MXPA98007927A - Composition repellent to water and ace - Google Patents
Composition repellent to water and aceInfo
- Publication number
- MXPA98007927A MXPA98007927A MXPA/A/1998/007927A MX9807927A MXPA98007927A MX PA98007927 A MXPA98007927 A MX PA98007927A MX 9807927 A MX9807927 A MX 9807927A MX PA98007927 A MXPA98007927 A MX PA98007927A
- Authority
- MX
- Mexico
- Prior art keywords
- water
- emulsion
- block
- isocyanate
- surfactant
- Prior art date
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 230000002940 repellent Effects 0.000 title claims abstract description 43
- 239000005871 repellent Substances 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 239000000839 emulsion Substances 0.000 claims abstract description 50
- IQPQWNKOIGAROB-UHFFFAOYSA-N [N-]=C=O Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003921 oil Substances 0.000 claims abstract description 46
- 239000004094 surface-active agent Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000004062 sedimentation Methods 0.000 claims abstract description 5
- 230000002035 prolonged Effects 0.000 claims abstract description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- 239000004753 textile Substances 0.000 claims description 6
- -1 isocyanate compound Chemical class 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 125000004432 carbon atoms Chemical group C* 0.000 description 12
- 239000004744 fabric Substances 0.000 description 11
- 239000002736 nonionic surfactant Substances 0.000 description 11
- 239000003760 tallow Substances 0.000 description 11
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 10
- 125000003709 fluoroalkyl group Chemical group 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 7
- WHIVNJATOVLWBW-SNAWJCMRSA-N Methylethyl ketone oxime Chemical compound CC\C(C)=N\O WHIVNJATOVLWBW-SNAWJCMRSA-N 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N Toluene diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920001451 Polypropylene glycol Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- LNWBFIVSTXCJJG-UHFFFAOYSA-N [diisocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)(N=C=O)C1=CC=CC=C1 LNWBFIVSTXCJJG-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 125000001165 hydrophobic group Chemical group 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N Hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 229920001213 Polysorbate 20 Polymers 0.000 description 3
- JNYAEWCLZODPBN-CTQIIAAMSA-N Sorbitan Chemical compound OCC(O)C1OCC(O)[C@@H]1O JNYAEWCLZODPBN-CTQIIAAMSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 125000005739 1,1,2,2-tetrafluoroethanediyl group Chemical group FC(F)([*:1])C(F)(F)[*:2] 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-Ethylhexanol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 240000007170 Cocos nucifera Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N Hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N Oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- 210000002268 Wool Anatomy 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N butylene glycol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002114 octoxynol-9 Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000001587 sorbitan monostearate Substances 0.000 description 2
- 235000011076 sorbitan monostearate Nutrition 0.000 description 2
- 229940035048 sorbitan monostearate Drugs 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2R,3R,4R,5S)-hexane-1,2,3,4,5,6-hexol;(Z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- WSEBKJRVPMLGFV-UHFFFAOYSA-M (3-chloro-2-hydroxypropyl)-(2-hydroxyethyl)-dimethylazanium;chloride Chemical compound [Cl-].OCC[N+](C)(C)CC(O)CCl WSEBKJRVPMLGFV-UHFFFAOYSA-M 0.000 description 1
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-Dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- QSMUFXXTSUEZJA-UHFFFAOYSA-N 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid Chemical compound O=C1N(CC=2C=CC=CC=2)C(C(=O)O)C(C(O)=O)N1CC1=CC=CC=C1 QSMUFXXTSUEZJA-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N 1,5-Pentanediol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- HPFDGTFXAVIVTH-UHFFFAOYSA-N 1-[1-(1-methoxypropan-2-yloxy)propan-2-yloxy]propan-2-ol Chemical compound COCC(C)OCC(C)OCC(C)O HPFDGTFXAVIVTH-UHFFFAOYSA-N 0.000 description 1
- LTIKIBFTASQKMM-UHFFFAOYSA-N 1-[bis(4-isocyanatophenyl)methyl]-4-isocyanatobenzene Chemical compound C1=CC(N=C=O)=CC=C1C(C=1C=CC(=CC=1)N=C=O)C1=CC=C(N=C=O)C=C1 LTIKIBFTASQKMM-UHFFFAOYSA-N 0.000 description 1
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- YSJGOMATDFSEED-UHFFFAOYSA-M Behentrimonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)C YSJGOMATDFSEED-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DWVKMLMUVCAGOG-UHFFFAOYSA-M C(C)(=O)[O-].C(CCCCCCCCCCC)[N+](CC)(CC)CC Chemical compound C(C)(=O)[O-].C(CCCCCCCCCCC)[N+](CC)(CC)CC DWVKMLMUVCAGOG-UHFFFAOYSA-M 0.000 description 1
- OWMCVSMNPFSHPF-UHFFFAOYSA-M C(CCCCCCCCCCCCCCCCC)C(C1=CC=CC=C1)N(C)C.[Cl-] Chemical compound C(CCCCCCCCCCCCCCCCC)C(C1=CC=CC=C1)N(C)C.[Cl-] OWMCVSMNPFSHPF-UHFFFAOYSA-M 0.000 description 1
