EP3186347B1 - Liquid detergent composition - Google Patents
Liquid detergent composition Download PDFInfo
- Publication number
- EP3186347B1 EP3186347B1 EP15750759.1A EP15750759A EP3186347B1 EP 3186347 B1 EP3186347 B1 EP 3186347B1 EP 15750759 A EP15750759 A EP 15750759A EP 3186347 B1 EP3186347 B1 EP 3186347B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- surfactant
- composition according
- composition
- weight
- foam
- 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 88
- 239000003599 detergent Substances 0.000 title claims description 23
- 239000007788 liquid Substances 0.000 title claims description 23
- 239000006260 foam Substances 0.000 claims description 61
- 239000004094 surface-active agent Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000002736 nonionic surfactant Substances 0.000 claims description 28
- -1 alkylbenzene sulphonate Chemical class 0.000 claims description 23
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 17
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 14
- 230000003254 anti-foaming effect Effects 0.000 claims description 13
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical group CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002280 amphoteric surfactant Substances 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 238000004851 dishwashing Methods 0.000 claims description 8
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 8
- 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 claims description 7
- 239000005639 Lauric acid Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- DWHIUNMOTRUVPG-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCO DWHIUNMOTRUVPG-UHFFFAOYSA-N 0.000 claims description 4
- 229940031674 laureth-7 Drugs 0.000 claims description 4
- 159000000000 sodium salts Chemical group 0.000 claims description 4
- QTDIEDOANJISNP-UHFFFAOYSA-N 2-dodecoxyethyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOCCOS(O)(=O)=O QTDIEDOANJISNP-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 229920002884 Laureth 4 Polymers 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- LAPRIVJANDLWOK-UHFFFAOYSA-N laureth-5 Chemical group CCCCCCCCCCCCOCCOCCOCCOCCOCCO LAPRIVJANDLWOK-UHFFFAOYSA-N 0.000 claims description 3
- 229940062711 laureth-9 Drugs 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 44
- 239000000194 fatty acid Substances 0.000 description 44
- 229930195729 fatty acid Natural products 0.000 description 44
- 150000004665 fatty acids Chemical class 0.000 description 44
- 230000000694 effects Effects 0.000 description 10
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 8
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 8
- 239000003945 anionic surfactant Substances 0.000 description 7
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229940043348 myristyl alcohol Drugs 0.000 description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 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
- 229940098691 coco monoethanolamide Drugs 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- VAXCXSDAWONRLI-UHFFFAOYSA-N 2,3-dihydroxypropyl hydrogen sulfate Chemical compound OCC(O)COS(O)(=O)=O VAXCXSDAWONRLI-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- ZTRXAIIXCCGSMH-UHFFFAOYSA-N azanium;2,3-dipentylnaphthalene-1-sulfonate Chemical compound [NH4+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCCC)C(CCCCC)=CC2=C1 ZTRXAIIXCCGSMH-UHFFFAOYSA-N 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- DHQIJSYTNIUZRY-UHFFFAOYSA-M sodium;2,3-di(nonyl)naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 DHQIJSYTNIUZRY-UHFFFAOYSA-M 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000008096 xylene 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2079—Monocarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C11D2111/14—
Definitions
- the present invention is in the field of hard surface cleaning compositions; in particular liquid detergent compositions having foaming and cleaning characteristics in the main wash, yet significant foam reduction during rinse.
- One way of saving water is to reuse the water and another way is to reduce the amount of water being used.
- Washing processes including laundry, dishwashing and other household cleaning processes, require large amounts of water throughout the world. These are daily chores in which the use of water and a detergent cannot be avoided. Consumers usually like to see a lot of foam while washing as they associate foaming with detergent efficiency. However, it's rinsing that often takes a lot of effort and uses excess of water.
- the amount of water required for rinse is entirely dependent on the detergent used. Therefore, the use of water can be reduced or controlled based on the detergent.
- WO 98/27189 discloses a mildly acid laundry detergent composition for improved protection of fine fabrics during washing and enhanced removal of generated foam during rinsing in hand wash comprising at least one anionic surfactant and/or at least one non-ionic surfactant and a rinse-active pH sensitive foam control agent comprising a fatty acid, whereby upon rinsing, at least a portion of said fatty acid is converted to a soap which functions to suppress foam during rinsing.
- the fatty acid may be selected from saturated or unsaturated fatty acids and preferably are lauric, myristic, oleic and stearic, natural coconut, palmitic and tallow fatty acids.
- a specific combination of saturated stearic acid and saturated lauric acid is preferred.
