In still another aspect, the invention also provides substrates having oil and water repellency when treated with the composition of the invention.
The further details of the invention will be more clearly understood by those skilled in the art after a consideration of the remainder of the disclosure including the detailed description of the preferred embodiment and the appended claims.
Detailed Description Of The Preferred Embodiment The fluorochemical compositions of the present invention are water based blends and can be applied to a variety of substrates at ambient conditions to provide a broad range of oil and water repellency properties, as described below. In describing the preferred embodiments of the invention, the individual components in the compositions are discussed and described separately, as indicated.
Alkylene Glycol Fluorochemical Acrylate Polymer
The compositions of the invention may include an alkylene glycol fluorochemical acrylate polymer (or "alkylene glycol fluoro acrylate") comprising
the reaction product of a fluorinated acrylate or methacrylate monomer, polyalkylene glycol acrylate or methacrylate monomer and polyalkylene glycol diacrylate or dimethacrylate monomer. The alkylene glycol fluoro acrylates are included within the more preferred embodiments of the invention to enhance the stability of the composition in the presence of minor amounts of coalescent solvents and especially in the presence of corrosion inhibitors added to the composition when formulating an aerosol blend. The alkylene glycol fluoro acrylates also aid in the wetting of a substrate with the compositions of the invention. Fluoro acrylate polymers useful in the present invention are disclosed, for example, in U.S. Pat. Nos. 5,350,795 (Smith et al.), 3,787,351 (Olson) and 4,795,793 (Amimoto et al.), all of which are incorporated herein by reference.
The preferred alkylene glycol fluoro acrylates have randomly arranged repeating units represented as
wherein Rf is a fluoroaliphatic radical, R3 is H or CH3, R4 is an alkylene group having 2 to 4 carbon atoms, Q is an organic linking group and x is an integer of at least 5, generally 10 to 75 and can be as high as 100.
The fluoroaliphatic group ( Rf) is a stable, inert, nonpolar, preferably saturated monovalent moiety which is both oleophobic and hydrophobic. The alkylene glycol fluoro acrylate preferably comprises from 2 to about 25 Rf groups and preferably comprises about 5 percent to about 30 percent, and more preferably about 8 percent to about 20 percent fluorine by weight based on the total weight of the oligomer, with the fluorine being essentially in the Regroups. Rf preferably contains at least about 3 carbon atoms, more preferably 3 to about 25 carbon atoms, and most preferably about 6 to about 12 carbon atoms. Rf can contain
straight chain, branched chain, or cyclic fluorinated alkyl groups or combinations thereof or combinations thereof with straight chain, branched chain, or cyclic alkyl groups. Rf is preferably free of polymerizable olefinic unsaturation and can optionally contain linking heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen. It is preferred that each Rf contain about 40% to about 78% fluorine by weight, more preferably about 50% to about 78% fluorine by weight. The terminal portion of the Regroup contains a fully fluorinated terminal group. This terminal group preferably contains at least 7 fluorine atoms, i.e., CF3CF2CF2-, (CF3)2CF-, -CF2SF5, or the like. Most preferred Rf are the perfluorinated aliphatic groups, i.e., those of the formula CnF2n+1.
The fluoroaliphatic group, Rf, is linked to the ester group by a linking group designated Q. Linking group Q can be a covalent bond, a heteroatom, e.g., O or S, or an organic moiety. Preferably, Q is an organic moiety containing 1 to about 20 carbon atoms, and optionally containing oxygen, nitrogen-, or sulfur-containing groups or a combination thereof, and preferably free of functional groups (e.g., polymerizable olefinic double bonds, thiols, easily abstracted hydrogen atoms such as cumyl hydrogens, and other such functionality known to those skilled in the art) that substantially interfere with free-radical polymerization. Examples of structures suitable for linking group Q include straight chain, branched chain, or cyclic alkylene, arylene, aralkylene, oxy, oxo, thio, sulfonyl, sulfinyl, imino, sulfonamido, carboxamido, carbonyloxy, urethanylene, ureylene, and combinations thereof such as sulfonamidoalkylene. Preferred linking groups Q can be selected according to ease of preparation and commercial availability. Below is a partial representative list of suitable organic Q groups. For the purposes of this list, each k is independently an integer from 1 to about 20, g is an integer from 0 to about 10, h is an integer from 1 to about 20, R' is hydrogen, phenyl, or alkyl of 1 to about 4 carbon atoms, and R" is alkyl of 1 to about 20 carbon atoms.
-SO2NR'(CH2)k- -CONR'(CH2)k- -(CH2)kO(O)C- -CH2CH(OH)CH2-
-CH2CH(OR")CH2- -(CH2)kC(O)- -(CH2)kSC(O)- -(CH2)kO(CH2)k- -(CH2)kS(CH2)k-
-(CH2)k(OCH2CH2)k- -(CH2)kSO2(CH2)k- -SO2NR(CH2)kO(CH2CH2)k- -(CH2)kSO2NR(CH2)k- -CH2)kSO2-
-SO2NR'(CH2)k-
-(CH2)kO((O)C(CH2)6O)gC(O)(CH2)6-
-(CH2)kO((O)C(CH2)6NH)gC(O)(CH2)6NHC(O)- -C(O)O(CH2)2OC(O)NH(CH2)2-
For linking Rf, Q is preferably alkylene or sulfonamido, or sulfonamidoalkylene.
In the poly(oxyalkylene) group, (OR4)x, R4 is an alkylene group having 2 to
4 carbon atoms, such as -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, and - CH(CH3)CH(CH3)-. The oxyalkylene units in the poly(oxyalkylene) may be the same, as in poly(oxypropylene), or may be a mixture, as in a straight or branched chain or randomly distributed oxyethylene and oxypropylene units or as in a
straight or branched chain of blocks of oxyethylene units and blocks of
oxypropylene units. The poly(oxyalkylene) chain can be interrupted by or include one or more catenary linkages, though it is preferred that such linkages be free of reactive functional groups containing active hydrogen atoms, providing such linkages do not substantially alter the solubility-imparting character of the poly(oxyalkylene) chain. The term "active hydrogen atom" as used in this application means a hydrogen atom (other than an amido hydrogen atom) which leads to chain transfer or chain termination during free radical polymerization. Where the catenary linkages have three or more valences, they provide a means for obtaining a branched chain of oxyalkylene units.
The poly(oxyalkylene) radicals in the oligomers can be the same or different, and they can be pendant. It is also preferred that the molecular weight of the poly(oxyalkylene) radical be between about 500 and 5000 or higher, i.e., 100,000 or more, more preferably 2000 to 4000, in order to obtain a desired solubility.
The alkylene glycol fluoro acrylate polymers can be prepared, or example, by free radical initiated copolymerization of a fluoroaliphatic radical-containing acrylate with a poly(oxyalkylene) monoacrylate, diacrylate or mixtures thereof. The molecular weight of the alkylene glycol fluoro acrylate polymer can be controlled by adjusting the concentration and activity of the initiator, concentration of monomers, and temperature, and by chain-transfer agents, such as thiols, e.g., n-octyl mercaptan. Fluoroaliphatic acrylates, such as those described in the above preparation, are known in the art (e.g., see U.S. Pat. Nos. 2,803,615, 2,642,416, 2,826,564, 3,102,103, 3,282,905, and 3,304,278). The poly(oxyalkylene) acrylates used in the above preparation, and other acrylates useful for such purposes, can be prepared from commercially available hydroxy and alkoxy poly(oxyalkylene) materials, such as those sold under the trade designations "PLURONIC" (available from BASF Corp. of Parsipanny, New Jersey), "CARBOWAX" and "TRITON" (available from Union Carbide Corp), by reacting such hydroxy materials in a known manner with acrylic acid, methacrylic acid, acryloyl chloride, or acrylic anhydride.
Other fluoroaliphatic radical-containing terminally ethylenically
unsaturated monomers suitable for the preparation of the polymers of this invention, for example by copolymerizing with corresponding poly(oxyalkylene)-containing, thermally ethylenically unsaturated comonomers, are known in the art (e.g., see U.S. Pat. Nos. 2,592,069, 2,995,542, 3,078,245, 3,081,274, 3,291,843 and 3,325,163, and the ethylenically unsaturated materials suitable for providing fluoroaliphatic radical-containing structural units disclosed in U.S. Pat. No.
3,574,791). The alkylene glycol fluorochemical acrylate polymers may also optionally contain units derived from other monomers such as alkyl acrylates, vinylidene chloride, and n-methylol acrylamide.
A preferred polyethoxylated alkylene glycol fluoro acrylate is a
polyoxyethylene terpolymer of
C8F17SO2N(CH3)C2H4OCOCH=CH2, (a)
CH2=C(CH3)COO(CH2CH2O)76H, (b)
and
CH2=C(CH3)COO(CH2CH2O)76COC(CH3)=CH2, (c)
preferably in a 1 :1 weight ratio of a:(b+c) and a 3:1 weight ratio of b:c.
