EP3122854B1 - Cleaning compositions containing cationic polymers in an aes-enriched surfactant system - Google Patents
Cleaning compositions containing cationic polymers in an aes-enriched surfactant system Download PDFInfo
- Publication number
- EP3122854B1 EP3122854B1 EP15767696.6A EP15767696A EP3122854B1 EP 3122854 B1 EP3122854 B1 EP 3122854B1 EP 15767696 A EP15767696 A EP 15767696A EP 3122854 B1 EP3122854 B1 EP 3122854B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mol
- structural unit
- laundry detergent
- cationic polymer
- surfactant system
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 229
- 229920006317 cationic polymer Polymers 0.000 title claims description 132
- 239000004094 surface-active agent Substances 0.000 title claims description 70
- 238000004140 cleaning Methods 0.000 title description 31
- 239000003599 detergent Substances 0.000 claims description 117
- -1 alkylalkoxy sulfate Chemical compound 0.000 claims description 40
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 37
- 125000002091 cationic group Chemical group 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 229920001296 polysiloxane Polymers 0.000 claims description 28
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 27
- 239000002518 antifoaming agent Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 11
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical class C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 8
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 7
- PDPMWBPGXYJRSF-UHFFFAOYSA-O trimethyl-[2-(2-methylprop-2-enoylamino)ethyl]azanium Chemical class CC(=C)C(=O)NCC[N+](C)(C)C PDPMWBPGXYJRSF-UHFFFAOYSA-O 0.000 claims description 6
- RUACIFFMSHZUKZ-UHFFFAOYSA-O 3-Acrylamidopropyl trimethylammonium Chemical class C[N+](C)(C)CCCNC(=O)C=C RUACIFFMSHZUKZ-UHFFFAOYSA-O 0.000 claims description 5
- 229920001897 terpolymer Polymers 0.000 claims description 5
- VZTGWJFIMGVKSN-UHFFFAOYSA-O trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium Chemical class CC(=C)C(=O)NCCC[N+](C)(C)C VZTGWJFIMGVKSN-UHFFFAOYSA-O 0.000 claims description 5
- KFYRJJBUHYILSO-YFKPBYRVSA-N (2s)-2-amino-3-dimethylarsanylsulfanyl-3-methylbutanoic acid Chemical compound C[As](C)SC(C)(C)[C@@H](N)C(O)=O KFYRJJBUHYILSO-YFKPBYRVSA-N 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 3
- JNDVNJWCRZQGFQ-UHFFFAOYSA-N 2-methyl-N,N-bis(methylamino)hex-2-enamide Chemical compound CCCC=C(C)C(=O)N(NC)NC JNDVNJWCRZQGFQ-UHFFFAOYSA-N 0.000 claims description 3
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical compound CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- NZQQFMVULBBDSP-FPLPWBNLSA-N bis(4-methylpentan-2-yl) (z)-but-2-enedioate Chemical compound CC(C)CC(C)OC(=O)\C=C/C(=O)OC(C)CC(C)C NZQQFMVULBBDSP-FPLPWBNLSA-N 0.000 claims description 3
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 claims description 3
- 238000007046 ethoxylation reaction Methods 0.000 claims description 2
- 238000005457 optimization Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 94
- 238000012360 testing method Methods 0.000 description 70
- 239000004744 fabric Substances 0.000 description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 52
- 239000000243 solution Substances 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 29
- 239000000523 sample Substances 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 238000005259 measurement Methods 0.000 description 22
- 238000005406 washing Methods 0.000 description 22
- 239000004615 ingredient Substances 0.000 description 20
- 235000014113 dietary fatty acids Nutrition 0.000 description 19
- 239000000194 fatty acid Substances 0.000 description 19
- 229930195729 fatty acid Natural products 0.000 description 19
- 150000004665 fatty acids Chemical class 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 230000008901 benefit Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 13
- 239000002689 soil Substances 0.000 description 13
- 239000006260 foam Substances 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 239000004927 clay Substances 0.000 description 11
- 235000021317 phosphate Nutrition 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 9
- 239000004327 boric acid Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000013068 control sample Substances 0.000 description 9
- 235000013772 propylene glycol Nutrition 0.000 description 9
- 229960004063 propylene glycol Drugs 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 8
- 238000004900 laundering Methods 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000007844 bleaching agent Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002304 perfume Substances 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000001448 refractive index detection Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 235000021314 Palmitic acid Nutrition 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- 239000006081 fluorescent whitening agent Substances 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001542 size-exclusion chromatography Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 241000372033 Andromeda Species 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- 235000019864 coconut oil Nutrition 0.000 description 3
- 238000007405 data analysis Methods 0.000 description 3
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- 238000004090 dissolution Methods 0.000 description 3
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- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000002736 nonionic surfactant 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
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 3
- 229940117958 vinyl acetate Drugs 0.000 description 3
- 210000000707 wrist Anatomy 0.000 description 3
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-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
- 235000021357 Behenic acid Nutrition 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 235000021360 Myristic acid Nutrition 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
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- 206010033296 Overdoses Diseases 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 239000002202 Polyethylene glycol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 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
- 238000003556 assay Methods 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
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- 238000011088 calibration curve Methods 0.000 description 2
- 150000005323 carbonate salts Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
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- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
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- 239000008162 cooking oil Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
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- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 2
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
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- GXJFCAAVAPZBDY-UHFFFAOYSA-N trimethyl-[2-(2-methylprop-2-enoylamino)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCC[N+](C)(C)C GXJFCAAVAPZBDY-UHFFFAOYSA-N 0.000 description 1
- HEQWURSBZKREPY-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;bromide Chemical compound [Br-].CC(=C)C(=O)NCCC[N+](C)(C)C HEQWURSBZKREPY-UHFFFAOYSA-N 0.000 description 1
- LIQTXOAKXLPUMS-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;fluoride Chemical compound [F-].CC(=C)C(=O)NCCC[N+](C)(C)C LIQTXOAKXLPUMS-UHFFFAOYSA-N 0.000 description 1
- XYAHMUGLVOAFIU-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCNC(=O)C=C XYAHMUGLVOAFIU-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0094—High foaming 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
-
- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
Definitions
- the present invention relates to cleaning compositions, and in particular it relates to a liquid laundry detergent composition, that comprising a cationic polymer in a specific surfactant system for optimizing sudsing profile.
- the present invention also relates to methods of making and using such cleaning compositions.
- Sudsing profile is important for a cleaning composition, particularly laundry detergent, where the appropriate volume and speed of suds formation, retention and dissolution in the wash and rinse cycles are considered key benchmarks of performance by consumers.
- laundry detergents While a sudsing profile is important for machine washing process, it is even more important in a typical hand-washing process as the consumer would see changes in the suds level in the wash and rinse cycles.
- consumers particularly hand-washing consumers, desire laundry detergent that dissolves in the wash liquor to give voluminous suds during the wash cycle to signify sufficient performance. The suds are then carried over to the rinse solution and require additional time, water and labor to thoroughly rinse from the laundered fabric.
- a cleaning composition preferably a laundry detergent composition
- a laundry detergent composition which enables strong suds formation (e.g., fast generation of large volume of suds and/or stability or sustainability of the suds already generated over time) during the wash cycle while reducing and eliminating the suds quickly during the rinse cycle(s), preferably across a range of consumer wash habits and fabric/material surfaces being washed. It may be advantageous to have a laundry detergent composition that only requires a single rinse cycle to effectively remove the suds, thereby enabling the "single rinse" concept.
- conventional de-foaming or anti-foaming agents especially the polymeric de-foaming or anti-foaming agents, are known to cause significant whiteness loss in fabrics after repeated wash cycles, i.e., the grey or dull color in fabrics that have been exposed to many wash cycles. Therefore, the usage of such polymeric de-foaming or anti-foaming agents has been limited in laundry detergent compositions.
- the present invention relates to a laundry detergent composition which exhibits significant suds reduction during the rinse cycle while minimizing reduction of suds volume during the wash cycle, and at the same time leading to less fabric whiteness loss after repeated washing. It has now been discovered that the challenges presented hereinabove for conventional laundry detergents can be met by employing a specific cationic polymer in a unique surfactant system.
- the cationic polymer contains a first, nonionic monomeric unit derived from (meth)acrylamide (AAm), a second, cationic monomeric unit, and optionally a third, nonionic monomeric unit (which is not AAm) at a specific monomeric ratio and having a Molecular Weight within a specific range.
- Laundry detergent compositions containing the cationic polymer of the present invention demonstrate outstanding sudsing profile with no or little fabric whiteness loss. Absence of any silicone-derived structural component in such cationic polymer may help to optimize wash suds generation and stability while reducing/minimizing the cost of synthesis. Further, a surfactant system enriched with an alkylalkoxy sulfate (AES) surfactant is employed by the present invention to further improve the sudsing benefit of the cationic polymer.
- AES alkylalkoxy sulfate
- the present invention relates to a liquid laundry detergent composition, containing:
- the cationic polymer may contain one or more additional structural units other than (i), (ii), and (iii).
- the total mol% of all structural units contained by the cationic polymer adds up to be 100%.
- the total mol% of (i), (ii) and (iii) adds up to 100 mol%, i.e., the cationic polymer contains no other structural units than (i), (ii), and (iii).
- the second, cationic structural unit of the cationic polymer is derived or made from DADMAS, and more preferably derived or made from diallyl dimethyl ammonium chloride (DADMAC).
- DADMAS diallyl dimethyl ammonium chloride
- the third, nonionic structural unit may be made from a monomer which is vinylpyrrolidone (VP).
- VP vinylpyrrolidone
- the Molecular Weight of the cationic polymer ranges from 10,000 to 1,000,000 Daltons, more preferably from 15,000 to 700,000 Daltons, and most preferably from 20,000 to 350,000 Daltons.
- the present invention relates to a liquid laundry detergent composition that comprises:
- the present invention relates to a liquid laundry detergent composition, containing:
- sucher indicates a non-equilibrium dispersion of gas bubbles in a relatively smaller volume of a liquid.
- suds indicates a non-equilibrium dispersion of gas bubbles in a relatively smaller volume of a liquid.
- suds can be used interchangeably within the meaning of the present invention.
- sudsing profile refers to the properties of a detergent composition relating to suds character during the wash and rinse cycles.
- the sudsing profile of a detergent composition includes, but is not limited to, the speed of suds generation upon dissolution in the laundering liquor, the volume and retention of suds in the wash cycle, and the volume and disappearance of suds in the rinse cycle.
- the sudsing profile includes the Wash Suds Index and Rinse Suds Index, as specifically defined by the testing methods disclosed hereinafter in the examples. It may further include additional suds-related parameters, such as suds stability measured during the washing cycle and the like.
- the term "cleaning composition” means a liquid or solid composition for treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, and includes hard surface cleaning and/or treatment including floor and bathroom cleaners (e.g., toilet bowl cleaners); hand dishwashing agents or light duty dishwashing agents, especially those of the high-foaming type; machine dishwashing agents; personal care compositions; pet care compositions; automotive care compositions; and household care compositions.
- the cleaning composition of the present invention is a hard surface cleaning composition, preferably wherein the hard surface cleaning composition impregnates a nonwoven substrate.
- laundry detergent composition is a subset of "cleaning composition”, and includes a liquid or solid composition, and includes, unless otherwise indicated, granular or powder-form all-purpose or “heavy-duty” washing agents for fabric, especially cleaning detergents as well as cleaning auxiliaries such as bleach, rinse aids, additives or pre-treat types.
- the laundry detergent composition is a solid laundry detergent composition, and preferably a free-flowing particulate laundry detergent composition (i.e., a granular detergent product).
- charge density refers to the net charge density of the polymer itself and may be different from the monomer feedstock.
- Charge density for a homopolymer may be calculated by dividing the number of net charges per repeating (structural) unit by the molecular weight of the repeating unit.
- the positive charges may be located on the backbone of the polymers and/or the side chains of polymers.
- the charge density depends on the pH of the carrier.
- charge density is calculated based on the charge of the monomer at pH of 7. Typically, the charge is determined with respect to the polymerized structural unit, not necessarily the parent monomer.
- CCD Cationic Charge Density
- E2 is the molar equivalents of charge of the cationic structural unit
- C2 is the molar percentage of the cationic structural unit
- C1 and C3 are the molar percentages of the first and second (if any) nonionic structural units
- W1, W2 and W3 are the molecular weights in g/mol of the first, nonionic structural unit, the cationic structural unit, and the second nonionic structural unit (if any), respectively.
- mol% refers to the relative molar percentage of a particular monomeric structural unit in a polymer. It is understood that within the meaning of the present invention, the relative molar percentages of all monomeric structural units that are present in the cationic polymer shall add up to 100 mol%.
- the term "derived from” refers to monomeric structural unit in a polymer that can be made from a compound, or salts or acids thereof, or any derivative of such compound, i.e., with one or more substituents. Preferably, such structural unit is made directly from the compound in issue.
- structural unit derived from (meth)acrylamide refers to monomeric structural unit in a polymer that can be made from (meth)acrylamide, or salts or acids thereof, or any derivative thereof with one or more substituents.
- such structural unit is made directly from (meth)acrylamide.
- the term "(meth)acrylamide” refers to either methacrylamide or acrylamide, and it is abbreviated herein as "AAm.”
- ammonium salt or “ammonium salts” as used herein refers to various compounds selected from the group consisting of ammonium chloride, ammonium fluoride, ammonium bromide, ammonium iodine, ammonium bisulfate, ammonium alkyl sulfate, ammonium dihydrogen phosphate, ammonium hydrogen alkyl phosphate, ammonium dialkyl phosphate, and the like.
- diallyl dimethyl ammonium salts as described herein include, but are not limited to: diallyl dimethyl ammonium chloride (DADMAC), diallyl dimethyl ammonium fluoride, diallyl dimethyl ammonium bromide, diallyl dimethyl ammonium iodine, diallyl dimethyl ammonium bisulfate, diallyl dimethyl ammonium alkyl sulfate, diallyl dimethyl ammonium dihydrogen phosphate, diallyl dimethyl ammonium hydrogen alkyl phosphate, diallyl dimethyl ammonium dialkyl phosphate, and combinations thereof.
- the ammonium salt is ammonium chloride.
- the terms “comprising,” “comprises,” “include”, “includes” and “including” are meant to be non-limiting.
- the term “consisting of' or “consisting essentially of' are meant to be limiting, i.e., excluding any components or ingredients that are not specifically listed except when they are present as impurities.
- the term “substantially free of' as used herein refers to either the complete absence of an ingredient or a minimal amount thereof merely as impurity or unintended byproduct of another ingredient.
- solid includes granular, powder, bar and tablet product forms.
- fluid includes liquid, gel, paste and gas product forms.
- liquid refers to a fluid having a liquid having a viscosity of from 1 to 2000 mPa*s at 25°C and a shear rate of 20 sec- 1 .
- the viscosity of the liquid may be in the range of from 200 to 1000 mPa*s at 25°C at a shear rate of 20 sec- 1 .
- the viscosity of the liquid may be in the range of from 200 to 500 mPa*s at 25°C at a shear rate of 20 sec- 1 .
- test methods that are disclosed in the Test Methods Section of the present application must be used to determine the respective values of the parameters of Applicants' inventions are described and claimed herein.
- the cationic polymer used in the present invention is a copolymer that consists of at least two types of structural units.
- the structural units, or monomers, can be incorporated in the cationic polymer in a random format or can be in a blocky format.
- such cationic polymer is a copolymer that contains only the first and second structural units as described hereinabove, i.e., it is substantially free of any other structural components, either in the polymeric backbone or in the side chains.
- such cationic polymer is a terpolymer that contains only the first, second and third structural units as described hereinabove, substantially free of any other structural components.
- it can include one or more additional structural units besides the first, second and third structural units described hereinabove.
- the first structural unit in the cationic polymer of the present invention is a nonionic structural unit derived from (meth)acrylamide (AAm).
- the cationic polymer contains from 60 mol% to 95 mol% of the AAm-derived structural unit.
- the second structural unit in the cationic polymer is a cationic structural unit that can be derived from any suitable water-soluble cationic ethylenically unsaturated monomer, such as, for example, N,N-dialkylaminoalkyl methacrylate, N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl acrylamide, N,N-dialkylaminoalkylmethacrylamide, methacylamidoalkyl trialkylammonium salts, acrylamidoalkylltrialkylamminium salts, vinylamine, vinyl imidazole, quaternized vinyl imidazole and diallyl dialkyl ammonium salts.
- any suitable water-soluble cationic ethylenically unsaturated monomer such as, for example, N,N-dialkylaminoalkyl methacrylate, N,N-dialkylaminoalkyl acrylate, N,N-dialkylamin
- the second, cationic structural unit is derived from a monomer selected from the group consisting of diallyl dimethyl ammonium salts (DADMAS), N,N-dimethyl aminoethyl acrylate, N,N-dimethyl aminoethyl methacrylate (DMAM), [2-(methacryloylamino)ethyl]trimethylammonium salts, N,N-dimethylaminopropyl acrylamide (DMAPA), N,N-dimethylaminopropyl methacrylamide (DMAPMA), acrylamidopropyl trimethyl ammonium salts (APTAS), methacrylamidopropyl trimethylammonium salts (MAPTAS), and quaternized vinylimidazole (QVi).
- DADMAS diallyl dimethyl ammonium salts
- DMAM N,N-dimethyl aminoethyl acrylate
- DMAM N,N-dimethyl aminoethyl methacrylate
- the second, cationic structural unit is derived from a diallyl dimethyl ammonium salt (DADMAS), as described hereinabove.
- DADMAS diallyl dimethyl ammonium salt
- the second, cationic structural unit can be derived from a [2-(methacryloylamino)ethyl]tri-methylammonium salt, such as, for example, [2-(methacryloylamino)ethyl]tri-methylammonium chloride, [2-(methacryloylamino)ethyl]trimethylammonium fluoride, [2-(methacryloylamino)ethyl]tri-methylammonium bromide, [2-(methacryloylamino)ethyl]tri-methylammonium iodine, [2 -(methacryloylamino)ethyl]trimethylammonium bisulfate, [2-(methacryloylamino)ethyl]tri-methylammonium alkyl sulfate, [2-(methacryloylamino)ethyl]tri-methylammonium dihydrogen phosphate, [2-(methacryloyla
- the second, cationic structural unit can be derived from APTAS, which include, for example, acrylamidopropyl trimethyl ammonium chloride (APTAC), acrylamidopropyl trimethyl ammonium fluoride, acrylamidopropyl trimethyl ammonium bromide, acrylamidopropyl trimethyl ammonium iodine, acrylamidopropyl trimethyl ammonium bisulfate, acrylamidopropyl trimethyl ammonium alkyl sulfate, acrylamidopropyl trimethyl ammonium dihydrogen phosphate, acrylamidopropyl trimethyl ammonium hydrogen alkyl phosphate, acrylamidopropyl trimethyl ammonium dialkyl phosphate, and combinations thereof.