- 240000000218 Cannabis sativa Species 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M Cetrimonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N Cetyl alcohol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N Chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- WKQQJKZKHLVNOP-UHFFFAOYSA-N ClC(C)(F)Cl.C(=C)(Cl)Cl Chemical compound ClC(C)(F)Cl.C(=C)(Cl)Cl WKQQJKZKHLVNOP-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N Diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N Dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Ethylene tetrachloride Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N Nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N Octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N Phenylisocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N Phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N Propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O Pyridinium Chemical class C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229940100515 SORBITAN Drugs 0.000 description 1
- 210000002374 Sebum Anatomy 0.000 description 1
- 229960005078 Sorbitan sesquioleate Drugs 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- 229960000391 Sorbitan trioleate Drugs 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N Stearyl alcohol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-GDQSFJPYSA-N Sucrose Natural products O([C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O1)[C@@]1(CO)[C@H](O)[C@@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-GDQSFJPYSA-N 0.000 description 1
- BGHCVCJVXZWKCC-UHFFFAOYSA-N Tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N Triethylene glycol dimethyl ether Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N Trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- NWGKJDSIEKMTRX-HSACVWGTSA-N [(2R)-2-[(2R,3R,4S)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] (E)-octadec-9-enoate Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-HSACVWGTSA-N 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2R)-2-[(2R,3R,4S)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
- PRXRUNOAOLTIEF-XDTJCZEISA-N [2-[(2R,3S,4R)-4-hydroxy-3-[(Z)-octadec-9-enoyl]oxyoxolan-2-yl]-2-[(Z)-octadec-9-enoyl]oxyethyl] (Z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@@H](O)[C@@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-XDTJCZEISA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
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- 239000003599 detergent Substances 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
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- 238000005108 dry cleaning Methods 0.000 description 1
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- 238000002338 electrophoretic light scattering Methods 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 235000012765 hemp Nutrition 0.000 description 1
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- 238000000265 homogenisation Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic Effects 0.000 description 1
- GJIDOLBZYSCZRX-UHFFFAOYSA-N hydroxymethyl prop-2-enoate Chemical compound OCOC(=O)C=C GJIDOLBZYSCZRX-UHFFFAOYSA-N 0.000 description 1
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
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- 239000004571 lime Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 235000012766 marijuana Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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Abstract
An isocyanate emulsion in block, containing a block isocyanate, a surfactant and a liquid medium, wherein the weight ratio of the block isocyanate to the surfactant is 60/40 to 90/10 and an average particle diameter is described. it is not higher than 250nm, giving a stable composition, water and oil repellent, which has no sedimentation for a prolonged period of time even if the emulsion of the block isocyanate is mixed with the water and oil repellent
Description
COMPOSITION REPELLENT TO WATER AND OIL
FIELD OF THE INVENTION "
The present invention relates to a block isocyanate emulsion, a water repellent composition and oil, and a textile material treated with the water and oil repellent composition.
BACKGROUND OF THE INVENTION
In order to improve wash durability and spot check properties, it has been suggested to date to add a block isocyanate compound to a water and oil repellent containing a component that includes a perfluoroalguylOj- group a water and oil repellent component (Japanese Patent Application Kokai No. 165072/1981 Japanese Patent Publication Kokoku No. 11239/1989, etc.). However, there was a problem in that, when a treatment liquid is produced by mixing a water and oil repellent emulsion with REF emulsion. 28408 block isocyanate, the mixing stability is poor, and therefore, sedimentation of the water and oil repellent component or block isocyanate compound arises, "so that a sediment adheres to a fabric, or the repellency deteriorates against water and oil.
BRIEF DESCRIPTION OF THE INVENTION
An object of the present invention is to provide a stable water and oil repellent composition, which has no sedimentation for a prolonged period of time even if a water and oil repellent is mixed with an isocyanate emulsion in block. present invention provides a block isocyanate emulsion comprising a block isocyanate, a surfactant containing at least one cationic surfactant, and a liquid medium, wherein a weight ratio of the block socianate to the surfactant is 60/40 to 90 / 10 and an average particle diameter of the emulsion particles is not at 250 nm., The present invention also provides a water and oil repellent composition comprising an isocyanate block emulsion, and a water repellent component. and to the oil having a polyfluoroalkyl group. In addition, the present invention provides a textile material treated with the water and oil repellent composition.
