CA2671878A1 - Hydrophobically modified polyalkylenimines for use as dye transfer inhibitors - Google Patents
Hydrophobically modified polyalkylenimines for use as dye transfer inhibitors Download PDFInfo
- Publication number
- CA2671878A1 CA2671878A1 CA002671878A CA2671878A CA2671878A1 CA 2671878 A1 CA2671878 A1 CA 2671878A1 CA 002671878 A CA002671878 A CA 002671878A CA 2671878 A CA2671878 A CA 2671878A CA 2671878 A1 CA2671878 A1 CA 2671878A1
- Authority
- CA
- Canada
- Prior art keywords
- alkylenimine
- poly
- use according
- hydrophobically modified
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000012546 transfer Methods 0.000 title claims abstract description 23
- 239000003112 inhibitor Substances 0.000 title claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 36
- 239000003599 detergent Substances 0.000 claims description 28
- 239000004569 hydrophobicizing agent Substances 0.000 claims description 20
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 238000005956 quaternization reaction Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000004753 textile Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- -1 fatty acid esters Chemical class 0.000 description 49
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- 229920002873 Polyethylenimine Polymers 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 27
- 239000000975 dye Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000002253 acid Substances 0.000 description 20
- 239000004744 fabric Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 150000001735 carboxylic acids Chemical class 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000003945 anionic surfactant Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004453 electron probe microanalysis Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- KJPHTXTWFHVJIG-UHFFFAOYSA-N n-ethyl-2-[(6-methoxypyridin-3-yl)-(2-methylphenyl)sulfonylamino]-n-(pyridin-3-ylmethyl)acetamide Chemical compound C=1C=C(OC)N=CC=1N(S(=O)(=O)C=1C(=CC=CC=1)C)CC(=O)N(CC)CC1=CC=CN=C1 KJPHTXTWFHVJIG-UHFFFAOYSA-N 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000007844 bleaching agent Substances 0.000 description 5
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 5
- 229920000578 graft copolymer Polymers 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- 235000021314 Palmitic acid Nutrition 0.000 description 4
- 229940100198 alkylating agent Drugs 0.000 description 4
- 239000002168 alkylating agent Substances 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000003899 bactericide agent Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 239000002979 fabric softener Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- QTTDXDAWQMDLOF-UHFFFAOYSA-J tetrasodium 3-[[4-[[4-[(6-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-6-sulfonatonaphthalen-1-yl]diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].Nc1ccc2c(O)c(N=Nc3ccc(N=Nc4ccc(N=Nc5cc(c6cccc(c6c5)S([O-])(=O)=O)S([O-])(=O)=O)c5ccccc45)c4ccc(cc34)S([O-])(=O)=O)c(cc2c1)S([O-])(=O)=O QTTDXDAWQMDLOF-UHFFFAOYSA-J 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 description 2
- HZLCGUXUOFWCCN-UHFFFAOYSA-N 2-hydroxynonadecane-1,2,3-tricarboxylic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)C(O)(C(O)=O)CC(O)=O HZLCGUXUOFWCCN-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000001792 White test Methods 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- LPTIRUACFKQDHZ-UHFFFAOYSA-N hexadecyl sulfate;hydron Chemical compound CCCCCCCCCCCCCCCCOS(O)(=O)=O LPTIRUACFKQDHZ-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 229920000962 poly(amidoamine) Polymers 0.000 description 2
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- 230000009257 reactivity Effects 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- 239000013042 solid detergent Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 1
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- CEGRHPCDLKAHJD-UHFFFAOYSA-N 1,1,1-propanetricarboxylic acid Chemical compound CCC(C(O)=O)(C(O)=O)C(O)=O CEGRHPCDLKAHJD-UHFFFAOYSA-N 0.000 description 1
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- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 description 1
- RNHWYOLIEJIAMV-UHFFFAOYSA-N 1-chlorotetradecane Chemical compound CCCCCCCCCCCCCCCl RNHWYOLIEJIAMV-UHFFFAOYSA-N 0.000 description 1
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- FYOYPNKQOLBKDB-UHFFFAOYSA-N 1-hexadec-1-enoxyhexadec-1-ene Chemical compound CCCCCCCCCCCCCCC=COC=CCCCCCCCCCCCCCC FYOYPNKQOLBKDB-UHFFFAOYSA-N 0.000 description 1
- GFLXBRUGMACJLQ-UHFFFAOYSA-N 1-isocyanatohexadecane Chemical compound CCCCCCCCCCCCCCCCN=C=O GFLXBRUGMACJLQ-UHFFFAOYSA-N 0.000 description 1
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 1
- CSMJMAQKBKGDQX-UHFFFAOYSA-N 1-isocyanatotetradecane Chemical compound CCCCCCCCCCCCCCN=C=O CSMJMAQKBKGDQX-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 1
- QIVYTYXBBRAXNG-UHFFFAOYSA-N 2-(2-hydroxyethylimino)acetic acid Chemical compound OCCN=CC(O)=O QIVYTYXBBRAXNG-UHFFFAOYSA-N 0.000 description 1
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- 239000004606 Fillers/Extenders Substances 0.000 description 1
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- 229940116226 behenic acid Drugs 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
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- 238000002296 dynamic light scattering Methods 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 125000004395 glucoside group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- FPBBPRPSGHHFSV-UHFFFAOYSA-N icos-1-en-1-one Chemical compound CCCCCCCCCCCCCCCCCCC=C=O FPBBPRPSGHHFSV-UHFFFAOYSA-N 0.000 description 1
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000004658 ketimines Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- MBXNQZHITVCSLJ-UHFFFAOYSA-N methyl fluorosulfonate Chemical compound COS(F)(=O)=O MBXNQZHITVCSLJ-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910021527 natrosilite Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- URLJMZWTXZTZRR-UHFFFAOYSA-N sodium myristyl sulfate Chemical compound CCCCCCCCCCCCCCOS(O)(=O)=O URLJMZWTXZTZRR-UHFFFAOYSA-N 0.000 description 1
- 229950005425 sodium myristyl sulfate Drugs 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- FIXVWFINKCQNFG-UHFFFAOYSA-M sodium;4-[(4-aminophenyl)diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 FIXVWFINKCQNFG-UHFFFAOYSA-M 0.000 description 1
- KVSYNOOPFSVLNF-UHFFFAOYSA-M sodium;4-nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=C(S([O-])(=O)=O)C=C1 KVSYNOOPFSVLNF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- QTFHTNFVUCUDIR-UHFFFAOYSA-K trisodium 6-[(2,4-diaminophenyl)diazenyl]-3-[[4-[4-[[7-[(2,4-diaminophenyl)diazenyl]-1-hydroxy-3-sulfonatonaphthalen-2-yl]diazenyl]-2-sulfonatoanilino]phenyl]diazenyl]-4-hydroxynaphthalene-2-sulfonate Chemical compound C1=CC(=CC=C1NC2=C(C=C(C=C2)N=NC3=C(C=C4C=CC(=CC4=C3[O-])N=NC5=C(C=C(C=C5)N)N)S(=O)(=O)O)S(=O)(=O)[O-])N=NC6=C(C=C7C=CC(=CC7=C6[O-])N=NC8=C(C=C(C=C8)N)N)S(=O)(=O)O.[Na+].[Na+].[Na+] QTFHTNFVUCUDIR-UHFFFAOYSA-K 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to the use of hydrophobically modified polyalkylenimines for use as dye transfer inhibitors.
Description
Hydrophobically modified polyalkylenimines for use as dye transfer inhibitors Description The invention relates to the use of hydrophobically modified polyalkylenimines as dye transfer inhibitors.
During the washing process, dye molecules are often detached from colored textiles;
these can in turn attach to other textiles. In order to counteract this undesired dye transfer, so-called dye transfer inhibitors are often used. These are frequently polymers which comprise monomers with nitrogen-heterocyclic radicals in copolymerized form.
Thus, for example, DE 4235798 describes copolymers of 1-vinylpyrrolidone, 1-vinylimidazole, 1-vinylimidazollum compounds or mixtures thereof; further nitrogen-containing, basic ethylenically unsaturated monomers; and, if appropriate, other monoethylenically unsaturated monomers and their use for inhibiting dye transfer during the washing process.
Similar copolymers are described for this purpose in DE 19621509 and WO
98/30664.
The copolymers described in these specifications are characterized in part by good inhibition of dye transfer in washing processes. However, they generally have poor compatibility with the other detergent constituents customarily used. Thus, particularly in the case of liquid detergents, there is the danger of incompatibilities, for example in the form of opacity or phase separations.
On several occasions, the use of hydrophobically modified polyalkylenimines in detergent and cleaner formulations has been described.
DE 2025829 describes reaction products of fatty acid glycidyl esters with polyethylenimines and their use as fabric softeners.
DE 2046304 describes reaction products of fatty acids or fatty acid esters with polyethylenimines and their use as fabric softeners.
DE 2165900 describes reaction products of alkyl glycidyl ethers with polyethylenimines and their use as graying inhibitors.
US 3,576341 describes alkylated polyethylenimines in which the alkyl groups have 16 to 30 carbon atoms, and use as fabric softeners.
WO 2002/l095122 describes the use of hydrophobically modified polyethylenimines as anticrease additives for detergent formulations.
An effect of the hydrophobically modified polyalkylenimines inhibiting dye transfer during washing is described in none of these citations.
It was an object of the present invention to provide substances with a good dye transfer-inhibiting effect during the washing process. These substances should additionally have good compatibility with conventional detergent constituents, especiaily in the case of liquid detergent formulations.
These and further objects are surprisingly achieved through hydrophobically modified poly-Cz-Ca-al kylenimines.
The invention therefore relates to the use of hydrophobically modified poly-C2-C4-alkylenimines, in particular hydrophobically modified polyethylenimines, as dye transfer inhibitors in detergent compositions for textiles.
Here and in what follows, hydrophobically modified poly-Cz-Cq-alkylenimines are to be understood as meaning poly-Cz-Ca-alkylenimines in which the hydrogen atoms of the primary and secondary amino groups are partially or completely replaCed by linear or branched aliphatic, saturated or unsaturated hydrocarbon radicals such as alkyl, alkenyl, alkadienyl or hydroxyalkyl radicals. The hydrocarbon radicals generally have at least 8, e.g. 8 to 30, carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms.
Depending on the hydrophobicizing agent used in each case, the hydrocarbon radicals can be linked to the nitrogen atom of the poly-C2-CQ-alkylenimine directly or via a functional group, e.g. via a carbonyl group (*-C(=O)-#), via an oxycarbonyl group (*-O-C(=0)-#), via an aminocarbonyl group (*-NH-C(=0)-#), via a carbonyloxyhydroxypropyl group (*-C(=0)-O-CH2-CH(OH)-CH2-#), via a 2-oxycarbonylethylenecarbonyl group (*-CH(COOH)-CHrCO-#), or via a radical of the formula *-CH2-C(=O)-CH '-C(=0)-# (in the formulae given above, * represents the linkage to the hydrocarbon radical and # represents the linkage to the nitrogen atom of the poly-C2-C4-alkylenimine). The hydrocarbon radical can also form an aidimine or ketimine group with the nitrogen of the poly-C2-C4-alkylenimine, or be linked to 2 nitrogen atoms of the pofy-C2-C4-alkylenimine via the carbon atom of a cyclic amidine group.