Polyalkoxylated Polyurethane
Compositions according to the present invention will include a
polyalkoxylated polyurethane ( hereinafter "polyurethane"), preferably having pendant perfluoroalkyl groups and comprising the reaction product of an aliphatic tri- or higher order isocyanate, a fluorinated alcohol, amine or mercaptan, and a poly(oxyalkylene) diol or dithiol. The urethanes useful in the compositions of the invention are commensurate in scope with those disclosed in the aforementioned U.S. Pat No. 5,350,795 (Smith et al.) and are represented by the formula:
wherein
Rf is a fluoroaliphatic radical,
Rh is a non-fluorinated hydrocarbon radical,
Q is an organic linking group,
A is a residue of a tri- or higher order isocyanate, i.e., the residue being that portion of the tri- or higher order isocyanate minus the reacted—NCO groups,
(R1)y is a poly(oxyalkylene) moiety, R1 being an oxyalkylene group with 2 to 6 carbon atoms or a cyclic ether or ester moiety having 2 to 6 carbon atoms and y is a number of about 10 to 50,
X is O, S or a linking group terminating in O or S, (e.g.,—CH2CH2O), R2 is a residue of a tri- or higher order isocyanate, two of the isocyanate groups of the tri- or higher order isocyanate forming the depicted urethane groups and the other isocyanate groups reacted to form pendant—QRf or—QRh groups, s is a number of at least 1 and can be 3 or higher,
z is zero or a number of up to about 4,
s + z is a number of about 4 or higher, and
t is a number of at least about 10, preferably 15 to 35.
Generally, the polyalkoxylated polyurethanes have a weight average molecular weight of at least about 40,000, preferably about 65.000 to 250,000.
In the preferred polyurethanes depicted above, there are a plurality of Rf radicals which can be the same or different. This also applies to a plurality of Q, A, R1 and R2 groups. Generally, the polyalkoxylated polyurethanes will contain about 5 to 40 weight percent, preferably about 10 to 30 weight percent, of carbon-bonded fluorine. If the fluorine content is less than about 10 weight percent, impractical large amounts of the polymer will generally be required, while fluorine contents greater than about 35 weight percent generally result in polymers which have too low a solubility to be efficiently used in the compositions of the invention.
The non-fluorinated hydrocarbon group Rh, is optionally included within the polyurethanes depicted above. In a preferred embodiment, z is zero (e.g., the polyurethane includes no Rh groups). When present, Rh can be a straight chain, branched chain, or cyclic alkyl. Rh is preferably free of polymerizable olefinic
unsaturation and can optionally contain catenary heteroatoms such as oxygen divalent or hexavalent sulfur, or nitrogen. Also the non-fluorinated hydrocarbon group can optionally contain epoxide or aziridine functionalities. Preferably, the non-fluorinated hydrocarbon group contains about 1 to 36 carbon atoms, more preferably 10 to 24 carbon atoms.
In the poly(oxyalkylene) radical, R1 y, R1 is an oxyalkylene group having 2 to 4 carbon atoms, such as -OCH2CH2-, -OCH2CH2CH2-, -OCH(CH3)CH2-, and -OCH(CH3)CH(CH3)-, the oxyalkylene units in the poly(oxyalkylene) may be the same, as in poly(oxypropylene), or they may be different such as in a mixture of straight or branched chain or randomly distributed oxyethylene and oxypropylene units or as in a straight or branched chain of blocks of oxyethylene units and blocks of oxypropylene units. The poly(oxyalkylene) chain can be interrupted by or include one or more catenary linkages which may have three or more valences to provide a means for obtaining a branched chain or oxyalkylene units. The molecular weight of the poly(oxyalkylene) radical can be about 750 to 2000, preferably about 900 to 1750.
R2, which is a residue of a tri- or higher order isocyanate, can be formed from such isocyanate compounds as polyaromatic polyisocyanate ("Papi") such as that available under the trade designation "VORANATE" M220 ( available from Dow Chemical Co. of Midland, Michigan) or "DESMODUR" N-100,
"DESMODUR" N-3200 and "DESMODUR" N-3300, available from
Farbenfabriken Bayer AG of New York, New York.
The fluoroaliphatic radical-containing oxyalkylene urethanes used in this invention can be prepared in a known manner such as by condensation
homopolymerization or copolymerization using solution, suspension, or bulk polymerization techniques, see e.g., Preparative Methods of Polymer Chemistry, Sorenson and Campbell, 2nd ed., Interscience Publishers (1968). Other
fluorochemical urethanes can be included in the compositions of the invention, as known by those skilled in the art. Further descriptions of useful fluorochemical oxyalkylenes can be found in U.S. Pat. No. 3,787,351 and U.S. Pat. No. 4,289,892, for example.
Fluorochemical Acrylate Polymers with Polymerizable Emulsifier
The compositions of the invention further include fluorochemical acrylate polymers having copolymerizable surfactants incorporated therein. Preferably, the fluorochemical acrylate polymers comprise the polymerized reaction product of a fluorinated (meth)acrylate monomer; at least one alkyl (meth)acrylate monomer; and a polymerizable cationic emulsifier comprising a quaternary amine surfactant. A preferred fluorochemical acrylate polymer is represented by the general formula
wherein
Rf is a fluoroaliphatic radical, as above,
Q is an organic linking group, as above,
Rb and Rb' are the same or different and are selected from the group
consisting of H and linear or branched hydrocarbons having from 1 to 4 carbon atoms or together forming a carbocyclic ring of from about 3 to about 12 members, and mixtures thereof,
Rd , Rd', Rd", Rd"' can be the same or different and are selected from the group consisting of H or -CH3,
Ra, Ra', Ra" can be the same or different and are selected from the group consisting of an alkyl group having from 1 to 18 carbon atoms,
Rc is a saturated aliphatic (linear or branched) or cyclic alkyl, or a
combination of cyclic and aliphatic alkyls having at least 1 and generally from 4 to 30 carbon atoms, and preferably from 8 to 20 carbon atoms;
Z is an anion selected from the group consisting of chloride, bromide, iodide, sulfonate, alkyl sulfonate, phosphate, and mixtures thereof; n1, n2, and n3 are numbers which may independently range from 10 to 70, and
n4 is a number which is at least 1 and generally is within the range from 1 to 6.
As mentioned, Rd, Rd', Rd", Rd'" can be the same or different and are selected from the group consisting of H or -CH3, so that the acrylate and the methacrylate species are equally plausible for use as monomers in the above fluorochemical acrylate polymers. Suitable fluorinated (meth)acrylate monomers useful in the invention are those selected from the group consisting of N-methyl perfluoro octylsulfonamidoethyl (meth)acrylate, N-ethyl perfluoro
octylsulfonamidoethyl (meth)acrylate, and the like. Most preferably, the fluorinated (meth)acrylate monomer is N-methyl perfluoro octylsulfonamidoethyl acrylate. Of the total polymerizable species present in the final copolymer, the fluorinated (meth)acrylate monomer comprises from about 15 to about 40 mole percent, and, more preferably, between 20 and 30 mole percent of the total polymerizable species present in the final copolymer.
The fluorochemical acrylate polymer is made with at least one alkyl
(meth)acrylate monomer. Preferably, two alkyl (meth)acrylate monomers are used in the preparation of the above polymer. Suitable alkyl (meth)acrylate monomers are alkyl esters of acrylic or methacrylic acid wherein the alkyl groups, Ra or Ra', are independently selected from the group of C1 to C18 alky Is which may be linear, branched, cyclic or polycyclic, within the above parameters. Preferred alkyl (meth)acrylates are selected from the group consisting of methylacrylate, ethylacrylate, butylacrylate, hexylacrylate, isooctylacrylate, isodecylacrylate, octadecylacrylate ethylmethacrylate, butylmethacrylate, cyclohexylmethacrylate and mixtures thereof. More preferably, the alkyl (meth)acrylate monomers comprise an alkyl acrylate and an alkyl methacrylate and, most preferably are n-butyl acrylate and n-butyl methacrylate.
The polymerizable cationic emulsifier comprises a quaternary amine surfactant capable of entering into free radical polymerization reactions with one or more of the monomers used to synthesize the fluorochemical acrylate polymer. Most preferably, the emulsifiers contain at least one carbon-carbon double bond situated so that the double bond is capable of entering into free radical
polymerization reactions (e.g., the double bond is not stearically or electronically hindered).
Most preferably, the copolymerizable cationic emulsifiers are quaternary ammonium salts of of alkyl acrylates of the general formula
wherein Ra", Rb, Rb', Rc, Rd'", and Z, are as described above.
Most preferably, the cationic copolymerizable emulsifier comprises the reaction product of N,N-dimethylaminoethyl methacrylate and an alkyl halide having a carbon chain length from about 4 to about 30 carbon atoms and, more preferably, from about 8 to about 20 carbon atoms. A preferred alkyl halide is hexadecylbromide because of its commercial availability as well as its ease of use in making emulsified polymers. Other quaternary salts of the above formula are described in U.S. Letters Patent Nos. 3,780,092; 3,928,423; 3,936,492 and
4,001,259, the disclosures of which are incorporated by reference herein. The cationic copolymerizable emulsifier preferably comprises from about 0.5 percent to about 10 percent based on the total weight of the other monomers present in the fluorochemical acrylate polymer, and most preferably, from about 2 to about 6 percent.