DETAILED DESCRIPTION OF THE INVENTION
The block isocyanate emulsion used in the present invention contains a block isocyanate, a surfactant and a liquid medium, and a weight ratio of block isocyanate to the surfactant that is 60/40 to 90/10 and an average diameter of particles in emulsion not greater than 250 nm. The block isocyanate used in the present invention is obtained by blocking a known polyfunctional isocyanate with a blocking agent. Examples of the polyfunctional isocyanate include toluene diisocyanate (eg, 2,4- or 2,6-tolylene diisocyanate), diphenylmethane diisocyanate (including isomers containing MDI such as 2,4 '-structure, 3, 4' - structure, etc.
In addition to 4, 4 '-symmetry structure, and the so-called polymeric MDI containing three or more polynuclear materials), triphenylmethane triisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, dimers or trimers thereof or adducts of these trimers and the like with polyols, a trimethylolpropane / toluene diisocyanate adduct, a trimethylolethane / toluene diisocyanate adduct, a glycerin / toluene diisocyanate adduct, and the like. Examples of the blocking agents include oximes such as methyl ethyl ketoxime, phenols, alcohols, e-caprolactam and the like. The surfactant for the emulsification of the block isocyanates is preferably nonionic surfactants and cationic surfactants. The nonionic surfactant is a surfactant having a hydroxyl group OH, an ether bond -O- or the like, which has no ionic dissociation in water, such as the hydrophilic group. The nonionic surfactant is crudely classified into a polyethylene glycol type surfactant and a polyhydric alcohol type surfactant. Examples of polyethylene glycol surfactants include a superior alcohol adduct / ethylene oxide, an ethylene alkylphenol / pxido adduct, a fatty acid / ethylene oxide adduct, an ethylene oxide / ethylene oxide fatty acid ester adduct, a higher alkylamine adduct / ethylene oxide adduct, an oxide adduct ethylene fatty acid amide, an adduct of ethylene oxide of oils and fats, an adduct of polypropylene glycol / ethylene oxide and the like. Examples of polyhydric alcohol surfactants include a glycerol fatty acid ester, a pentaerythritol fatty acid ester, a sorbitan sorbitol sorbitan acid ester, a sucrose fatty acid ester, an alkyl ether of polyhydric alcohol, an fatty acid amide of alkanolamines and the like. There are also some types of surfactants such as an amine oxide (for example, -N + (CH3) 2-0-), a sulfoxide (for example, -S + CH3) -0), an aminaimide (for example ^, -N + (CH3) 2-N ~ CO ~), etc., which behave as a cationic surfactant in an aqueous acid solution. Also, there are silicone surfactants having a siloxane group or group, hydrophobic and a polyether group (for example polyethylene oxide and polypropylene oxide) as the hydrophilic group, and fluorine-containing surfactants, which have a group fluoroalkyl as the hydrophobic group. Specific examples of the non-ionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, pplioxyethylene-polyoxypropylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene nonylphonylic ether, polyoxyethylene octylphenyl ether ., polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monopallate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, monopalmitat polyoxyethylene sorbitan, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, a polyoxyethylene-polyoxypropylene block copolymer, a polyglycerol fatty acid ester, a commercial polyether modified silicone oil: SH3746, SH3748, SH3749 and SH3771, manufactured by Toray Dow Corning Silicone Co., Ltd), a perfluoroalkyl / ethylene oxide adduct (trade name:
Unidine DS-401 and DS-403, manufactured by Daikin Industries Ltd.), a fluoroalkyl / ethylene oxide adduct (trade name: Unidine DS-406, manufactured by Daikin Industries Ltd.), a perfluoroalkyl oligomer (trade name: Unidine DS-451, manufactured by Daikin Industries Ltd.) and simil.ars ^ Cationic surfactant is a surfactant that has a long chain cyclic group or hydrophobic group and a group, which is ionized to form a cation in an aqueous solution, such as the hydrophilic group. The cationic surfactant generally contains an amine salt, a quaternary ammonium salt (-N + (CH3") 3X ~ (X is halogen or OCOCH3), a pyridinium salt
a sulfonium salt (-S + (CH3) 2C1 ~), a phosphonium salt (-P + (CH3) 3CI "), or a polyethylene-poaamine (~ NH (C2H4NH) mH), as the hydrophilic group. cationic surfactants include a (dialkyl of 12 to 22 carbon atoms) -dimethylammonium chloride, an alkyl- (coconut) -dimethylbenzylammonium chloride, an octadecylamine acetate salt, a tetradecylamine acetate salt, a tallow acetate salt -alkylpropylendia ina, octadecytrimethylammonium chloride, alkyl- (tallow) -trimethylammonium chloride, dodecyltrimethylammonium chloride, alkyl- (coconut) -trimethylammonium chloride, hexadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, a quaternary salt of alkyl- (sebum.) -imidazoline, tetradecyldimethylbenzylammonium chloride, octadecyldimethylbenzylamine chloride, dioleyldimethylammonium chloride, polyoxyethylene-dodecyl-methyl-ammonium chloride, pplioxyethylene- (alkyl of 12 to 22 carbon atoms) -benzylammonium chloride, ppli chloride oxyethylene-laurylmonomethylammonium, a quaternary salt of l-hydroxyethyl-2-alkyl- (tallow) -imidazoline, a cationic silicone surfactant having a siloxane group as the hydrophobic group, a cationic surfactant containing fluorine gu.e has a fluoroalkyl group as the hydrophobic group (trade name; Unidine DS-202, manufactured by Daikin Industries Ltd.) and the like. A combination of the nonionic surfactant and the cationic surfactant can be used.