Preference is given to those hydrophobically modified poly-C2-C4-alkylenimines in which the hydrocarbon radical is linked to one nitrogen atom of the poly-C2-C4-alkylenimine directly or via a carbonyl group, the latter being particularly preferred.
During the washing process, dye molecules are often detached from colored textiles;
these can in turn attach to other textiles. In order to counteract this undesired dye transfer, so-called dye transfer inhibitors are often used. These are frequently polymers which comprise monomers with nitrogen-heterocyclic radicals in copolymerized form.
Thus, for example, DE 4235798 describes copolymers of 1-vinylpyrrolidone, 1-vinylimidazole, 1-vinylimidazollum compounds or mixtures thereof; further nitrogen-containing, basic ethylenically unsaturated monomers; and, if appropriate, other monoethylenically unsaturated monomers and their use for inhibiting dye transfer during the washing process.
Similar copolymers are described for this purpose in DE 19621509 and WO
98/30664.
The copolymers described in these specifications are characterized in part by good inhibition of dye transfer in washing processes. However, they generally have poor compatibility with the other detergent constituents customarily used. Thus, particularly in the case of liquid detergents, there is the danger of incompatibilities, for example in the form of opacity or phase separations.
On several occasions, the use of hydrophobically modified polyalkylenimines in detergent and cleaner formulations has been described.
DE 2025829 describes reaction products of fatty acid glycidyl esters with polyethylenimines and their use as fabric softeners.
DE 2046304 describes reaction products of fatty acids or fatty acid esters with polyethylenimines and their use as fabric softeners.
DE 2165900 describes reaction products of alkyl glycidyl ethers with polyethylenimines and their use as graying inhibitors.
US 3,576341 describes alkylated polyethylenimines in which the alkyl groups have 16 to 30 carbon atoms, and use as fabric softeners.
WO 2002/l095122 describes the use of hydrophobically modified polyethylenimines as anticrease additives for detergent formulations.
An effect of the hydrophobically modified polyalkylenimines inhibiting dye transfer during washing is described in none of these citations.
It was an object of the present invention to provide substances with a good dye transfer-inhibiting effect during the washing process. These substances should additionally have good compatibility with conventional detergent constituents, especiaily in the case of liquid detergent formulations.
These and further objects are surprisingly achieved through hydrophobically modified poly-Cz-Ca-al kylenimines.
The invention therefore relates to the use of hydrophobically modified poly-C2-C4-alkylenimines, in particular hydrophobically modified polyethylenimines, as dye transfer inhibitors in detergent compositions for textiles.
Here and in what follows, hydrophobically modified poly-Cz-Cq-alkylenimines are to be understood as meaning poly-Cz-Ca-alkylenimines in which the hydrogen atoms of the primary and secondary amino groups are partially or completely replaCed by linear or branched aliphatic, saturated or unsaturated hydrocarbon radicals such as alkyl, alkenyl, alkadienyl or hydroxyalkyl radicals. The hydrocarbon radicals generally have at least 8, e.g. 8 to 30, carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms.
Depending on the hydrophobicizing agent used in each case, the hydrocarbon radicals can be linked to the nitrogen atom of the poly-C2-CQ-alkylenimine directly or via a functional group, e.g. via a carbonyl group (*-C(=O)-#), via an oxycarbonyl group (*-O-C(=0)-#), via an aminocarbonyl group (*-NH-C(=0)-#), via a carbonyloxyhydroxypropyl group (*-C(=0)-O-CH2-CH(OH)-CH2-#), via a 2-oxycarbonylethylenecarbonyl group (*-CH(COOH)-CHrCO-#), or via a radical of the formula *-CH2-C(=O)-CH '-C(=0)-# (in the formulae given above, * represents the linkage to the hydrocarbon radical and # represents the linkage to the nitrogen atom of the poly-C2-C4-alkylenimine). The hydrocarbon radical can also form an aidimine or ketimine group with the nitrogen of the poly-C2-C4-alkylenimine, or be linked to 2 nitrogen atoms of the pofy-C2-C4-alkylenimine via the carbon atom of a cyclic amidine group.
Preference is given to those hydrophobically modified poly-C2-C4-alkylenimines in which the hydrocarbon radical is linked to one nitrogen atom of the poly-C2-C4-alkylenimine directly or via a carbonyl group, the latter being particularly preferred.
Preferably, the hydrocarbon radicals are iinear. Preferably, the hydrocarbon radicals are saturated.
Accordingly, the hydrocarbon radicals in the preferred hydrophobically modified poly-Ci-Ca-alkylenimines are present in the form of Ca-Cao-alkyl, Ca-Cao-alkylcarbonyl, Ca-Cao-alkenyl, C$-Cso-alkenylcarbonyl, Ca-Cao-alkadienyl, Ca-C3o-alkadienylcarbonyl and/or hydroxy-C$-Cao-alkyl groups, in particular in the form of C1o-C22-alkyl, CGo-C22-alkylcarbonyl, C,o-C22-alkenyl, C,o-Czz-alkenylcarbonyl, C,o-C22-aikadienyi, C1o-C22-alkadienylcarbonyl andlor hydroxy-C,o-C22-alkyl groups, particularly preferably in the form of Go-C,a-alkyl, C,o-C,a-alkyicarbonyl, C,o-C,a-alkenyl, Cio-C,a-alkenylcarbonyl, C,o-C,a-alkadienyl, C,o-C,s-alkadienylcarbonyl and/or hydroxy-C,o-C,$-alkyl groups, where the alkyl, hydroxyalkyl, aikenyl, alkadienyl radicals of the aforementioned groups are preferably linear.
In the particularly preferred hydrophobically modified poly-C2-C4-alkylenimines, the hydrocarbon radicals are present in the form of Ca-Cao-alkytcarbonyi or Cs-Cso-alkenylcarbonyl groups, in particular in the form of C,o-C22-alkylcarbonyl or C,o-C22-alkenylcarbonyl groups and specifically in the form of C,o-Cis-alkylcarbonyl or Cio-C,s-alkenylcarbonyl groups, where the alkyl und alkenyl radicals of the aforementioned groups are preferably linear.
Preference is furthermore given to those hydrophobically modified poly-C2-C4-alkylenimines in which at least 10 mol%, in particular at least 15 mol%
and particularly preferably at least 20 mol%, e.g. 5 to 80 moI%, in particular 15 to 70 mol%
and specifically 20 to 60 mol%, of the nitrogen atoms of the paly-C2-C4-alkylenimine carry a hydrocarbon radical.
Correspondingly, the fraction of the hydrocarbon radicals constitutes preferably 25 to 95% by weight, in particular 30 to 90% by weight and specifically 40 to 80% by weight, based on the total weight of the hydrophobicaEly modified poly-C2-C4-alkylenimine.
The weight-average molecular weight Mw of hydrophobically modified poly-C2-C4-alkylenimines suitable according to the invention is typically in the range from 1000 to 1 000 000 Daltons. For the use according to the invention, it has furthermore proven advantageous if the hydrophobically modified poly-C2-Ca~-alkylenimine has a number-average molecular weight in the range from 3000 to 300 000 Daltons and in particular in the range from 6000 to 200 000 Daltons. The molecular weights given here refer to the molecular weights specified by means of dynamic light scattering and measured on dilute aqueous solutions at 25 C which correspond to the weight-average molecular weight.
Accordingly, the hydrocarbon radicals in the preferred hydrophobically modified poly-Ci-Ca-alkylenimines are present in the form of Ca-Cao-alkyl, Ca-Cao-alkylcarbonyl, Ca-Cao-alkenyl, C$-Cso-alkenylcarbonyl, Ca-Cao-alkadienyl, Ca-C3o-alkadienylcarbonyl and/or hydroxy-C$-Cao-alkyl groups, in particular in the form of C1o-C22-alkyl, CGo-C22-alkylcarbonyl, C,o-C22-alkenyl, C,o-Czz-alkenylcarbonyl, C,o-C22-aikadienyi, C1o-C22-alkadienylcarbonyl andlor hydroxy-C,o-C22-alkyl groups, particularly preferably in the form of Go-C,a-alkyl, C,o-C,a-alkyicarbonyl, C,o-C,a-alkenyl, Cio-C,a-alkenylcarbonyl, C,o-C,a-alkadienyl, C,o-C,s-alkadienylcarbonyl and/or hydroxy-C,o-C,$-alkyl groups, where the alkyl, hydroxyalkyl, aikenyl, alkadienyl radicals of the aforementioned groups are preferably linear.
In the particularly preferred hydrophobically modified poly-C2-C4-alkylenimines, the hydrocarbon radicals are present in the form of Ca-Cao-alkytcarbonyi or Cs-Cso-alkenylcarbonyl groups, in particular in the form of C,o-C22-alkylcarbonyl or C,o-C22-alkenylcarbonyl groups and specifically in the form of C,o-Cis-alkylcarbonyl or Cio-C,s-alkenylcarbonyl groups, where the alkyl und alkenyl radicals of the aforementioned groups are preferably linear.
Preference is furthermore given to those hydrophobically modified poly-C2-C4-alkylenimines in which at least 10 mol%, in particular at least 15 mol%
and particularly preferably at least 20 mol%, e.g. 5 to 80 moI%, in particular 15 to 70 mol%
and specifically 20 to 60 mol%, of the nitrogen atoms of the paly-C2-C4-alkylenimine carry a hydrocarbon radical.
Correspondingly, the fraction of the hydrocarbon radicals constitutes preferably 25 to 95% by weight, in particular 30 to 90% by weight and specifically 40 to 80% by weight, based on the total weight of the hydrophobicaEly modified poly-C2-C4-alkylenimine.
The weight-average molecular weight Mw of hydrophobically modified poly-C2-C4-alkylenimines suitable according to the invention is typically in the range from 1000 to 1 000 000 Daltons. For the use according to the invention, it has furthermore proven advantageous if the hydrophobically modified poly-C2-Ca~-alkylenimine has a number-average molecular weight in the range from 3000 to 300 000 Daltons and in particular in the range from 6000 to 200 000 Daltons. The molecular weights given here refer to the molecular weights specified by means of dynamic light scattering and measured on dilute aqueous solutions at 25 C which correspond to the weight-average molecular weight.
The hydrophobically modified poly-CrCa-alkylenimines used according to the invention, in particular the hydrophobically modified polyethylenimines, can, based on the poly-C2-C4-alkylenimine on which they are based, be linear or branched, preference being given to those which are branched in the poly-C2-C4-alkylenimine mpiety.
Whereas linear poly-C2-C4-alkylenimines are composed exclusively of repeat units of formula A, in which Q is C2-C4-alkylene, branched poly-Cz-C4-alkylenimines have, besides the linear repeat units, tertiary nitrogen atoms according to the structural unit B:
*+H~---Q~-H-* N-Q~'N-*
* Q
A B
Preference is given to those branched, hydrophobically modified poly-C2-C4 alkylenimines, in particular branched, hydrophobically modified polyethylenimines, which, based on the poly-C2-C4-alkylenimine on which they are based, have, on average, per polyalkylenimine molecule at least one, preferably at least 5 or at least 10, branching points according to formula B. In particular, at least 5%, in particular at least 10% and particularly preferably at least 15%, e.g.