The quaternary ammonium salt can be prepared first by reacting N,N-dimethylaminoethyl methacrylate and an alkyl halide according to the General Preparative Procedure A herein. The emulsifier and the other monomers are then emulsion polymerized. Water, the fluorinated monomer(s) the alkyl (meth)acrylate monomer(s) and the surfactant are homogenized in a known manner at elevated temperatures (e.g., 55 to 70 °C). Next, the emulsion is treated with a suitable water
soluble free-radical initiator under a nitrogen blanket. The initiator is preferably added to the emulsion to provide a concentration of initiator of between about 0.05% to 2% and preferably 0.1 to 0.5% by weight based on the total weight of the monomers in the emulsion. The selection of a suitable a initiator is within the skill of those practicing in the field. Suitable initiators include 2,2'-azobis-(2-cyanopropane-1-sulfonate), 2,2'-azobis-(2-amidinopropane)dihydrochloride, α,α-azobis-butyramidinium chloride, and azobis-(N,N'-dimethylene isobutyramidine) and its salts with strong acids and mixtures thereof. A preferred water soluble initiator is 2,2'-azobis-(2-amidinopropane)dihydrochloride, available under the trade designation "V-50" from Wako Chemicals USA, Inc. of Richmond, Virginia. The resulting polymeric emulsion may be diluted with water prior to blending the polymer with the other components in the compositions of the invention, as is further described below. Fluorochemical Esters
Optionally, fluorochemical esters may be included within the compositions of the invention. The esters useful in the compositions of the invention are commensurate in scope with those disclosed in the aforementioned U.S. Pat No. 5,350,795. These esters may be included within the compositions to help maintain a high level of repellency for the treated fabric after the fabric is abraded, for example. In the absence of esters in the compositions of the invention, the treated substrates may experience somewhat diminished repellency after being subjected to conditions of abrasion, but the compositions are still useful in the treatment of substrates, as described herein. Fluorochemical esters useful in the present invention can be formed by reacting a perfluoroalkyl aliphatic alcohol or mixture of alcohols with mono- or polycarboxylic acids which can contain other
substituents and which contain from 3 to 30 carbon atoms. Optionally a mixture of perfluoroalkyl aliphatic alcohol and hydrocarbon alcohols can be esterified with the polycarboxylic acids. Such esters are described, for example, in U.S. Pat. No. 4,029,585 (Dettre et al.).
A particularly preferred fluorochemical ester is the fluorochemical adipate ester which represented by the formula
{RfQ[OCH2CH(CH2Cl)]nO2CCH2CH2— }-2 wherein Rf and Q are as defined above and n is a number from about 1 to 5, preferably 1 to 3.
The fluorochemical adipate ester can be prepared by reacting a precursor fluoroaliphatic radical- and chlorine-containing alcohol with adipic acid. A most preferred ester is represented by the formula
A method of preparing the alcohol precursors is by reaction of
epichlorohydrin with a fluoroaliphatic radical-containing alcohol. Readily available alcohols which can be used in this preparation are those corresponding to the formula
Rf and Q are as defined above,
R5 is hydrogen or a lower alkyl, and
R6 is hydrogen, lower alkyl, or aryl of 6 to 12 carbons and R5 and R6 can be connected together to form a cyclic structure, aromatic or cycloaliphatic, including the hydroxyl-bearing carbon atom. When the fluoroaliphatic radical-containing alcohols are reacted with epichlorohydrin to form the corresponding fluoroaliphatic alcohols, the latter can correspond to the formula
where Rf, Q, R1 and R2 are as defined above and p is an integer from 1 to 5.
Representative species of fluoroaliphatic compounds containing epoxy-reactive hydrogen atoms which can be used to make the corresponding
fluoroaliphatic radical- and chlorine-containing alcohols are those disclosed, for example, in U.S. Pat. No. 4,043,823 (Loudas) and U.S. Pat. No. 4,289,892 (Soch).
Suitable fluorochemical adipate esters are disclosed in U.S. Pat. No.
4,264,484 (Patel) which is incorporated herein by reference.
Preferred Compositions
The compositions of the invention comprise a blend of the above described ingredients and the preparation of such blends is set forth in detail in the General Preparative Procedures and in the Examples herein. In general, the compositions of the present invention comprise a blend of first and second major components wherein the first major component comprises polyalkoxylated polyurethane, preferably with polyalkylene glycol fluorochemical acrylate copolymer and, optionally including a fluorochemical adipate ester, all as described above. The second major component comprises fluorochemical acrylate polymer with the polymerizable cationic emulsifier, also as described above.
Regarding the first major component, the polyurethane, in aqueous emulsion, can be used alone and may be prepared following the General
Preparative Procedure B herein (e.g., about 15% solids), allowing for changes in the monomers and the substituent groups according to the parameters set forth above. The alkylene glycol fluoro acrylate may be prepared according to the General Preparative Procedure C, allowing for changes in the monomers and the
substituent groups according to the parameters set forth above. The alkylene glycol fluoro acrylate is blended with the polyurethane to provide a weight ratio of polyurethane:alkylene glycol fluoro acrylate of about 3:2. Where the optional adipate ester is included within the first major component, the polyurethane, the alkylene glycol fluoro acrylate and the ester are blended in deionized water, stirred to promote thorough mixing and excess solvent is stripped from the mixture to give a blend which is preferably from about 5% to about 20% solids in water and more preferably between 10% and 16%. Preferably, the polyurethane is present within the first component at a weight percent of between about 50% and 90% and most preferably about 50%. The alkylene glycol fluoro acrylate may be present at a weight percent of 10% to 50% and most preferably about 33%. The optional adipate ester is generally present at a weight percent of 10% to 20% and most preferably about 17%.
Regarding the second major component, the fluorochemical acrylate polymer is made as an aqueous emulsion and generally following the General Preparative Procedure A while allowing for changes of the monomers and the substituent groups according to the general parameters set forth herein. The two major components are blended in deionized water to achieve a preferred solids content of about 3 percent by weight and a solids weight ratio between the two components ranging from about 25 : 1 and 1 :25 and more preferably from 9: 1 to 1 :9. Most preferably, the two major components are blended to achieve a solids weight ratio of about 1 :1 in the finished composition.
Minor amounts of coalescing solvents are then added along with minor amounts of other solvent (e.g., alcohol) to increase fabric wetting, improve the stability of the composition and reduce the likelihood of residue formation on the treated substrate. Aerosol propellants such as isobutane and the like are used in packaging the compositions in aerosol form. Likewise, known corrosion inhibitors are preferably included within such aerosol products to prevent corrosion within the steel cans normally used to package such products.
Suitable coalescing solvents include the alkylene glycol ethers such as dipropylene glycol mono n-butyl ether, propylene glycol mono methyl ether,
dipropylene glycol mono n-propyl ether, esters thereof and mixtures of the foregoing. Assuming a preferred solids concentration in the composition of about 3%, The coalescing solvents are present within the composition at a total weight percentage from about 2% to 10% and preferably about 4%. A small amount of an of an alkylol such as ethyl alcohol or isopropanol may be added to as an additional solvent as an aid to the stability of the composition and to prevent freezing.
Preferably, the alcohol is present at a weight percent in the finished composition of between about 0.5% and 3% and most preferably 1%. The selection of suitable solvents and their relative concentrations within the composition is within the skill of those practicing in the field. Suitable corrosion inhibitors include morpholine, ammonium hydroxide (30%), sodium nitrite, alkyl amines and combinations thereof. The concentrations of corrosion inhibitors is typically less than 1% by weight and most preferably is between about 0.5% and 1.0%, assuming a solids concentration in the composition of about 3%.
A fast-breaking foam composition can be formulated with the addition of pH modifiers to the aerosol formulation mentioned above. A foam product may be desirable to enable the user of the composition to easily see where a treatment has been applied to thereby avoid over application of the composition as well as increased drying times.
Anti-soiling agents may also be added to the compositions of the invention.
Such agents are defined as materials which are solid, non-tacky water soluble or water dispersible and which, upon drying of the composition, are capable of rendering the substrate non-tacky and resistant to soiling. The inclusion of the anti-soiling agents within the compositions of the invention is optional.
The compositions described herein may be applied to a wide variety of fiber-containing substrates. These substrates include textile fibers (or filaments) and fabrics, (including fabrics made into finished products) made from cotton, polyester, polyolefin, nylon, acrylic, acetate or blends thereof, as well as leather, finished garments, upholstered furniture and installed carpet. Individual fibers or filaments can be treated with the compositions of the invention as well as aggregate forms of such filaments or fibers (e.g., yarn, tow, web as well as woven or knit
fabric). These substrates can be treated with the compositions of the invention by applying the compositions thereto using known techniques customarily used in applying fluorochemicals to fibers and fabrics. These compositions can be applied to finished products such as apparel and upholstered furniture without the need for thermal curing and will provide excellent oil and water repellency without the inclusion of significant amounts of organic solvents. Suitable application techniques for applying these compositions include, for example, spraying, brushing, immersion or foaming. The amount of the compositions applied to the substrate is typically about 0.5 to 6 weight % solids and, more preferably, 1 to 4 weight % solids based on the weight of the fiber or fabric.