3
A weight ratio of the nonionic surfactant to the cationic surfactant can be from 5:95 to 95: 5, for example, 10:90 to 90:10. Particularly preferred combinations of the nonionic surfactant and the cationic surfactant are as follows: (i) dialkyl- (hardened tallow) -dimethylammonium chloride and polyoxyethylene-polyoxypropylene block polymer, (ii) dialkyl- (hardened tallow) -dimethylammonium chloride and polyoxyethylene - polyoxypropylene block polymer, and / or octylphenyl ether of. polyoxyethylene, (iii) dialkyl- (hardened tallow) -dimethylammonium chloride and c -polmermer "in polyoxyethylene-polyoxypropylene block, and / or polyoxyethylene octylphenyl ether, and / or polyoxyethylene sorbitan onplaterate.The liquid medium is water or a mixture of water an organic solvent, the amount of the organic solvent is not more than 10% by weight based on water.Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. these are such as ethyl acetate, propyl acetate and butyl acetate;
alcohols such as ethanol, isopropanol, butanol, 1,3-butanediol and 1,5-pentanediol; halogenated hydrocarbons such as _ perchlorethylene, tricylene, 1,1-dichloro-2,2,3,3,3-pentafluropropane, 1,3-dichloro-1,2,3,3-pentafluropropane and 1,1-dichloroethylene dichloro-1-fluoroethane; hydrocarbons such as octane, petroleum, toluene and xylene; dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, polypropylene glycol, triethylene glycol dimethyl ether, propylene glycol and ethylene glycol. The block isocyanate emulsion can be produced, for example, in the following manner. An isocyanate block compound is dissolved in an organic solvent (for example, toluene and methyl isobutyl ketone) and an emulsifier (for example a cationic emulsifier and a nonionic emulsifier) is dissolved therein, and then water is slowly added with stirring p >for emulsifiers. After emulsification, the organic solvent can be distilled under reduced pressure. After the water was added to complete a phase inversion emulsification, the homogenization can also be conducted by a homomixer or a high pressure emulsification device. A weight ratio of block isocyanate to the surfactant is 60/40 to 90/10, preferably 60/40 to 85/15. When the amount of the surfactant is greater than 40% by weight, the durability to washing is poor. When the amount is smaller than 10% by weight, the stability at the time of mixing with the water and oil repellent is poor. An average particle diameter, of the particles dispersed in the emulsion, is no greater than 250 nm, for example, 50 nm to 250 n. When the particle diameter is greater than 250 n, the stability of the block isocyanate emulsion is poor. The average particle diameter is measured by a laser particle diameter analysis system LPA-3000/3100 manufactured by Ohtsuka Denshi Co. , Ltd. It is preferred that a zeta potential of the emulsion be greater than 0 V and be no greater than 100 V. When the zeta potential is smaller than 0 V, the stability at the time of mixing with the water and oil repellent It is poor. The zeta potential is measured by an electrophoretic light scattering photometer ELS-800 manufactured by Ohtsuka Denshi Co., Ltd. After the emulsion is diluted with an aqueous solution of 1 mM KCl pH 7.0 ± 0.3, the zeta potential is measured at 25 ° C. According to X-ray diffraction, the block isocyanate preferably has at most five glass peaks. X-ray diffraction is measured with an X-ray diffraction device, Model RAD-RA., Manufactured by Rigaku Denki Co . , Ltd, according to the method d reflection. The water and oil repellent component used in the present invention is a compound containing a polyfluoroalkyl group, and the polyfluoroalkyl group has a fluoroalkyl group having from 3 to 21 carbon atoms, preferably from 6 to 16 carbon atoms. Examples of such a compound include the following. (1) Homopolymer of a vinyl monomer containing a fluoroalkyl group having from 3 to 21 carbon atoms or cq polymer of said vinyl monomer with a vinyl monomer that does not contain fluorine.