5 to 40%
and specifically 15 to 35%, of the nitrogen atoms of the parent poly-C2-C4-alkylenimine are tertiary nitrogen atoms.
Particularly in the case of relatively high degrees of branching, i.e. if at least 10%, in particular at least 15%, e.g. 10 to 40%, in particular 15 to 35% of the nitrogen atoms of the parent poly-C2-C4-alkylenimine are tertiary nitrogen atoms, the hydrophobically modified poly-C2-C4-alkylenimines have a structure similar to a core-shell structure, where the poly-C2-C4-alkylenimine moieties form the core and the hydrophobic radicals form the shell.
The hydrophobically modified poly-CrCa-alkylenimines can be present in uncrosslinked or crosslinked form, and, besides the hydrophobic modification, may be quaternized and/or modified through reaction with alkylene oxides, di-Ci-C4-alkyl carbonates, C2-C4-alkylene carbonates or C,-C4-carboxyfic acids.
Preferably, the hydrophobically modified poly-C2-C4-alkylenimines are uncrosslinked.
According to a first preferred embodiment of the invention, the hydrophobically modified poly-C2-C4-alkylenimines have no further modification besides the hydrophobic modification.
According to a second preferred embodiment of the invention, the hydrophobically modified poly-C2-C4-alkylenimines are quaternized in addition to the hydrophobic modification. Such quaternized hydrophobically modified poly-C2-C4-alkylenimines preferably have no further modffication. The degree of quaternization, i.e.
the number 5 of quaternized nitrogen atoms, based on the total amount of the nitrogen atoms of the hydrophobically modified poly-C2-C4-alkylenimine, is preferably not more than 80 mol%, in particular not more than 50 mol%, e.g. 1 to 80 mol%, in particular 5 to 50 mol%, based on the nitrogen atoms of the poly-CrCa-aikylenimine.
The hydrophobically modified poly-C2-C4-alkylenimines which are used according to the invention are in part known from the prior art cifed at the beginning or can be prepared analogously to the methods described there. As a nale, hydrophobically modified poly-Cz-Cd-alkylenimines are prepared by polymer-analogous reaction of unmodified poly-C2-C4-alkylenimines with a hydrophobicizing agent.
Accordingly, one embodiment of the invention relates to the use of a hydrophobically modified poly-C2-C4-alkylenimine obtainable by a process which comprises the reaction of a nonmodified poly-C2-C4-alkylenimine, in particular a nonmodified, branched poly-C2-C4-alkylenimine, and specifically a nonmodified, branched polyethylenimine, with a hydrophobicizing agent.
Examples of suitable hydrophobicizing agents are:
i) long-chain, linear or branched carboxylic acids having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the alkyl or alkenyl radical, such as caprylic acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, paimitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid and mixtures thereof, preferably lauric acid, stearic acid, paimitic acid and oleic acid, or their amide-forming derivatives, such as acid chlorides, esters or anhydrides of the specified carboxylic acids and mixtures thereof, ii) linear or branched alkyl halides having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the linear or branched alkyl radical, such as octyl chloride, nonyl chloride, decyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride, octadecyl chloride and mixtures thereof, iii) alkyl epoxides having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms in the linear or branched alkyl radical, such as hexadecenyl oxide, dodecenyl oxide and octadecenyl oxide and mixtures thereof, iv) alkyl ketene dimers having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms in the linear or branched alkyl radical, such as lauryl ketene, paimityl ketene, stearyl ketene and oleyl ketene dimers and mixtures thereof, v) cyclic dicarboxylic acid anhydrides, in particular alkyl-substituted succinic anhydrides having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the linear or branched alkyl radical, such as dodecenyisuccinic anhydride, tetradecylsuccinic anhydride, hexadecenyisuccinic anhydride and mixtures thereof, vi) alkyl isocyanates having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms in the linear or branched alkyl radical, such as tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate and mixtures thereof, vii) chtoroformic acid esters of linear or branched alkanols or alkenols having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms and mixtures thereof, and viii) linear or branched aliphatic aldehydes having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, and dialkyl ketones having in total 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the two alkyl groups and mixtures thereof.
Preferred hydrophobicizing agents are long-chain, linear or branched carboxylic acids having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the alkyl or alkenyl radical and amide-forming derivatives thereof, in particular linear saturated carboxylic acids having 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms in the alkyl radical.
Preferred hydrophobicizing agents are also alkyl epoxides having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atorns.
The unmodified poly-CrC4-alkylenimines which form the basis of the hydrophobically modified poly-C2-Ca-alkylenimines used according to the invention comprise homopolymers of ethylenimine (aziridine) and higher homologs thereof, propylenimine (methylaziridine) and butylenimines (1,2-dimethylaziridine, 1,1-dimethylaziridine and 1-ethylaziridine), copolymers of ethylenimine with its higher homologs, and the graft polymers of polyamidoamines or polyvinylamines with ethylenimine and/or its higher homologs.
Also suitable are the graft polymers of C2-C4-alkylenimines described in WO 02/095122, such as ethylenimine onto polyamidoamines or onto polyvinylamines.' Such graft polymers generally have a weight fraction of C2-G4-alkylenimines of at least 10% by weight, in particular at least 30% by weight, e.g. 10 to 90% by weight in particular 10 to 85% by weight, based on the total weight of the unmodified poly-C2-C4-alkylenimine.
In particular, the unmodified poly-CrC4-alkylenimines are branched poly-C2-C4-alkylenimines, preferably polyethylenimines, in particular branched polyethylenimines and specifically homopolymers of ethylenimine, which are in particular branched.
Preferably, the unmodified poly-C2-Ca-aikylenimine used for the preparation is branched, where, with regard to the degree of branching, that stated above for hydrophobically modified poly-C2-C4-alkylenimines applies.
Preferably, the unmodified poly-CrCa-alkylenimine used for the preparation has a number-average molecular weight in the range from 1000 to 200 000 Daltons, in particular in the range from 2000 to 100 000 Daltons.
The reaction of the unmodified poly-C2-Ca-alkylenimine with the hydrophobicizing agent can take place analogously to known processes in the prior art. The reaction conditions naturally depend on the type and functionality of the hydrophobicizing agent.
The reaction can take place without a diluent or in solution. The reaction is preferably carried out in a solvent suitable for the reaction. Examples of suitable solvents are hydrocarbons, in particular aromatic hydrocarbons, e.g. alkylbenzenes such as xylenes, toluene, cumene, tert-butylbenzene and the like.
If appropriate, the reaction can be carried out in the presence of catalysts which improve the reactivity of the hydrophobicizing agent toward the poly-C2-C4-alkylenimine. The type of catalyst depends in a manner known per se on the type and reactivity of the hydrophobicizing agent. The catalysts are usually Lewis acids or Bronstedt acids. Often, for example in the case of carboxylic acids, it is possible to dispense with the use of catalysts.
In the case of the carboxylic acids and carboxylic acid derivatives preferred according to the invention, it has proven advantageous to remove the low molecular weight products (water, alcohols or hydrogen chloride) which form during the reaction from the reaction mixture. For example, in the case of the carboxylic acids, the water formed will preferably be removed from the reaction mixture via an entrainer. Typical entrainers are hydrocarbons, in particular alkyl aromatics such as toluene or xylenes.
Preferably, the reaction will then be carried out in an organic solvent suitable as entrainer.
As a rule, the hydrophobicizing agent will be used in an amount which corresponds to the desired functionality, it also being possible to use the hydrophobicizing agent in excess. In this respect, that stated previously for the functionalization of the hydrophobicized polyalkylenimine applies analogously for the molar ratio of hydrophobicizing agent to nitrogen atoms in the unmodified polyalkylenimine.
In particular, the hydrophobicizing agent, calculated as the parts of the hydrophobicizing agent remaining in the product (thus the amount of hydrophobicizing agent minus any low molecular weight products such as water), will be used in an amount of from 0.35 to 20 parts by weight, in particular in an amount of from 0.5 to 10 parts by weight, per part by weight of unmodified poly-C2-C4-alkylenimine.
According to a preferred embodiment of the invention, the hydrophobically modified poly-C2-Ca-alkylenimines are quaternized. Accordingly, the preparation of the hydrophobically modified poly-Cz-C4-alkylenimines additionally comprises a quaternization. The quaternization can take place before or in parl:icular after the hydrophobicization.
For the quatemization, in particular alkylating agents such as alkyl halides which generally have 1 to 10 carbon atoms in the alkyl radical, or dialkyl sulfates, which generally comprise alkyl radicals having 1 to 10 carbon atoms, are used.
Examples of suitable alkylating agents from these groups are methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride, and dimethyl sulfate and diethyl sulfate. Further suitable alkylating agents are, for example, benzyl halides, in particular benzyl chloride and benzyl bromide; chloroacetic acid; fluorosulfuric acid methyl ester;
diazomethane;
oxonium compounds, such as trimethyloxonium tetrafluoroborate; alkylene oxides, such as ethylene oxide, propylene oxide and glycidol, which are used in the presence of acids; cationic epichlorohydrins. Preferred quaternizing agents are methyl chloride, dimethyl suffate and diethyl sulfate. During the quaternization, the secondary or in particular the tertiary nitrogen atoms of the parent poly-CrCa-alkylenimine moiety are converted into quatemary nitrogen atoms, ergo ammonium groups, as a result of which the hydrophobically modified poly-Cz-Ca-alkylenimine is given an overall positive charge.
The hydrophobically modified poly-C2-C4-alkylenimines are generally water-soluble or water-dispersible and can be used in solid and liquid detergents and in laundry aftertreatment compositions. They are characterized in particular by high compatibility with conventional detergent constituents, in particular with the constituents of liquid detergent formulations, specifically those which have a low content of anionic surfactants.
The incorporation into the respective detergent or laundry aftertreatment composition formulation takes place in a manner known per se, the hydrophobically modified polyalkylenimines often being used in liquid form, i.e. dissolved or dispersed form. The hydrophobically modified polyalkylenimines can also be used in powder or granule form.
The dye transfer onto fabric washed at the same time and the associated undesired discoloration of this fabric is effectively inhibited. Even at concentrations of from 10 to 150 ppm of the hydrophobically modified poly-C2-C4-alkylenimine in the wash or rinse liquor, good to very good dye transfer-inhibiting effects are achieved which lie significantly above the reference substances such as polyvinylpyrrolidone.
The solid detergent formulations comprise in particular the following components:
(a) 0.05 to 20% by weight of at least one hydrophobically modified poly-C2-C4-alkylenimine, (b) 0.5 to 40% by weight of at least one nonionic, anionic and/or cationic surfactant, (c) 0.5 to 50% by weight of an inorganic builder, (d) 0 to 10% by weight of an organic cobuilder and (e) 0.1 to 60% by weight of other customary ingredients, such as extenders, enzymes, perfume, complexing agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, further color protection additives and dye transfer inhibitors, graying inhibitors, soil release polyesters, fiber protection additives, silicones, dyes, bactericides and preservatives, dissolution improvers and/or disintegrants, water;
where the sum of components (a) to (e) is 100% by weight.