Test Methods
In the examples which follow, treated substrates are tested for oil and water repellency according to the following test methods.
Oil Repellency
The oil repellency of treated substrates is measured by the American Association of Textile Chemists and Colorists (AATCC) Test Method No.
1 18-1966. This test gives a relative value of the oily stain resistance for the substrate being tested. Drops of different test liquids are gently placed on the substrate and are allowed to remain for 30 seconds. The drops are then removed from the substrate by wicking or wiping with a paper tissue and the substrate is observed for remaining signs of wetting. Eight different oil challenge liquids are used with the number 1 liquid ("Nujol" mineral oil) being the easiest to repel and the number 8 liquid (n-Heptane) being the most difficult. The various test liquids are shown in Table 1 below. The substrate are tested in a systematic manner starting with the first liquid and progressing to the other liquids until one of the liquids is observed to wet the substrate after 30 seconds. Oil repellency is reported as the number value of the highest numbered liquid which did not wet the substrate. For detailed comparisons, multiple drops of each liquid are tested and
whole numbers and fractions may be reported. In general, an oil repellency rating of 5 or higher is desired.
The abraded oil repellency test also provides a relative value of the substrates' oily stain resistance. In this test method, however, the treated substrate is first placed on an ATTCC Crockmeter (as used in AATCC Test Method 8-1985 and commercially available from Atlas Electric Devices Co. of Chicago, Illinois) and subjected to 20 cycles of rubbing abrasion using a 1.6 centimeter disk of grade 600 abrasive paper (available under the trade designation "Wetordry Tri-M-ite" from Minnesota Mining and Manufacturing Company of St. Paul, Minnesota). After being abraded, the test substrate is treated in the same manner as in the oil repellency test described above using the same test oils. In general, an oil repellency of 4 or greater is desirable.
Water/Alcohol Drop Repellency
The water/alcohol drop repellency test tests the ability of the substrate to repel various blends of water and isopropyl alcohol. Test drops of the liquid solutions are progressively applied to the treated substrate and, after 30 seconds, if the applied solution does not soak into the substrate, the solution is wicked or wiped away with a paper tissue and the surface of the substrate is observed for surface wetting. Eleven blends of water and alcohol are used (see table 2, below)
with 100% water being the easiest to repel and 100% isopropyl alcohol being the most difficult. The treated substrate is given a number value corresponding to the solution having the highest concentration of isopropyl alcohol which the treated substrate was able to repel without observed wetting. For example, a substrate is given a value of 4 if it is able to repel the solution of 60% water and 40% isopropyl alcohol.
Water Spray Test
The water spray test follows AATCC Test Method 22. The treated substrate is rated for water repellency as determined by the pattern of surface wetting described in table 3 below. During the test, the treated substrate is held taut within a 15-centimeter diameter ring at a 45° angle. 250 milliliters of water at a temperature of 27°C (±1°C) is dropped onto the substrate from a distance of 15.2 centimeters above the center of the substrate. After the application of water, the substrate is tapped lightly to remove excess water and is rated in a manner consistent with that shown in table 3. A higher number indicates better water repellency and, in general, a number of 65 or higher is desirable.
Wet-Through Rating
The wet-through rating is performed on a treated substrate immediately following the water spray test, described above. The treated substrate which was rated in the above water spray test is immediately turned over and the back side of the substrate is visually observed and is touched by the observer to determine whether water has seeped through. A wet-through value from 1 to 6 is then given to the treated substrate, depending on the degree of "wetness." A value of " 1 " signifies the back of the substrate is thoroughly wet, while a value of "6" indicates the substrate is completely dry.
Composite Repellency Rating
A composite repellency rating is tabulated for each composition on each substrate by summing the values obtained in each of the above test methods with the exception that the rating obtained in the water spray test is first divided by 10. The maximum composite repellency rating possible is 42.
General Preparative Procedure A
Fluorochemical Acrylate Polymer With Polymerizable Cationic Emulsifier A reaction vessel fitted with a condenser, a mechanical stirer, and a thermometer is charged with 9.0 grams of N,N-dimethylaminoethyl methacrylate (available from Aldrich Chemicals of Milwaukee, Wisconsin), 0.036 grams of butylated hydroxy toluene (BHT) (Aldrich Chemicals ), 18.8 grams acetone and 17.5 grams 1-bromohexadecane (Aldrich Chemicals) The mixture is heated at 75°C (165°-170° F) until the unreacted amine is below 0.05%, as determined by gas
chromatography. The reaction solution is then cooled and the formation of a precipitate is observed. 18.1 grams ethylacetate (Aldrich Chemicals) is then added to the reaction solution and the solution is cooled to 16°C (60° F). A white solid (2-(dimethyl hexadecylamino) ethylmethacrylate bromide) precipitates from the solution and the solid is filtered and washed twice with cold ethyl acetate and is dried in a vacuum oven at 50° C for 8 hours.
In a suitable flask quipped with a mechanical stir and a thermometer, a mixture of 139.46 grams deionized water and 2.34 grams of the 2-(dimethyl hexadecylamino) ethylmethacrylate bromide is emulsified using a lab homogenizer (e.g., model HC-8000 available from Microfluidics Corp. of Newton,
Massachusetts) at 60° C for about 10 minutes. To a 16 ounce (0.47 liter) amber bottle, 34.86 grams N-methyl perfluorooctylsulfonamidoethyl acrylate (available from Minnesota Mining and Manufacturing Company of St. Paul, Minnesota), 17.40 grams butylacrylate (Aldrich Chemicals), and 5.86 grams butylmethacrylate (Aldrich Chemicals) are added. The bottle is capped and the mixture is warmed to 60° C with gentle agitation. The mixture is slowly added to the homogenizing bromide salt solution and the resulting emulsion is passed through the lab homogenizer twice. The emulsion is transferred to a 16 ounce (0.47 liter) amber bottle and is treated with 0.06 grams of a free radical initiator, 2,2'-azobis-(2-amidinopropane)dihydrochloride ("V-50" from Wako Chemicals USA, Inc.), and nitrogen is bubbled through the emulsion for 1 minute. The bottle is capped and kept at 60°C while mixing at about 50 rpm in a launderometer for 5 hours. The resulting latex (about 30% solids) is cooled, filtered and is then ready for use in the formulations below.
General Preparative Procedure B
Polyurethane
1.062 grams (1.8 moles) of N-methyl perfluorooctanesulfonamidoethyl alcohol and 708 grams ethyl acetate (available from Mallinckrodt, Inc. of Paris, Kentucky) are added to a 5-liter, 3-necked flask equipped with a mechanical stirrer, thermometer, reflux condenser, nitrogen inlet tube and heating mantle. After
heating with stirring to about 55° C under a nitrogen atmosphere, a premixed solution of 616 grams (1.08 moles) of a trifunctional isocyanate ("DESMODUR" N-100 from Farbenfabriken Bayer AG) and 300 grams ethyl acetate is added. Next, 0.84 gram stannous octoate (Sigma Chemical Co. of St. Louis, Missouri) is added and the reaction mixture is stirred at about 75° C for about six hours. A premixed solution of 1,044 gram (0.72 moles) of an alkoxypolyethylene glycol (available under the trade designation "CARBOWAX" 1450 from Union Carbide) and 807 grams ethyl acetate is added. The resulting mixture is stirred and heated at reflux (about 83° C) for about 16 hours. 150 grams of the thus prepared
polyurethane solution is added to a 1-liter, 3-necked flask equipped with a mechanical stirrer, dropping funnel, thermometer and a heating mantle and heated to 65° C. Distilled water (510 grams) heated to 65° C is slowly added with vigorous stirring. The resulting mixture is stirred for 10 minutes and ethyl acetate is removed by vacuum stripping to provide a translucent dispersion of about 15% solids.
General Preparative Procedure C
Alkylene glycol fluoroacrylate
A poly (oxyalkalene) acrylate solution is first prepared by adding 120 grams toluene, 90 grams of a difunctional block-polymer with terminal hydroxyl groups (available under the trade designation "PLURONIC" 44 from BASF
Company of Parsippany, New Jersey), 0.05 grams phenothiazine (Aldrich
Chemicals), 4.45 grams acrylic acid (Aldrich Chemicals ) and 1 gram p-toluene sulphonic acid (Aldrich Chemicals) are added to a glass reactor fitted for stirring, heating, cooling and reflux. The contents of the reactor are heated to reflux at 1 10-120° C with stirring until the acid content is constant. The contents of the reactor are then cooled to 50°C and neutralized with 2 grams powdered calcium hydroxide and the contents are stirred further for about 0.5 hours.