- APTAS acrylamidopropyl trimethyl ammonium chloride
- APTAS acrylamidopropyl trimethyl ammonium fluoride
- the second, cationic structural unit can be derived from a MAPTAS, which includes, for example, methacrylamidopropyl trimethylammonium chloride (MAPTAC), methacrylamidopropyl trimethylammonium fluoride, methacrylamidopropyl trimethylammonium bromide, methacrylamidopropyl trimethylammonium iodine, methacrylamidopropyl trimethylammonium bisulfate, methacrylamidopropyl trimethylammonium alkyl sulfate, methacrylamidopropyl trimethylammonium dihydrogen phosphate, methacrylamidopropyl trimethylammonium hydrogen alkyl phosphate, methacrylamidopropyl trimethylammonium dialkyl phosphate, and combinations thereof.
- MAPTAS methacrylamidopropyl trimethylammonium chloride
- MAPTAS methacrylamidopropyl trimethylammonium fluor
- the second, cationic structural unit is derived from DADMAC, MAPTAC, APTAC, or QVi. Most preferably, the second, cationic structural unit as mentioned herein is made directly from DADMAC.
- the second, cationic structural unit is preferably present in the cationic polymer in an amount ranging from 5 mol% to 40 mol%.
- the third structural unit which is optional for the cationic polymer of the present invention, is a nonionic structural unit that is different from the first, nonionic structure unit. It may be derived from a vinyl-based nonionic monomer, such as vinylpyrrolidone (VP), vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ether, vinyl pyridine, vinyl imidazole, vinyl caprolactam, and combinations thereof. More preferably, the third, nonionic structural unit of the cationic polymer is derived from VP.
- the cationic polymer may contain from 0 mol% to 25 mol% of the third, nonionic structural unit.
- the cationic polymer does not contain any of the third, nonionic structural unit (i.e., the third, nonionic structural unit is present at 0 mol%) and consists essentially only of the first and second structural units as described hereinabove.
- Such cationic polymer is a copolymer consisting essentially of: (i) from 70 mol% to 90 mol%, of the AAm-derived first structural unit; and (ii) from 10 mol% to 30 mol%, of the second, cationic structural unit as described hereinabove.
- the cationic polymer contains the first, second and third structural units as described hereinabove, and is substantially free of any other structural unit.
- Such cationic polymer is a terpolymer consisting essentially of: (i) from 65 mol% to 90 mol% of the AAm-derived first structural unit; (ii) from 10 mol% to 20 mol%, of the second, cationic structural unit as described hereinabove; and (iii) f from 1 mol% to 20 mol%, of the third, nonionic structural unit as described hereinabove.
- the specific molar percentage ranges of the first, second, and optionally third structural units of the cationic polymer as specified hereinabove is critical for optimizing the sudsing profile generated by the laundry detergent compositions containing such cationic polymer during the wash and rinse cycles.
- Laundry detergent compositions containing the cationic polymer of the present invention are characterized by an optimized sudsing profile defined by: (1) a Wash Suds Index (WSI) of more than 70%, preferably more than 80%, and more preferably more than 100%; and (2) a Rinse Suds Index (RSI) of less than 40%, preferably less than 30%, and more preferably less than 20%, as determined by the Sudsing Profile Test described hereinafter.
- WSI Wash Suds Index
- RSI Rinse Suds Index
- the laundry detergent composition of the present invention has an optimal sudsing profile that is defined by a WSI of more than 70% and a RSI of less than 40%, preferably a WSI of more than 80% and RSI of less than 30%, and more preferably a WSI of more than 100% and a RSI of less than 20%.
- the specific Molecular Weight range for the cationic polymer as specified hereinabove also provides improved sudsing profile. More importantly, such Molecular Weight range is particularly effective in reducing the whiteness loss that is commonly seen in fabrics after they have been exposed to multiple washes. Cationic polymers have been known to contribute to fabric whiteness loss, which is a limiting factor for wider usage of such polymers. However, inventors of the present invention have discovered that by controlling the Molecular Weight of the cationic polymer within a specific range, i.e., from 10,000 to 1,000,000 Daltons, and preferably from 15,000 to 700,000 Daltons, and most preferably from 20,000 to 350,000 Daltons, the fabric whiteness loss can be effectively reduced in comparison with conventional cationic polymers.
- laundry detergent compositions containing the cationic polymer of the present invention are characterized by a Relative Whiteness Loss Percentage (WLP) of not more than 100%, preferably not more than 50%, and more preferably not more than 10%, as determined by the Whiteness Loss Test described hereinafter.
- WLP Relative Whiteness Loss Percentage
- cationic polymers containing the above-described first, second, and optionally third structural units in various combinations have been previously used in laundry detergent compositions, typically as deposition aid polymers.
- the conventional cationic polymers used as deposition aids in laundry detergents have different monomeric ratios and/or significantly higher Molecular Weights from the cationic polymers of this invention.
- the inventors of the present invention have discovered, surprisingly and unexpectedly, that cationic polymers with the specific monomeric make-up and the specific Molecular Weight as defined hereinabove can provide superior sudsing profile and reduced fabric whiteness loss, in comparison with the conventional cationic polymers. Further, there seem to be absent of any terpolymer containing or consisting of all three structural units.
- product viscosity can be impacted by Molecular Weight and cationic content of the cationic polymer.
- Molecular weights of polymers of the present invention are also selected to minimize impact on product viscosity to avoid product instability and stringiness associated with high molecular weight and/or broad molecular weight distribution.
- the amount of the cationic polymer of the present invention in the laundry detergent or cleaning composition is not particularly limited, as long as it is effective for providing an optimal sudsing profile as defined herein above, i.e., with significant suds volume reduction during the rinse cycle and insignificant suds volume reduction during the wash cycle.
- the cationic polymer is provided in the cleaning or laundry detergent composition at an amount ranging from 0.01 wt% to 15 wt%, from 0.05 wt% to 10 wt%, from 0.1 wt% to 5 wt%, and from 0.2 wt% to 1wt%.
- the cationic polymer is substantially free of carrier particles or coating. This is advantageous as it avoids an extra step and cost associated with the incorporation of these materials.
- Cleaning compositions or laundry detergent compositions of the present invention includes a unique surfactant system that is enriched with an anionic surfactant that is selected from the group consisting of C 10 -C 20 linear or branched alkylalkoxy sulfates (AES) having an average degree of alkoxylation ranging from 0.1 to 5.
- AES alkylalkoxy sulfates
- the term "enriched” as used herein refers to the relatively higher weight ratio of the AES surfactant(s) over other surfactants, i.e., the AES surfactant(s) is present in the surfactant system in an amount that is equal to or greater than any other detersive surfactant contained by the surfactant system. Without being bound by any theory, it is believed that such an AES-enriched surfactant system is particularly effective in optimizing the sudsing benefit of the cationic polymers of the present invention.
- the AES surfactants preferably are C 10 -C 20 linear or branched alkylethoxy sulfates. More preferably, the AES surfactants have an average degree of alkoxylation ranging from 0.3 to 4, and most preferably from 0.5 to 3.
- the AES surfactants is provided at levels ranging from 20% or more (i.e., from 20% to 100%), more preferably at 40% or more (i.e., from 40% to 100%), still more preferably at 50% or more (i.e., from 50% to 100%), and most preferably at 60% or more (i.e., from 60% to 100%), by total weight of the surfactant system.
- the surfactant system of the present invention may contain, in addition to the AES surfactants, one or more other detersive surfactants selected from the group consisting of anionic, nonionic, zwitterionic, amphoteric or cationic type or can comprise compatible mixtures of these types.
- Useful other anionic surfactants can themselves be of several different types.
- water-soluble salts of the higher fatty acids i.e., "soaps"
- alkali metal soaps such as the sodium, potassium, ammonium, and alkyl ammonium salts of higher fatty acids containing from 8 to 24 carbon atoms, and preferably from 12 to 18 carbon atoms.
- Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
- Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
- non-soap other anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group (included in the term "alkyl” is the alkyl portion of acyl groups) containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- Examples of this group of synthetic anionic surfactants include, but are not limited to: a) the sodium, potassium and ammonium alkyl sulfates with either linear or branched carbon chains, especially those obtained by sulfating the higher alcohols (C 10 -C 20 carbon atoms), such as those produced by reducing the glycerides of tallow or coconut oil; b) the sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from 10 to 20 carbon atoms in either a linear or a branched carbon chain configuration, preferably a linear carbon chain configuration; c) the sodium, potassium and ammonium alkyl sulphonates in which the alkyl group contains from 10 to 20 carbon atoms in either a linear or a branched configuration; d) the sodium, potassium and ammonium alkyl phosphates or phosphonates in which the alkyl group contains from 10 to 20 carbon atoms in either a linear or a branched configuration,
- Preferred for the practice of the present invention are surfactant systems that contain one or more C 10 -C 20 linear alkyl benzene sulphonates (LAS) in addition to the AES surfactants described hereinabove.
- the LAS is present in an amount ranging from 1% to 45%, more preferably from 5% to 40%, and most preferably from 10% to 35%, by total weight of the surfactant system.
- the weight ratio of AES to LAS is equal to or greater than 1.2, more preferably equal to or greater than 1.5, still more preferably equal to or greater than 2, and most preferably equal to or greater than 5.
- the surfactant system contains one or more nonionic surfactants in addition to the AES surfactants described hereinabove.
- Suitable nonionic surfactants are those of the formula R 1 (OC 2 H 4 ) n OH, wherein R 1 is a C 8 -C 18 alkyl group or alkyl phenyl group, and n is from 1 to 20.
- Suitable nonionic surfactants are C 8 -C 18 alkyl alkoxylated alcohols (NI) having an average degree of alkoxylation from 1 to 20.
- the NI can be present in an amount ranging from 1% to 45%, more preferably from 5% to 40%, and most preferably from 10% to 35%, by total weight of the surfactant system.
- the weight ratio of AES to NI is equal to or greater than 1.2, more preferably equal to or greater than 1.5, still more preferably equal to or greater than 2, and most preferably equal to or greater than 5.
- the surfactant system contains both LAS and NI in addition to AES.
- the weight ratio between LAS and NI may range from 1:20 to 20:1, preferably from 1:15 to 15:1, more preferably from 1:10 to 10:1, and most preferably from 1:5 to 5:1.
- a surfactant system that is particularly preferred for the practice of the present invention is one that comprising or consisting essentially of AES, LAS and NI at weight ratios ranging from 9:0.5:0.5 to 5:4:1 to 5:0.1:5.
- Particularly preferred amphoteric surfactants are amine oxides, such as, for example, alkyl dimethyl amine oxide or alkyl amido propyl dimethyl amine oxide, more preferably alkyl dimethyl amine oxide and especially coco dimethyl amino oxide.
- Amine oxides may contain a linear or branched alkyl moiety.
- amphoteric and/or cationic surfactants are well known for use in laundry detergents and are typically present at levels from 0.2% or 1% to 40% or 50%, by total weight of the surfactant system.
- the surfactant system may be present in an amount ranging from 1% to 99%, more preferably from 1% to 80%, and more preferably from 5% to 50% by total weight of the cleaning or detergent compositions of the present invention.
- the present invention provides a cleaning composition comprising the cationic polymer and the surfactant system as mentioned hereinabove.
- the cleaning composition is suitable for laundry detergent application, for example: laundry, including automatic washing machine laundering or hand-washing, or cleaning auxiliaries, such as for example, bleach, rinse aids, additives or pre-treat types.
- the laundry detergent composition is a liquid laundry detergent and can be a fully formulated laundry detergent product. Liquid compositions contained in encapsulated and/or unitized dose products are included, as are compositions which comprise two or more separate but jointly dispensable portions. More preferably, the laundry detergent composition is a liquid laundry detergent composition designed for hand-washing, where the improved suds benefit or superior sudsing profile is most evident to the consumer.
- the liquid laundry detergent composition preferably contains water as an aqueous carrier, and it can contain either water alone or mixtures of organic solvent(s) with water as carrier(s).
- Suitable organic solvents are linear or branched lower C 1 -C 8 alcohols, diols, glycerols or glycols; lower amine solvents such as C 1 -C 4 alkanolamines, and mixtures thereof.
- Exemplary organic solvents include 1,2-propanediol, ethanol, glycerol, monoethanolamine and triethanolamine.
- the carriers are typically present in a liquid composition at levels in the range of from 0.1% to 98%, preferably from 10% to 95%, more preferably from 25% to 75% by total weight of the liquid composition.
- water is from 85 to 100 wt% of the carrier.
- the liquid laundry detergent composition of the present invention has a viscosity from 1 to 2000 centipoise (1-2000 mPa ⁇ s), or from 200 to 800 centipoises (200-800 mPa ⁇ s).
- the viscosity can be determined using a Brookfield viscometer, No. 2 spindle, at 60 RPM/s, measured at 25°C.
- a silicone-derived anti-foaming agent is used in combination with the cationic polymer and the surfactant system in a cleaning composition, or preferably a laundry detergent composition.
- a cleaning composition or preferably a laundry detergent composition.
- such silicone-derived anti-foaming agent may further improve the sudsing profile of the cleaning composition.
- the silicone-derived anti-foaming agent can be any suitable organosilicones, including, but not limited to: (a) non-functionalized silicones such as polydimethylsiloxane (PDMS); and (b) functionalized silicones such as silicones with one or more functional groups selected from the group consisting of amino, amido, alkoxy, alkyl, phenyl, polyether, acrylate, siliconehydride, mercaptoproyl, carboxylate, sulfate phosphate, quaternized nitrogen, and combinations thereof.
- the organosilicones suitable for use herein have a viscosity ranging from 10 to 700,000 CSt (centistokes) at 20°C. In other embodiments, the suitable organosilicones have a viscosity from 10 to 100,000 CSt.
- Polydimethylsiloxanes can be linear, branched, cyclic, grafted or cross-linked or cyclic structures.
- the detergent compositions comprise PDMS having a viscosity of from 100 to 700,000 CSt at 20°C.
- Exemplary functionalized silicones include but are not limited to aminosilicones, amidosilicones, silicone polyethers, alkylsilicones, phenyl silicones and quaternary silicones.
- a preferred class of functionalized silicones comprises cationic silicones produced by reacting a diamine with an epoxide.
- composition of the present invention contains organosilicone emulsions, which comprise organosilicones dispersed in a suitable carrier (typically water) in the presence of an emulsifier (typically an anionic surfactant).
- organosilicones are in the form of microemulsions having an average particle size in the range from 1 nm to 150 nm, or from 10 nm to 100 nm, or from 20 nm to 50 nm.
- the silicone-derived anti-foaming agent as mentioned hereinabove can be present in the cleaning composition in an amount ranging from 0.01% to 5%, preferably from 0.05% to 2%, and more preferably from 0.1 % to 1 %, by total weight of the composition.
- the liquid laundry detergent composition contains from 0.1 wt% to 5 wt%, preferably from 0.5 wt% to 3 wt%, more preferably from 1 wt% to 1.5 wt%, of one or more fatty acids and/or alkali salts thereof.
- Suitable fatty acids and/or salts that can be used in the present invention include C 10 -C 22 fatty acids or alkali salts thereof.
- alkali salts include monovalent or divalent alkali metal salts like sodium, potassium, lithium and/or magnesium salts as well as the ammonium and/or alkylammonium salts of fatty acids, preferably the sodium salt.
- Preferred fatty acids for use herein contain from 12 to 20 carbon atoms, and more preferably 12 to 18 carbon atoms.
- Exemplary fatty acids that can be used maybe selected from caprylic acid, capric acid, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, sapienic acid, stearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, ⁇ -linoelaidic acid, arachidic acid, arachidonic acid, eicosapentaenoic acid, behenic acid, erucic acid, and docosahexaenoic acid, and mixtures thereof.
- the liquid detergent composition of the present invention comprises one or more saturated fatty acids, such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and mixtures thereof.
- saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and mixtures thereof.
- lauric acid, myristic acid and palmitic acid are particularly preferred.
- the balance of the laundry detergent typically contains from 5 wt% to 70 wt%, or 10 wt% to 60 wt% adjunct ingredients.
- Suitable detergent ingredients include: transition metal catalysts; imine bleach boosters; enzymes such as amylases, carbohydrases, cellulases, laccases, lipases, bleaching enzymes such as oxidases and peroxidases, proteases, pectate lyases and mannanases; source of peroxygen such as percarbonate salts and/or perborate salts, preferred is sodium percarbonate, the source of peroxygen is preferably at least partially coated, preferably completely coated, by a coating ingredient such as a carbonate salt, a sulphate salt, a silicate salt, borosilicate, or mixtures, including mixed salts, thereof; bleach activator such as tetraacetyl ethylene diamine, oxybenzene sulphonate bleach activators such as nonanoyl oxybenzene sul
- laundry detergent powder may also be especially preferred for the laundry detergent powder to comprise low levels, or even be essentially free, of builder.
- the term “essentially free” means that the composition "comprises no deliberately added” amount of that ingredient.
- the laundry detergent composition of the present invention comprises no builder.
- the cationic polymer as received from the manufacturer can be introduced directly into a preformed mixture of two or more of the other components of the final composition. This can be done at any point in the process of preparing the final composition, including at the very end of the formulating process. That is, the cationic polymer can be added to a pre-made liquid laundry detergent to form the final composition of the present invention.
- the cationic polymer can be premixed with an emulsifier, a dispersing agent or a suspension agent to form an emulsion, a latex, a dispersion, a suspension, and the like, which is then mixed with other components (such as the AES, LAS, NI, and/or silicone-derived anti-foaming agent, etc.) of the final composition.
- these components can be added in any order and at any point in the process of preparing the final composition.
- a third example involves mixing the cationic polymer with one or more adjuncts of the final composition and adding this premix to a mixture of the remaining adjuncts.