Examples of vinyl monomer having a fluoroalkyl group include the following:
CF3 (CF2) 7S? 2N (CH3) (CH2) 2? COC (CH3) = CH2 CF3 (CF2) 7S? 2N (C2H5) (CH2) 2? COCH = CH2 '-' -
(CF3) 2CF (CF2) 6CH2CH (OH) CH2? COCH = CH2 __ CF3 (CF2) 9 (CH2) 2? COCHßCH2 CF3 (CF2) 9CONH (CH2) 2? COC (CH3) = CH2 t (CF2Cl) (CF3 ) CF (CF2) 6CONH (CH2) 2? COCH = CH2 'r
CsF-i CH = CH2 Examples of the non-fluorine containing vinyl monomer include "ethylene, propylene, butylene, butadiene, isoprene, chloroprene, vinyl chloride, vinylidene chloride, styrene, an ester or amide of (meth) acrylic acid and an alcohol or an alkylamine
(all of them have no more than 22 carbon atoms), diacetone, lime, N-methylolacrylamide, acrylonitrile, acrylamide, vinyl acetate,
(meth) hydroxymethyl acrylate and a vinyl compound having a siloxane bond. Any monomers can be used in combination. Although these homopolymers or copolymers can be produced by a known method of vinyl polymerization, emulsion polymerization is generally used. In the emulsion polymerization, the water or a mixture of water and an organic solvent can be used as the medium. In the present invention, the emulsion polymerization is preferably conducted by the use of a cationic surfactant and a non-ionic surfactant. Examples of the cationic surfactant which may be used include dodecyltrimethylammonium chloride, dodecyltri ethylammonium acetate, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, dimethyloctadecylammonium chloride, dimethylhexadecylammonium chloride and (dodecyl ethylbenzyl) trimethylammonium chloride. Examples of the nonionic surfactant include condensation products of ethylene oxide with isooctylphenol, nonylphenol, hexadecanol, oleic acid, (alkylamine of 12 to 18 carbon atoms) and / or the like. A preferred weight ratio of the cationic surfactant to the nonionic surfactant is from 10:90 to 90:10. (2) (Poly) ester of an optionally fluorinated monocarboxylic or pyrcarboxylic acid, with a monohydric alcohol or polyhydric alcohol containing a fluoroalguyl group having from 3 to 21 carbon atoms, or (poly) ester of a monohydric alcohol or A fluoroalkyl polyhydric with a monocarboxylic or polycarboxylic acid containing a fluoroalkyl group has from 3 to 21 carbon atoms. Examples of the component used in this case include the following:
C8F? CH2CH2? H, C8F17SO2N (C3H7) CH2CH2OH, C8F17S? 2N (CH2CH2? H) 2,; CgF17S? 2N (C2H5) CH2CH (OH) CH2OH > C7F15COOH, C8F17S? 2N (C3H7) CH2COOH,! C8F17CH2CH2CHCOOH COOH
benzoic acid, adipic acid, sebasic acid, phthalic acid, maleic acid, trimethyl acid, ethylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol, glycerin, polypropylene glycol, 2-ethylhexanol and stearyl alcohol. It is preferred that the (poly) ester has a molecular weight of at least 1,000, (3) The fluorine-containing polyester copolymer as described in Japanese Patent Publication Kokai No. 103550/1983. It is "possible to use a fluorine-containing polyester copolymer having the following repeating units;
(a) Rf I (CH2) n - (OCHCH2) - or Rf I (CH2) p - (CHCH2O) -
wherein Rf is a perfluoroalkyl group having from 3 to 21 carbon atoms, and n is 0 or 1, and (b)
R is a residue that remains after the removal of -COOCO- from a cyclic acid anhydride, and if necessary, c) - (OCR ^ CRaR ^ - where Ri to R4 represents a hydrogen atom, an alkyl group or an "alkyl group" having a substituent, or an aryl group or an aryl group having a substituent and / or
- [N (CH2) m] - O = C-R5 _,
wherein R5 is a hydrogen atom, an alkyl group or an aryl group, and ra is an integer of 2 or 3. (4) (Poly) urethane of a monohydric or polyhydric alcohol having a fluoroalguyl group which has at 21 carbon atoms (a monohydric or polyhydric alcohol which does not contain a fluorine atom can optionally be added) and a mono- or jppi-functional isocyanate.For example, phenyl isocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and polymethylene polyphenylisocyanate. The (poly) urethane preferably has a molecular weight of at least 700, (5) The compound containing a polyfluoroalkyl group and a reactive group capable of reacting with an isocyanate (eg, a hydroxyl group, an amino group and a carboxyl group) ). Examples of these include CBF17-CH2CH2-OH, C6Fi3-CH2CH2-QH, CIQF2- | CH2CH2-OH,
C8F? SO2N-CH2CH2-OH CH3
C8F17-S02N-CH2CH2-OH ', CH2CH3 >
C8F17- (CH2CH2O) nH,
C9F19CH2-CH-CH2 -O- (CH2CH2O) nH OH C8F17SO2N - (CH2CH2O) nH CH3
C8F17-COOH, C8F17-CONHC3H6NHCH3, C8F17SO2NHCH3,
n is an integer from 1 to 200, for example 2 to 30. (6) Aliphatic polycarbonate containing fluorine having, as an essential unit, (a) an oxyethylene group represented by the formula;
Rf j CH2 1 - (CH-CH2-O) -
Rf | CH2 1 - (CH2-CH-O) -