90 grams of the foregoing poly (oxyalkalene) acrylate solution are added to a glass reactor fitted for stirring, vacuum, nitrogen inlet, heating, cooling, and distillation along with 120 grams toluene and 36 grams N-butylperfluorooctane-
sulfonamidoethyl acrylate (Minnesota Mining and Manufacturing Company ). The contents of the reactor are heated with stirring at 55° C for .5 hour and then 6 grams n-octyl mercaptan (Aldrich Chemicals), chain transfer agent, and 0.9 gram tertiary butylhydroperoxide promoter (t-C4H9OOH) (Aldrich Chemicals) are added. The reactor is purged of oxygen by evacuation and repressurized with nitrogen. The contents are then stirred for 65° C for about 16 hours. Solvent is then removed from the reactor under vacuum (1 hour at 95° C at a pressure of about 200 mm mercury). General Preparative Procedure D
Adipate ester
In a glass flask fitted with an addition funnel, condenser, stirrer, heating mantle and thermometer are place 670 grams alcohol (made according to Example 2 of U.S. Pat. No. 4,264,484), 73 grams adipic acid and 480 grams toluene. The contents of the flask are heated slowly with stirring to about 80° C and 2.2 grams concentrated sulfuric acid are then added. The reaction mixture is heated to reflux. Water is then removed by using a modified dean-stark trap. After 16 hours of reflux, the reaction is complete. Toluene is then removed by distillation at atmospheric pressure leaving 691 grams of residual product, a light tan, solid melting at 64° - 82° C.
General Preparative Procedure E
Blending Components Made According To Procedures B, C, and D
To a 2-liter, 3-necked flask equipped with an overhead stirrer, a
thermometer and a reflux condenser are added 184.6 grams of the polyurethane reaction mixture (in ethyl acetate and before adding water), as in General
Preparative Procedure B, 178.7 grams of acrylate copolymer made according to General Preparative Procedure C, 36 grams fluorochemical adipate ester made according to General Preparative Procedure D, 125 grams ethyl acetate and 960 grams deionized water. The resulting mixture is vigorously stirred for 1 hour while be heated to 65° - 70° C. Solvent is removed by vacuum stripping and about 750
grams of water is added as necessary to make a stable dispersion of about 12% solids.
General Preparative Procedure F
Blending Components Made According To Procedures B and C
To a 500 liter 3-necked flask equipped with an overhead stirrer, a thermometer and a reflux condenser is added 27.5 grams of the polyurethane reaction mixture (in ethyl acetate and before adding water), as in General
Preparative Procedure B, 25.0 grams of acrylate copolymer made according to the above General Preparative Procedure C and 144 grams deionized water. The resulting mixture is vigorously stirred for 60 minutes while being heated at 70° C. The solvent is removed by vacuum stripping to give a stable dispersion of about 14% solids. General Preparative Procedure G
To a 16 oz.(0.47 liter) amber bottle, 36 grams of N-methylperfluorooctylsulfonamidoethyl acrylate (Minnesota Mining and Manufacturing Company), 18 grams of butyl acrylate, 6 grams of butyl methacrylate, 28 grams ethanol, 1 12 grams deionized water and 3 grams of methylpolyoxyethylene (15) octadecyl ammonium chloride cationic surfactant (available under the trade designation
"ETHOQUAD" 18/25 from Akzo Chemicals of Chicago, Illinois) are added. The mixture is warmed to 60° C in a launderometer. To the warmed mixture, 0.06 grams of free radical initiator, 2,2'-azobis-(2-amidinopropane)dihydrochloride ("V-50" from Wako Chemicals USA, Inc.), is added and nitrogen is bubbled through the mixture for one minute. The bottle is capped and kept at 60° C while mixing it in a launderometer for 5 hours. The resulting latex is filtered and can be used in the comparative examples herein.
The following Examples illustrate the preparation and the comparative advantages of the compositions of the present invention. The materials and amounts thereof, as well as other conditions and details, recited in the Examples
are not to be construed as unduly limiting. All percentages are by weight unless otherwise indicated.
EXAMPLES
Example 1
In a 200 ml flask equipped with a mechanical stir, 78 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer emulsion made according to the above Procedure A, 12.5 grams of a blend made according to the above Procedure E were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer: [polyurethane + polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester] was about 1 :1.
Example 2
Another composition was made as in Example 1, except that 0.5 grams of the fluorochemical acrylate polymer, 23.8 grams of a blend made according to the above Procedure E and 71.2 grams deionized water were used to formulate a blend having a weight ratio of the fluorochemical acrylate polymer: [polyurethane + polyalkylene glycol fluorochemical acrylate copolymer + adipate ester] of about 1 :19.
Example 3
Another composition was made as in Example 1, except that 1.0 grams of the fluorochemical acrylate polymer, 22.5 grams of a blend made according to the above Procedure E and 72 grams deionized water were used to formulate a blend having a weight ratio of the fluorochemical acrylate polymer: [polyurethane + polyalkylene glycol fluorochemical acrylate copolymer + adipate ester] of about 1 :9.
Example 4
Another composition was made as in Example 1, except that 9.0 grams of the fluorochemical acrylate polymer, 2.5 grams of a blend made according to the above Procedure E and 84 grams deionized water were used to formulate a blend having a weight ratio of the fluorochemical acrylate polymer:[polyurethane + polyalkylene glycol fluorochemical acrylate copolymer + adipate ester] of about 9:1.
Example 5
Another composition was made as in Example 1, except that 9.5 grams of the fluorochemical acrylate polymer, 1.25 grams of a blend made according to the above Procedure E and 84.75 grams deionized water were used to formulate a blend having a weight ratio of the fluorochemical acrylate polymer: [polyurethane + polyalkylene glycol fluorochemical acrylate copolymer + adipate ester] of about 19:1.
Example 6
Another composition was made as in Example 1, except that 1.7 grams of the fluorochemical acrylate polymer, 4.2 grams of a blend made according to the above Procedure E and 89.6 grams deionized water were used to formulate a blend comprising about 1% solids. The weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester] was about 1 :1.
Example 7
Another composition was made as in Example 1 , except that 10 grams of the fluorochemical acrylate polymer, 25 grams of a blend made according to the above Procedure E and 60.5 grams deionized water were used to formulate a blend comprising about 6% solids. The weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester] was about 1 :1.
Example 8
A fluorochemical acrylate polymer was made according to the above Procedure A except that the bromide salt monomer was substituted with 3.12 grams of a 75% solids solution of 2-(trimethyl-amino)ethylmethacrylate chloride salt in water. 78.0 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer and 12.5 grams of a blend made according to the above Procedure E were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer:
[polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester] was about 1 :1.
Example 9
A fluorochemical acrylate polymer was made according to the above
Procedure A except that bromodocosane replaced the bromohexadecane to make 2-(dimethyldocosaneamino)ethylmethacrylate bromide salt. As in Example 1, 78.0 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer and 12.5 grams of a blend made according to the above Procedure E were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester] was about 1 :1.
Example 10
A fluorochemical acrylate polymer was made according to the above Procedure A except that the butyl acrylate and butyl methacrylate were substituted with 23.26 grams of methyl acrylate. As in Example 1, 78.0 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer and 12.5 grams of a blend made according to the above Procedure E were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester] was about 1 :1.
Example 1 1
A fluorochemical acrylate polymer was made according to the above Procedure A except that the butyl acrylate and butyl methacrylate were substituted with 23.26 grams of octadecyl acrylate. As in Example 1, 78.0 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer and 12.5 grams of a blend made according to the above Procedure E were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer+ adipate ester] was about 1 :1.
Example 12
In a 200 ml flask equipped with a mechanical stir, 80.5 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer made according to the above Procedure A and 10 grams of a polyurethane emulsion made according to the above Procedure B were blended under constant stirring. 2.5 grams
dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring.
The resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer:polyurethane was about 1 :1.
Example 13
In a 200 ml flask equipped with a mechanical stir, 80.5 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer made according to the above Procedure A and 10 grams of a polyurethane/acrylate polymer blend made according to the above Procedure F were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer] was about 1 :1. Example 14
A fluorochemical acrylate polymer was made according to the above Procedure A except that the butyl acrylate and butyl methacrylate were substituted with 23.26 grams of methyl acrylate. 81.7 grams deionized water, 6.7 grams of the fluorochemical acrylate polymer and 7.1 grams of a polyurethane/acrylate polymer blend made according to the above Procedure F were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer] was about 2: 1.
Example 15
Another composition was prepared as in Example 13 except that 81.7 grams deionized water, 6.7 grams of the fluorochemical acrylate polymer made according to the above Procedure A and 7.1 grams of a polyurethane/acrylate polymer blend made according to the above Procedure F were used. The resulting
solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer: [polyurethane+ polyalkylene glycol fluorochemical acrylate copolymer] was about 2:1 Example 16
A polyurethane polymer was prepared according to the above Procedure B except that a propylene oxide, ethylene oxide copolymer available under the trade designation "Pluronic" L62 (from BASF Corporation of Parsippany, New Jersey) was used in place of the ethylene glycol ("Carbowax" 1450). In a 200 ml flask equipped with a mechanical stir, 80.5 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer made according to the above Procedure A and 10 grams of the polyurethane were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether. 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate polymer:polyurethane was about 1 : 1.