- the present invention is directed to a method of cleaning fabric, the method comprising the steps of: (i) providing a laundry detergent as described above; (ii) forming a laundry liquor by diluting the laundry detergent with water; (iii) washing fabric in the laundry liquor; and (iv) rinsing the fabric in water, wherein after 2 or less rinses, preferably after 1 rinse, the laundry liquor is substantially free of suds, or at least 75%, preferably at least 85%, more preferably 95%, and even more preferably at least 99% of a surface area of the laundry liquor is free from suds.
- the present invention is also directed to a method of saving water during laundering, the method comprising the steps of: (i) providing a laundry detergent as described above; (ii) diluting the cleaning composition with wash water in a container to form a laundry liquor; (iii) washing laundry in the laundry liquor; and (iv) rinsing the laundry, wherein after 2 or less rinses, preferably after 1 rinse, the laundry liquor is substantially free of suds.
- the method of laundering fabric may be carried out in a top-loading or front-loading automatic washing machine, or can be used in a hand-wash laundry application, which is particularly preferred in the present invention.
- compositions of the present invention comprising the cationic polymer.
- assays must be used in order that the invention described and claimed herein may be fully understood.
- the weight-average molecular weight (Mw or "Molecular Weight") of a polymer material of the present invention is determined by Size Exclusion Chromatography (SEC) with differential refractive index detection (RI).
- SEC Size Exclusion Chromatography
- RI differential refractive index detection
- One suitable instrument is Agilent® GPC-MDS System using Agilent® GPC/SEC software, Version 1.2 (Agilent, Santa Clara, USA).
- SEC separation is carried out using three hydrophilic hydroxylation polymethyl methacrylate gel columns (Ultrahydrogel 2000-250-120 manufactured by Waters, Milford, USA) directly joined to each other in a linear series and a solution of 0.1M sodium chloride and 0.3% trifluoroacetic acid in DI-water, which is filtered through 0.22 ⁇ m pore size GVWP membrane filter (MILLIPORE, Massachusetts, USA).
- the RI detector needs to be kept at a constant temperature of 5 -10°C above the ambient temperature to avoid baseline drift. It is set to 35°C.
- the injection volume for the SEC is 100 ⁇ L. Flow rate is set to 0.8 mL/min.
- Each test sample is prepared by dissolving the concentrated polymer solution into the above-described solution of 0.1M sodium chloride and 0.3% trifluoroacetic acid in DI water, to yield a test sample having a polymer concentration of 1 to 2 mg/mL.
- the sample solution is allowed to stand for 12 hours to fully dissolve, and then stirred well and filtered through a 0.45 ⁇ m pore size nylon membrane (manufactured by WHATMAN, UK) into an auto sampler vial using a 5mL syringe.
- Samples of the polymer standards are prepared in a similar manner. Two sample solutions are prepared for each test polymer. Each solution is measured once. The two measurement results are averaged to calculate the Mw of the test polymer.
- the solution of 0.1M sodium chloride and 0.3% trifluoroacetic acid in DI water is first injected onto the column as the background.
- the weight-average molecular weight (Mw or "Molecular Weight”) of the test sample polymer is calculated using the software that accompanies the instrument and selecting the menu options appropriate for narrow standard calibration modelling.
- a third-order polynomial curve is used to fit the calibration curve to the data points measured from the Poly(2-vinylpyridin) standards.
- the data regions used for calculating the weight-average molecular weight are selected based upon the strength of the signals detected by the RI detector. Data regions where the RI signals are greater than 3 times the respective baseline noise levels are selected and included in the Mw calculations. All other data regions are discarded and excluded from the Mw calculations. For those regions which fall outside of the calibration range, the calibration curve is extrapolated for the Mw calculation.
- the selected data region is cut into a number of equally spaced slices.
- the height or Y-value of each slice from the selected region represents the abundance (Ni) of a specific polymer (i), and the X-value of each slice from the selected region represents the molecular weight (Mi) of the specific polymer (i).
- Each of the monomers in the cationic polymer is quantified by high pressure liquid chromatography (HPLC) according to the follows: Measuring device: L-7000 series (Hitachi Ltd.) Detector: UV detector, L-7400 (Hitachi Ltd.) Column: SHODEX RSpak DE-413 (product of Showa Denko K. K.) Temperature: 40°C Eluent: 0.1% phosphoric acid aqueous solution Flow Velocity: 1.0 mL/ min
- the sudsing profile of the detergent composition herein are measured by employing a suds cylinder tester (SCT).
- SCT suds cylinder tester
- the SCT has a set of 8 cylinders. Each cylinder is typically 60 cm long and 9 cm in diameter and may be together rotated at a rate of 20-22 revolutions per minute (rpm).
- This method is used to assay the performance of laundry detergent to obtain a reading on ability to generate suds as well as its suds stability and rinse suds performance.
- the following factors affect results and therefore should be controlled properly: (a) concentration of detergent in solution, (b) water hardness, (c) water temperature of water, (d) speed and number of revolutions, (e) soil load in the solution, and (f) cleanliness of the inner part of the tubes.
- the performance is determined by comparing the suds height generated during the washing stage by the laundry detergent containing the cationic polymer of the present invention or a comparative cationic polymer not falling within the scope of the present invention, versus control laundry detergent that does not contain any cationic polymer.
- the height of suds generated by each test composition is measured by recording the total suds height (i.e., height of suds plus wash liquor) minus the height of the wash liquor alone. 1.
- 2. Pour the sample aliquot to the tubes. Put in the rubber stopper and lock the tubes in place. 3.
- Average suds height of different categories described above are calculated by average the height data of each replicate.
- the WSI is indicative of how much suds is generated during the wash cycle by a test sample containing a cationic polymer (either an inventive cationic polymer with the specific monomeric composition and Molecular Weight as defined hereinabove, or a comparative cationic polymer not falling within the scope of the present invention) that may have adverse impact on the wash suds, in comparison with the suds generated by a control sample that does not contain any of such cationic polymer. Therefore, the higher the WSI percentage, the more suds are generated during wash, and the better the performance.
- a cationic polymer either an inventive cationic polymer with the specific monomeric composition and Molecular Weight as defined hereinabove, or a comparative cationic polymer not falling within the scope of the present invention
- the RSI is indicative of how much suds is left during the rinse cycle by a test sample containing a cationic polymer (either an inventive cationic polymer with the specific monomeric composition and Molecular Weight as defined hereinabove, or a comparative cationic polymer not falling within the scope of the present invention) that may be effective in reducing the rinse suds, in comparison with the suds left by a control sample that does not contain any of such cationic polymer. Therefore, the lower the RSI percentage, the more suds reduction is effectuated during rinse, and the better the performance.
- a cationic polymer either an inventive cationic polymer with the specific monomeric composition and Molecular Weight as defined hereinabove, or a comparative cationic polymer not falling within the scope of the present invention
- An optimal sudsing profile as defined within the meaning of this invention includes a WSI of more than 70% and a RSI of less than 40%, preferably a WSI of more than 80% and a RSI of less than 30%, and more preferably a WSI of more than 100% (i.e., a suds boosting effect during wash) and a RSI of less than 20%.
- Test 4 Fabric Whiteness Loss Test (Fast Wash Method)
- the steps for assaying the whiteness maintenance of the laundry detergent of the present invention are as follows: (1) Formulation preparation: Formulate detergent compositions with or without polymers of interest. (2) Solution Preparation:
- WLP is the relative fabric whiteness loss (expressed in percentage) caused by a detergent composition containing a cationic polymer (which is typically known to cause some fabric whiteness loss) over that caused by a control detergent composition not containing such cationic polymer
- a larger WLP is indicative of more relative fabric whiteness loss observed in comparison with the control sample. Therefore, it is in turn indicative of poorer whiteness performance of the cationic polymer, i.e., its presence causes more fabric whiteness loss in the laundry detergent.
- the WLP is a negative number, it is indicative of the fact that the presence of the cationic polymer not only does not cause fabric whiteness loss, but actually imparts whiteness benefit to the fabric, which is the most desirable.
- the wash and rinse suds volumes of the laundry detergent compositions of the present invention can also be measured via the SITA Foam Tester (model: R-2000) made by SITA Messtechnik GmbH (Germany).
- the SITA Foam Tester R-2000 utilizes a patented rotor of defined geometry for foam generation. The rotor mechanically inserts air bubbles into the liquid. The foam volume is measured by an array of sensor needles, which scan the foam surface. Using an array of sensor needles permits exact measurement of the foam volume even with uneven foam surfaces. The output is given as average milliliters of foam height per measure. Foam height measurements are recorded every 10 seconds while stirring of the test composition continues - this occurs 15 times in total (i.e., resulting in 15 measurements in total).
- the Stir Count as used herein, means the total number of stirring intervals in one test.
- the instrument settings below are used in the suds volume measurements.
- the final suds volume for each detergent composition is the average of 6 suds readings from the 10 th to 15 th measurement.
- This method is used to evaluate the sudsing profile of laundry detergent and obtain a reading on wash suds and rinse suds volume.
- the following factors affect results and therefore should be controlled properly: (a) concentration of detergent in solution, (b) water hardness, (c) water temperature, (d) soil load in the solution, (e) instrument settings, and (f) cleanliness of the sample vessel of SITA.
- the performance is determined by comparing the suds volume generated by a laundry detergent containing the cationic polymer versus the laundry detergent without the cationic polymer.
- test liquid laundry detergent compositions are prepared, including: (1) a control composition containing no cationic polymer, (2) a first inventive composition containing 0.5 wt% of the inventive polymer 3 as described hereinabove in Table II of Example I; (3) a second inventive composition containing 0.5 wt% of the inventive polymer 4 as described hereinabove in Table II of Example I; (4) a third inventive composition containing 0.5 wt% of the inventive polymer 5 as described hereinabove in Table II of Example I; (5) a first inventive composition containing 0.5 wt% of the inventive polymer 11 as described hereinabove in Table II of Example I; (6) a second inventive composition containing 0.5 wt% of the inventive polymer 12 as described hereinabove in Table II of Example I; and (7) a third inventive composition containing 0.5 wt% of the inventive polymer 13 as described hereinabove in Table II of Example I.
- inventive compositions containing inventive cationic polymers of the present invention provide optimized sudsing profiles characterized by a satisfactory wash suds volume (a WSI of more than 70%) and significantly lower rinse suds volume (a RSI of less than 40%) in comparison with the control composition.
- the cationic polymers of the present invention also demonstrate observable sudsing benefit across different detergent dosing levels, i.e., the laundry detergent composition containing such cationic polymers may be added into water at different amounts to form laundering liquor of different detergent concentrations. Because different consumers may have very different dosing habits when it comes to laundry detergents, with some more prone to over-dosing and others more prone to under-dosing, it is an important advantage if the sudsing benefit of the present invention is observable across a wider dosing range, thereby accommodating different consumer dosing habits.
- test liquid laundry detergent compositions including: (1) a control composition containing no cationic polymer, (2) 5 inventive compositions, each of which containing the same ingredients as the control composition but further including 0.5 wt% of an inventive polymer within the scope of the present invention; and (3) 7 comparative compositions, each of which containing the same ingredients as the control composition but further including 0.5 wt% of a comparative polymer that has either AAm/DADMAC molar percentages falling outside of the scope of the present invention, or a Molecular Weight falling outside of the scope of the present invention.
- Sudsing Profile Test as described hereinabove is carried out for each of these thirteen (13) test compositions by dissolving each composition in water having a water hardness level of 16 gpg to form a laundering liquor containing 5000ppm of the test composition.
- the Sudsing Profile Test is repeated several times (the number of actual tests conducted for each test composition is listed at below), and the suds data provided hereinafter is obtained by averaging the data obtained from the repetition.
- the Wash Suds Index (WSI) and Rinse Suds Index (RSI) of each of the seven (7) comparative compositions and five (5) inventive compositions are calculated based on the wash suds volume and rinse suds volume measured for such compositions in comparison with the control composition.
- the comparative polymers contained in the comparative compositions have either AAm/DADMAC molar percentages or Molecular Weights falling outside of the scope of the present invention.
- the above data shows that only the inventive polymers with the appropriate AAm/DADMAC molar percentages and Molecular Weights provide optimal sudsing profiles, i.e., having a satisfactory wash suds volume quantified by a WSI of more than 70% and a sufficiently reduced rinse suds volume quantified by a RSI of less than 40%.
- Three (3) liquid laundry detergent compositions are prepared, including: (1) a control composition containing no cationic polymer, (2) a comparative composition containing 0.5 wt% of a comparative polymer, MerquatTM S, which contains 70 mol% of AAm and 30 mol% of DADMAC with a Molecular Weight of 3552.2K Dalton; (3) an inventive composition containing 0.5 wt% of the inventive polymer 2 as described hereinabove in Table II of Example I, MerquatTM 740, which contains 76 mol% of AAm and 24 mol% of DADMAC with a Molecular Weight of 61.5K Dalton.
- Fabric Whiteness Loss Test using the fast wash method as described in Test 4 hereinabove is carried out for each of these three (3) test compositions.
- the fabric used for conducting the test is polyester.
- the Whiteness Loss Index (i.e., ⁇ WLI) is measured for each of the control composition, the comparative composition, and the inventive composition.
- the Relative Whiteness Loss Percentage (WLP) of both the comparative composition and inventive composition are calculated based on their ⁇ WLI in comparison with that of the control composition. Following are the measurement results: Table X Control Composition Comparative Composition Inventive Composition ⁇ WLI 26.8 53.5 13.9 WLP 0% 99.6% -48.1% * Measured at 90-110 revolutions. ** Measured at 130-150 revolutions.
- WLP is the relative percentage fabric whiteness loss caused by a detergent composition containing a cationic polymer (either an inventive polymer or a comparative polymer) over that caused by a control detergent composition not containing such cationic polymer, the larger the WLP, the more relative fabric whiteness loss is caused by addition of the specific cationic polymer, which is indicative of poorer whiteness performance of such cationic polymer.
- the comparative polymer contained in the comparative composition and the inventive polymer 2 contained in the inventive composition have similar AAm and DADMAC molar percentages, but the inventive polymer 2 has a significantly lower Molecular Weight that falls within the scope of the present invention, while the comparative polymer has a high Molecular Weight that does not fall within the scope of the present invention.
- the comparative composition has a WLP as high as 99.6%, which is indicative of very poor whiteness performance of the comparative cationic polymer.
- the inventive composition has a negative WLP of -48.1%, which indicates that the presence of the inventive cationic polymer 2 not only does not cause fabric whiteness loss, but actually imparts whiteness benefit to the fabric tested.
- a total of six (6) test liquid laundry detergent compositions are prepared, which include: (1) a Composition A containing a LAS-enriched surfactant system without any cationic polymer; (2) Composition A plus a cationic polymer of the present invention, which contains 80 mol% of AAm, 16 mol% of DADMAC, and 4 mol% of VP and has a Mw of 165,300 Daltons; (3) a Composition B containing a NI-enriched surfactant system without any cationic polymer; (4) Composition B plus the cationic polymer; (5) a Composition C containing an AES-enriched surfactant system without any cationic polymer; and (6) Composition C plus the cationic polymer.
- the wash suds volume and the rinse suds volume of each test liquid laundry detergent composition are measured using the Sudsing Volume Test (SITA) described in Test 5.
- SITA Sudsing Volume Test
- wash Suds Change ⁇ Sw
- a positive ⁇ Sw is indicative of a wash suds boosting effect
- a negative ⁇ Sw is indicative of a wash suds suppressing effect. The more positive the ⁇ Sw, the stronger the suds boosting effect.
- ⁇ S R Rinse Suds Change
- a positive ⁇ S R is indicative of more rinse suds, which is undesirable, while a negative ⁇ S R is indicative of less rinse suds, which is desirable. The more negative the ⁇ S R , the stronger the suds suppressing effect.
- the overall sudsing benefit achieved by the inventive cationic polymer from the wash cycle to the rinse cycle is recorded as a Total Suds Change ( ⁇ S W - ⁇ S R ).
- heaving duty liquid detergents are made by mixing the ingredients listed below via conventional processes. Such heavy duty liquid detergents are used to launder fabrics that are then dried by line drying and/or machine drying. Such fabrics may be treated with a fabric enhancer prior to and/or during drying. Such fabrics exhibit a clean appearance and have a soft feel.
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Description
- The present invention relates to cleaning compositions, and in particular it relates to a liquid laundry detergent composition, that comprising a cationic polymer in a specific surfactant system for optimizing sudsing profile. The present invention also relates to methods of making and using such cleaning compositions.
- Sudsing profile is important for a cleaning composition, particularly laundry detergent, where the appropriate volume and speed of suds formation, retention and dissolution in the wash and rinse cycles are considered key benchmarks of performance by consumers. For laundry detergents, while a sudsing profile is important for machine washing process, it is even more important in a typical hand-washing process as the consumer would see changes in the suds level in the wash and rinse cycles. Typically, consumers, particularly hand-washing consumers, desire laundry detergent that dissolves in the wash liquor to give voluminous suds during the wash cycle to signify sufficient performance. The suds are then carried over to the rinse solution and require additional time, water and labor to thoroughly rinse from the laundered fabric.
- However, reducing the suds level overall is not a viable option because when the consumer sees little or no suds during the washing cycle, it causes the consumer to believe that the laundry detergent is not as active. In addition, the current market demands are for laundry detergents with improved environmental sustainability (e.g., less water consumption) without negatively impacting cleaning performance or the perception of cleaning performance (i.e., appearance of suds on fabric or in the rinse solution). This, of course, reinforces the preference for laundry detergents having improved foam control composition for faster suds dissolution during the rinse cycle so as to reduce extra rinse cycles needed to remove the suds from the cleaned fabrics/rinse solution. Thus, there is a need for a cleaning composition having a sudsing profile where there is strong level of suds volume during the washing cycle, and yet quickly collapses in the rinsing solution for substantially reduced or zero suds for cost savings and environmental conservation purposes. This is known as the "single rinse" concept.