wherein Rf is a perfluoroalkyl group having from 3 to 21 carbon atoms, and (b) an oxycarbonyl group represented by the formula:
- (C-O) - II O
It is preferred that the compounds (2) to (6) containing fluoroalkyl group are also emulsified by the use of the aforementioned cationic surfactant and nonionic surfactant. In the water and oil repellent composition, an amount of block isocyanate is preferably from 5 to 600 parts by weight, based on 2J
in 100 parts by weight of the water and oil repellent component. When the amount is greater than 600 parts by weight, the water and oil repellency is poor. When the smallest amount is 5 parts by weight, the durability to washing and the durability to dry cleaning are poor. Although the block isocyanate is usually converted to a waterborne oil and oil repellent form, the block isocyanate can be added to a processing bath containing the water and oil repellent. In both cases, it is extremely stable. For the purpose of making a soft treated fabric, it is prevented that the treated fabric was electrically charged, improving water and oil repellency or improving the shrinkage resistance, and antistatic agents, aminoplast resins, acrylic polymers, resins, etc. may be added. gloxal, melamine resins, natural waxes and silicone resins as long as the effect of the present invention is not impaired. The water and oil repellent processing of the present invention can be carried out by a spray method and a coating method, in addition to an immersion method. When a substrate to be treated (e.g. textile) is treated with the water and oil repellent composition of the present invention, the substrate to be treated can be heat treated at a temperature of at least 100 ° C, preferably about 110-170 ° C, for 10 seconds to 60 minutes, preferably for 1 minute to 20 minutes after applying the water and oil repellent composition by the various methods above, to improve the durability. By such thermal treatment, the block isocyanate is converted to a highly active -N = C = 0 group, and is reacted with various substrates, so that the block isocyanate and the water and oil repellent are adhered to the substrate . Accordingly, in the present invention it is particularly preferred to use a substrate containing a functional group such as an active hydrogen group, capable of reacting with the group -N = C = 0. The substrate to be treated with the water and oil repellent composition of the present invention is not specifically limited, and various substrates can be exemplified. Examples thereof include, textiles, glass, paper, wool, leather, leather, asbestos, brick, cement, metal and oxide, ceramics, plastic, coated surface and dresser. Examples of textile materials include natural fibers of animal or vegetable origin, such as cotton, hemp, wool and silk; synthetic fibers such as polyamide, polyester, joolivinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene; semisynthetic fibers such as rayon and acetate, - inorganic fibers such as glass fibers and asbestos fibers; a mixture of these fibers; and a yarn a fabric (for example, a woven fabric, a non-woven fabric and a knitted fabric) prepared from these fibers.
PREFERRED MODALITY OF THE INVENTION
The present invention will be illustrated by the following Examples and Comparative Examples, which do not limit the present invention. In the examples and in the Comparative Example, the "parts" and "%" are by weight, unless otherwise specified.
Water repellency and oil repellency are evaluated as follows. Water repellency is expressed by repellency No. (see the following Table 1) determined by the dew method according to JIS (Japanese Industrial Standard) L-1092. The oil repellency is determined by dropping a drop (diameter: about 5 mmj of a test solution shown in the following Table 2 on a surface of a sample cloth, and observing the state of penetration of the drop after 30 seconds). seconds (AATCC-TM118-1992) The "+" and "-" supra-indexes for water repellency No. represent that the result is slightly better and slightly worse than said water repellency, respectively.
Table 1
Water repellent No. State 100 No wetting on surface 90 Slightly wet on surface 80 Partly wet on surface 70 Wet on surface 50 Wet on full surface 0 Completely wet on front and back surfaces
Table 2 ~
Repellency al- Test solution Surface oil tension (dyne / cm, 25 ° C) 8 n-Heptane 20.0 7 n-Qctane 21 ^ 3 6 n-Decano 23.5 5 n-Dodecano 25.0 4 n-Tetradecane 26.7 3 n-Hexadecane 27.3 2 mixture (35/65) of 29.6 n-Hexadecane / Nuj ol 1 Nujol 31.2 0 Bottom, to 1
A durability test was conducted as follows. With respect to a wash durability test, a test cloth is to be "treated, washed in water containing 0.83 g / L of a detergent.