Example 17
A polyurethane polymer was prepared according to the above Procedure B except that the "Desmodur"N100 triisocyanate was replaced with "Desmodur" N3300 triisocyanate and the "Carbowax" 1450 ethylene glycol was replaced with "Carbowax" 400 ethylene glycol. In a 200 ml flask equipped with a mechanical stir, 80.5 grams deionized water, 5.0 grams of the fluorochemical acrylate polymer made according to the above Procedure A and 10 grams of the polyurethane were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting solution comprised about 3% solids and the weight ratio of the fluorochemical acrylate
polymer:polyurethane was about 1 :1.
Example 18
A composition was formulated as in Example 1 except that 72.5 grams of deionized water was used and the glycol ethers and the alcohol of Example 1 were substituted with 10 grams dipropylene glycol mono-n-propyl ether.
Example 19
99.45 grams of a composition prepared according to Example 1 was formulated as an aerosol with 0.2 grams morpholine, 0.2 grams sodium nitrite and 0.15 grams ammonium hydroxide solution (30% in water) with stirring. The liquid was packaged in an aerosol can and 5.0 to 5.5 grams of isobutane was added as a propellant.
Comparative Example A
In a 200 ml flask equipped with a mechanical stir, 85.5 grams deionized water and 10 grams of a fluorochemical acrylate polymer made according to the above Procedure A were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting emulsion comprised about 3% solids.
Comparative Example B
In a 200 ml flask equipped with a mechanical stir, 70.5 grams deionized water and 25 grams of a blend made according to the above Procedure E were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting emulsion comprised about 3% solids.
Comparative Example C
In a 200 ml flask equipped with a mechanical stir, 78 grams deionized water, 5 grams of a blend made according to the above Procedure G and 12.5 grams of a blend made according to the above Procedure E were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask while constantly stirring. The resulting emulsion comprised about 3% solids. Comparative Example D
In a 200 ml flask equipped with a mechanical stir, 85.5 grams deionized water and 10 grams of a blend made according to the above Procedure G were blended under constant stirring. 2.5 grams dipropylene glycol mono-n-butyl ether, 1.0 gram propylene glycol mono methyl ether and 1.0 gram ethanol were then added to the flask with constant stirring. The resulting emulsion comprised about 3% solids.
Comparative Example E
A commercial solvent based fabric protector was selected for this
Comparative Example E. The commercial product was an aerosol version of a fabric protector available under the trade designation "ScotchGard" from
Minnesota Mining and Manufacturing Company of St. Paul. Minnesota.
Comparative Example F
99.45 grams of a composition prepared as in Comparative Example C was formulated as an aerosol with the addition of 0.2 grams morpholine, 0.2 grams sodium nitrite and 0.15 grams ammonium hydroxide solution (30% in water) with stirring. The composition was packaged in a 6-8 oz. (0.18-0.23 liter) aerosol can and 5.0-5.5 grams of isobutane were added as a propellant.
The compositions of the above Examples and the Comparative Examples were tested on different substrates according to the above Test Procedures. All
substrates were prepared by hand-spraying 20.3cm by 22.9cm areas with the compositions. Care was taken to apply an even coverage of each composition used so that the dried add-on weight was about 2-3% of the weight of the dried fabric. The treated substrates were dried overnight at ambient conditions prior to testing.
The fabric substrates employed in the testing are identified as follows:
Fabric A is a bleached and washed polyester/cotton blend (65% polyester/35% cotton) commercially available under the style no. 7436 from Testfabrics, Inc. of Middlerex, New Jersey.
Fabric B is a cotton sateen (100% cotton) weave which is desized and bleached available under the style no. 428 from Testfabrics, Inc
Fabric C is an untreated, unfinished green rayon velvet upholstery fabric available from Collins & Aikman, Decorative Fabrics Division of Roxboro, North Carolina.
Fabric D is a polypropylene velvet upholstery fabric available under the style no.62521 from Joan Fabrics of Lowell, Massachusetts.
Fabric E is a woven upholstery fabric comprising 48% olefin/18% rayon/34% polyester available under the style no. 9352 from Chromatex of West Hazelton, Pa.
Examples 1 -18 and Comparative Examples A-E
Examples 1-18 and Comparatives A-E were tested according to the above Test Methods on Fabrics A and B. The comparative data is given below in Tables 4 (Fabric A) and 5 (Fabric B).
The above data shows the superior protective properties of the
compositions of the invention as compared with the compositions of the
Comparative Examples. Table 4, for example, shows the compositions of the present invention include a broader range of protective properties than the compositions of the Comparative Examples. Also, aerosol stability is typical for compositions of the invention.
The data for the fabric treated with the compostion of Example 1 set forth in Table 4, for example, demonstrates better abraded oil resistance than the fabric treated with the composition of Comparative A. Also, the composition of Example 1 provides aerosol stability which is not provided by the Comparative A
composition. The data for the Comparatives B-D show markedly poorer performance than the inventive composition of Example 1 in almost all of the testing conducted. As shown by a comparison of the data for Example 1 with that for Examples 2-7, the repellent properties of the inventive compositions are influenced by the relative weight ratios well as the percent solids of components within the compositions. Examples 8-1 1 represent inventive compositions made from monomers different than those used in the formulation of Example 1.
Comparative E represents a solvent based formulation. The data demonstrates that the compositions of the invention provide oil and water repellency which is at least as effective as that provided by such a solvent based formulation (e.g.. compare Comparative E with Example 1). Example 12-18 demonstrate the effeciveness of inventive compositions comprising variations of components, consistent with the above description.
Example 19 and Comparative Examples E and F
Comparative test data was collected for the aerosol preparations of
Example 19 and Comparative Examples E and F. Data was collected for Fabrics A, B, C, D and E and is set forth in Table 6 below.
The above data demonstrates the superior protective abilities of the inventive composition of Example 19 when compared with the water-based aerosol formulations of Comparative Example F, especially for Fabrics A, D and E, as reflected in the composite scores. The water based aerosol of Example 19 gave at least comparable performance for the solvent based composition of Comparative Example E overall, with improved performance over Comparative E noted on Fabric D.
Although the preferred embodiments of the invention have been described in some detail herein, the described embodiments are meant as merely illustrative and are not to be construed as limiting in any way. Those skilled in the art will understand that various changes and modifications can be made to the described embodiments without departing from the true spirit and scope of the invention, as defined in the following claims.
Claims
1. A composition for treating fiber containing substrates to impart improved oil and water repellency thereto, comprising:
(a) A polyalkoxylated polyurethane having pendant perfluoroalkyl groups, said polyalkoxylated polyurethane comprising the reaction product of an aliphatic or aromatic tri- or higher order isocyanate, a fluorinated alcohol, amine, or mercaptan, and a poly(oxyalkylene) diol or dithiol; and
(b) A fluorochemical acrylate polymer comprising the reaction product of a fluorinated acrylate or methacrylate monomer, at least one alkyl acrylate or methacrylate monomer, and a polymerizable cationic emulsifier comprising a quaternary amine surfactant.
2. The composition as defined in claim 1 further comprising:
(c) An alkylene glycol fluorochemical acrylate copolymer comprising the reaction product of a fluorinated acrylate or methacrylate monomer, polyalkylene glycol acrylate or methacrylate, and polyalkylene glycol diacrylate or dimethacrylate; and
(d) a fluorochemical adipate ester.
3. The composition as defined in claim 2 wherein said fluorochemical adipate ester is represented by the formula
[RfQ[OCH2CH(CH2Cl)]nO2C(CH2)2]2
wherein
Rf is a fluoroaliphatic radical,
Q is an organic linking group, and
n is a number from 1 to 5.
4. The composition as defined in claim 3 wherein said fluorochemical adipate ester is represented by the formula
5. The composition as defined in claim 2 wherein the composition is a blend comprising a first component consisting of (a), (c), and (d), and a second component consisting of (b), said first component and said second component present in said blend at a weight ratio from 1 :25 to 25: 1.
6. The composition as defined in claim 5 wherein said first component and said second component within said blend are present at a weight ratio of about 1 :1.
7. The composition as defined in claim 2 wherein said alkylene glycol
fluorochemical acrylate polymer comprises the randomly arranged repeating units represented by
8. The composition as defined in claim 7 wherein said alkylene glycol fluorochemical acrylate polymer is a polyoxyethylene terpolymer of
(a) C8F17SO2N(CH3)C2H4OCOCH=CH2,
(b) CH2=C(CH3)COO(CH2CH2O)76H,
and
(c) CH2=C(CH3)COO(CH2CH2O)76COC(CH3)=CH2. in a weight ratio of a:(b+c) of 1 : 1 and a weight ratio of b:c of 3 : 1.
9. The composition as defined in claim 1 wherein said polyalkoxylated
polyurethane is represented by the formula:
Rf is a fluoroaliphatic radical,
Rh is a non-fluorinated hydrocarbon radical,
Q is an organic linking group,
A is a residue of tri- or higher order isocyanate, i.e., the residue being that portion of the tri- or higher order isocyanate minus the reacted—NCO groups,
(R1)y is a poly(oxyalkylene) moiety, R1 being an oxyalkylene group with 2 to 6 carbon atoms or a cyclic ether or ester moiety having 2 to 6 carbon atoms and y is a number of about 10 to 50,
X is O, S or a linking group terminating in O or S,
R2 is a residue of a tri- or higher order isocyanate, two of the
isocyanate groups of the tri- or higher order isocyanate forming the depicted urethane groups and the other isocyanate groups reacted to form pendant—QRf or -QRh groups,
s is a number of at least 1 and can be 3 or higher,
z is zero or a number of about 4 or higher, and
t is a number of at least about 10.