- One solution has been to add a de-foaming agent during the rinse cycles, but this option is cost prohibitive for most hand-washing consumers. Additionally, the prior art discloses laundry detergent compositions with various foam-control or anti-foaming agents in an attempt to address this problem. For example,
PCT Publication No. WO2011/107397 (Unilever) discloses a laundry detergent composition comprising a delayed-release amino-silicone based anti-foaming agent that is absorbed onto a carrier or filler to act in the rinsing cycle to reduce or eliminate suds, preferably after two rinse cycles. However, the suds control benefit imparted by such amino-silicone based anti-foaming agent may still come at the expense of wash suds, i.e., the wash suds volume can be significantly reduced since the silicone release timing is difficult to control. Inopportune release of the silicone anti-foam may lead to significant reduction of wash suds volume, which will give consumer the impression that the detergent composition contains lower surfactant level and is therefore of lower quality/value. EP Publication No.EP0685250A1 (Dow Corning) discloses a foam control composition for use in laundry detergents that inhibits the formation of new suds during the post-wash rinsing cycles, but which does not appear to quicken the elimination of already existing suds carried over from the wash cycle. - Accordingly, there is a need for a cleaning composition, preferably a laundry detergent composition, which enables strong suds formation (e.g., fast generation of large volume of suds and/or stability or sustainability of the suds already generated over time) during the wash cycle while reducing and eliminating the suds quickly during the rinse cycle(s), preferably across a range of consumer wash habits and fabric/material surfaces being washed. It may be advantageous to have a laundry detergent composition that only requires a single rinse cycle to effectively remove the suds, thereby enabling the "single rinse" concept.
- Further, conventional de-foaming or anti-foaming agents, especially the polymeric de-foaming or anti-foaming agents, are known to cause significant whiteness loss in fabrics after repeated wash cycles, i.e., the grey or dull color in fabrics that have been exposed to many wash cycles. Therefore, the usage of such polymeric de-foaming or anti-foaming agents has been limited in laundry detergent compositions.
- Correspondingly, it will be an advantage for laundry detergent compositions to also have reduced whiteness loss in fabrics after repeated wash.
- The present invention relates to a laundry detergent composition which exhibits significant suds reduction during the rinse cycle while minimizing reduction of suds volume during the wash cycle, and at the same time leading to less fabric whiteness loss after repeated washing. It has now been discovered that the challenges presented hereinabove for conventional laundry detergents can be met by employing a specific cationic polymer in a unique surfactant system. The cationic polymer contains a first, nonionic monomeric unit derived from (meth)acrylamide (AAm), a second, cationic monomeric unit, and optionally a third, nonionic monomeric unit (which is not AAm) at a specific monomeric ratio and having a Molecular Weight within a specific range. Laundry detergent compositions containing the cationic polymer of the present invention demonstrate outstanding sudsing profile with no or little fabric whiteness loss. Absence of any silicone-derived structural component in such cationic polymer may help to optimize wash suds generation and stability while reducing/minimizing the cost of synthesis. Further, a surfactant system enriched with an alkylalkoxy sulfate (AES) surfactant is employed by the present invention to further improve the sudsing benefit of the cationic polymer.
- The present invention relates to a liquid laundry detergent composition, containing:
- (a) a cationic polymer which is either:
a copolymer that consists essentially of: (i) from 70 mol% to 90 mol% of a first, nonionic structural unit; and (ii) from 10 mol% to 30 mol%, of a second, cationic structural unit; or:
a terpolymer that consists essentially of: (i) from 65 mol% to 90 mol% of the first, nonionic structural unit; (ii) from 10 mol% to 20 mol% of the second, cationic structural unit; and (iii) from 1 mol% to 20 mol%, of a third, nonionic structural unit; wherein:- the first, nonionic structural unit made from (meth)acrylamide (AAm);
- the second, cationic structural unit is made from a monomer selected from the group consisting of diallyl dimethyl ammonium salts (DADMAS), N,N-dimethyl aminoethyl acrylate, N,N-dimethyl aminoethyl methacrylate (DMAM), [2-(methacryloylamino)ethyl]tri-methylammonium salts, N,N-dimethylaminopropyl acrylamide (DMAPA), N,N-dimethylaminopropyl methacrylamide (DMAPMA), acrylamidopropyl trimethyl ammonium salts (APTAS), methacrylamidopropyl trimethylammonium salts (MAPTAS), quaternized vinylimidazole (QVi), and combinations thereof; and
- the third, nonionic structural unit that is different from the first, nonionic structural unit and is made from a monomer which is vinylpyrrolidone (VP);
- wherein said cationic polymer is characterized by a Weight Average Molecular Weight of from 10,000 to 1,000,000 Daltons and is free of any silicone-derived structural component; and
- (b) a surfactant system comprising: (i) from 20% or more, by total weight of the surfactant system, of a C10-C20 linear or branched alkylethoxy sulfate (AES) having an average degree of ethoxylation ranging from 0.3 to 4; (ii) from 1% to 45%, by total weight of the surfactant system, of a C10-C20 linear alkyl benzene sulphonate (LAS); and (iii) from 1% to 45%, by total weight of the surfactant system, of a C8-C18 alkyl alkoxylated alcohol having an average degree of alkoxylation from 1 to 20 (NI), wherein the weight ratio of AES to LAS is equal to or greater than 1.2, and wherein the weight ratio of AES to NI is equal to or greater than 1.2.
- Preferably, the weight ratio of AES to the combination of LAS and NI is equal to or greater than 1 (i.e., AES/(LAS+NI) >= 1). More preferably, AES is present in an amount of 50% or more by total weight of the surfactant system.
- The cationic polymer may contain one or more additional structural units other than (i), (ii), and (iii). The total mol% of all structural units contained by the cationic polymer adds up to be 100%. Preferably but not necessarily, the total mol% of (i), (ii) and (iii) adds up to 100 mol%, i.e., the cationic polymer contains no other structural units than (i), (ii), and (iii).
- Preferably, the second, cationic structural unit of the cationic polymer is derived or made from DADMAS, and more preferably derived or made from diallyl dimethyl ammonium chloride (DADMAC).
- The third, nonionic structural unit may be made from a monomer which is vinylpyrrolidone (VP).
- The Molecular Weight of the cationic polymer ranges from 10,000 to 1,000,000 Daltons, more preferably from 15,000 to 700,000 Daltons, and most preferably from 20,000 to 350,000 Daltons.
- In a particularly preferred aspect, the present invention relates to a liquid laundry detergent composition that comprises:
- (a) from 0.2 wt% to 1 wt% of a cationic polymer having a Molecular Weight of from 20,000 to 350,000 Daltons, said cationic polymer consisting essentially of: (i) from 70 mol% to 90 mol% of a first, nonionic structural unit derived from (meth)acrylamide (AAm); and (ii) from 10 mol% to 30 mol% of a second, cationic structural unit derived from diallyl dimethyl ammonium chloride (DADMAC); and
- (b) from 1 wt% to 99 wt% of a surfactant system comprising: (i) from 60% to 100%, by total weight of said surfactant system, of a C10-C20 linear or branched alkylalkoxy sulfate (AES) having an average degree of alkoxylation ranging from 0.1 to 5; (ii) from 0% to 40%, by total weight of said surfactant system, of a C10-C20 linear alkyl benzene sulphonate (LAS); and (iii) from 0% to 40%, by total weight of said surfactant system, of a C8-C18 alkyl alkoxylated alcohol having an average degree of alkoxylation from 1 to 20 (NI).
- In another preferred aspect, the present invention relates to a liquid laundry detergent composition, containing:
- (a) from 0.2 wt% to 1wt% of a cationic polymer, which has a Molecular Weight of from 20,000 to 350,000 Daltons, said cationic polymer consisting essentially of: (i) from 65 mol% to 90 mol% of a first, nonionic structural unit derived from (meth)acrylamide (AAm); (ii) from 10 mol% to 20 mol% of a second, cationic structural unit derived from diallyl dimethyl ammonium chloride (DADMAC); and (iii) from 1 mol% to 20 mol% of a third, nonionic structural unit derived from vinylpyrrolidone (VP); and
- (b) from 1 wt% to 99 wt% of a surfactant system comprising: (i) from 60% to 100%, by total weight of said surfactant system, of a C10-C20 linear or branched alkylalkoxy sulfate (AES) having an average degree of alkoxylation ranging from 0.1 to 5; (ii) from 0% to 40%, by total weight of said surfactant system, of a C10-C20 linear alkyl benzene sulphonate (LAS); and (iii) from 0% to 40%, by total weight of said surfactant system, of a C8-C18 alkyl alkoxylated alcohol having an average degree of alkoxylation from 1 to 20 (NI).
- These and other features of the present invention will become apparent to one skilled in the art upon review of the following detailed description when taken in conjunction with the appended claims.
- As used herein, "suds" indicates a non-equilibrium dispersion of gas bubbles in a relatively smaller volume of a liquid. The terms like "suds", "foam" and "lather" can be used interchangeably within the meaning of the present invention.
- As used herein, "sudsing profile" refers to the properties of a detergent composition relating to suds character during the wash and rinse cycles. The sudsing profile of a detergent composition includes, but is not limited to, the speed of suds generation upon dissolution in the laundering liquor, the volume and retention of suds in the wash cycle, and the volume and disappearance of suds in the rinse cycle. Preferably, the sudsing profile includes the Wash Suds Index and Rinse Suds Index, as specifically defined by the testing methods disclosed hereinafter in the examples. It may further include additional suds-related parameters, such as suds stability measured during the washing cycle and the like.
- As used herein, the term "cleaning composition" means a liquid or solid composition for treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, and includes hard surface cleaning and/or treatment including floor and bathroom cleaners (e.g., toilet bowl cleaners); hand dishwashing agents or light duty dishwashing agents, especially those of the high-foaming type; machine dishwashing agents; personal care compositions; pet care compositions; automotive care compositions; and household care compositions. In one embodiment, the cleaning composition of the present invention is a hard surface cleaning composition, preferably wherein the hard surface cleaning composition impregnates a nonwoven substrate.
- As used herein, the term "laundry detergent composition" is a subset of "cleaning composition", and includes a liquid or solid composition, and includes, unless otherwise indicated, granular or powder-form all-purpose or "heavy-duty" washing agents for fabric, especially cleaning detergents as well as cleaning auxiliaries such as bleach, rinse aids, additives or pre-treat types. In one embodiment, the laundry detergent composition is a solid laundry detergent composition, and preferably a free-flowing particulate laundry detergent composition (i.e., a granular detergent product).
- As used herein, "charge density" refers to the net charge density of the polymer itself and may be different from the monomer feedstock. Charge density for a homopolymer may be calculated by dividing the number of net charges per repeating (structural) unit by the molecular weight of the repeating unit. The positive charges may be located on the backbone of the polymers and/or the side chains of polymers. For some polymers, such as those with amine structural units, the charge density depends on the pH of the carrier. For these polymers, charge density is calculated based on the charge of the monomer at pH of 7. Typically, the charge is determined with respect to the polymerized structural unit, not necessarily the parent monomer.
- As used herein, the term "Cationic Charge Density" (CCD) means the amount of net positive charge present per gram of the polymer. Cationic charge density (in units of milliequivalents of charge per gram of polymer) may be calculated according to the following equation:
- As used herein, the term "Molecular Weight" refers to the weight average molecular weight of the polymer chains in a polymer composition. Further, the "weight average molecular weight" ("Mw") may be calculated using the equation:
- As used herein "mol%" refers to the relative molar percentage of a particular monomeric structural unit in a polymer. It is understood that within the meaning of the present invention, the relative molar percentages of all monomeric structural units that are present in the cationic polymer shall add up to 100 mol%.
- As used herein, the term "derived from" refers to monomeric structural unit in a polymer that can be made from a compound, or salts or acids thereof, or any derivative of such compound, i.e., with one or more substituents. Preferably, such structural unit is made directly from the compound in issue. For example, the term "structural unit derived from (meth)acrylamide" refers to monomeric structural unit in a polymer that can be made from (meth)acrylamide, or salts or acids thereof, or any derivative thereof with one or more substituents. Preferably, such structural unit is made directly from (meth)acrylamide. The term "(meth)acrylamide" refers to either methacrylamide or acrylamide, and it is abbreviated herein as "AAm."
- The term "ammonium salt" or "ammonium salts" as used herein refers to various compounds selected from the group consisting of ammonium chloride, ammonium fluoride, ammonium bromide, ammonium iodine, ammonium bisulfate, ammonium alkyl sulfate, ammonium dihydrogen phosphate, ammonium hydrogen alkyl phosphate, ammonium dialkyl phosphate, and the like. For example, the diallyl dimethyl ammonium salts as described herein include, but are not limited to: diallyl dimethyl ammonium chloride (DADMAC), diallyl dimethyl ammonium fluoride, diallyl dimethyl ammonium bromide, diallyl dimethyl ammonium iodine, diallyl dimethyl ammonium bisulfate, diallyl dimethyl ammonium alkyl sulfate, diallyl dimethyl ammonium dihydrogen phosphate, diallyl dimethyl ammonium hydrogen alkyl phosphate, diallyl dimethyl ammonium dialkyl phosphate, and combinations thereof. Preferably but not necessarily, the ammonium salt is ammonium chloride.
- As used herein, articles such as "a" and "an" when used in a claim, are understood to mean one or more of what is claimed or described.
- As used herein, the terms "comprising," "comprises," "include", "includes" and "including" are meant to be non-limiting. The term "consisting of' or "consisting essentially of' are meant to be limiting, i.e., excluding any components or ingredients that are not specifically listed except when they are present as impurities. The term "substantially free of' as used herein refers to either the complete absence of an ingredient or a minimal amount thereof merely as impurity or unintended byproduct of another ingredient.
- As used herein, the term "solid" includes granular, powder, bar and tablet product forms.
- As used herein, the term "fluid" includes liquid, gel, paste and gas product forms.
- As used herein, the term "liquid" refers to a fluid having a liquid having a viscosity of from 1 to 2000 mPa*s at 25°C and a shear rate of 20 sec-1. In some embodiments, the viscosity of the liquid may be in the range of from 200 to 1000 mPa*s at 25°C at a shear rate of 20 sec-1. In some embodiments, the viscosity of the liquid may be in the range of from 200 to 500 mPa*s at 25°C at a shear rate of 20 sec-1.
- All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. Unless otherwise specified, all measurements herein are conducted at 20°C and under the atmospheric pressure.
- In all embodiments of the present invention, all percentages are by weight of the total composition, unless specifically stated otherwise. All ratios are weight ratios, unless specifically stated otherwise. The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."
- It is understood that the test methods that are disclosed in the Test Methods Section of the present application must be used to determine the respective values of the parameters of Applicants' inventions are described and claimed herein.
- The cationic polymer used in the present invention is a copolymer that consists of at least two types of structural units. The structural units, or monomers, can be incorporated in the cationic polymer in a random format or can be in a blocky format.
- In a particularly preferred embodiment of the present invention, such cationic polymer is a copolymer that contains only the first and second structural units as described hereinabove, i.e., it is substantially free of any other structural components, either in the polymeric backbone or in the side chains. In another preferred embodiment of the present invention, such cationic polymer is a terpolymer that contains only the first, second and third structural units as described hereinabove, substantially free of any other structural components. Alternatively, it can include one or more additional structural units besides the first, second and third structural units described hereinabove.
- The first structural unit in the cationic polymer of the present invention is a nonionic structural unit derived from (meth)acrylamide (AAm). Preferably, the cationic polymer contains from 60 mol% to 95 mol% of the AAm-derived structural unit.
- The second structural unit in the cationic polymer is a cationic structural unit that can be derived from any suitable water-soluble cationic ethylenically unsaturated monomer, such as, for example, N,N-dialkylaminoalkyl methacrylate, N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl acrylamide, N,N-dialkylaminoalkylmethacrylamide, methacylamidoalkyl trialkylammonium salts, acrylamidoalkylltrialkylamminium salts, vinylamine, vinyl imidazole, quaternized vinyl imidazole and diallyl dialkyl ammonium salts.
- Preferably, the second, cationic structural unit is derived from a monomer selected from the group consisting of diallyl dimethyl ammonium salts (DADMAS), N,N-dimethyl aminoethyl acrylate, N,N-dimethyl aminoethyl methacrylate (DMAM), [2-(methacryloylamino)ethyl]trimethylammonium salts, N,N-dimethylaminopropyl acrylamide (DMAPA), N,N-dimethylaminopropyl methacrylamide (DMAPMA), acrylamidopropyl trimethyl ammonium salts (APTAS), methacrylamidopropyl trimethylammonium salts (MAPTAS), and quaternized vinylimidazole (QVi).
- More preferably, the second, cationic structural unit is derived from a diallyl dimethyl ammonium salt (DADMAS), as described hereinabove.
- Alternatively, the second, cationic structural unit can be derived from a [2-(methacryloylamino)ethyl]tri-methylammonium salt, such as, for example, [2-(methacryloylamino)ethyl]tri-methylammonium chloride, [2-(methacryloylamino)ethyl]trimethylammonium fluoride, [2-(methacryloylamino)ethyl]tri-methylammonium bromide, [2-(methacryloylamino)ethyl]tri-methylammonium iodine, [2 -(methacryloylamino)ethyl]trimethylammonium bisulfate, [2-(methacryloylamino)ethyl]tri-methylammonium alkyl sulfate, [2-(methacryloylamino)ethyl]tri-methylammonium dihydrogen phosphate, [2-(methacryloylamino)ethyl]tri-methylammonium hydrogen alkyl phosphate, [2-(methacryloylamino)ethyl]tri-methylammonium dialkyl phosphate, and combinations thereof.
- Further, the second, cationic structural unit can be derived from APTAS, which include, for example, acrylamidopropyl trimethyl ammonium chloride (APTAC), acrylamidopropyl trimethyl ammonium fluoride, acrylamidopropyl trimethyl ammonium bromide, acrylamidopropyl trimethyl ammonium iodine, acrylamidopropyl trimethyl ammonium bisulfate, acrylamidopropyl trimethyl ammonium alkyl sulfate, acrylamidopropyl trimethyl ammonium dihydrogen phosphate, acrylamidopropyl trimethyl ammonium hydrogen alkyl phosphate, acrylamidopropyl trimethyl ammonium dialkyl phosphate, and combinations thereof.
- Still further, the second, cationic structural unit can be derived from a MAPTAS, which includes, for example, methacrylamidopropyl trimethylammonium chloride (MAPTAC), methacrylamidopropyl trimethylammonium fluoride, methacrylamidopropyl trimethylammonium bromide, methacrylamidopropyl trimethylammonium iodine, methacrylamidopropyl trimethylammonium bisulfate, methacrylamidopropyl trimethylammonium alkyl sulfate, methacrylamidopropyl trimethylammonium dihydrogen phosphate, methacrylamidopropyl trimethylammonium hydrogen alkyl phosphate, methacrylamidopropyl trimethylammonium dialkyl phosphate, and combinations thereof.