The solid detergent formulations may be present in powder, granule, extrudate or tablet form.
The liquid detergent formulations preferably have the following composition:
(a) 0.05 to 20% by weight of at least one hydrophobically modified poly-C2-Ca-aikylenimine, (b) 0.5 to 70% by weight of at least one nonionic, anionic and/or cationic surfactant, (c) 0 to 20% by weight of an inorganic builder, (d) 0 to 10% by weight of an organic cobuilder, (e) 0.1 to 60% by weight of other customary ingredients, such as sodium carbonate, enzymes, perfume, complexing agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, further color protection additives and dye transfer inhibitors, graying inhibitors, soil release polyesters, fiber protection additives, silicones, dyes, bactericides and preservatives, organic solvents, solubility promoters, hydrotropes, thickeners and/or alkanolamines and (f) 0 to 99.35% by weight of water, where the sum of the components (a) to (f) is 100% by weight.
The laundry aftertreatment compositions, in particular laundry care rinse compositions, preferably comprise (a) 0.05 to 20% by weight of at least one hydrophobically modified poly-C2-C4-alkylenimine, (b) 0.1 to 40% by weight of at least one cationic surfactant, (c) 0 to 30% by weight of at least one nonionic surfactant, (d) 0.1 to 30% by weight of other customary ingredients, such as silicones, other lubricants, wetting agents, film-forming polymers, fragrances and dyes, stabilizers, fiber protection additives, further color protection additives and dye 5 transfer inhibitors, complexing agents, viscosity modifiers, soil release additives, solubility promoters, hydrotropes, corrosion protection additives, bactericides and preservatives and (e) 0 to 99.75% by weight of water, where the sum of the components (a) to (e) is 100% by weight.
Suitable nonionic surfactants (B) here are primarily: -- alkoxylated Cs-C22-alcohofs, such as fatty alcohol alkoxylates, oxo alcohol =
alkoxylates and Guerbet alcohol ethoxylates: the alkoxylation can take place with ethylene oxide, propylene oxide and/or butylene oxide. Block copolymers or random copolymers may be present. Per mole of alcohol, they usually comprise 2 to 50 mol, preferably 3 to 20 mol, of at least one alkylene oxide. A preferred alkylene oxide is ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms;
- alkylphenol alkoxylates, in particular alkylphenol ethoxylates, which comprise C6-C14-alkyl chains and 5 to 30 mol of alkylene oxide/mol;
- alkyl polyglucosides which comprise Ca-C=-, preferably C,o-Cia-alkyl chains and as a rule 1 to 20, preferably 1.1 to 5, glucoside units;
- N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, long-chain amine oxides, polyhydroxy(alkoxy) fatty acid 'derivatives, such as, for example, polyhydroxy fafty acid amides, gemini surfactants, and block copolymers of ethylene oxide, propylene oxide and/or butylene oxide;
and their mixtures.
Suitable anionic surfactants are, for example:
- sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18, carbon atoms, in particular CsCõ-alcohol sulfates, C12C,4-alcohol sulfates, CV-C18-alcohot sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate;
- sulfated alkoxylated Ca-C22-alcohols (alkyl ether sulfates): compounds of this type are prepared, for example, by firstly alkoxylating a Ca-Cz2-, preferably a C,o-C,s-alcohol, e.g. a fatty alcohol, and then sulfating the alkoxylation product.
For the alkoxylation, ethylene oxide is preferably used;
- linear Ca-C2o-alkylbenzenesulfonates (LAS), preferably linear Cs-C,3-alkylbenzenesulfonates and alkyftoluenesulfonates;
- alkanesulfonates, in particular Ca-C24-, preferably C,o-C,a-afkanesulfonates;
- olefinsulfonates;
- faity acid and fatty acid ester sulfonates;
- soaps, such as the Na and K safts of C8-C24-carboxylic acids, and mixtures thereof.
The anionic surfactants are preferably added to the detergent in the form of salts.
Suitable salts here are, for example, alkali metal salts, such as sodium, potassium and lithium salts, and ammonium salts, such as hydroxyethylammonium, di(hydroxyethy!)ammonium and tri(hydroxyethyi)ammonium salts.
Particularly suitable cationic surFactants which may be mentioned are:
- C7-C25-alkylamines;
- N,N-dimethyi-N-(hydroxy-C7-C25-alkyl)ammonium salts;
- mono- and di(C7-C25-alkyl)dimethylammonium compounds quaternized with alkylating agents;
- ester quats, in particular quatemary esterified mono-, di- and trialkanolamines which have been esterified with Ca-Crrcarboxylic acids;
- imidazoline quats, in particular 1-alkylimidazolinium salts of the formulae II or III
R
R9 N Rs N+
N~
Rao/ Rt1 Rio/
II III
in which the variables have the following meaning:
R9 is C,-C2s-alkyl or C2-C25-alkenyl;
R'O is CI-Ca-alkyl or hydroxy-C1-C4-alkyl;
R" is CrCa-alkyl, hydroxy-CrCa-alkyl or a radical Rl-(CO)-X-(CH2)rn- (X: -0-or -NH-; m: 2 or 3), where at least one radical R9 is C7-C22-alkyl.
Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates and amphoteric imidazolium compounds.
The advantages according to the invention of the hydrophobically modified polyalkylenimines come in useful especially in those detergent formulations which comprise only a small fraction of anionic surfactants. Preferably, the fraction of anionic surfactants, based on the total amount of surfactant in the detergent or laundry aftertreatment composition formulation, is not more than 50% by weight, in particular not more than 30% by weight and specifically not more than 10% by weight.
Preferably, the anionic surfactant constitutes not more than 8% by weight, in particular not more than 5% by weight, based on the total weight of the formulation.
Suitable inorganic builders are, in particular:
- crystalline and amorphous alumosilicates with ion-exchanging properties, such as in particular zeolites: various types of zeolites are suitable, in particular the zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially replaced by other cations such as Li, K, Ca, Mg or ammonium;
- crystalline silicates, such as in particular disilicates and sheet silicates, e.g. S-and (3-Na2Si2O5. The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preference being given to the Na, Li and Mg silicates;
- amorphous silicates, such as sodium metasilicate and amorphous disilicate;
- carbonates and hydrogencarbonates: these can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to Na, Li and Mg carbonates and hydrogencarbonates, in particular sodium carbonate and/or sodium hydrogencarbonate; and - polyphosphates, such as pentasodium triphosphate.
Suitable organic cobuilders are in particular:
- low molecular weight carboxylic acids, such as citric acid, hydrophobically modified citric acid, e.g. agaricic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, oxydisuccinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl- and alkenylsuccinic acids and aminopolycarboxylic acids, e.g. nitrilotriacetic acid, 0-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, N-(2-hydroxyethyl)iminoacetic acid, ethylenediaminedisuccinic acid and methyl-and ethylglycinediacetic acid or alkali metal salts thereof;
- oligomeric and polymeric carboxylic acids, such as homopolymers of acrylic acid and aspartic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid or Cz-Czz-olefins, e.g. isobutene or long-chain a-olefins, vinyl C1-C8-alkyl ethers, vinyl acetate, vinyl propionate, (meth)acrylic acid esters of C,-Ca-alcohols and styrene. Preference is given to the homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid. The oligomeric and polymeric carboxylic acids are used in acid form or as sodium salt;
- phosphonic acids, such as, for example, 1-hydroxyethylene(1,1-diphosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylene-phosphonic acid) and diethylenetriaminepenta(methylenephosphonic acid) and alkali metal salts thereof.
Suitable graying inhibitors are, for example, carboxymethylcellulose and graft polymers of vinyl acetate onto polyethylene glycol.
= 0000058734 Suitable bleaches are, for example, adducts of hydrogen peroxide onto inorganic salts, such as sodium perboratemonohydrate, sodium perboratetetrahydrate and sodium carbonate perhydrate, and percarboxylic acids, such as phthalimidopercaproic acid.
Suitable bleach activators are, for example, N,N,N',N'-tetraacetylethylenediamine (TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile methyl sulfate.
Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases and peroxidases.
Suitable further dye transfer inhibitors are, for example, homopolymers, copolymers and graft polymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine N-oxide.
Homopolymers and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as dye transfer inhibitors.
Detergent ingredients are otherwise generally known. Detailed descriptions can be found, for example, in WO-A-99/06524 and 99/04313; in Liquid Detergents, Editor:
Kuo-Yann Lai, Surfactant Sci. Ser., Vol. 67, Marcel Decker, New York, 1997, p. 272-304.
Application of hydrophobically modified poly-C2-C4-alkylenimines according to the invention.
Selected coiored fabric (EMPA 130, EMPA 132, EMPA 133 or EMPA 134) was washed in the presence of white test fabric made of cotton and ballast fabric made of cotton/polyester and also of polyester using a detergent at 60 C with the addition of the LCST polymers. After the washing cycle, the fabrics were rinsed, spun and dried. In order to determine the dye transfer-inhibiting effect, the coloration of the white test fabric was determined photometrically (Photometer: Elrepho 2000 from Datacolor).
The reflectance values measured at the test fabric were used to determine the color intensity of the coloration in accordance with the method described in A. Kud, Seifen, Ole, Fette, Wachse, volume 119, pages 590-594 (1993). The color intensity for the experiment with the respective test substance, the color intensity for the experiment without test substance and the color intensity of the test fabric before washing were used to ascertain the dye transfer-inhibiting effect of the test substance according to the following formula in ~o.
DTI effect [%] = color intensity (without polymer) - color intensity (with polymer) x 100 color intensity (without polymer) - color intensity (before washing) The washing conditions are given in Table 1. The composition of detergent A
used is given in Table 2. The test results. for the dye transfer inhibition are listed in Table 3.
Table 1 Washing conditions Washing conditions main wash cycle Machine Launder-o-meter from Atlas, Chicago, USA
Detergent dosing 5.0 g/l of liquor detergent A
Water hardness 3 mmol/i Ca : Mg 4: 1 Liquor ratio 1 :16 Wash temperature 60 C
Wash time 30 min Polymer dosing 0.05 g/l liquor Colored fabric 1 g EMPA 130 (C.I. Direct Red 83:1) 1 g EMPA 132 (C.I. Direct Black 22) 1 g EMPA 133 (C.I. Direct Blue 71) 0.5 g EMPA 134 (C.I. Direct Orange 39) (all Swiss Federal Laboratories for Materials Testing, St. Gallen, SwÃtzeriand) Test fabric 5 g cotton fabric 221 (bleached) Ballast fabric 5 g blended fabric 768 (65 : 35 polyester : cotton) +
g polyester fabric 854 Table 2 Composition of detergent A (liquid detergent) Ingredients [% by wt.]