(trade name: Hi-Top manufactured by Lion Co.,
Ltd.) under the conditions of a temperature of 40 ° C and a bath ratio of 1:40 (cloth: treatment liquid (g: g)) with a domestic washing machine for 5 minutes, rinsed with water for 15 minutes , and then air dried (1 cycle). After this cycle, it repeats 10, 20 ^ 30 times, the water and oil repellency is measured to register a value for durability to washing,
Preparatory Example 1
Production of isocyanate emulsion in block 1 (an emulsion of a material in methyl-ethyl-ketoxime blog of trimethylolpropane adduct / toluene diisocyanate)
50 Parts of a methyl ethyl ketoxime block material of a trimethylolpropane / toluene diisocyanate adduct were dissolved in 50 parts of methyl isobutyl ketone. Then, 1.5 parts of dialguil- chloride was added. { hardened tallow) -dimethyl-ammonium and 7.4 parts of polyoxyethylene-polyoxypropylene block polymer, and stirring was initiated. 72 parts of water were added slowly with stirring and, after completion of the addition, the dispersing operation was further conducted by a homomixer. Then, the methyl isobutyl ketone was distilled off under reduced pressure to give an emulsion having a solids content of 45%. In the resulting emulsion, a zeta potential was +39 mV and an average particle diameter was 204 mm. As a result of X-ray diffraction, no crystalline peak was observed.
Preparatory Example 2
Production of isocyanate emulsion in block 2 juna emulsion of a methyl-ethyl-ketoxime block material of aductp dB diphenylmethane diisocyanate / polyol)
50 Parts of a methyl ethyl ketoxime block material of an adduct of diphenylmethane diisocyanate / 1,3-butanediol was dissolved in 50 parts of methyl isobutyl ketone. Then, 4.1 parts of hardened tallow dialguyl chloride) -dimethyl-ammonium and 8.2 parts of block polymer of 25 were added.
polyoxyethylene-polyoxypropylene, and the stirring was started. 76 parts of water were slowly added with stirring and, after completion of the addition, the dispersing operation was further conducted by a homomixer. Then, the methyl isobutyl ketone was distilled off under reduced pressure to leave an emulsion having a solids content of 45%. In the resulting emulsion, a zeta potential was +30 mV and an average particle diameter was 168 nm. As a result of light scattering
X, no crystalline peak was observed.
Preparation Example 3
Production of isocyanate emulsion in block 3 (an emulsion of a methyl-ethyl-ketoxime block material of hexamethylene diisocyanate trimer.)
In the same manner as in Preparative Example 2, except that 50 Parts of a block material were dissolved in 50 parts of methyl isobutyl ketone and 1 part of dialkyl chloride (hardened tallow) dimethylammonium chloride and 10 parts of polymer In a block of polyoxyethylene-polyoxypropylene that were "added, an emulsion was obtained which
it had a solids content of 44.5%. In the resulting emulsion, a zeta potential was +20 mV and an average particle diameter was 220 nm. As a result of X-ray diffraction, only a crystalline peak was observed.
Preparatory Example 4
Production of liquid A containing the water and oil repellent component.
60 Grams of a compound represented by the formula .: (CF3) 2CF (CF2CF2) nCH2CH200CCH = CH2 (a mixture of compounds where n is 3, 4 6 5 in weight ratio of 5: 3: 1), 39 g of _ C18H3700CCH = CH2, 1 g of CH2 = C (CH3) C00CH2CH (OH) CH2C1, 250 _g of deoxygenated water of high purity, 30 g of dipropylene glycol monomethyl ether, 0.2 g of n-dodecyl mercaptan,, 3 g of chloride of Octadecyltrimethylammonium and 3 g of polyoxyethylene alkyl phenol were charged to a flask, followed by stirring under a flow of nitrogen gas at 60 ° C for one hour. Subsequently, a solution prepared by dissolving 1 g of azobisisobutylamidine hydrochloride in 10 g of water was added and the copolymerization reaction was conducted with stirring under a flow of nitrogen gas at 60 ° C for 5 hours. A chromatography analysis revealed that a degree of conversion to the copolymerization reaction was at least 99%. This degree of conversion revealed that a proportion of each constituent unit in the resulting copolymer corresponds approximately to that of the charged monomer. The resulting emulsified dispersion (a liquid containing the water and oil repellent component) of a copolymer had a solids content of 25.9%.
Preparatory Example 5
Production of isocyanate emulsion in block 4 (an emulsion of a methyl-ethyl-ketoxime block material from a trimethylolpropane / tolyl diisocyanate adduct.)