- More preferably, the second, cationic structural unit is derived from DADMAC, MAPTAC, APTAC, or QVi. Most preferably, the second, cationic structural unit as mentioned herein is made directly from DADMAC.
- The second, cationic structural unit is preferably present in the cationic polymer in an amount ranging from 5 mol% to 40 mol%.
- The third structural unit, which is optional for the cationic polymer of the present invention, is a nonionic structural unit that is different from the first, nonionic structure unit. It may be derived from a vinyl-based nonionic monomer, such as vinylpyrrolidone (VP), vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ether, vinyl pyridine, vinyl imidazole, vinyl caprolactam, and combinations thereof. More preferably, the third, nonionic structural unit of the cationic polymer is derived from VP. The cationic polymer may contain from 0 mol% to 25 mol% of the third, nonionic structural unit.
- In a specific embodiment of the present invention, the cationic polymer does not contain any of the third, nonionic structural unit (i.e., the third, nonionic structural unit is present at 0 mol%) and consists essentially only of the first and second structural units as described hereinabove. Such cationic polymer is a copolymer consisting essentially of: (i) from 70 mol% to 90 mol%, of the AAm-derived first structural unit; and (ii) from 10 mol% to 30 mol%, of the second, cationic structural unit as described hereinabove.
- In another specific embodiment of the present invention, the cationic polymer contains the first, second and third structural units as described hereinabove, and is substantially free of any other structural unit. Such cationic polymer is a terpolymer consisting essentially of: (i) from 65 mol% to 90 mol% of the AAm-derived first structural unit; (ii) from 10 mol% to 20 mol%, of the second, cationic structural unit as described hereinabove; and (iii) f from 1 mol% to 20 mol%, of the third, nonionic structural unit as described hereinabove.
- The specific molar percentage ranges of the first, second, and optionally third structural units of the cationic polymer as specified hereinabove is critical for optimizing the sudsing profile generated by the laundry detergent compositions containing such cationic polymer during the wash and rinse cycles.
- Laundry detergent compositions containing the cationic polymer of the present invention are characterized by an optimized sudsing profile defined by: (1) a Wash Suds Index (WSI) of more than 70%, preferably more than 80%, and more preferably more than 100%; and (2) a Rinse Suds Index (RSI) of less than 40%, preferably less than 30%, and more preferably less than 20%, as determined by the Sudsing Profile Test described hereinafter. Specifically, the laundry detergent composition of the present invention has an optimal sudsing profile that is defined by a WSI of more than 70% and a RSI of less than 40%, preferably a WSI of more than 80% and RSI of less than 30%, and more preferably a WSI of more than 100% and a RSI of less than 20%.
- The specific Molecular Weight range for the cationic polymer as specified hereinabove also provides improved sudsing profile. More importantly, such Molecular Weight range is particularly effective in reducing the whiteness loss that is commonly seen in fabrics after they have been exposed to multiple washes. Cationic polymers have been known to contribute to fabric whiteness loss, which is a limiting factor for wider usage of such polymers. However, inventors of the present invention have discovered that by controlling the Molecular Weight of the cationic polymer within a specific range, i.e., from 10,000 to 1,000,000 Daltons, and preferably from 15,000 to 700,000 Daltons, and most preferably from 20,000 to 350,000 Daltons, the fabric whiteness loss can be effectively reduced in comparison with conventional cationic polymers.
- Preferably, laundry detergent compositions containing the cationic polymer of the present invention are characterized by a Relative Whiteness Loss Percentage (WLP) of not more than 100%, preferably not more than 50%, and more preferably not more than 10%, as determined by the Whiteness Loss Test described hereinafter.
- It is noted that cationic polymers containing the above-described first, second, and optionally third structural units in various combinations have been previously used in laundry detergent compositions, typically as deposition aid polymers. However, the conventional cationic polymers used as deposition aids in laundry detergents have different monomeric ratios and/or significantly higher Molecular Weights from the cationic polymers of this invention. The inventors of the present invention have discovered, surprisingly and unexpectedly, that cationic polymers with the specific monomeric make-up and the specific Molecular Weight as defined hereinabove can provide superior sudsing profile and reduced fabric whiteness loss, in comparison with the conventional cationic polymers. Further, there seem to be absent of any terpolymer containing or consisting of all three structural units.
- Further, product viscosity can be impacted by Molecular Weight and cationic content of the cationic polymer. Molecular weights of polymers of the present invention are also selected to minimize impact on product viscosity to avoid product instability and stringiness associated with high molecular weight and/or broad molecular weight distribution.
- The amount of the cationic polymer of the present invention in the laundry detergent or cleaning composition is not particularly limited, as long as it is effective for providing an optimal sudsing profile as defined herein above, i.e., with significant suds volume reduction during the rinse cycle and insignificant suds volume reduction during the wash cycle. Preferably but not necessarily, the cationic polymer is provided in the cleaning or laundry detergent composition at an amount ranging from 0.01 wt% to 15 wt%, from 0.05 wt% to 10 wt%, from 0.1 wt% to 5 wt%, and from 0.2 wt% to 1wt%. Further, it is preferred, although not necessary, that the cationic polymer is substantially free of carrier particles or coating. This is advantageous as it avoids an extra step and cost associated with the incorporation of these materials.
- Cleaning compositions or laundry detergent compositions of the present invention includes a unique surfactant system that is enriched with an anionic surfactant that is selected from the group consisting of C10-C20 linear or branched alkylalkoxy sulfates (AES) having an average degree of alkoxylation ranging from 0.1 to 5. The term "enriched" as used herein refers to the relatively higher weight ratio of the AES surfactant(s) over other surfactants, i.e., the AES surfactant(s) is present in the surfactant system in an amount that is equal to or greater than any other detersive surfactant contained by the surfactant system. Without being bound by any theory, it is believed that such an AES-enriched surfactant system is particularly effective in optimizing the sudsing benefit of the cationic polymers of the present invention.
- The AES surfactants preferably are C10-C20 linear or branched alkylethoxy sulfates. More preferably, the AES surfactants have an average degree of alkoxylation ranging from 0.3 to 4, and most preferably from 0.5 to 3. The AES surfactants is provided at levels ranging from 20% or more (i.e., from 20% to 100%), more preferably at 40% or more (i.e., from 40% to 100%), still more preferably at 50% or more (i.e., from 50% to 100%), and most preferably at 60% or more (i.e., from 60% to 100%), by total weight of the surfactant system.
- The surfactant system of the present invention may contain, in addition to the AES surfactants, one or more other detersive surfactants selected from the group consisting of anionic, nonionic, zwitterionic, amphoteric or cationic type or can comprise compatible mixtures of these types.
- Useful other anionic surfactants can themselves be of several different types. For example, water-soluble salts of the higher fatty acids, i.e., "soaps", are useful other anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkyl ammonium salts of higher fatty acids containing from 8 to 24 carbon atoms, and preferably from 12 to 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
- Additional non-soap other anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group (included in the term "alkyl" is the alkyl portion of acyl groups) containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. Examples of this group of synthetic anionic surfactants include, but are not limited to: a) the sodium, potassium and ammonium alkyl sulfates with either linear or branched carbon chains, especially those obtained by sulfating the higher alcohols (C10-C20 carbon atoms), such as those produced by reducing the glycerides of tallow or coconut oil; b) the sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from 10 to 20 carbon atoms in either a linear or a branched carbon chain configuration, preferably a linear carbon chain configuration; c) the sodium, potassium and ammonium alkyl sulphonates in which the alkyl group contains from 10 to 20 carbon atoms in either a linear or a branched configuration; d) the sodium, potassium and ammonium alkyl phosphates or phosphonates in which the alkyl group contains from 10 to 20 carbon atoms in either a linear or a branched configuration, e) the sodium, potassium and ammonium alkyl carboxylates in which the alkyl group contains from 10 to 20 carbon atoms in either a linear or a branched configuration, and combinations thereof.
- Preferred for the practice of the present invention are surfactant systems that contain one or more C10-C20 linear alkyl benzene sulphonates (LAS) in addition to the AES surfactants described hereinabove. The LAS is present in an amount ranging from 1% to 45%, more preferably from 5% to 40%, and most preferably from 10% to 35%, by total weight of the surfactant system. The weight ratio of AES to LAS is equal to or greater than 1.2, more preferably equal to or greater than 1.5, still more preferably equal to or greater than 2, and most preferably equal to or greater than 5.
- For the practice of the present invention, the surfactant system contains one or more nonionic surfactants in addition to the AES surfactants described hereinabove. Suitable nonionic surfactants are those of the formula R1(OC2H4)nOH, wherein R1 is a C8-C18 alkyl group or alkyl phenyl group, and n is from 1 to 20. Suitable nonionic surfactants are C8-C18 alkyl alkoxylated alcohols (NI) having an average degree of alkoxylation from 1 to 20. The NI can be present in an amount ranging from 1% to 45%, more preferably from 5% to 40%, and most preferably from 10% to 35%, by total weight of the surfactant system. The weight ratio of AES to NI is equal to or greater than 1.2, more preferably equal to or greater than 1.5, still more preferably equal to or greater than 2, and most preferably equal to or greater than 5.
- The surfactant system contains both LAS and NI in addition to AES. The weight ratio between LAS and NI may range from 1:20 to 20:1, preferably from 1:15 to 15:1, more preferably from 1:10 to 10:1, and most preferably from 1:5 to 5:1. A surfactant system that is particularly preferred for the practice of the present invention is one that comprising or consisting essentially of AES, LAS and NI at weight ratios ranging from 9:0.5:0.5 to 5:4:1 to 5:0.1:5.
- Other surfactants useful for incorporating into the surfactant system of the present invention include amphoteric surfactants and/or cationic surfactants. Particularly preferred amphoteric surfactants are amine oxides, such as, for example, alkyl dimethyl amine oxide or alkyl amido propyl dimethyl amine oxide, more preferably alkyl dimethyl amine oxide and especially coco dimethyl amino oxide. Amine oxides may contain a linear or branched alkyl moiety. Such amphoteric and/or cationic surfactants are well known for use in laundry detergents and are typically present at levels from 0.2% or 1% to 40% or 50%, by total weight of the surfactant system.
- The surfactant system may be present in an amount ranging from 1% to 99%, more preferably from 1% to 80%, and more preferably from 5% to 50% by total weight of the cleaning or detergent compositions of the present invention.
- The present invention provides a cleaning composition comprising the cationic polymer and the surfactant system as mentioned hereinabove. The cleaning composition is suitable for laundry detergent application, for example: laundry, including automatic washing machine laundering or hand-washing, or cleaning auxiliaries, such as for example, bleach, rinse aids, additives or pre-treat types.
- The laundry detergent composition is a liquid laundry detergent and can be a fully formulated laundry detergent product. Liquid compositions contained in encapsulated and/or unitized dose products are included, as are compositions which comprise two or more separate but jointly dispensable portions. More preferably, the laundry detergent composition is a liquid laundry detergent composition designed for hand-washing, where the improved suds benefit or superior sudsing profile is most evident to the consumer. The liquid laundry detergent composition preferably contains water as an aqueous carrier, and it can contain either water alone or mixtures of organic solvent(s) with water as carrier(s). Suitable organic solvents are linear or branched lower C1-C8 alcohols, diols, glycerols or glycols; lower amine solvents such as C1-C4 alkanolamines, and mixtures thereof. Exemplary organic solvents include 1,2-propanediol, ethanol, glycerol, monoethanolamine and triethanolamine. The carriers are typically present in a liquid composition at levels in the range of from 0.1% to 98%, preferably from 10% to 95%, more preferably from 25% to 75% by total weight of the liquid composition. In some embodiments, water is from 85 to 100 wt% of the carrier. In other embodiments, water is absent and the composition is anhydrous. Highly preferred compositions afforded by the present invention are clear, isotropic liquids.
- The liquid laundry detergent composition of the present invention has a viscosity from 1 to 2000 centipoise (1-2000 mPa·s), or from 200 to 800 centipoises (200-800 mPa·s). The viscosity can be determined using a Brookfield viscometer, No. 2 spindle, at 60 RPM/s, measured at 25°C.
- In a specific embodiment of the present invention, a silicone-derived anti-foaming agent is used in combination with the cationic polymer and the surfactant system in a cleaning composition, or preferably a laundry detergent composition. Although not necessary for carrying out the present invention, such silicone-derived anti-foaming agent may further improve the sudsing profile of the cleaning composition.
- The silicone-derived anti-foaming agent can be any suitable organosilicones, including, but not limited to: (a) non-functionalized silicones such as polydimethylsiloxane (PDMS); and (b) functionalized silicones such as silicones with one or more functional groups selected from the group consisting of amino, amido, alkoxy, alkyl, phenyl, polyether, acrylate, siliconehydride, mercaptoproyl, carboxylate, sulfate phosphate, quaternized nitrogen, and combinations thereof. In typical embodiments, the organosilicones suitable for use herein have a viscosity ranging from 10 to 700,000 CSt (centistokes) at 20°C. In other embodiments, the suitable organosilicones have a viscosity from 10 to 100,000 CSt.
- Polydimethylsiloxanes (PDMS) can be linear, branched, cyclic, grafted or cross-linked or cyclic structures. In some embodiments, the detergent compositions comprise PDMS having a viscosity of from 100 to 700,000 CSt at 20°C. Exemplary functionalized silicones include but are not limited to aminosilicones, amidosilicones, silicone polyethers, alkylsilicones, phenyl silicones and quaternary silicones. A preferred class of functionalized silicones comprises cationic silicones produced by reacting a diamine with an epoxide. One embodiment of the composition of the present invention contains organosilicone emulsions, which comprise organosilicones dispersed in a suitable carrier (typically water) in the presence of an emulsifier (typically an anionic surfactant). In another embodiment, the organosilicones are in the form of microemulsions having an average particle size in the range from 1 nm to 150 nm, or from 10 nm to 100 nm, or from 20 nm to 50 nm.
- The silicone-derived anti-foaming agent as mentioned hereinabove can be present in the cleaning composition in an amount ranging from 0.01% to 5%, preferably from 0.05% to 2%, and more preferably from 0.1 % to 1 %, by total weight of the composition.
- In yet another preferred embodiment of the present invention, the liquid laundry detergent composition contains from 0.1 wt% to 5 wt%, preferably from 0.5 wt% to 3 wt%, more preferably from 1 wt% to 1.5 wt%, of one or more fatty acids and/or alkali salts thereof. Suitable fatty acids and/or salts that can be used in the present invention include C10-C22 fatty acids or alkali salts thereof. Such alkali salts include monovalent or divalent alkali metal salts like sodium, potassium, lithium and/or magnesium salts as well as the ammonium and/or alkylammonium salts of fatty acids, preferably the sodium salt. Preferred fatty acids for use herein contain from 12 to 20 carbon atoms, and more preferably 12 to 18 carbon atoms. Exemplary fatty acids that can be used maybe selected from caprylic acid, capric acid, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, sapienic acid, stearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, α-linoelaidic acid, arachidic acid, arachidonic acid, eicosapentaenoic acid, behenic acid, erucic acid, and docosahexaenoic acid, and mixtures thereof. Further, it is preferred that the liquid detergent composition of the present invention comprises one or more saturated fatty acids, such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and mixtures thereof. Among the above-listed saturated fatty acids, lauric acid, myristic acid and palmitic acid are particularly preferred.
- The balance of the laundry detergent typically contains from 5 wt% to 70 wt%, or 10 wt% to 60 wt% adjunct ingredients. Suitable detergent ingredients include: transition metal catalysts; imine bleach boosters; enzymes such as amylases, carbohydrases, cellulases, laccases, lipases, bleaching enzymes such as oxidases and peroxidases, proteases, pectate lyases and mannanases; source of peroxygen such as percarbonate salts and/or perborate salts, preferred is sodium percarbonate, the source of peroxygen is preferably at least partially coated, preferably completely coated, by a coating ingredient such as a carbonate salt, a sulphate salt, a silicate salt, borosilicate, or mixtures, including mixed salts, thereof; bleach activator such as tetraacetyl ethylene diamine, oxybenzene sulphonate bleach activators such as nonanoyl oxybenzene sulphonate, caprolactam bleach activators, imide bleach activators such as N-nonanoyl-N-methyl acetamide, preformed peracids such as N,N-pthaloylamino peroxycaproic acid, nonylamido peroxyadipic acid or dibenzoyl peroxide; suds suppressing systems such as silicone based suds suppressors; brighteners; hueing agents; photobleach; fabric-softening agents such as clay, silicone and/or quaternary ammonium compounds; flocculants such as polyethylene oxide; dye transfer inhibitors such as polyvinylpyrrolidone, poly 4-vinylpyridine N-oxide and/or co-polymer of vinylpyrrolidone and vinylimidazole; fabric integrity components such as oligomers produced by the condensation of imidazole and epichlorhydrin; soil dispersants and soil anti-redeposition aids such as alkoxylated polyamines and ethoxylated ethyleneimine polymers; anti-redeposition components such as polyesters and/or terephthalate polymers, polyethylene glycol including polyethylene glycol substituted with vinyl alcohol and/or vinyl acetate pendant groups; perfumes such as perfume microcapsules, polymer assisted perfume delivery systems including Schiff base perfume/polymer complexes, starch encapsulated perfume accords; soap rings; aesthetic particles including coloured noodles and/or needles; dyes; fillers such as sodium sulphate, although it may be preferred for the composition to be substantially free of fillers; carbonate salt including sodium carbonate and/or sodium bicarbonate; silicate salt such as sodium silicate, including 1.6R and 2.0R sodium silicate, or sodium metasilicate; co-polyesters of di-carboxylic acids and diols; cellulosic polymers such as methyl cellulose, carboxymethyl cellulose, hydroxyethoxycellulose, or other alkyl or alkylalkoxy cellulose, and hydrophobically modified cellulose; carboxylic acid and/or salts thereof, including citric acid and/or sodium citrate; and any combination thereof.
- It may also be especially preferred for the laundry detergent powder to comprise low levels, or even be essentially free, of builder. The term "essentially free" means that the composition "comprises no deliberately added" amount of that ingredient. In a preferred embodiment, the laundry detergent composition of the present invention comprises no builder.