C13C15-oXo alcohol x 7 EO 12 C -afcohoi x 5 EO 5 Citric acid 3 Propylene glycol 10 Ethanol 2 Diethylenetriaminepenta(methylenephosphonic acid) 1.0 Water ad 100 Adjust to pFf 9 with sodium hydroxide solution.
Preparation of hydrophobically modified polyethylenimine derivatives:
Starting materials:
Polyethylenimine A: Mw 25 000 g/mol; amine number: 20.14 mmol/g ratio of primary:secondary:tertiary nitrogen atoms: 1.0:1.1:0.7, determined by means of 13C-NMR.
Polyethylenimine B: Mw 5000 g/mol; amine number: 9.22 mmol/g ratio of primary:secondary:tertiary nitrogen atoms: 1.0:1.0:0.7, determined by means of 13C-NMR.
Polymer 1 350 g of polyethylenimine A were initially introduced into toluene (300 mi).
Heating to 100 C was then carried out. After adding palmitic acid (179 g), the reaction mixture was brought to 120 C and, while stirring, the water which formed was distilled off via a 10 water separator (7h). Toiuene was then removed under reduced pressure. The product was obtained as an orange, very viscous oil (503 g).
Polymer 2 210 g of polyethylenimine A were initially introduced into toluene (300 mi).
Heating to 15 100 C was then carried out. After adding palmitic acid (322 g), the reaction mixture was brought to 120 C and, while stirring, the water which formed was distilled off via a water separator (50h). Toluene was then removed under reduced pressure. The product was obtained as an orange wax (501 g).
Polymer 3 200 g of polyethylenimine A were initially introduced into toluene (700 ml).
Heating to 100 C was then carried out. After adding palmitic acid (502 g), the reaction mixture was brought to 120 C and, while stirring, the water which formed was distilled off via a water separator (30h). 400 mi of toluene were removed from the reaction mixture and then water was distilled off for a further 12 h. The toluene was then removed under reduced pressure. The product was obtained as a brown wax (670 g).
Polymer 4 231 g of polyethylenimine A were initially introduced and heated to 100 C. The epoxide (Vikolox 12; 425 g) was added dropwise. The mixture was then stirred at 100 C for 9 h. The yellow, highly viscous oil was obtained (656 g).
Polymer 5 199 g of polyethylenimine A were initially introduced into toluene (400 ml).
Heating to 100 C was then carried out. After adding dodecylic acid (396 g), the reaction mixture was brought to 120 C and, while stirring, the water which formed was distilled off via a water separator (30h). The toluene was then removed under reduced pressure. A
viscous reddish-brown product was obtained (558 g).
Polymer 6 149 g of polyethylenimine A were initially introduced into toluene (400 mi) and heated to 100 C. After adding stearic acid (424 g), the reaction mixture was brought to 120 C
and, while stirring, the water which formed was distilled off via a water separator (30h).
The toluene was then removed under reduced pressure. The product was obtained as a yellow-pale brown wax (451 g).
Polymer 7 550 g of polyethylenimine B were initially introduced into toluene (500 mi).
Heating to 100 C was then carried out. After adding palmitic acid (258 g), the reaction mixture was brought to 120 C and, while stirring; the water which formed was distilled off via a water separator (3d). The toluene was then removed under reduced pressure. The product was obtained as an orange wax (510 g).
Polymer 8 434 g of polyethylenimine B were initially introduced into toluene (400 ml).
Heating to 100 C was carried out. After adding paimitic acid (497 g), the reaction mixture was brought to 120 C and, while stirring, the water which formed was distilled off via a water separator (3d). The toluene was then removed under reduced pressure. The product was obtained as an orange wax (680 g).
Polymer 9 Polymer 8 (666 g) was heated to 75 C. Dimethyl suifate was then metered in (71.8 g;
Dosimat 2.5 milmin). The excess dimethyl sulfate was then removed under reduced pressure. The product was obtained as a brown amorphous substance (407.5 g).
Table 3: Application liquid detergent A
DTI effect [%]
Polymer 1 53.6 45.6 70.5 67.1 Polymer 2 84.3 64.7 89.1 83.1 Polymer 3 87.9 68.3 91.4 78.7 Polymer 4 66.1 30.8 80.3 68.0 Polymer 5 86.2 62.7 91.1 84.7 Polymer 6 86.9 72.9 90.9 84.7 Polymer 7 51.8 37.4 72.7 62.5 Polymer 8 85.3 63.5 90.1 75.0 Polymer 9 84.1 67.1 91.4 80.3 PEI 25 000 neg. effect 46.1 40.2 41.7 PE1 5000 neg. effect 54.3 25.8 53.2 PVP* 22.9 33.7 94.0 35.8 PVP = polyvinylpyrrolidone with K value 30 PEI 25 000 = polyethylenimine A
PEI 5000 = polyethylenimine B
Negative effect: polymer does not exhibit inhibition of the dye transfer, but favors it.
*Polyvinylpyrrolidone: reference substance
Whereas linear poly-C2-C4-alkylenimines are composed exclusively of repeat units of formula A, in which Q is C2-C4-alkylene, branched poly-Cz-C4-alkylenimines have, besides the linear repeat units, tertiary nitrogen atoms according to the structural unit B:
*+H~---Q~-H-* N-Q~'N-*
* Q
A B
Preference is given to those branched, hydrophobically modified poly-C2-C4 alkylenimines, in particular branched, hydrophobically modified polyethylenimines, which, based on the poly-C2-C4-alkylenimine on which they are based, have, on average, per polyalkylenimine molecule at least one, preferably at least 5 or at least 10, branching points according to formula B. In particular, at least 5%, in particular at least 10% and particularly preferably at least 15%, e.g.
5 to 40%
and specifically 15 to 35%, of the nitrogen atoms of the parent poly-C2-C4-alkylenimine are tertiary nitrogen atoms.
Particularly in the case of relatively high degrees of branching, i.e. if at least 10%, in particular at least 15%, e.g. 10 to 40%, in particular 15 to 35% of the nitrogen atoms of the parent poly-C2-C4-alkylenimine are tertiary nitrogen atoms, the hydrophobically modified poly-C2-C4-alkylenimines have a structure similar to a core-shell structure, where the poly-C2-C4-alkylenimine moieties form the core and the hydrophobic radicals form the shell.
The hydrophobically modified poly-CrCa-alkylenimines can be present in uncrosslinked or crosslinked form, and, besides the hydrophobic modification, may be quaternized and/or modified through reaction with alkylene oxides, di-Ci-C4-alkyl carbonates, C2-C4-alkylene carbonates or C,-C4-carboxyfic acids.
Preferably, the hydrophobically modified poly-C2-C4-alkylenimines are uncrosslinked.
According to a first preferred embodiment of the invention, the hydrophobically modified poly-C2-C4-alkylenimines have no further modification besides the hydrophobic modification.
According to a second preferred embodiment of the invention, the hydrophobically modified poly-C2-C4-alkylenimines are quaternized in addition to the hydrophobic modification. Such quaternized hydrophobically modified poly-C2-C4-alkylenimines preferably have no further modffication. The degree of quaternization, i.e.
the number 5 of quaternized nitrogen atoms, based on the total amount of the nitrogen atoms of the hydrophobically modified poly-C2-C4-alkylenimine, is preferably not more than 80 mol%, in particular not more than 50 mol%, e.g. 1 to 80 mol%, in particular 5 to 50 mol%, based on the nitrogen atoms of the poly-CrCa-aikylenimine.
The hydrophobically modified poly-C2-C4-alkylenimines which are used according to the invention are in part known from the prior art cifed at the beginning or can be prepared analogously to the methods described there. As a nale, hydrophobically modified poly-Cz-Cd-alkylenimines are prepared by polymer-analogous reaction of unmodified poly-C2-C4-alkylenimines with a hydrophobicizing agent.
Accordingly, one embodiment of the invention relates to the use of a hydrophobically modified poly-C2-C4-alkylenimine obtainable by a process which comprises the reaction of a nonmodified poly-C2-C4-alkylenimine, in particular a nonmodified, branched poly-C2-C4-alkylenimine, and specifically a nonmodified, branched polyethylenimine, with a hydrophobicizing agent.
Examples of suitable hydrophobicizing agents are:
i) long-chain, linear or branched carboxylic acids having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the alkyl or alkenyl radical, such as caprylic acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, paimitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid and mixtures thereof, preferably lauric acid, stearic acid, paimitic acid and oleic acid, or their amide-forming derivatives, such as acid chlorides, esters or anhydrides of the specified carboxylic acids and mixtures thereof, ii) linear or branched alkyl halides having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the linear or branched alkyl radical, such as octyl chloride, nonyl chloride, decyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride, octadecyl chloride and mixtures thereof, iii) alkyl epoxides having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms in the linear or branched alkyl radical, such as hexadecenyl oxide, dodecenyl oxide and octadecenyl oxide and mixtures thereof, iv) alkyl ketene dimers having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms in the linear or branched alkyl radical, such as lauryl ketene, paimityl ketene, stearyl ketene and oleyl ketene dimers and mixtures thereof, v) cyclic dicarboxylic acid anhydrides, in particular alkyl-substituted succinic anhydrides having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the linear or branched alkyl radical, such as dodecenyisuccinic anhydride, tetradecylsuccinic anhydride, hexadecenyisuccinic anhydride and mixtures thereof, vi) alkyl isocyanates having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms in the linear or branched alkyl radical, such as tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate and mixtures thereof, vii) chtoroformic acid esters of linear or branched alkanols or alkenols having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms and mixtures thereof, and viii) linear or branched aliphatic aldehydes having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, and dialkyl ketones having in total 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the two alkyl groups and mixtures thereof.
Preferred hydrophobicizing agents are long-chain, linear or branched carboxylic acids having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the alkyl or alkenyl radical and amide-forming derivatives thereof, in particular linear saturated carboxylic acids having 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms in the alkyl radical.
Preferred hydrophobicizing agents are also alkyl epoxides having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atorns.
The unmodified poly-CrC4-alkylenimines which form the basis of the hydrophobically modified poly-C2-Ca-alkylenimines used according to the invention comprise homopolymers of ethylenimine (aziridine) and higher homologs thereof, propylenimine (methylaziridine) and butylenimines (1,2-dimethylaziridine, 1,1-dimethylaziridine and 1-ethylaziridine), copolymers of ethylenimine with its higher homologs, and the graft polymers of polyamidoamines or polyvinylamines with ethylenimine and/or its higher homologs.
Also suitable are the graft polymers of C2-C4-alkylenimines described in WO 02/095122, such as ethylenimine onto polyamidoamines or onto polyvinylamines.' Such graft polymers generally have a weight fraction of C2-G4-alkylenimines of at least 10% by weight, in particular at least 30% by weight, e.g. 10 to 90% by weight in particular 10 to 85% by weight, based on the total weight of the unmodified poly-C2-C4-alkylenimine.
In particular, the unmodified poly-CrC4-alkylenimines are branched poly-C2-C4-alkylenimines, preferably polyethylenimines, in particular branched polyethylenimines and specifically homopolymers of ethylenimine, which are in particular branched.