10. The composition as defined in claim 1 wherein said fluorochemical acrylate polymer is represented by the general formula
Rf is a fluoroaliphatic radical,
Q is an organic linking group,
Rb and Rb are the same or different and are selected from the group
consisting of H and linear or branched hydrocarbons having from 1 to 4 carbon atoms or together forming a carbocyclic ring of from about 3 to about 12 members, and mixtures thereof,
Rd , Rd', Rd", Rd'" can be the same or different and are selected from the group consisting of H or -CH3,
Ra, Ra', Ra" can be the same or different and are selected from the group consisting of an alkyl group having from 1 to 18 carbon atoms,
Rc is a saturated aliphatic (linear or branched) or cyclic alkyl, or a
combination of cyclic and aliphatic alkyls having at least 1 and generally from 4 to 30 carbon atoms, and preferably from 8 to 20 carbon atoms;
Z is an anion selected from the group consisting of chloride, bromide, iodide, sulfonate, alkyl sulfonate, phosphate, and mixtures thereof; n1, n2, and n3 are numbers which may independently range from 10 to 70, and
n4 is a number which is at least 1 and generally is within the range from 1 to 6.
11. The composition as defined in claim 10 wherein said fluorochemical
acrylate polymer is represented by the formula
12. The composition as defined in claim 1 wherein said fluorinated acrylate or methacrylate monomer of said fluorochemical acrylate polymer is selected from the group consisting of N-methyl perfluoro octylsulfonamidoethyl methacrylate, N-ethyl perfluoro octylsulfonamidoethyl methacrylate, N-methyl perfluoro octylsulfonamidoethyl acrylate, N-ethyl perfluoro octylsulfonamidoethyl acrylate and combinations thereof.
13. The composition as defined in claim 1 wherein said at least one alkyl acrylate or methacrylate monomer of said fluorochemical acrylate polymer is selected from the group consisting of methylacrylate, ethylacrylate, butylacrylate, hexylacrylate, isooctylacrylate, isodecylacrylate, ethylmethacrylate,
butylmethacrylate, cyclohexylmethacrylate and mixtures thereof.
14. The composition as defined in claim 13 wherein said butylacrylate is n-butyl acrylate and said butylmethacrylate is n-butyl methacrylate.
15. The composition as defined in claim 1 wherein said polymerizable cationic emulsifier comprises a quaternary ammonium salt of the general formula
wherein
Ra" is an alkyl group having 1 to 18 carbon atoms,
Rb and Rb' are the same or different and are selected from the group
consisting of H and linear or branched hydrocarbons having from 1 to 4 carbon atoms or together forming a carbocyclic ring of from about 3 to about 12 members, and mixtures thereof,
Rd"' is -H or -CH3,
Rc is a saturated aliphatic (linear or branched) or cyclic alkyl, or a
combination of cyclic and aliphatic alkyls having at least 1 and generally from 4 to 30 carbon atoms, and preferably from 8 to 20 carbon atoms, and
Z is an anion selected from the group consisting of chloride, bromide, iodide, sulfonate, alkyl sulfonate, phosphate, and mixtures thereof.
16. The composition as defined in claim 1 wherein said polymerizable cationic emulsifier comprises the reaction product of N,N-dimethylaminoethyl methacrylate and an alkyl halide having a carbon chain length from about 4 to about 30 carbon atoms.
17. The composition as defined in claim 16 wherein said alkyl halide is hexadecylbromide.
18. A method for the treatment of fiber containing substrates, comprising:
applying the composition of claim 1 at ambient conditions to said substrate; and
drying said substrate at ambient conditions.
19. Substrates treated with the composition of claim 1.
20. A composition for treating fiber containing substrates to impart improved oil and water repellency thereto, comprising:
(a) A polyalkoxylated polyurethane having pendant perfluoroalkyl groups, said polyurethane comprising the reaction product of an aliphatic or aromatic tri- or higher order isocyanate, a fluorinated alcohol, amine, or mercaptan, and a poly(oxyalkylene) diol or dithiol;
(b) A fluorochemical acrylate polymer comprising the polymerized reaction product of a fluorinated acrylate or methacrylate monomer, a first alkyl acrylate or methacrylate monomer, a second alkyl acrylate or methacrylate monomer, and a polymerizable cationic emulsifier comprising a quaternary amine surfactant;
(c) A polyalkylene glycol fluorochemical acrylate copolymer
comprising the reaction product of a fluorinated acrylate or methacrylate monomer, polyalkylene glycol acrylate or methacrylate, and polyalkylene glycol diacrylate or dimethacrylate; and
(d) a fluorochemical adipate ester
wherein the above components are blended together in a weight ratio of (a)+(c)+(d):(b) within the composition of from 25 : 1 to 1 :25.
21. The composition as defined in claim 20 wherein said polyalkoxylated polyurethane is represented by the formula
wherein
Rf is a fluoroaliphatic radical,
Rh is a non-fluorinated hydrocarbon radical,
Q is an organic linking group,
A is a residue of tri- or higher order isocyanate, i.e., the residue being that portion of the tri- or higher order isocyanate minus the reacted—NCO groups,
(R1)y is a poly(oxyalkylene) moiety, R1 being an oxyalkylene group with 2 to 6 carbon atoms and y is a number of about 20 to
40,
X is O, S or a linking group terminating in O or S, R2 is a residue of a tri- or higher order isocyanate, two of the
isocyanate groups of the tri- or higher order isocyanate forming the depicted urethane groups and the other isocyanate groups reacted to form pendant—QRf or—QRh groups,
s is a number of at least 1 and can be 3 or higher,
z is zero, and
t is a number of at least about 10.
22. The composition as defined in claim 20 wherein said alkylene glycol
fluorochemical acrylate polymer is a polyoxyethylene terpolymer of (a) C8F17SO2N(CH3)C2H4OCOCH=CH2,
(b) CH2= C(CH3)COO(CH2CH2O)76H,
and
(c) CH2=C(CH3)COO(CH2CH2O)76COC(CH3) =CH2. in a weight ratio of a:(b+c) of 1 : 1 and a weight ratio of b:c of 3:1.
23. The composition as defined in claim 20 wherein said fluorochemical adipate ester is represented by the formula
24. The composition as defined in claim 20 wherein said fluorochemical acrylate polymer is represented by the general formula
wherein
Rf is a fluoroaliphatic radical,
Q is an organic linking group,
Rb and Rb' are the same or different and are selected from the group
consisting of H and linear or branched hydrocarbons having from 1 to 4 carbon atoms or together forming a carbocyclic ring of from about 3 to about 12 members, and mixtures thereof, Rd , Rd', Rd", Rd"' can be the same or different and are selected from the group consisting of H or -CH3,
Ra, Ra', Ra" can be the same or different and are selected from the group consisting of an alkyl group having from 1 to 18 carbon atoms, Rc is a saturated aliphatic (linear or branched) or cyclic alkyl, or a
combination of cyclic and aliphatic alkyls having at least 1 and generally from 4 to 30 carbon atoms, and preferably from 8 to 20 carbon atoms;
Z is an anion selected from the group consisting of chloride, bromide, iodide, sulfonate, alkyl sulfonate, phosphate, and mixtures thereof; n1, n2, and n3 are numbers which may independently range from 10 to 70, and
n4 is a number which is at least 1 and generally is within the range from 1 to 6.
25. The composition as defined in claim 24 wherein said fluorochemical
acrylate polymer is represented by the formula
26. The composition as defined in claim 20 wherein said fluorinated acrylate or methacrylate monomer of said fluorochemical acrylate polymer is selected from the group consisting of N-methyl perfluoro octylsulfonamidoethyl methacrylate, N-ethyl perfluoro octylsulfonamidoethyl methacrylate, N-methyl perfluoro octylsulfonamidoethyl acrylate, N-ethyl perfluoro octylsulfonamidoethyl acrylate and combinations thereof.
27. The composition as defined in claim 20 wherein said at least one alkyl acrylate or methacrylate monomer of said fluorochemical acrylate polymer is selected from the group consisting of methylacrylate, ethylacrylate, butylacrylate, hexylacrylate, isooctylacrylate, isodecylacrylate, ethylmethacrylate,
butylmethacrylate, cyclohexylmethacrylate and combinations thereof.
28. The composition as defined in claim 27 wherein said butylacrylate is n-butyl acrylate and said butylmethacrylate is n-butyl methacrylate.
29. The composition as defined in claim 20 wherein said polymerizable cationic emulsifier comprises a quaternary ammonium salt of the general formula
wherein
Ra is an alkyl group having 1 to 18 carbon atoms,
Rb and Rb' are the same or different and are selected from the group
consisting of H and linear or branched hydrocarbons having from 1 to 4 carbon atoms or together forming a carbocyclic ring of from about 3 to about 12 members, and mixtures thereof,
Rd"' is -H or -CH3,
Rc is a saturated aliphatic (linear or branched) or cyclic alkyl, or a
combination of cyclic and aliphatic alkyls having at least 1 and generally from 4 to 30 carbon atoms, and preferably from 8 to 20 carbon atoms, and
Z is an anion selected from the group consisting of chloride, bromide, iodide, sulfonate, alkyl sulfonate, phosphate, and mixtures thereof.