- Incorporation of the cationic polymer and various other ingredients as described hereinabove into cleaning or laundry detergent compositions of the invention can be done in any suitable manner and can, in general, involve any order of mixing or addition.
- For example, the cationic polymer as received from the manufacturer can be introduced directly into a preformed mixture of two or more of the other components of the final composition. This can be done at any point in the process of preparing the final composition, including at the very end of the formulating process. That is, the cationic polymer can be added to a pre-made liquid laundry detergent to form the final composition of the present invention.
- In another example, the cationic polymer can be premixed with an emulsifier, a dispersing agent or a suspension agent to form an emulsion, a latex, a dispersion, a suspension, and the like, which is then mixed with other components (such as the AES, LAS, NI, and/or silicone-derived anti-foaming agent, etc.) of the final composition. These components can be added in any order and at any point in the process of preparing the final composition.
- A third example involves mixing the cationic polymer with one or more adjuncts of the final composition and adding this premix to a mixture of the remaining adjuncts.
- The present invention is directed to a method of cleaning fabric, the method comprising the steps of: (i) providing a laundry detergent as described above; (ii) forming a laundry liquor by diluting the laundry detergent with water; (iii) washing fabric in the laundry liquor; and (iv) rinsing the fabric in water, wherein after 2 or less rinses, preferably after 1 rinse, the laundry liquor is substantially free of suds, or at least 75%, preferably at least 85%, more preferably 95%, and even more preferably at least 99% of a surface area of the laundry liquor is free from suds.
- The present invention is also directed to a method of saving water during laundering, the method comprising the steps of: (i) providing a laundry detergent as described above; (ii) diluting the cleaning composition with wash water in a container to form a laundry liquor; (iii) washing laundry in the laundry liquor; and (iv) rinsing the laundry, wherein after 2 or less rinses, preferably after 1 rinse, the laundry liquor is substantially free of suds.
- The method of laundering fabric may be carried out in a top-loading or front-loading automatic washing machine, or can be used in a hand-wash laundry application, which is particularly preferred in the present invention.
- Various techniques are known in the art to determine the properties of the compositions of the present invention comprising the cationic polymer. However, the following assays must be used in order that the invention described and claimed herein may be fully understood.
- The weight-average molecular weight (Mw or "Molecular Weight") of a polymer material of the present invention is determined by Size Exclusion Chromatography (SEC) with differential refractive index detection (RI). One suitable instrument is Agilent® GPC-MDS System using Agilent® GPC/SEC software, Version 1.2 (Agilent, Santa Clara, USA). SEC separation is carried out using three hydrophilic hydroxylation polymethyl methacrylate gel columns (Ultrahydrogel 2000-250-120 manufactured by Waters, Milford, USA) directly joined to each other in a linear series and a solution of 0.1M sodium chloride and 0.3% trifluoroacetic acid in DI-water, which is filtered through 0.22 µm pore size GVWP membrane filter (MILLIPORE, Massachusetts, USA). The RI detector needs to be kept at a constant temperature of 5 -10°C above the ambient temperature to avoid baseline drift. It is set to 35°C. The injection volume for the SEC is 100 µL. Flow rate is set to 0.8 mL/min. Calculations and calibrations for the test polymer measurements are conducted against a set of 10 narrowly distributed Poly(2-vinylpyridin) standards from Polymer Standard Service (PSS, Mainz Germany) with peak molecular weights of: Mp=1110 g/mol; Mp=3140 g/mol; Mp=4810 g/mol; Mp=11.5k g/mol; Mp=22k g/mol; Mp=42.8k g/mol; Mp=118k g/mol; Mp=256k g/mol; Mp=446k g/mol; and Mp=1060k g/mol.
- Each test sample is prepared by dissolving the concentrated polymer solution into the above-described solution of 0.1M sodium chloride and 0.3% trifluoroacetic acid in DI water, to yield a test sample having a polymer concentration of 1 to 2 mg/mL. The sample solution is allowed to stand for 12 hours to fully dissolve, and then stirred well and filtered through a 0.45 µm pore size nylon membrane (manufactured by WHATMAN, UK) into an auto sampler vial using a 5mL syringe. Samples of the polymer standards are prepared in a similar manner. Two sample solutions are prepared for each test polymer. Each solution is measured once. The two measurement results are averaged to calculate the Mw of the test polymer.
- For each measurement, the solution of 0.1M sodium chloride and 0.3% trifluoroacetic acid in DI water is first injected onto the column as the background. A correction sample (a solution of 1 mg/mL polyethylene oxide with Mp=111.3k g/mol) is analysed six times prior to other sample measurements, so as to verify repeatability and accuracy of the system.
- The weight-average molecular weight (Mw or "Molecular Weight") of the test sample polymer is calculated using the software that accompanies the instrument and selecting the menu options appropriate for narrow standard calibration modelling. A third-order polynomial curve is used to fit the calibration curve to the data points measured from the Poly(2-vinylpyridin) standards. The data regions used for calculating the weight-average molecular weight are selected based upon the strength of the signals detected by the RI detector. Data regions where the RI signals are greater than 3 times the respective baseline noise levels are selected and included in the Mw calculations. All other data regions are discarded and excluded from the Mw calculations. For those regions which fall outside of the calibration range, the calibration curve is extrapolated for the Mw calculation.
- To measure the average molecular weight of a test sample containing a mixture of polymers of different molecular weights, the selected data region is cut into a number of equally spaced slices. The height or Y-value of each slice from the selected region represents the abundance (Ni) of a specific polymer (i), and the X-value of each slice from the selected region represents the molecular weight (Mi) of the specific polymer (i). The weight average molecular weight (Mw or "Molecular Weight") of the test sample is then calculated based on the equation described hereinabove, i.e., Mw = (∑i Ni Mi2) / (∑i Ni Mi).
- Each of the monomers in the cationic polymer is quantified by high pressure liquid chromatography (HPLC) according to the follows:
Measuring device: L-7000 series (Hitachi Ltd.) Detector: UV detector, L-7400 (Hitachi Ltd.) Column: SHODEX RSpak DE-413 (product of Showa Denko K. K.) Temperature: 40°C Eluent: 0.1% phosphoric acid aqueous solution Flow Velocity: 1.0 mL/ min - The sudsing profile of the detergent composition herein are measured by employing a suds cylinder tester (SCT). The SCT has a set of 8 cylinders. Each cylinder is typically 60 cm long and 9 cm in diameter and may be together rotated at a rate of 20-22 revolutions per minute (rpm). This method is used to assay the performance of laundry detergent to obtain a reading on ability to generate suds as well as its suds stability and rinse suds performance. The following factors affect results and therefore should be controlled properly: (a) concentration of detergent in solution, (b) water hardness, (c) water temperature of water, (d) speed and number of revolutions, (e) soil load in the solution, and (f) cleanliness of the inner part of the tubes.
- The performance is determined by comparing the suds height generated during the washing stage by the laundry detergent containing the cationic polymer of the present invention or a comparative cationic polymer not falling within the scope of the present invention, versus control laundry detergent that does not contain any cationic polymer. The height of suds generated by each test composition is measured by recording the total suds height (i.e., height of suds plus wash liquor) minus the height of the wash liquor alone.
1. Weigh 1.5 grams of product and dissolve it in 300ml of water with a water hardness of 16gpg for at least 15 min to form a solution containing the test product at 5000ppm. Dissolve the samples simultaneously.
2. Pour the sample aliquot to the tubes. Put in the rubber stopper and lock the tubes in place.
3. Spin for 10 revolutions. Lock in an upright position. Wait 1 min and check the suds height very quickly (∼ 10 sec) left to right. Record the total suds height (i.e., height of the suds plus wash liquor) and the height of the wash liquor alone. This marks the after 10 revolutions data.
4. Spin for additional 20 revolutions. This marks the after 30 revolutions data. Take recordings from left to right.
5. Spin for 20 revolutions more. This marks the after 50 revolutions data. Take readings from left to right. Repeat this step one more time; thus, the data gathered are for after 70 revolutions.
6. Open the tubes. Add 1 piece of fabric with clay and ¼ piece of fabric with dirty cooking oil (DCO) into each tube. Put in the rubber stopper. Spin for 20 revolutions. This marks the after 90 revolutions data. Take readings. Repeat this step one time; thus, the data gathered are for after 110 revolutions.
The addition of the artificial soil is intended to mimic the real world washing conditions where more soils dissolve into the wash liquor from the fabrics being wash. Therefore, this test is relevant for determing the initial sudsing profile of a composition and its sudsing profile in a washing cycle.
(Note: Preparation of fabric with clay is conduted as follows: - Disperse 20g of BJ-clay (clay collected from 15cm below the earth surface in Beijing, China) into 80 ml of DI water via agitation to make a clay suspension.
- Keep agitating the suspension during the preparation process, while brushing 2g of such clay suspension onto the center of a 10cm∗10cm cotton fabric to form a round shape stain (d=5cm).
- The cotton fabric with clay is left dry at room temperature and then used for the performance evaluation.
- 100 grams of peanut oil is used to fry 20 grams of salty fish for 2 hrs at 150-180°C to form the dirty cooking oil (DCO).
- Brush 0.6ml of the DCO onto the center of a 10cm∗10cm cotton fabric to form a round shape stain (d=5cm).
- Cut the 10cm∗10cm cotton fabric into 4 equal pieces and use one for the performance evaluation.)
- Average suds height of different categories described above are calculated by average the height data of each replicate.
- Washing Suds Index (WSI) is calculated by the average suds height generated by the control sample (WSHC) during the wash cycle when suds stability is observed (i.e., 90-110 revolutions) divided by that generated by a test sample (WSHT), i.e., containing either a cationic polymer of the present invention or a comparative cationic polymer not within the scope of the present invention, and then converted into a percentage, as follows:
- The WSI is indicative of how much suds is generated during the wash cycle by a test sample containing a cationic polymer (either an inventive cationic polymer with the specific monomeric composition and Molecular Weight as defined hereinabove, or a comparative cationic polymer not falling within the scope of the present invention) that may have adverse impact on the wash suds, in comparison with the suds generated by a control sample that does not contain any of such cationic polymer. Therefore, the higher the WSI percentage, the more suds are generated during wash, and the better the performance.
-
- The RSI, on the other hand, is indicative of how much suds is left during the rinse cycle by a test sample containing a cationic polymer (either an inventive cationic polymer with the specific monomeric composition and Molecular Weight as defined hereinabove, or a comparative cationic polymer not falling within the scope of the present invention) that may be effective in reducing the rinse suds, in comparison with the suds left by a control sample that does not contain any of such cationic polymer. Therefore, the lower the RSI percentage, the more suds reduction is effectuated during rinse, and the better the performance.
- An optimal sudsing profile as defined within the meaning of this invention includes a WSI of more than 70% and a RSI of less than 40%, preferably a WSI of more than 80% and a RSI of less than 30%, and more preferably a WSI of more than 100% (i.e., a suds boosting effect during wash) and a RSI of less than 20%.
- This test is intended to measure the ability of a laundry detergent to prevent loss in whiteness (i.e., whiteness maintenance) of fabrics. Whiteness maintenance of fabrics is evaluated by image analysis after single or multi-cycle washes. Typically, "whiteness" can be reported by its whiteness index, which is conveniently converted from CIELAB, which is an internationally recognized color scale system developed by CIE ("Commission International de I'Eclairage"). CIE color scale for whiteness is the most commonly used whiteness index and refers to measurements made under D65 illumination, which is the standard representation of outdoor daylight. In technical terms, whiteness is a single number index referencing the relative degree of whiteness (of near-white materials under specific lighting conditions), so the higher the number, the whiter the material. As an example, for a perfect reflecting, non-fluorescent white material, the CIE whiteness index (L*) would be 100.
- The steps for assaying the whiteness maintenance of the laundry detergent of the present invention are as follows:
(1) Formulation preparation: Formulate detergent compositions with or without polymers of interest.
(2) Solution Preparation: - Solution A: Dissolve laundry detergent prepared in step (1) with deionized water (DI water) at the concentration of 7500ppm (Solution A need to be more than 10 ml).
- Solution B: prepared according to the following procedure. Into a 1 L beaker, add 4.829 g CaCl2-2H20 and 1.669 g MgCl2-6H20. Add 800 mL of DI water. Using a stir bar and
- stirring plate, stir the solution until the mixture is dissolved and the solution turns clear. Pour the solution into a 1 L volumetric flask and fill to 1 L line.
- Solution C: Disperse 2.25g of Arizona clay (Nominal 0-3 micron Arizona Test Dust, Powder Technology Inc.) into 50 ml of DI water via agitation, this solution is agitated during the whole test solution preparation process.
- Since WLP is the relative fabric whiteness loss (expressed in percentage) caused by a detergent composition containing a cationic polymer (which is typically known to cause some fabric whiteness loss) over that caused by a control detergent composition not containing such cationic polymer, a larger WLP is indicative of more relative fabric whiteness loss observed in comparison with the control sample. Therefore, it is in turn indicative of poorer whiteness performance of the cationic polymer, i.e., its presence causes more fabric whiteness loss in the laundry detergent. If the WLP is a negative number, it is indicative of the fact that the presence of the cationic polymer not only does not cause fabric whiteness loss, but actually imparts whiteness benefit to the fabric, which is the most desirable.
- The wash and rinse suds volumes of the laundry detergent compositions of the present invention can also be measured via the SITA Foam Tester (model: R-2000) made by SITA Messtechnik GmbH (Germany). The SITA Foam Tester R-2000 utilizes a patented rotor of defined geometry for foam generation. The rotor mechanically inserts air bubbles into the liquid. The foam volume is measured by an array of sensor needles, which scan the foam surface. Using an array of sensor needles permits exact measurement of the foam volume even with uneven foam surfaces. The output is given as average milliliters of foam height per measure. Foam height measurements are recorded every 10 seconds while stirring of the test composition continues - this occurs 15 times in total (i.e., resulting in 15 measurements in total). The Stir Count, as used herein, means the total number of stirring intervals in one test. The instrument settings below are used in the suds volume measurements. The final suds volume for each detergent composition is the average of 6 suds readings from the 10th to 15th measurement.
- This method is used to evaluate the sudsing profile of laundry detergent and obtain a reading on wash suds and rinse suds volume. The following factors affect results and therefore should be controlled properly: (a) concentration of detergent in solution, (b) water hardness, (c) water temperature, (d) soil load in the solution, (e) instrument settings, and (f) cleanliness of the sample vessel of SITA. The performance is determined by comparing the suds volume generated by a laundry detergent containing the cationic polymer versus the laundry detergent without the cationic polymer.
- 1. Weigh 5 grams of the test product and mix it with 320 mg soil blend, which is made by mixing Arizona Clay with the technical body soil (TBS) as described hereinabove in Test 4, Table I. Specifically, the soil blend is made by the following steps:
- a. TBS is pre-heated to the temperature range of 70-90°C.
- b. Add Arizona Clay (available from Powder Technology Inc, with particle size of 0.7-18um) to the pre-heated TBS at 1:2 weight ratio.
- c. The mixture is then manually agitated with a spatula at 60-70°C, until a homogeneous paste is made.
- d. The soil blend is stored in refridgeator for next use and is melted at 60°C before use.
- 2. Dissolve the mixture from step (1) in 1L water with a water hardness of 16 gpg to form a solution containing the test product at 5000 ppm and soil level at 320 ppm.
- 3. Feed 250 ml of the solution into the SITA sample vessel (setting detailed below) to start suds volume measurement at wash solution concentration.
- 4. After 15 consecutive measurements with agitation, withdraw 40 ml solution out of the vessel and mix it with 360 ml water with a water hardness of 16 gpg to make a total of 400 ml 1/10 diluted solution at 500 ppm.
- 5. After the sample vessel is thoroughly cleaned via the automatic program, feed 250 ml of the diluted solution into the SITA unit again to start suds volume measurement for rinse solution concentration.
- 6. Repeat the wash and rinse measurements 5 times to calculate the average results.