Preferably, the unmodified poly-C2-Ca-aikylenimine used for the preparation is branched, where, with regard to the degree of branching, that stated above for hydrophobically modified poly-C2-C4-alkylenimines applies.
Preferably, the unmodified poly-CrCa-alkylenimine used for the preparation has a number-average molecular weight in the range from 1000 to 200 000 Daltons, in particular in the range from 2000 to 100 000 Daltons.
The reaction of the unmodified poly-C2-Ca-alkylenimine with the hydrophobicizing agent can take place analogously to known processes in the prior art. The reaction conditions naturally depend on the type and functionality of the hydrophobicizing agent.
The reaction can take place without a diluent or in solution. The reaction is preferably carried out in a solvent suitable for the reaction. Examples of suitable solvents are hydrocarbons, in particular aromatic hydrocarbons, e.g. alkylbenzenes such as xylenes, toluene, cumene, tert-butylbenzene and the like.
If appropriate, the reaction can be carried out in the presence of catalysts which improve the reactivity of the hydrophobicizing agent toward the poly-C2-C4-alkylenimine. The type of catalyst depends in a manner known per se on the type and reactivity of the hydrophobicizing agent. The catalysts are usually Lewis acids or Bronstedt acids. Often, for example in the case of carboxylic acids, it is possible to dispense with the use of catalysts.
In the case of the carboxylic acids and carboxylic acid derivatives preferred according to the invention, it has proven advantageous to remove the low molecular weight products (water, alcohols or hydrogen chloride) which form during the reaction from the reaction mixture. For example, in the case of the carboxylic acids, the water formed will preferably be removed from the reaction mixture via an entrainer. Typical entrainers are hydrocarbons, in particular alkyl aromatics such as toluene or xylenes.
Preferably, the reaction will then be carried out in an organic solvent suitable as entrainer.
As a rule, the hydrophobicizing agent will be used in an amount which corresponds to the desired functionality, it also being possible to use the hydrophobicizing agent in excess. In this respect, that stated previously for the functionalization of the hydrophobicized polyalkylenimine applies analogously for the molar ratio of hydrophobicizing agent to nitrogen atoms in the unmodified polyalkylenimine.
In particular, the hydrophobicizing agent, calculated as the parts of the hydrophobicizing agent remaining in the product (thus the amount of hydrophobicizing agent minus any low molecular weight products such as water), will be used in an amount of from 0.35 to 20 parts by weight, in particular in an amount of from 0.5 to 10 parts by weight, per part by weight of unmodified poly-C2-C4-alkylenimine.
According to a preferred embodiment of the invention, the hydrophobically modified poly-C2-Ca-alkylenimines are quaternized. Accordingly, the preparation of the hydrophobically modified poly-Cz-C4-alkylenimines additionally comprises a quaternization. The quaternization can take place before or in parl:icular after the hydrophobicization.
For the quatemization, in particular alkylating agents such as alkyl halides which generally have 1 to 10 carbon atoms in the alkyl radical, or dialkyl sulfates, which generally comprise alkyl radicals having 1 to 10 carbon atoms, are used.
Examples of suitable alkylating agents from these groups are methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride, and dimethyl sulfate and diethyl sulfate. Further suitable alkylating agents are, for example, benzyl halides, in particular benzyl chloride and benzyl bromide; chloroacetic acid; fluorosulfuric acid methyl ester;
diazomethane;
oxonium compounds, such as trimethyloxonium tetrafluoroborate; alkylene oxides, such as ethylene oxide, propylene oxide and glycidol, which are used in the presence of acids; cationic epichlorohydrins. Preferred quaternizing agents are methyl chloride, dimethyl suffate and diethyl sulfate. During the quaternization, the secondary or in particular the tertiary nitrogen atoms of the parent poly-CrCa-alkylenimine moiety are converted into quatemary nitrogen atoms, ergo ammonium groups, as a result of which the hydrophobically modified poly-Cz-Ca-alkylenimine is given an overall positive charge.
The hydrophobically modified poly-C2-C4-alkylenimines are generally water-soluble or water-dispersible and can be used in solid and liquid detergents and in laundry aftertreatment compositions. They are characterized in particular by high compatibility with conventional detergent constituents, in particular with the constituents of liquid detergent formulations, specifically those which have a low content of anionic surfactants.
The incorporation into the respective detergent or laundry aftertreatment composition formulation takes place in a manner known per se, the hydrophobically modified polyalkylenimines often being used in liquid form, i.e. dissolved or dispersed form. The hydrophobically modified polyalkylenimines can also be used in powder or granule form.
The dye transfer onto fabric washed at the same time and the associated undesired discoloration of this fabric is effectively inhibited. Even at concentrations of from 10 to 150 ppm of the hydrophobically modified poly-C2-C4-alkylenimine in the wash or rinse liquor, good to very good dye transfer-inhibiting effects are achieved which lie significantly above the reference substances such as polyvinylpyrrolidone.
The solid detergent formulations comprise in particular the following components:
(a) 0.05 to 20% by weight of at least one hydrophobically modified poly-C2-C4-alkylenimine, (b) 0.5 to 40% by weight of at least one nonionic, anionic and/or cationic surfactant, (c) 0.5 to 50% by weight of an inorganic builder, (d) 0 to 10% by weight of an organic cobuilder and (e) 0.1 to 60% by weight of other customary ingredients, such as extenders, enzymes, perfume, complexing agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, further color protection additives and dye transfer inhibitors, graying inhibitors, soil release polyesters, fiber protection additives, silicones, dyes, bactericides and preservatives, dissolution improvers and/or disintegrants, water;
where the sum of components (a) to (e) is 100% by weight.
The solid detergent formulations may be present in powder, granule, extrudate or tablet form.
The liquid detergent formulations preferably have the following composition:
(a) 0.05 to 20% by weight of at least one hydrophobically modified poly-C2-Ca-aikylenimine, (b) 0.5 to 70% by weight of at least one nonionic, anionic and/or cationic surfactant, (c) 0 to 20% by weight of an inorganic builder, (d) 0 to 10% by weight of an organic cobuilder, (e) 0.1 to 60% by weight of other customary ingredients, such as sodium carbonate, enzymes, perfume, complexing agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, further color protection additives and dye transfer inhibitors, graying inhibitors, soil release polyesters, fiber protection additives, silicones, dyes, bactericides and preservatives, organic solvents, solubility promoters, hydrotropes, thickeners and/or alkanolamines and (f) 0 to 99.35% by weight of water, where the sum of the components (a) to (f) is 100% by weight.
The laundry aftertreatment compositions, in particular laundry care rinse compositions, preferably comprise (a) 0.05 to 20% by weight of at least one hydrophobically modified poly-C2-C4-alkylenimine, (b) 0.1 to 40% by weight of at least one cationic surfactant, (c) 0 to 30% by weight of at least one nonionic surfactant, (d) 0.1 to 30% by weight of other customary ingredients, such as silicones, other lubricants, wetting agents, film-forming polymers, fragrances and dyes, stabilizers, fiber protection additives, further color protection additives and dye 5 transfer inhibitors, complexing agents, viscosity modifiers, soil release additives, solubility promoters, hydrotropes, corrosion protection additives, bactericides and preservatives and (e) 0 to 99.75% by weight of water, where the sum of the components (a) to (e) is 100% by weight.
Suitable nonionic surfactants (B) here are primarily: -- alkoxylated Cs-C22-alcohofs, such as fatty alcohol alkoxylates, oxo alcohol =
alkoxylates and Guerbet alcohol ethoxylates: the alkoxylation can take place with ethylene oxide, propylene oxide and/or butylene oxide. Block copolymers or random copolymers may be present. Per mole of alcohol, they usually comprise 2 to 50 mol, preferably 3 to 20 mol, of at least one alkylene oxide. A preferred alkylene oxide is ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms;
- alkylphenol alkoxylates, in particular alkylphenol ethoxylates, which comprise C6-C14-alkyl chains and 5 to 30 mol of alkylene oxide/mol;
- alkyl polyglucosides which comprise Ca-C=-, preferably C,o-Cia-alkyl chains and as a rule 1 to 20, preferably 1.1 to 5, glucoside units;
- N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, long-chain amine oxides, polyhydroxy(alkoxy) fatty acid 'derivatives, such as, for example, polyhydroxy fafty acid amides, gemini surfactants, and block copolymers of ethylene oxide, propylene oxide and/or butylene oxide;
and their mixtures.
Suitable anionic surfactants are, for example:
- sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18, carbon atoms, in particular CsCõ-alcohol sulfates, C12C,4-alcohol sulfates, CV-C18-alcohot sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate;
- sulfated alkoxylated Ca-C22-alcohols (alkyl ether sulfates): compounds of this type are prepared, for example, by firstly alkoxylating a Ca-Cz2-, preferably a C,o-C,s-alcohol, e.g. a fatty alcohol, and then sulfating the alkoxylation product.
For the alkoxylation, ethylene oxide is preferably used;
- linear Ca-C2o-alkylbenzenesulfonates (LAS), preferably linear Cs-C,3-alkylbenzenesulfonates and alkyftoluenesulfonates;
- alkanesulfonates, in particular Ca-C24-, preferably C,o-C,a-afkanesulfonates;
- olefinsulfonates;
- faity acid and fatty acid ester sulfonates;
- soaps, such as the Na and K safts of C8-C24-carboxylic acids, and mixtures thereof.
The anionic surfactants are preferably added to the detergent in the form of salts.
Suitable salts here are, for example, alkali metal salts, such as sodium, potassium and lithium salts, and ammonium salts, such as hydroxyethylammonium, di(hydroxyethy!)ammonium and tri(hydroxyethyi)ammonium salts.
Particularly suitable cationic surFactants which may be mentioned are:
- C7-C25-alkylamines;
- N,N-dimethyi-N-(hydroxy-C7-C25-alkyl)ammonium salts;
- mono- and di(C7-C25-alkyl)dimethylammonium compounds quaternized with alkylating agents;
- ester quats, in particular quatemary esterified mono-, di- and trialkanolamines which have been esterified with Ca-Crrcarboxylic acids;
- imidazoline quats, in particular 1-alkylimidazolinium salts of the formulae II or III
R
R9 N Rs N+
N~
Rao/ Rt1 Rio/
II III
in which the variables have the following meaning:
R9 is C,-C2s-alkyl or C2-C25-alkenyl;
R'O is CI-Ca-alkyl or hydroxy-C1-C4-alkyl;
R" is CrCa-alkyl, hydroxy-CrCa-alkyl or a radical Rl-(CO)-X-(CH2)rn- (X: -0-or -NH-; m: 2 or 3), where at least one radical R9 is C7-C22-alkyl.
Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates and amphoteric imidazolium compounds.
The advantages according to the invention of the hydrophobically modified polyalkylenimines come in useful especially in those detergent formulations which comprise only a small fraction of anionic surfactants. Preferably, the fraction of anionic surfactants, based on the total amount of surfactant in the detergent or laundry aftertreatment composition formulation, is not more than 50% by weight, in particular not more than 30% by weight and specifically not more than 10% by weight.
Preferably, the anionic surfactant constitutes not more than 8% by weight, in particular not more than 5% by weight, based on the total weight of the formulation.