30. The composition as defined in claim 20 wherein said polymerizable cationic emulsifier comprises the reaction product of N,N-dimethylaminoethyl methacrylate and an alkyl halide having a carbon chain length from about 4 to about 30 carbon atoms.
31. The composition as defined in claim 30 wherein said alkyl halide is hexadecylbromide.
32. The composition as defined in claim 20 wherein said fluorochemical
adipate ester is represented by the formula
[RfQ[OCH2CH(CH2Cl)]nO2C(CH2)2]2 wherein
Rf is a fluoroaliphatic radical,
Q is an organic linking group, and
n is a number from 1 to 5.
33. The composition as defined in claim 32 wherein said fluorochemical
adipate ester is represented by the formula
34. A method for the treatment of fiber containing substrates comprising: applying the composition of claim 20 at ambient conditions to said substrate; and
drying said substrate at ambient conditions.
35. Substrates treated with the composition of claim 20.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019960706775A KR970703465A (en) | 1995-03-31 | 1995-03-31 | AQUEOUS OIL AND WATER REPELLENT COMPOSITIONS |
US08/737,686 US5725789A (en) | 1995-03-31 | 1995-03-31 | Aqueous oil and water repellent compositions |
JP1996529298A JP3760219B6 (en) | 1995-03-31 | Oil and water repellent aqueous composition | |
CA002191229A CA2191229C (en) | 1995-03-31 | 1995-03-31 | Aqueous oil and water repellent compositions |
JP8529298A JPH10501591A (en) | 1995-03-31 | 1995-03-31 | Oil and water repellent aqueous composition |
MX9605989A MX9605989A (en) | 1995-03-31 | 1995-03-31 | Aqueous oil and water repellent compositions. |
AU22018/95A AU686369B2 (en) | 1995-03-31 | 1995-03-31 | Aqueous oil and water repellent compositions |
PCT/US1995/003949 WO1996030584A1 (en) | 1995-03-31 | 1995-03-31 | Aqueous oil and water repellent compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002191229A CA2191229C (en) | 1995-03-31 | 1995-03-31 | Aqueous oil and water repellent compositions |
PCT/US1995/003949 WO1996030584A1 (en) | 1995-03-31 | 1995-03-31 | Aqueous oil and water repellent compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996030584A1 true WO1996030584A1 (en) | 1996-10-03 |
Family
ID=25678856
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1995/003949 WO1996030584A1 (en) | 1995-03-31 | 1995-03-31 | Aqueous oil and water repellent compositions |
Country Status (2)
Country | Link |
---|---|
CA (1) | CA2191229C (en) |
WO (1) | WO1996030584A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1001073A1 (en) * | 1998-11-13 | 2000-05-17 | Asahi Glass Company Ltd. | Aqueous dispersion type antisoiling composition and textile fibres treated therewith |
WO2005007967A3 (en) * | 2003-07-11 | 2005-03-24 | Du Pont | Fluorochemical finishes for paint applicators |
WO2006046643A1 (en) * | 2004-10-29 | 2006-05-04 | Daikin Industries, Ltd. | Fluorine-containing treatment composition |
CN1300192C (en) * | 2004-09-17 | 2007-02-14 | 浙江大学 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
WO2009009280A1 (en) * | 2007-07-10 | 2009-01-15 | E. I. Du Pont De Nemours And Company | Amphoteric fluorochemicals for paper |
CN103255683A (en) * | 2013-04-26 | 2013-08-21 | 李素英 | Intermediate isolation paper product processing method and isolation paper |
WO2016073222A1 (en) * | 2014-11-03 | 2016-05-12 | 3M Innovative Properties Company | Fluorochemical compositions, methods, and articles |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0109171A1 (en) * | 1982-10-13 | 1984-05-23 | Minnesota Mining And Manufacturing Company | Fluorochemical copolymers and ovenable paperboard and textile fibers treated therewith |
WO1993001349A1 (en) * | 1991-07-10 | 1993-01-21 | Minnesota Mining And Manufacturing Company | Aqueous oil and water repellent compositions |
-
1995
- 1995-03-31 CA CA002191229A patent/CA2191229C/en not_active Expired - Fee Related
- 1995-03-31 WO PCT/US1995/003949 patent/WO1996030584A1/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0109171A1 (en) * | 1982-10-13 | 1984-05-23 | Minnesota Mining And Manufacturing Company | Fluorochemical copolymers and ovenable paperboard and textile fibers treated therewith |
WO1993001349A1 (en) * | 1991-07-10 | 1993-01-21 | Minnesota Mining And Manufacturing Company | Aqueous oil and water repellent compositions |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1001073A1 (en) * | 1998-11-13 | 2000-05-17 | Asahi Glass Company Ltd. | Aqueous dispersion type antisoiling composition and textile fibres treated therewith |
US6251984B1 (en) | 1998-11-13 | 2001-06-26 | Asahi Glass Company Ltd. | Aqueous dispersion type antisoiling composition |
WO2005007967A3 (en) * | 2003-07-11 | 2005-03-24 | Du Pont | Fluorochemical finishes for paint applicators |
US7258925B2 (en) | 2003-07-11 | 2007-08-21 | E.I. Du Pont De Nemours And Company | Fluorochemical finishes for paint applicators |
CN1300192C (en) * | 2004-09-17 | 2007-02-14 | 浙江大学 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
WO2006046643A1 (en) * | 2004-10-29 | 2006-05-04 | Daikin Industries, Ltd. | Fluorine-containing treatment composition |
US8197590B2 (en) | 2004-10-29 | 2012-06-12 | Daikin Industries, Ltd. | Fluorine-containing treatment composition |
WO2009009280A1 (en) * | 2007-07-10 | 2009-01-15 | E. I. Du Pont De Nemours And Company | Amphoteric fluorochemicals for paper |
US8071489B2 (en) | 2007-07-10 | 2011-12-06 | E. I. Du Pont De Nemours And Company | Amphoteric fluorochemicals for paper |
CN103255683A (en) * | 2013-04-26 | 2013-08-21 | 李素英 | Intermediate isolation paper product processing method and isolation paper |
WO2016073222A1 (en) * | 2014-11-03 | 2016-05-12 | 3M Innovative Properties Company | Fluorochemical compositions, methods, and articles |
Also Published As
Publication number | Publication date |
---|---|
CA2191229C (en) | 2006-10-10 |
CA2191229A1 (en) | 1996-10-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5725789A (en) | Aqueous oil and water repellent compositions | |
US5350795A (en) | Aqueous oil and water repellent compositions which cure at ambient temperature | |
JP6435320B2 (en) | Urethane polymer extenders for compositions that modify the surface properties of substrates | |
AU653629B2 (en) | Fluorochemical water- and oil- repellent treating compositions | |
KR100214321B1 (en) | Composition for providing oil and water repellency | |
JP4009749B2 (en) | Fluorochemical polyurethane that provides excellent washing air drying performance | |
CN107223144B (en) | Fluorine-free fiber treatment composition comprising oligomers containing isocyanate-derived ethylenically unsaturated monomers and method of treatment | |
US7214736B2 (en) | Fluorochemical composition for treatment of a fibrous substrate | |
JP3242920B2 (en) | Fluorochemical surface modifier, fluorinated compound, and method for stabilizing aqueous dispersion | |
AU2007320011B2 (en) | Polyfluoroether based polymers | |
JP6735763B2 (en) | Fluorine-free fiber treatment composition containing polycarbodiimide and optionally paraffin wax, and treatment method | |
US20040077237A1 (en) | Fluorochemical composition comprising perfluoropolyether and an extender for the treatment of fibrous substrates | |
WO1993001349A1 (en) | Aqueous oil and water repellent compositions | |
JPH08325220A (en) | Carbodiimide compound and water-repellent composition | |
AU1990092A (en) | Fluoroacrylate monomers and polymers, processes for preparing the same and their use | |
KR20070050062A (en) | Hydrocarbon Extenders for Surface Effect Compositions | |
TWI523870B (en) | Fluoropolymers and surface treatment agent | |
US8821984B2 (en) | Composition and method for imparting increased water repellency to substrates and substrates treated with same | |
JP2017534713A (en) | Polyurethanes derived from non-fluorinated or partially fluorinated polymers | |
CA2191229C (en) | Aqueous oil and water repellent compositions | |
AU2007322323B2 (en) | Fluoropolymer compositions and treated substrates | |
AU686369B2 (en) | Aqueous oil and water repellent compositions | |
CN1077935C (en) | Aqueous oil and water repellent compositions | |
JP3760219B6 (en) | Oil and water repellent aqueous composition | |
JP3760219B2 (en) | Oil and water repellent aqueous composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 95193390.6 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU CA CN JP KR MX US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 08737686 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2191229 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/1996/005989 Country of ref document: MX |