- Following is a list of exemplary cationic polymers within the scope of the present invention:
Table II AAm (mol%) DADMAC (mol%) VP (mol%) MW (K Dalton) Calculated. Charge Density meq/g) Polymer 1 87.2 12.8 0 102.7 1.55 Polymer 2* 76 24 0 61.5 2.59 Polymer 3 84.1 15.9 0 350.7 1.86 Polymer 4 84.1 15.9 0 118.8 1.86 Polymer 5 84.1 15.9 0 56.6 1.86 Polymer 6 69 11 20 656.5 1.24 Polymer 7 73 23 4 212.4 2.46 Polymer 8 71 17 12 517.2 1.86 Polymer 9 78 11 11 441.9 1.29 Polymer 10 79.9 16.2 3.9 294.1 1.86 Polymer 11 79.9 16.2 3.9 113.3 1.86 Polymer 12 79.9 16.2 3.9 50.6 1.86 *Merquat™740 from the Lubrizol Corporation (Wickliffe, OH). - Seven (7) test liquid laundry detergent compositions are prepared, including: (1) a control composition containing no cationic polymer, (2) a first inventive composition containing 0.5 wt% of the inventive polymer 3 as described hereinabove in Table II of Example I; (3) a second inventive composition containing 0.5 wt% of the inventive polymer 4 as described hereinabove in Table II of Example I; (4) a third inventive composition containing 0.5 wt% of the inventive polymer 5 as described hereinabove in Table II of Example I; (5) a first inventive composition containing 0.5 wt% of the inventive polymer 11 as described hereinabove in Table II of Example I; (6) a second inventive composition containing 0.5 wt% of the inventive polymer 12 as described hereinabove in Table II of Example I; and (7) a third inventive composition containing 0.5 wt% of the inventive polymer 13 as described hereinabove in Table II of Example I. Following is the detailed compositional breakdown of the control composition and the six inventive compositions:
Table III Ingredients (wt%) (1) Control (2) (3) (4) (5) (6) (7) Inventive Polymer 3 -- 0.5 -- -- -- -- -- Inventive Polymer 4 -- -- 0.5 -- -- -- -- Inventive Polymer 5 -- -- -- 0.5 -- -- -- Inventive Polymer 10 -- -- -- -- 0.5 -- -- Inventive Polymer 11 -- -- -- -- -- 0.5 -- Inventive Polymer 12 -- -- -- -- -- -- 0.5 C24AE3S Paste 8.320 8.320 8.320 8.320 8.320 8.320 8.320 HLAS 5.520 5.520 5.520 5.520 5.520 5.520 5.520 Nonionic 24-7 1.210 1.210 1.210 1.210 1.210 1.210 1.210 Citric Acid 2.000 2.000 2.000 2.000 2.000 2.000 2.000 Fatty acid (DTPK) 1.210 1.210 1.210 1.210 1.210 1.210 1.210 Subtotal Builder 3.210 3.210 3.210 3.210 3.210 3.210 3.210 Boric acid 2.100 2.100 2.100 2.100 2.100 2.100 2.100 DTPA 0.190 0.190 0.190 0.190 0.190 0.190 0.190 FWA-49 0.057 0.057 0.057 0.057 0.057 0.057 0.057 Hexamethylene diamine (ethoxylated, quaternized, sulfated) 70% 0.460 0.460 0.460 0.460 0.460 0.460 0.460 1, 2 propanediol 1.210 1.210 1.210 1.210 1.210 1.210 1.210 NaOH 3.130 3.130 3.130 3.130 3.130 3.130 3.130 Acticide MBS 0.015 0.015 0.015 0.015 0.015 0.015 0.015 Proxel GXL 0.001 0.001 0.001 0.001 0.001 0.001 0.001 Silicone emulsion 0.003 0.003 0.003 0.003 0.003 0.003 0.003 Andromeda 0.600 0.600 0.600 0.600 0.600 0.600 0.600 Liquitint Blue 297 0.002 0.002 0.002 0.002 0.002 0.002 0.002 Water Balance Balance Balance Balance Balance Balance Balance Total: 100.000 100.000 100.000 100.000 100.000 100.000 100.000 - Sudsing Profile Test as described hereinabove is carried out for each of the seven (7) test liquid compositions by dissolving each composition in water having a water hardness level of 16 gpg to form a laundering liquor containing 5000ppm of the test composition. The Wash Suds Index (WSI) and Rinse Suds Index (RSI) of all six (6) inventive compositions are calculated based on the wash suds volume and rinse suds volume measured for these two compositions in comparison with the control composition. Following are the measurement results:
Table IV Control (1) (2) (3) (4) (5) (6) (7) Wash Suds Stability* (cm) 28.24 25.38 23.18 20.98 25.58 23.18 20.20 1/8 Rinse Suds** (cm) 8.18 1.76 2.14 1.45 1.90 1.93 1.43 Wash Suds Index (WSI) -- 90% 82% 74% 91% 82% 72% Rinse Suds Index (RSI) -- 22% 26% 18% 23% 24% 17% * Measured at 90-110 revolutions.
**Measured at 130-150 revolutions. - All six inventive compositions containing inventive cationic polymers of the present invention provide optimized sudsing profiles characterized by a satisfactory wash suds volume (a WSI of more than 70%) and significantly lower rinse suds volume (a RSI of less than 40%) in comparison with the control composition.
- The cationic polymers of the present invention also demonstrate observable sudsing benefit across different detergent dosing levels, i.e., the laundry detergent composition containing such cationic polymers may be added into water at different amounts to form laundering liquor of different detergent concentrations. Because different consumers may have very different dosing habits when it comes to laundry detergents, with some more prone to over-dosing and others more prone to under-dosing, it is an important advantage if the sudsing benefit of the present invention is observable across a wider dosing range, thereby accommodating different consumer dosing habits.
- A control liquid detergent composition containing no cationic polymer and an inventive liquid detergent composition containing 0.5 wt% of the inventive polymer 2 as described hereinabove in Table II of Example I, which contains 76 mol% of AAm and 24 mol% of DADMAC with a Molecular Weight of 61.5K Daltons, are provided. Following is the detailed compositional breakdown of the control composition and the inventive composition:
Table V Control Composition (wt%) Inventive Composition (wt%) Inventive Polymer 2 -- 0.500 C24AE3S Paste 8.320 8.320 HLAS 5.520 5.520 Nonionic 24-7 1.210 1.210 Citric Acid 2.000 2.000 Fatty acid (Double topped whole cut palm kernel fatty acid or DTPK) 1.210 1.210 Subtotal Builder 3.210 3.210 Boric acid 2.100 2.100 DTPA 0.190 0.190 FWA-49 0.057 0.057 Water Balance Balance Total: 100.000 100.000 - Sudsing Profile Test as described hereinabove is carried out for both the control composition and the inventive composition by dissolving each composition in water having a water hardness level of 16 gpg in different quantities to form laundering liquors of different dosing levels, including 2500ppm (under-dose 2X), 5000ppm (normal dosage), 10000ppm (over-dose at 2X), and 15000ppm (over-dose at 3X). The Wash Suds Index (WSI) and Rinse Suds Index (RSI) of the inventive composition at different dosing levels are calculated based on the wash suds volume and rinse suds volume measured thereof at different dosing levels in comparison with the control composition at similar dosing levels. Following are the measurement results:
Table VI Dosing Level 2500ppm 5000ppm 10000ppm 15000ppm Control Sample Inventive Sample Control Sample Inventive Sample Control Sample Inventive Sample Control Sample Inventive Sample Suds Stability* (cm) 29.03 15.73 37.53 28.90 40.90 40.15 38.10 42.83 WSI -- 54% -- 77% -- 98% -- 112% First Rinse** (cm) 4.08 1.13 11.58 2.90 19.53 7.68 24.08 13.60 RSI -- 28% -- 25% -- 39% -- 56% * Measured at 90-110 revolutions.
**Measured at 1/8 rinse with 130-150 revolutions. - The data shows that the sudsing benefit of the cationic polymer of the present invention is observable across different dosing levels. More interestingly, such cationic polymer at 3X overdose (15000ppm) exhibits a suds boosting effect during the wash cycle (i.e., a WSI of more than 100%), while at the same time still providing significant suds reduction during the rinse cycle (i.e., a RSI of less than 60%).
- Thirteen (13) test liquid laundry detergent compositions are prepared, including: (1) a control composition containing no cationic polymer, (2) 5 inventive compositions, each of which containing the same ingredients as the control composition but further including 0.5 wt% of an inventive polymer within the scope of the present invention; and (3) 7 comparative compositions, each of which containing the same ingredients as the control composition but further including 0.5 wt% of a comparative polymer that has either AAm/DADMAC molar percentages falling outside of the scope of the present invention, or a Molecular Weight falling outside of the scope of the present invention. Following is the detailed compositional breakdown of the control composition:
Table VII Ingredients Wt% C24AE3S Paste 8.320 HLAS 5.520 Nonionic 24-7 1.210 Citric Acid 2.000 Fatty acid (DTPK) 1.210 Subtotal Builder 3.210 Boric acid 2.100 DTPA 0.190 FWA-49 0.057 Hexamethylene diamine (ethoxylated, quaternized, sulfated) 70% 0.460 1, 2 propanediol 1.210 NaOH 3.130 Acticide MBS 0.015 Proxel GXL 0.001 Silicone emulsion 0.003 Andromeda 0.600 Liquitint Blue 297 0.002 Water Balance Total 100.000 - Sudsing Profile Test as described hereinabove is carried out for each of these thirteen (13) test compositions by dissolving each composition in water having a water hardness level of 16 gpg to form a laundering liquor containing 5000ppm of the test composition. For certain compositions, the Sudsing Profile Test is repeated several times (the number of actual tests conducted for each test composition is listed at below), and the suds data provided hereinafter is obtained by averaging the data obtained from the repetition. The Wash Suds Index (WSI) and Rinse Suds Index (RSI) of each of the seven (7) comparative compositions and five (5) inventive compositions are calculated based on the wash suds volume and rinse suds volume measured for such compositions in comparison with the control composition. Following are the measurement results:
Table VIII Polymer in Composition AAm (mol%) DADMAC (mol%) MW (K Dalton) Calculated Charge Density (meq/g) Total Test Times Suds Stability (cm)* First Rinse Suds (cm)** WSI RSI Nil polymer (Control) -- -- -- NA 8 30.5 9.1 -- -- Inventive Polymer 1 87.2 12.8 102.7 1.55 2 22.0 2.0 72% 22% Inventive Polymer 2 76 24 61.5 2.59 5 24.9 3.1 82% 34% Inventive Polymer 3 84.1 15.9 350.7 1.86 2 25.4 1.8 83% 20% Inventive Polymer 4 84.1 15.9 118.8 1.86 2 23.2 2.1 76% 23% Inventive Polymer 5 84.1 15.9 56.6 1.86 2 22.8 1.7 75% 19% Comparative Polymer 1 16.4 83.6 40.9 5.69 1 30.5 6.6 100% 73% Comparative Polymer 2 16.4 83.6 18.9 5.69 1 28.1 7.3 92% 80% Comparative Polymer 3 30 70 84.8 5.20 1 28.5 4.8 93% 53% Comparative Polymer 4 50 50 18.1 4.30 1 29.2 5.7 96% 63% Comparative Polymer 5a 70 30 3832.0 3.05 1 30.7 5.5 101% 60% Comparative Polymer 6b 70 30 3862.0 3.05 1 32.0 4.9 105% 54% Comparative Polymer 7c 70 30 3552.2 3.05 1 34.1 5.2 112% 57% * Measured at 90-110 revolutions.
**Measured at 130-150 revolutions.
a Merquat™ 550 commercially available from from the Lubrizol Corporation (Wickliffe, OH).
b Merquat™ 550L commercially available from from the Lubrizol Corporation (Wickliffe, OH).
c Merquat™ S commercially available from from the Lubrizol Corporation (Wickliffe, OH). - The comparative polymers contained in the comparative compositions have either AAm/DADMAC molar percentages or Molecular Weights falling outside of the scope of the present invention. The above data shows that only the inventive polymers with the appropriate AAm/DADMAC molar percentages and Molecular Weights provide optimal sudsing profiles, i.e., having a satisfactory wash suds volume quantified by a WSI of more than 70% and a sufficiently reduced rinse suds volume quantified by a RSI of less than 40%.
- Three (3) liquid laundry detergent compositions are prepared, including: (1) a control composition containing no cationic polymer, (2) a comparative composition containing 0.5 wt% of a comparative polymer, Merquat™ S, which contains 70 mol% of AAm and 30 mol% of DADMAC with a Molecular Weight of 3552.2K Dalton; (3) an inventive composition containing 0.5 wt% of the inventive polymer 2 as described hereinabove in Table II of Example I, Merquat™ 740, which contains 76 mol% of AAm and 24 mol% of DADMAC with a Molecular Weight of 61.5K Dalton. Following is the detailed compositional breakdown of the control composition, the comparative composition, and the inventive composition:
Table IX Control Composition (wt%) Comparative Composition (wt%) Inventive Composition (wt%) Comparative Polymer -- 0.500 -- Inventive Polymer 2 -- -- 0.500 C24AE3S Paste 8.320 8.320 8.320 HLAS 5.520 5.520 5.520 Nonionic 24-7 1.210 1.210 1.210 Citric Acid 2.000 2.000 2.000 Fatty acid (DTPK) 1.210 1.210 1.210 Subtotal Builder 3.210 3.210 3.210 Boric acid 2.100 2.100 2.100 DTPA 0.190 0.190 0.190 FWA-49 0.057 0.057 0.057 Hexamethylene diamine (ethoxylated, quaternized, sulfated) 70% 0.460 0.460 0.460 1, 2 propanediol 1.210 1.210 1.210 NaOH 3.130 3.130 3.130 Acticide MBS 0.015 0.015 0.015 Proxel GXL 0.001 0.001 0.001 Silicone emulsion 0.003 0.003 0.003 Andromeda 0.600 0.600 0.600 Liquitint Blue 297 0.002 0.002 0.002 Water Balance Balance Balance Total 100.000 100.000 100.000 - Fabric Whiteness Loss Test using the fast wash method as described in Test 4 hereinabove is carried out for each of these three (3) test compositions. The fabric used for conducting the test is polyester.
- The Whiteness Loss Index (i.e., ΔWLI) is measured for each of the control composition, the comparative composition, and the inventive composition. The Relative Whiteness Loss Percentage (WLP) of both the comparative composition and inventive composition are calculated based on their ΔWLI in comparison with that of the control composition. Following are the measurement results:
Table X Control Composition Comparative Composition Inventive Composition ΔWLI 26.8 53.5 13.9 WLP 0% 99.6% -48.1% * Measured at 90-110 revolutions.
** Measured at 130-150 revolutions. - As mentioned hereinabove, WLP is the relative percentage fabric whiteness loss caused by a detergent composition containing a cationic polymer (either an inventive polymer or a comparative polymer) over that caused by a control detergent composition not containing such cationic polymer, the larger the WLP, the more relative fabric whiteness loss is caused by addition of the specific cationic polymer, which is indicative of poorer whiteness performance of such cationic polymer.
- The comparative polymer contained in the comparative composition and the inventive polymer 2 contained in the inventive composition have similar AAm and DADMAC molar percentages, but the inventive polymer 2 has a significantly lower Molecular Weight that falls within the scope of the present invention, while the comparative polymer has a high Molecular Weight that does not fall within the scope of the present invention. As shown hereinabove, the comparative composition has a WLP as high as 99.6%, which is indicative of very poor whiteness performance of the comparative cationic polymer. In contrast, the inventive composition has a negative WLP of -48.1%, which indicates that the presence of the inventive cationic polymer 2 not only does not cause fabric whiteness loss, but actually imparts whiteness benefit to the fabric tested.
- A total of six (6) test liquid laundry detergent compositions are prepared, which include: (1) a Composition A containing a LAS-enriched surfactant system without any cationic polymer; (2) Composition A plus a cationic polymer of the present invention, which contains 80 mol% of AAm, 16 mol% of DADMAC, and 4 mol% of VP and has a Mw of 165,300 Daltons; (3) a Composition B containing a NI-enriched surfactant system without any cationic polymer; (4) Composition B plus the cationic polymer; (5) a Composition C containing an AES-enriched surfactant system without any cationic polymer; and (6) Composition C plus the cationic polymer. Detailed compositional breakdown of the six (6) test liquid laundry detergent compositions are provided hereinbelow:
Table XI Ingredients (wt%) A A + Polymer B B + Polymer C C + Polymer Linear alkylbenzene sulfonate (LAS) 12.00 12.00 1.50 1.50 0.75 0.75 Alkyl ether (E03) sulfate (AES) 1.50 1.50 1.50 1.50 13.50 13.50 Alkyl (EO7) ethoxylate (NI) 1.50 1.50 12.00 12.00 0.75 0.75 Fatty acid 1.21 1.21 1.21 1.21 1.21 1.21 Boric acid 2.10 2.10 2.10 2.10 2.10 2.10 Citric acid 2.00 2.00 2.00 2.00 2.00 2.00 NaOH 3.15 3.15 2.00 2.00 2.00 2.00 1,2-propane diol 1.21 1.21 1.21 1.21 1.21 1.21 Inventive Cationic Polymer - 0.50 - 0.50 - 0.50 Water Balance Balance Balance Balance Balance Balance Total 100.00 100.00 100.00 100.00 100.00 100.00 - The wash suds volume and the rinse suds volume of each test liquid laundry detergent composition are measured using the Sudsing Volume Test (SITA) described in Test 5.
- The effect of the inventive cationic polymer on wash suds volume for each comparative or inventive detergent composition is measured as a Wash Suds Change (ΔSw), which equals the wash suds volume measured for a specific test composition containing the inventive cationic polymer minus the wash suds volume measured for a similar test composition but without the inventive cationic polymer. A positive ΔSw is indicative of a wash suds boosting effect, while a negative ΔSw is indicative of a wash suds suppressing effect. The more positive the ΔSw, the stronger the suds boosting effect.
- Similarly, the effect of the inventive cationic polymer on rinse suds volume for each comparative or inventive detergent composition is measured as a Rinse Suds Change (ΔSR), which equals the rinse suds volume measured for a specific test composition containing the inventive cationic polymer minus the rinse suds volume measured for a similar composition but without the inventive cationic polymer. A positive ΔSR is indicative of more rinse suds, which is undesirable, while a negative ΔSR is indicative of less rinse suds, which is desirable. The more negative the ΔSR, the stronger the suds suppressing effect.
- The overall sudsing benefit achieved by the inventive cationic polymer from the wash cycle to the rinse cycle is recorded as a Total Suds Change (ΔSW-ΔSR). The more positive the Total Suds Change, the more desirable the overall suds benefit achieved by the inventive cationic polymer on the test composition.
- The Total Suds Change (ΔSW-ΔSR) achieved by the inventive cationic polymer in Composition A (LAS-enriched), Composition B (NI-enriched), and Composition C (AES-enriched) are recorded in the following table:
Table XII Composition A (LAS-Enriched) B (NI-Enriched) C (AES-Enriched) ΔSW-ΔSR (ml) 16 21 38 - It is evident that the Total Suds Change (ΔSW-ΔSR) achieved by the inventive cationic polymer of the present invention in an AES-enriched surfactant system is stronger and more desirable than that achieved by the same polymer in comparative LAS-enriched or NI-enriched surfactant systems. This indicates that the inventive cationic polymer is more desirable to be used in combination with an AES-enriched surfactant system in order to optimize sudsing profile of the resulting laundry detergent compositions.
- The following heaving duty liquid detergents are made by mixing the ingredients listed below via conventional processes. Such heavy duty liquid detergents are used to launder fabrics that are then dried by line drying and/or machine drying. Such fabrics may be treated with a fabric enhancer prior to and/or during drying. Such fabrics exhibit a clean appearance and have a soft feel.