Suitable inorganic builders are, in particular:
- crystalline and amorphous alumosilicates with ion-exchanging properties, such as in particular zeolites: various types of zeolites are suitable, in particular the zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially replaced by other cations such as Li, K, Ca, Mg or ammonium;
- crystalline silicates, such as in particular disilicates and sheet silicates, e.g. S-and (3-Na2Si2O5. The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preference being given to the Na, Li and Mg silicates;
- amorphous silicates, such as sodium metasilicate and amorphous disilicate;
- carbonates and hydrogencarbonates: these can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to Na, Li and Mg carbonates and hydrogencarbonates, in particular sodium carbonate and/or sodium hydrogencarbonate; and - polyphosphates, such as pentasodium triphosphate.
Suitable organic cobuilders are in particular:
- low molecular weight carboxylic acids, such as citric acid, hydrophobically modified citric acid, e.g. agaricic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, oxydisuccinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl- and alkenylsuccinic acids and aminopolycarboxylic acids, e.g. nitrilotriacetic acid, 0-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, N-(2-hydroxyethyl)iminoacetic acid, ethylenediaminedisuccinic acid and methyl-and ethylglycinediacetic acid or alkali metal salts thereof;
- oligomeric and polymeric carboxylic acids, such as homopolymers of acrylic acid and aspartic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid or Cz-Czz-olefins, e.g. isobutene or long-chain a-olefins, vinyl C1-C8-alkyl ethers, vinyl acetate, vinyl propionate, (meth)acrylic acid esters of C,-Ca-alcohols and styrene. Preference is given to the homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid. The oligomeric and polymeric carboxylic acids are used in acid form or as sodium salt;
- phosphonic acids, such as, for example, 1-hydroxyethylene(1,1-diphosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylene-phosphonic acid) and diethylenetriaminepenta(methylenephosphonic acid) and alkali metal salts thereof.
Suitable graying inhibitors are, for example, carboxymethylcellulose and graft polymers of vinyl acetate onto polyethylene glycol.
= 0000058734 Suitable bleaches are, for example, adducts of hydrogen peroxide onto inorganic salts, such as sodium perboratemonohydrate, sodium perboratetetrahydrate and sodium carbonate perhydrate, and percarboxylic acids, such as phthalimidopercaproic acid.
Suitable bleach activators are, for example, N,N,N',N'-tetraacetylethylenediamine (TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile methyl sulfate.
Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases and peroxidases.
Suitable further dye transfer inhibitors are, for example, homopolymers, copolymers and graft polymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine N-oxide.
Homopolymers and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as dye transfer inhibitors.
Detergent ingredients are otherwise generally known. Detailed descriptions can be found, for example, in WO-A-99/06524 and 99/04313; in Liquid Detergents, Editor:
Kuo-Yann Lai, Surfactant Sci. Ser., Vol. 67, Marcel Decker, New York, 1997, p. 272-304.
Application of hydrophobically modified poly-C2-C4-alkylenimines according to the invention.
Selected coiored fabric (EMPA 130, EMPA 132, EMPA 133 or EMPA 134) was washed in the presence of white test fabric made of cotton and ballast fabric made of cotton/polyester and also of polyester using a detergent at 60 C with the addition of the LCST polymers. After the washing cycle, the fabrics were rinsed, spun and dried. In order to determine the dye transfer-inhibiting effect, the coloration of the white test fabric was determined photometrically (Photometer: Elrepho 2000 from Datacolor).
The reflectance values measured at the test fabric were used to determine the color intensity of the coloration in accordance with the method described in A. Kud, Seifen, Ole, Fette, Wachse, volume 119, pages 590-594 (1993). The color intensity for the experiment with the respective test substance, the color intensity for the experiment without test substance and the color intensity of the test fabric before washing were used to ascertain the dye transfer-inhibiting effect of the test substance according to the following formula in ~o.
DTI effect [%] = color intensity (without polymer) - color intensity (with polymer) x 100 color intensity (without polymer) - color intensity (before washing) The washing conditions are given in Table 1. The composition of detergent A
used is given in Table 2. The test results. for the dye transfer inhibition are listed in Table 3.
Table 1 Washing conditions Washing conditions main wash cycle Machine Launder-o-meter from Atlas, Chicago, USA
Detergent dosing 5.0 g/l of liquor detergent A
Water hardness 3 mmol/i Ca : Mg 4: 1 Liquor ratio 1 :16 Wash temperature 60 C
Wash time 30 min Polymer dosing 0.05 g/l liquor Colored fabric 1 g EMPA 130 (C.I. Direct Red 83:1) 1 g EMPA 132 (C.I. Direct Black 22) 1 g EMPA 133 (C.I. Direct Blue 71) 0.5 g EMPA 134 (C.I. Direct Orange 39) (all Swiss Federal Laboratories for Materials Testing, St. Gallen, SwÃtzeriand) Test fabric 5 g cotton fabric 221 (bleached) Ballast fabric 5 g blended fabric 768 (65 : 35 polyester : cotton) +
g polyester fabric 854 Table 2 Composition of detergent A (liquid detergent) Ingredients [% by wt.]
C13C15-oXo alcohol x 7 EO 12 C -afcohoi x 5 EO 5 Citric acid 3 Propylene glycol 10 Ethanol 2 Diethylenetriaminepenta(methylenephosphonic acid) 1.0 Water ad 100 Adjust to pFf 9 with sodium hydroxide solution.
Preparation of hydrophobically modified polyethylenimine derivatives:
Starting materials:
Polyethylenimine A: Mw 25 000 g/mol; amine number: 20.14 mmol/g ratio of primary:secondary:tertiary nitrogen atoms: 1.0:1.1:0.7, determined by means of 13C-NMR.
Polyethylenimine B: Mw 5000 g/mol; amine number: 9.22 mmol/g ratio of primary:secondary:tertiary nitrogen atoms: 1.0:1.0:0.7, determined by means of 13C-NMR.
Polymer 1 350 g of polyethylenimine A were initially introduced into toluene (300 mi).
Heating to 100 C was then carried out. After adding palmitic acid (179 g), the reaction mixture was brought to 120 C and, while stirring, the water which formed was distilled off via a 10 water separator (7h). Toiuene was then removed under reduced pressure. The product was obtained as an orange, very viscous oil (503 g).
Polymer 2 210 g of polyethylenimine A were initially introduced into toluene (300 mi).
Heating to 15 100 C was then carried out. After adding palmitic acid (322 g), the reaction mixture was brought to 120 C and, while stirring, the water which formed was distilled off via a water separator (50h). Toluene was then removed under reduced pressure. The product was obtained as an orange wax (501 g).
Polymer 3 200 g of polyethylenimine A were initially introduced into toluene (700 ml).
Heating to 100 C was then carried out. After adding palmitic acid (502 g), the reaction mixture was brought to 120 C and, while stirring, the water which formed was distilled off via a water separator (30h). 400 mi of toluene were removed from the reaction mixture and then water was distilled off for a further 12 h. The toluene was then removed under reduced pressure. The product was obtained as a brown wax (670 g).
Polymer 4 231 g of polyethylenimine A were initially introduced and heated to 100 C. The epoxide (Vikolox 12; 425 g) was added dropwise. The mixture was then stirred at 100 C for 9 h. The yellow, highly viscous oil was obtained (656 g).
Polymer 5 199 g of polyethylenimine A were initially introduced into toluene (400 ml).
Heating to 100 C was then carried out. After adding dodecylic acid (396 g), the reaction mixture was brought to 120 C and, while stirring, the water which formed was distilled off via a water separator (30h). The toluene was then removed under reduced pressure. A
viscous reddish-brown product was obtained (558 g).
Polymer 6 149 g of polyethylenimine A were initially introduced into toluene (400 mi) and heated to 100 C. After adding stearic acid (424 g), the reaction mixture was brought to 120 C
and, while stirring, the water which formed was distilled off via a water separator (30h).
The toluene was then removed under reduced pressure. The product was obtained as a yellow-pale brown wax (451 g).
Polymer 7 550 g of polyethylenimine B were initially introduced into toluene (500 mi).
Heating to 100 C was then carried out. After adding palmitic acid (258 g), the reaction mixture was brought to 120 C and, while stirring; the water which formed was distilled off via a water separator (3d). The toluene was then removed under reduced pressure. The product was obtained as an orange wax (510 g).
Polymer 8 434 g of polyethylenimine B were initially introduced into toluene (400 ml).
Heating to 100 C was carried out. After adding paimitic acid (497 g), the reaction mixture was brought to 120 C and, while stirring, the water which formed was distilled off via a water separator (3d). The toluene was then removed under reduced pressure. The product was obtained as an orange wax (680 g).
Polymer 9 Polymer 8 (666 g) was heated to 75 C. Dimethyl suifate was then metered in (71.8 g;
Dosimat 2.5 milmin). The excess dimethyl sulfate was then removed under reduced pressure. The product was obtained as a brown amorphous substance (407.5 g).
Table 3: Application liquid detergent A
DTI effect [%]
Polymer 1 53.6 45.6 70.5 67.1 Polymer 2 84.3 64.7 89.1 83.1 Polymer 3 87.9 68.3 91.4 78.7 Polymer 4 66.1 30.8 80.3 68.0 Polymer 5 86.2 62.7 91.1 84.7 Polymer 6 86.9 72.9 90.9 84.7 Polymer 7 51.8 37.4 72.7 62.5 Polymer 8 85.3 63.5 90.1 75.0 Polymer 9 84.1 67.1 91.4 80.3 PEI 25 000 neg. effect 46.1 40.2 41.7 PE1 5000 neg. effect 54.3 25.8 53.2 PVP* 22.9 33.7 94.0 35.8 PVP = polyvinylpyrrolidone with K value 30 PEI 25 000 = polyethylenimine A
PEI 5000 = polyethylenimine B
Negative effect: polymer does not exhibit inhibition of the dye transfer, but favors it.
*Polyvinylpyrrolidone: reference substance
Claims (15)
1. The use of hydrophobically modified poly-C2-C4-alkylenimines as dye transfer inhibitors in detergent compositions for textiles.
2. The use according to claim 1, where, on average, at least 10 mol% of the nitrogen atoms of the poly-C2-C4-alkylenimine carry an aliphatic, saturated or unsaturated hydrocarbon radical which has at least 8 carbon atoms.
3. The use according to claim 2, where the fraction of the hydrocarbon radicals, based on the total weight of the poly-C2-C4-alkylenimine, constitutes 25 to 95%
by weight.
by weight.
4. The use according to claim 2 or 3, where the hydrocarbon radicals are present in the form of C8-C30-alkyl-, C8-C30-alkylcarbonyl, C8-C30-alkenyl-, C8-C30-alkenylcarbonyl-, C8-C30-alkadienyl-, C8-C30-alkadienylcarbonyl- and/or hydroxy-C8-C30-alkyl groups.
5. The use according to any one of the preceding claims, where the hydrophobically modified poly-C2-C4-alkylenimine has a number-average molecular weight in the range from 3000 to 300 000 Daltons.