In the same way as in the Example
Preparative 2, except for the addition of only one emulsifier (a polyoxyethylene-polyoxypropylene block polymer (4.2 parts)), an emulsion having a solids content of 43% was obtained. In the resulting emulsion, a zeta potential was +0 mV and an average particle size was 295 nm.
Preparatory Example 6
Production of isocyanate emulsion in block 5
In the same manner as in Preparative Example 2, except for the use of "a mixture of 2.5 parts of dialkyl chloride (hardened tallow) -dimethylammonium chloride, 2.5 parts of polyoxyethylene-polyoxypropylene block polymer, 3.7 parts of ether polyoxyethylene octylphenyl and 3.6 parts of polyoxyethylene sorbitan monolaurate as an emulsifier, an emulsion having a content of 45% was obtained In the resulting emulsion, a zeta potential was 35 mV and an average particle diameter was 160 nm.
Preparatory Example 7
Production of isocyanate emulsion in block 6
In the same way as in the Example
Preparative 2, except for the use of a 6.2-part mixture of polyoxyethylene-alkyl- (hardened tallow) -benzylammonium chloride, 3.1 parts of polyoxythylene-octylphenol and 3.1 parts of polyoxyethylene sorbitan monolaurate as an __ emulsifier, an emulsion was obtained which had a solids content of 45%. In the resulting emulsion, a zeta potential was +30 mV and an average particle diameter was 230 nm.
Preparatory Example 8
Production of isocyanate emulsion in block 7
In the same way as in, the Example
Preparative 2, except for the use of a mixture of 2.5 parts of an ammonium salt of polyoxyethylene alkyl phenyl ether sulfate and 9.8 parts of polyoxyethylene-polyoxypropylene block polymer as an emulsifier, an emulsion having a content of %. In the resulting emulsion, a zeta potential was -10 mV and an average particle diameter was 350 nm.
Examples 1 to 5 and Comparative Examples 1 to 2
The emulsion and the liguid containing the water and oil repellent component, produced in the above formulation, were respectively diluted with deionized water, so that the solids content was 18%. Then, 50 parts by weight of the emulsion and 50 parts by weight of the liquid it contains, the water repellent and the oil, were mixed to give a water and oil repellent composition, and the stability of the water and water repellent composition. The oil at 40 ° C was examined. The water and oil repellent composition preserved at 40 ° C for 20 days was diluted with water to prepare a treatment bath having a solids content of 1.8%. A woven, wide fabric (100% cotton) was treated with the water and oil repellent composition by immersion in the treatment bath, squeezing it with a roller, preheating at 110 ° C for 3 minutes and heat treatment at 160 ° C for 3 minutes.
This treated fabric was subjected to a water and oil repellent test and a wash durability test. The results are shown in Table 3, One spot of the fabric was evaluated visually.
Table 3
•
(Note) Stability: 0: Good, X: Sedimentation arose In the durability column of water and oil repellency, the numerical value on the left indicates water repellency and that on the right indicates oil repellency * : A water and oil repellent composition was used to preserve
40 ° C for 20 days.
•
It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects to which it relates. Having described the invention as above, property is claimed as contained in the following:
Claims (5)
1. An isocyanate block emulsion, comprising a block isocyanate, a surfactant containing at least one cationic surfactant, and a liquid medium, characterized in that the weight ratio of the block isocyanate to the surfactant is 60/40 to 90/10 and the average particle diameter of emulsion particles is not greater than 250 nm.
2. The block isocyanate emulsion according to claim 1, characterized in that the block isocyanate is a low crystallinity or non-crystalline block isocyanate having at most five crystalline peaks in an X-ray diffraction analysis,
3. The block isocyanate emulsion according to claim 1, characterized in that the liquid medium is water, or a mixture of water and an organic solvent, the amount of the organic solvent is not more than 10% by weight based on water.
4. A water and oil repellent composition, characterized in that it comprises the block isocyanate emulsion according to claim 1, and a water and oil repellent component having a polyfluoroalkyl group.
5. A textile material, characterized in that it is treated with the water and oil repellent composition according to claim 4. «Or _ + 40 SUMMARY OF THE INVENTION An isocyanate block emulsion containing a block isocyanate, a surfactant and a liquid medium is described, wherein the weight ratio of the block isocyanate to the surfactant is 60/40 to 90/10 and an average particle diameter it is no greater than 250 nm, giving a stable composition, water and oil repellent, which has no sedimentation for a prolonged period of time even if the emulsion of the block isocyanate is mixed with the water and oil repellent.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8-76265 | 1996-03-29 | ||
JP8/76265 | 1996-03-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
MXPA98007927A true MXPA98007927A (en) | 1999-04-27 |
Family
ID=
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