Table XIII Ingredients (wt%) Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Alkyl ether sulfate (EO=1-3) 8-15 11-14 12.07 12.07 8.32 13.5 13.5 Linear alkylbenzene sulfonate 0-8 1-6 1.86 1.66 5.52 1.5 -- Amine oxide 0-2 0.5-1 -- 0.75 -- -- -- Alkyl ethoxylate (EO7) 0-5 1-2 1.12 0.65 1.21 -- 1.5 Citric acid 0.1-6 1-3 1.5-2.5 1.5-2.5 1.5-2.5 1.5-2.5 1.5-2.5 Fatty acid (DTPK) 0-3 1-1.5 1.21 1.21 1.21 1.0 1.0 Boric acid 0-4 1-3 1.5-2.5 1.5-2.5 1.5-2.5 1.5-2.5 1.5-2.5 Polyethyleneimine ethoxylate/propoxylate 0-3 0-2 -- -- -- 0.5-1.5 0.5-1.5 Hexamethylene diamine (ethoxylated,quaternized, sulfated) 0-1 0-0.5 0-0.5 0-0.5 0-0.5 -- -- DTPA 0-0.5 0.1-0.3 0.1-0.3 0.1-0.3 0.1-0.3 0.1-0.3 0.1-0.3 Fluorescent whitening agent 0-0.1 0.02-0.1 0.05-0.1 0.05-0.1 0.05-0.1 0.05-0.1 0.05-0.1 Propylene glycol 0-3 1-2 1-2 1-2 1-2 1-2 1-2 NaOH 0-5 1-4 2-3 2-3 3-3.5 2.5-3 2.5-3 Polymers 1-12 in Table II of Example I 0.05-1 0.1-0.5 0.125-0.25 0.125-0.25 0.1-0.5 0.5 0.5 Water and miscellaneous Balance Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 100 Table XIV Ingredient (wt%) Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Alkyl ether sulfate (EO=1-3) 5-15 8-10 10 9 12 8.0 Linear alkylbenzene sulfonate 0-5 1-5 1.5 -- 2.8 6.2 Alkyl ethoxylate (EO=7 or 9) 0-5 4-8 8 6 4.9 7.7 Alkyl alkoxylate (C12,14,16 EO20-25 PO1-2) 0-5 -- -- 2 -- -- Citric acid 0.5-6 1-3 1-3 1-3 -- 1.6 Fatty acids 0-4 0.5-2 1.0 1.0 1.2 1.9 Boric acid 0-5 1-3 1-3 1-3 -- -- Calcium and sodium formate -- -- -- -- 2.2 -- Polyethyleneimine ethoxylate/propoxylate 0-3 0.5-2 0.5-2 0.5-2 -- -- Hexamethylene diamine (ethoxylated,quaternized, sulfated) 0-1 0-0.5 0-0.5 0-0.5 -- -- Polyacrylate 0-2 -- -- -- 1.0 0.1 DTPA 0-0.5 0.1-0.2 0.1-0.2 0.1-0.2 -- -- Diethylene triamine penta methylene phosphonic acid 0-0.5 -- -- -- 0.25 -- Fluorescent whitening agent 0-0.2 0.05-0.1 0.05-0.1 0.05-0.1 - 0.06 Glycerine -- -- -- -- 2.0 -- Propylene glycol 0-5 1-2 1-2 1-2 -- -- Ethanolamine 0-5 -- -- -- -- 1.2 NaOH 0-5 0-5 2.0 2.8 1.6 1.9 Polymers 1-12 in Table II of Example I 0.05-1 0.1-0.5 0.5 0.5 0.1-0.5 0.1-0.5 Water and miscellaneous Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 Table XV Ingredient (wt%) Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Alkyl ether sulfate (EO=1-3) 8-15 4-10 8-10 10 9 12 Linear alkylbenzene sulfonate 2-8 0-4 4-7 8 6 4.9 Alkyl ethoxylate (EO=7 or 0-5 0-4 1-5 1.5 - 2.8 Citric acid 0.5-6 0.5-6 1-3 1-3 1-3 1-3 Fatty acid 0-3 0-3 0.5-2 1.0 1.0 1.0 Boric acid 0-5 0-5 1-3 1-3 1-3 1-3 Polyethyleneimine ethoxylate/propoxylate 0-2 0-2 0.5-1.5 0.5-1.5 0.5-1.5 0.5-1.5 Hexamethylene diamine (ethoxylated,quaternized, sulfated) 0-1 0-1 0.3-0.5 0.3-0.5 0.3-0.5 0.3-0.5 DTPA 0-0.5 0-0.5 0.1-0.25 0.1-0.25 0.1-0.25 0.1-0.25 Fluorescent whitening agent 0-0.2 0-0.2 0.05-0.1 0.05-0.1 0.05-0.1 0.05-0.1 Propylene glycol 0-12 0-12 4-10 4-10 4-10 4-10 NaOH 0-5 0-5 1-4 1-4 1-4 1-4 Polymers 1-12 in Table II of Example I 0.05-1 0.05-1 0.1-0.5 0.5 0.5 0.25 Water and miscellaneous Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 Table XVI Ingredient (wt%) Ex. 20 Ex. 21 Ex. 22 Ex. 23 Ex. 24 Ex. 25 Ex. 26 Alkyl ether sulfate (EO=1-3) 7-10 6-7 8.63 14.32 9.07 7.5 8.4 Linear alkylbenzene sulfonate 6-7 4-6 6.00 1.28 -- -- -- Amine Oxide -- 0.3-0.7 -- -- -- -- 0-0.5 Alkyl ethoxylate (EO=7 or 9) 1-1.5 4-6 6.60 5.40 4.90 7.5 3.6 Citric acid 1.5-2 1-1.5 0-2 0-2 1-2 1.5-2 1.5-2 Fatty acid 1-1.5 1-1.5 1.86 2.65 2.35 2-4 4 Enzymes 0-1 0.2-0.5 0-1 0-1 0-1 0-1 0-1 Boric acid 1.5-2.5 1.5-2.5 - 0-2 0-2 2-2.5 2-2.5 Hexamethylene diamine (ethoxylated, quaternized, sulfated) 0.25-0.75 0.25-0.75 -- -- -- 0.25-0.75 -- Polyethyleneimine ethoxylate/propoxylate -- 0.5-2 -- -- -- 0-1 0-1 Ethyleneglycol/Vinylacetate copolymer -- -- -- -- -- -- -- Polyacrylate 0-2 0-0.5 0-1 1.57 -- -- -- DTPA 0.1-0.5 0.1-0.2 -- - -- 0.2 0.2 Diethylene triamine penta methylene phosphonic acid -- -- 0-0.1 0.04 0.04 -- -- Fluorescent whitening agent 0.05-0.1 0.05-0.1 0.05 0.05-0.1 0.05-0.1 0.05-0.1 0.05-0.1 Glycerine -- -- 2 0-0.5 -- -- -- Ethanol/Propylene glycol 2-3 2-3 1-2 1-2 1-2 1-3 1-2 Ethanolamine/Triethanolamine -- -- 1.47 -- -- -- -- NaOH 3-4 2-3 -- 2.5-4 3-4 2-3 2-3 NaCS -- 0.1-0.5 -- -- -- -- 0.1-0.3 Polymers 1-12 in Table II of Example I 0.05-1 0.5 0.5 0.5 0.1-0.5 0.25-0.5 0.1-0.5 Water and miscellaneous Balance Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 100 - While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Preparation of fabric with DCO is conducted as follows:
7. Pour 37.5 ml solution out of the tube gently into beaker and add 262.5 ml of water with desired hardness level into the beaker to make a toal of 300 ml 1/8 diluted solution. Dispose the remaining solution in the tube and wash the tube with tap water. Pour the 300 ml 1/8 diluted solution into the same tube.
8. Spin for 20 revolutions. This marks the after 130 revolutions data. Take readings from left to right. Repeat this step one time; thus data gathered are for after 150 revolutions.
9. Pour 150 ml solution out of the tube gently into beaker and add 150 ml water with desired hardness level into the beaker to make a total of 300ml 1/16 diluted solution. Dispose the remaining solution in the tube and wash the tube with tap water. Pour the 300 mL 1/16 diluted solution into the same tube.Repeat steps 8. Data gathered are for 190 revolutions data.
10. In a typical sudsing profile test, Steps 1-9 are repeated at least once to ensure the test repeatibility.
11. Data Analysis:
Flush Suds | 10 revolutions data | Flush Suds |
Suds generation | 30-70 revolutions data | Washing Cycle |
Suds stability | 90-110 revolutions data | Wash data analysis is focused on Suds stability |
1/8 Rinse | 130-150 revolutions data | Rinsing Cycle: Rinse data analysis is focused on Rinse (1:8) |
1/16 Rinse | 170-190 revolutions data | Rinsing Cycle: 1/16 Rinse |
(3) Transfer 10 mL of the solution A into 40 mL plastic vials. Add clean magnets for additional agitation.
(4) Add 1 mL of Solution B into the plastic vials above.
(5) Add 1 mL of Solution C into the plastic vials above.
(6) Add 3 mL of DI water into the plastic vials above.
(7) Add 6.1 µL technical body soil into the plastic vials above. The technical body soil composition is prepared according to the following table:
Ingredients | wt% | Supplier |
Coconut Oil | 15 | Gold Metal Products |
Oleic Acid | 15 | Spectrum |
Paraffin Oil | 15 | EMD |
Olive Oil | 15 | Spectrum |
Cottonseed Oil | 15 | Spectrum |
Squalene Oil | 5 | Alfa Aesar |
Cholesterol | 5 | Amresco, Inc |
Myristic Acid | 5 | SIGMA |
Palmitic Acid | 5 | SIGMA |
Stearic Acid | 5 | SIGMA |
(8) Test fabrics are selected from 1.5 cm diameter polyester fabrics (PW19) and/or 1.5 cm diameter cotton fabrics (CW98) purchased from Empirical Manufacturing Company (Blue Ash, Cincinnati). Add eight of the polyester fabrics and eight cotton fabrics to solution prepared in Step (7). Secure 40 mL wash vial tightly to Wrist Action Shaker Model 75 (Burrell Scientific, Pittsburgh, Pennsylvania). Use a timer and run the wash for 30 minutes. At the end of the wash empty the contents of the plastic vial wash solution on a Buchner funnel. Transfer the test fabric disks to another 40 mL vial and add 14 mL DI water of rinse solution.
(9) To prepare the rinse solution, add 1 ml solution B to 14 mL of DI water. Secure vial to Wrist Action Shaker and rinse for 3 minutes. At the end of the rinse remove from Wrist Action Shaker and place the test fabrics on black plastic board template. Let air dry for at least two hours. For multi-cycle washes, just repeat the above steps.
(10) For each test fabric, two whiteness index measurements from before (i.e., initial) and after the wash cycle (i.e., treated) are taken using the CIELab color parameters with a Datacolor spectrometer. The relative whiteness index (i.e., whiteness loss) between the initial unwashed fabric and final washed fabric is reported.
(11) A Whiteness Loss Index (i.e., ΔWLI), representing the normalized difference in the whiteness index measurements between the initial fabric (before treatment) and the treated fabric, is determined for a tested fabric sample treated by a sample detergent composition, and represented by the following calculation:
The larger the ΔWLI, the more whiteness loss in the treated fabric is observed, which means that the performance of the laundry detergent used for treating the fabric sample is poorer from the whiteness perspective. If the ΔWLI is negative, it means that the treated fabric is actually whiter than the initial fabric, which means that the washing not only does not reduce the whiteness, but actually increases it.
(12) Further, a Relative Whiteness Loss Percentage (WLP) is calculated for each test sample by comparing the ΔWLI measured for such test sample (ΔWLI1), which may contain either an inventive cationic polymer of the present invention or a comparative cationic polymer not falling within the scope of the present invention, with the ΔWLI measured for a control detergent composition that does not contain any cationic polymer (ΔWLIC), according to the following equation:
Mixing Rotor Speed (rpm) | 1000 |
Stir Count | 15 |
Stir Time (sec) | 10 |
Claims (10)
- A liquid laundry detergent composition, comprising:(a) a cationic polymer which is either:
a copolymer that consists essentially of: (i) from 70 mol% to 90 mol% of a first, nonionic structural unit; and (ii) from 10 mol% to 30 mol%, of a second, cationic structural unit; or:
a terpolymer that consists essentially of: (i) from 65 mol% to 90 mol% of the first, nonionic structural unit; (ii) from 10 mol% to 20 mol% of the second, cationic structural unit; and (iii) from 1 mol% to 20 mol%, of a third, nonionic structural unit;
wherein:the first, nonionic structural unit made from (meth)acrylamide (AAm);the second, cationic structural unit is made from a monomer selected from the group consisting of diallyl dimethyl ammonium salts (DADMAS), N,N-dimethyl aminoethyl acrylate, N,N-dimethyl aminoethyl methacrylate (DMAM), [2-(methacryloylamino)ethyl]tri-methylammonium salts, N,N-dimethylaminopropyl acrylamide (DMAPA), N,N-dimethylaminopropyl methacrylamide (DMAPMA), acrylamidopropyl trimethyl ammonium salts (APTAS), methacrylamidopropyl trimethylammonium salts (MAPTAS), quaternized vinylimidazole (QVi), and combinations thereof; andthe third, nonionic structural unit that is different from the first, nonionic structural unit and is made from a monomer which is vinylpyrrolidone (VP);wherein said cationic polymer is characterized by a Weight Average Molecular Weight of from 10,000 to 1,000,000 Daltons and is free of any silicone-derived structural component; and(b) a surfactant system comprising: (i) from 20% or more, by total weight of said surfactant system, of a C10-C20 linear or branched alkylethoxy sulfate (AES) having an average degree of ethoxylation ranging from 0.3 to 4; (ii) from 1% to 45%, by total weight of said surfactant system, of a C10-C20 linear alkyl benzene sulphonate (LAS); and (iii) from 1% to 45%, by total weight of said surfactant system, of a C8-C18 alkyl alkoxylated alcohol having an average degree of alkoxylation from 1 to 20 (NI), wherein the weight ratio of AES to LAS is equal to or greater than 1.2, and wherein the weight ratio of AES to NI is equal to or greater than 1.2. - The laundry detergent composition of claim 1, wherein the weight ratio of AES to the combination of LAS and NI is equal to or greater than 1.
- The laundry detergent composition of claim 1 or 2, wherein AES is present in an amount of 50% or more by total weight of the surfactant system.
- The laundry detergent composition of any one of claims 1 to 3, wherein the second, cationic structural unit is made from DADMAS, and preferably made from diallyl dimethyl ammonium chloride (DADMAC).
- The laundry detergent composition of any one of claims 1 to 4, wherein the Weight Average Molecular Weight of the cationic polymer ranges from 15,000 to 700,000 Daltons, and preferably from 20,000 to 350,000 Daltons.
- The laundry detergent composition of any one of claims 1 to 5, wherein said cationic polymer is present in an effective amount for sudsing profile optimization, and wherein said cationic polymer is present in an amount ranging from 0.01% to 15%, preferably from 0.05% to 10%, from 0.1% to 5%, and most preferably from 0.2% to 1% by total weight of the laundry detergent composition.
- The laundry detergent composition of any one of claims 1 to 6, further comprising a silicone-derived anti-foaming agent, which is present in an amount ranging from 0.01% to 5%, preferably from 0.05% to 2%, and more preferably from 0.1% to 1%, by total weight of the laundry detergent composition.
- The laundry detergent composition according to claim 1 wherein the laundry composition comprises:(a) from 0.2 wt% to 1 wt% of a cationic polymer having a Weight Average Molecular Weight of from 20,000 to 350,000 Daltons, said cationic polymer consisting essentially of: (i) from 70 mol% to 90 mol% of a first, nonionic structural unit made from (meth)acrylamide (AAm); and (ii) from 10 mol% to 30 mol% of a second, cationic structural unit made from diallyl dimethyl ammonium chloride (DADMAC); and(b) from 1 wt% to 99 wt% of a surfactant system comprising: (i) from 60% to 100%, by total weight of said surfactant system, of a C10-C20 linear or branched alkylalkoxy sulfate (AES) having an average degree of alkoxylation ranging from 0.1 to 5; (ii) from 0% to 40%, by total weight of said surfactant system, of a C10-C20 linear alkyl benzene sulphonate (LAS); and (iii) from 0% to 40%, by total weight of said surfactant system, of a C8-C18 alkyl alkoxylated alcohol having an average degree of alkoxylation from 1 to 20 (NI).
- The laundry detergent composition according to claim 1 wherein the laundry composition comprises:(a) from 0.2 wt% to 1wt% of a cationic polymer, which has a Weight Average Molecular Weight of from 20,000 to 350,000 Daltons, said cationic polymer consisting essentially of: (i) from 65 mol% to 90 mol% of a first, nonionic structural unit made from (meth)acrylamide (AAm); (ii) from 10 mol% to 20 mol% of a second, cationic structural unit made from diallyl dimethyl ammonium chloride (DADMAC); and (iii) from 1 mol% to 20 mol% of a third, nonionic structural unit made from vinylpyrrolidone (VP); and(b) from 1 wt% to 99 wt% of a surfactant system comprising: (i) from 60% to 100%, by total weight of said surfactant system, of a C10-C20 linear or branched alkylalkoxy sulfate (AES) having an average degree of alkoxylation ranging from 0.1 to 5; (ii) from 0% to 40%, by total weight of said surfactant system, of a C10-C20 linear alkyl benzene sulphonate (LAS); and (iii) from 0% to 40%, by total weight of said surfactant system, of a C8-C18 alkyl alkoxylated alcohol having an average degree of alkoxylation from 1 to 20 (NI).
- The liquid laundry detergent composition of claim 8 or 9, further comprising from 0.1 wt% to 1 wt% of a silicone-derived antifoaming agent.
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PCT/CN2014/090775 WO2016074142A1 (en) | 2014-11-11 | 2014-11-11 | Detergent or cleaning compositions with improved sudsing profile |
PCT/CN2015/072994 WO2016127387A1 (en) | 2015-02-13 | 2015-02-13 | Cleaning compositions containing alkyl sulfate surfactants and cationic polymer for holistic improvement of sudsing profile |
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- 2015-03-13 CN CN201580016211.7A patent/CN106459842B/en active Active
- 2015-03-13 WO PCT/CN2015/074145 patent/WO2015143997A1/en active Application Filing
- 2015-03-25 EP EP15767696.6A patent/EP3122854B1/en active Active
- 2015-03-25 CN CN201580016213.6A patent/CN106795461B/en active Active
- 2015-03-25 WO PCT/CN2015/075008 patent/WO2015144053A1/en active Application Filing
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Also Published As
Publication number | Publication date |
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CN106459842B (en) | 2020-05-12 |
WO2015143997A1 (en) | 2015-10-01 |
CN106795461A (en) | 2017-05-31 |
CN106795461B (en) | 2020-11-24 |
WO2015144053A8 (en) | 2016-12-08 |
WO2015144053A1 (en) | 2015-10-01 |
EP3122854A1 (en) | 2017-02-01 |
EP3122856A1 (en) | 2017-02-01 |
CN106459842A (en) | 2017-02-22 |
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