6. The use according to any one of the preceding claims, where the hydrophobically modified poly-C2-C4-alkylenimine in the poly-C2-C4-alkylenimine moiety is branched.
7. The use according to any one of the preceding claims, where the hydrophobically modified poly-C2-C4-alkylenimine has quaternized nitrogen atoms.
8. The use according to any one of the preceding claims, where the hydrophobically modified poly-C2-C4-alkylenimine is obtainable by a process which comprises the reaction of a nonmodified poly-C2-C4-alkylenimine with a hydrophobicizing agent.
9. The use according to claim 8, where the hydrophobicizing agent is selected from saturated, mono- or polyunsaturated aliphatic C9-C31-carboxylic acids, their amide-forming derivatives and C8-C30-alkylene oxides.
10. The use according to claim 8 or 9, where the hydrophobicizing agent, calculated as the parts of the hydrophobicizing agent remaining in the product, is used in an amount of from 0.35 to 20 parts by weight per part by weight of unmodified poly-C2-C4-alkylenimine.
11. The use according to any one of claims 8 to 10, where the preparation of the hydrophobically modified poly-C2-C4-alkylenimine additionally comprises a quaternization.
12. The use according to any one of claims 8 to 11, where the unmodified poly-C2-C4-alkylenimine used for the preparation is branched.
13. The use according to any one of claims 8 to 12, where the unmodified poly-C2-C4-alkylenimine used for the preparation has a number-average molecular weight in the range from 1000 to 200 000 Daltons.
14. The use according to any one of the preceding claims, where the fraction of nonionic surfactants in the detergent composition, based on the total amount of surfactant in the detergent composition, is at least 50% by weight.
15. The use according to any one of the preceding claims, where the hydrophobically modified poly-C2-C4-alkylenimine is used in a concentration of from 5 to 150 ppm in the wash liquor.
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EP06127179 | 2006-12-22 | ||
PCT/EP2007/064486 WO2008077952A1 (en) | 2006-12-22 | 2007-12-21 | Hydrophobically modified polyalkylenimines for use as dye transfer inhibitors |
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US (1) | US20100017973A1 (en) |
EP (1) | EP2126020B1 (en) |
JP (1) | JP2010513644A (en) |
KR (1) | KR20090096723A (en) |
CN (1) | CN101568630B (en) |
AT (1) | ATE534722T1 (en) |
BR (1) | BRPI0720573A2 (en) |
CA (1) | CA2671878A1 (en) |
ES (1) | ES2376369T3 (en) |
MX (1) | MX2009005829A (en) |
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WO (1) | WO2008077952A1 (en) |
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DE102005049015A1 (en) * | 2005-10-11 | 2006-03-30 | Gebr. Becker Gmbh | Cationically equipped partially knitted textile material, useful for preventing discoloration and/or repulsion of textiles during washing and/or for inhibiting deposition of color on textile, comprises textile fabric from textile fiber |
RU2564036C2 (en) * | 2009-12-16 | 2015-09-27 | Басф Се | Functionalised highly branched melamine- and polyamine-based polymers |
CN102666657B (en) * | 2009-12-17 | 2014-09-03 | 巴斯夫欧洲公司 | Aqueous coating formulation |
CN103199865B (en) * | 2012-01-10 | 2016-06-15 | 武汉凯默电气有限公司 | A kind of light adaptive serial port decoding circuit |
TWI643884B (en) | 2013-09-06 | 2018-12-11 | 盧伯利索先進材料有限公司 | Multi-acid multi-base graft copolymer dispersants |
WO2015127326A1 (en) * | 2014-02-21 | 2015-08-27 | Cocona, Inc. | Incorporation of active particles into substrates |
WO2016094026A1 (en) | 2014-12-09 | 2016-06-16 | Lubrizol Advanced Materials, Inc. | Additive to prevent phase separation of low profile additive in unsaturated thermoset polyester compositions |
US10537187B2 (en) * | 2015-10-02 | 2020-01-21 | Walmart Apollo, Llc | Augmented refrigerated display unit |
MX2019006772A (en) | 2016-12-15 | 2019-08-22 | Colgate Palmolive Co | Color protection in fabrics using citric acid and iminodisuccinate in fine fabric liquid detergent. |
EP3421583A1 (en) | 2017-06-26 | 2019-01-02 | Basf Se | Use of cationic vinylcarboxamide/vinylamine copolymers as a color care agent for laundering formulations |
WO2019060278A1 (en) | 2017-09-19 | 2019-03-28 | Lubrizol Advanced Materials, Inc. | Multi-amine polyester dispersant made via an anhydride intermediate |
US20210331130A1 (en) | 2018-09-10 | 2021-10-28 | Lubrizol Advanced Materials, Inc. | Multi-amine polyester dispersant and method of making |
WO2020053001A1 (en) | 2018-09-11 | 2020-03-19 | Basf Se | A fabric care composition comprising hydrophobically modified polyalkyleneimine as dye fixative polymer |
CN113795534B (en) | 2019-03-14 | 2024-01-05 | 路博润先进材料公司 | Polyamine dispersants prepared via anhydride intermediates |
JP2022526249A (en) | 2019-03-14 | 2022-05-24 | ルブリゾル アドバンスド マテリアルズ, インコーポレイテッド | Multiamine polyester dispersant made via an anhydride intermediate |
WO2021094127A1 (en) | 2019-11-14 | 2021-05-20 | Basf Se | A fabric care composition comprising hydrophobically modified polyalkyleneimine and a biocide |
WO2021115912A1 (en) | 2019-12-09 | 2021-06-17 | Basf Se | Formulations comprising a hydrophobically modified polyethyleneimine and one or more enzymes |
CN116568724A (en) | 2020-12-18 | 2023-08-08 | 路博润先进材料公司 | Method for producing polymers using pigment dispersions |
CN116745386A (en) | 2020-12-18 | 2023-09-12 | 路博润先进材料公司 | Stable pigment dispersion composition |
KR20240034749A (en) * | 2021-07-09 | 2024-03-14 | 바스프 에스이 | Novel modified polyalkyleneimine as dyeing aid |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3676341A (en) * | 1971-03-15 | 1972-07-11 | Colgate Palmolive Co | Textile softening compositions |
US3844952A (en) * | 1972-05-03 | 1974-10-29 | Procter & Gamble | Detergent compositions |
DE3124210A1 (en) * | 1981-06-19 | 1982-12-30 | Henkel KGaA, 4000 Düsseldorf | "LIQUID DETERGENT WITH ADDITIVES TO PREVENT THE TRANSFER OF DYE" |
DE3413292A1 (en) * | 1984-04-09 | 1985-10-17 | Henkel KGaA, 4000 Düsseldorf | TEXTILE DETERGENT FOR COLORED TEXTILES |
JPH057106A (en) * | 1991-06-27 | 1993-01-14 | Harada Ind Co Ltd | Broad band ungrounded microwave antenna |
DE4136661A1 (en) * | 1991-11-07 | 1993-05-13 | Basf Ag | PETROLEUM EMULSION SPLITTER |
JPH08511811A (en) * | 1992-07-15 | 1996-12-10 | ザ、プロクター、エンド、ギャンブル、カンパニー | Dye transfer inhibiting composition comprising a polymeric dispersion aid |
JP3406970B2 (en) * | 1993-12-27 | 2003-05-19 | ミヨシ油脂株式会社 | Amphoteric surfactant |
JP3526661B2 (en) * | 1995-06-23 | 2004-05-17 | ミヨシ油脂株式会社 | Antibacterial agent, antibacterial resin and antibacterial paint |
JP3688040B2 (en) * | 1995-12-14 | 2005-08-24 | ミヨシ油脂株式会社 | Antibacterial agent |
EP0907703B1 (en) * | 1996-05-03 | 2002-06-26 | The Procter & Gamble Company | Detergent compositions comprising modified polyamines as dye transfer inhibitors |
DE19621509A1 (en) * | 1996-05-29 | 1997-12-04 | Basf Ag | Use of water-soluble copolymers containing N-vinylimidazole units as color transfer inhibitors in detergents |
US6127331A (en) * | 1998-06-23 | 2000-10-03 | The Procter & Gamble Company | Laundry compositions comprising alkoxylated polyalkyleneimine dispersants |
US6020302A (en) * | 1997-09-18 | 2000-02-01 | The Procter & Gamble Company | Color care compositions |
JP4032465B2 (en) * | 1997-10-22 | 2008-01-16 | 東レ株式会社 | Thrombogenic substance adsorbent and extracorporeal circulation column |
US6228783B1 (en) * | 1998-12-31 | 2001-05-08 | National Starch And Chemical Investment Holding Corporation | Laundry article which attracts soil and dyes |
US6833336B2 (en) * | 2000-10-13 | 2004-12-21 | The Procter & Gamble Company | Laundering aid for preventing dye transfer |
EP1239025A3 (en) * | 2001-03-03 | 2003-09-03 | Clariant GmbH | Detergent composition and laundry treatment compositon comprising dye transfer inhibiting and dye fixing agent |
DE10124387A1 (en) * | 2001-05-18 | 2002-11-28 | Basf Ag | Hydrophobically modified polyethyleneimine and polyvinylamine as anticrease agents for treatment of cellulose containing textiles, useful as textile finishing agents in both solid and liquid formulations |
GB0221942D0 (en) * | 2002-09-20 | 2002-10-30 | Univ Strathclyde | Drug delivery |
JP2005248144A (en) * | 2004-02-05 | 2005-09-15 | Nippon Shokubai Co Ltd | Polyalkyleneimine-based polymer, producing method therefor, and its application |
EP1621604B1 (en) * | 2004-07-29 | 2008-10-01 | Orlandi S.p.A. | Colour scavenger material |
GB0419266D0 (en) * | 2004-08-31 | 2004-09-29 | Givaudan Sa | Compositions |
EP1856184A1 (en) * | 2005-02-08 | 2007-11-21 | Basf Aktiengesellschaft | Method of making an alkoxylated polyethylenimine product |
ITMI20060096A1 (en) * | 2006-01-20 | 2007-07-21 | Bolton Manitoba S P A | TEXTILE PRODUCT |
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- 2007-12-21 BR BRPI0720573-2A patent/BRPI0720573A2/en not_active IP Right Cessation
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- 2007-12-21 ES ES07858097T patent/ES2376369T3/en active Active
- 2007-12-21 US US12/519,379 patent/US20100017973A1/en not_active Abandoned
- 2007-12-21 EP EP07858097A patent/EP2126020B1/en not_active Not-in-force
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- 2007-12-21 CN CN2007800475653A patent/CN101568630B/en not_active Expired - Fee Related
- 2007-12-21 KR KR1020097014867A patent/KR20090096723A/en not_active Application Discontinuation
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WO2008077952A1 (en) | 2008-07-03 |
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EP2126020B1 (en) | 2011-11-23 |
CN101568630B (en) | 2012-02-08 |
BRPI0720573A2 (en) | 2014-02-04 |
ATE534722T1 (en) | 2011-12-15 |
ES2376369T3 (en) | 2012-03-13 |
US20100017973A1 (en) | 2010-01-28 |
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