- the composition of WO98/27189 also does not disclose the specific surfactant system of the present invention.
- JP 2004-203989 discloses a liquid detergent composition for tableware washing comprising 5-50 mass % of a sulfuric ester and/or a sulfonate type anionic surfactant, 1-30 mass % of a specific alkoxylate type nonionic surfactant and an 8-20C saturated and/or unsaturated fatty acid/salt and has pH of 4-8.
- the fatty acid may be selected from saturated or unsaturated C8-20 fatty acids.
- a specific combination of saturated stearic acid and saturated lauric acid is preferred.
- US 6090764 discloses a manual dishwashing detergent composition containing 0.2 to 10% by weight of a glycerol sulfate, 1 to 50% by weight of a C 6-22 alkyl sulfate, C 6-22 alkyl ether sulfate, C 9-13 alkyl benzene sulfonate or a mixture thereof and 1 to 20% by weight based on the detergent as a whole of an alkyl glucoside.
- the composition of US 6090764 does not include fatty acids, however very small quantities of soap may be present.
- CN 102876483 discloses a low foam easy bleaching liquid detergent composition and its preparation method.
- the liquid detergent composition comprises 0.1 to 20% unsaturated fatty acid, 0.1 to 5% saturated fatty acids, 0.1 to 5% alkali neutralizing agent, 1 to 25% non-ionic surfactant, 1 to 25% anionic surfactant, 0.5 to 20% of other additives and water.
- This formulation uses saturated and unsaturated fatty acids to reduce the amount of the liquid detergent wash foam, to solve the problem of difficulty in rinsing.
- a specific combination of saturated stearic acid and saturated lauric acid is preferred.
- WO 2013/038750 discloses a liquid detergent composition which contains one or more kinds of anionic surfactant selected from the group consisting of polyoxyalkylene alkyl ether sulfuric acid ester salts and alkylbenzene sulfonic acid salts, a fatty acid and/or a salt thereof, an alkanol amine, a carbonate, a nonionic surfactant and water.
- anionic surfactant selected from the group consisting of polyoxyalkylene alkyl ether sulfuric acid ester salts and alkylbenzene sulfonic acid salts, a fatty acid and/or a salt thereof, an alkanol amine, a carbonate, a nonionic surfactant and water.
- anionic surfactant selected from the group consisting of polyoxyalkylene alkyl ether sulfuric acid ester salts and alkylbenzene sulfonic acid salts, a fatty acid and/or a salt thereof, an alkanol amine
- an antifoaming effect may be obtained only during rinse in hard surface cleaning processes by a liquid detergent comprising a surfactant system of a primary and a secondary surfactant, a combination of saturated fatty acids selected from lauric and stearic acid and a non-ionic surfactant.
- the present invention provides a liquid detergent composition
- a surfactant system comprising a primary surfactant of the formula R 1 -OR') n -SO 3 - M + , wherein: R 1 is saturated or unsaturated C 8 -C 16 alkyl chain; R' is ethylene; n is from 1 to 18; M + is a suitable cation which provides charge neutrality selected from sodium, calcium, potassium and magnesium; and a secondary surfactant selected from alkylbenzene sulphonate and derivatives; and alkyl sulphates; less than or equal to 1 % by weight of a combination of saturated fatty acids selected from lauric and stearic acid; less than or equal to 3% by weight of a non-ionic surfactant; and water.
- R 1 is saturated or unsaturated C 8 -C 16 alkyl chain
- R' is ethylene
- n is from 1 to 18
- M + is a suitable cation which provides charge neutrality selected from sodium, calcium, potassium and
- the invention provides a process of reducing foam during rinse in dishwashing comprising the steps of applying onto the hard surface in neat or diluted form a liquid composition according to the invention; cleaning the hard surface with a cleaning implement; and rinsing the hard surface.
- the invention provides use of a composition according to the invention for providing anti-foaming activity upon rinse.
- hard surface typically means utensils or kitchenware, kitchen tops, kitchen floors, sinks and platforms, floors and bathrooms.
- the invention relates to a liquid detergent composition
- a liquid detergent composition comprising a surfactant system, a combination of fatty acids, a non-ionic surfactant and water.
- the liquid detergent composition of the present invention comprises a surfactant system.
- the surfactant system comprises a primary and a secondary surfactant. Both the primary and the secondary surfactants are selected from anionic surfactants.
- the primary surfactant of the present invention is a surfactant of the formula:
- the secondary surfactant of the present invention may be selected from alkylbenzene sulphonates and derivatives; and alkyl sulphates.
- Alkylbenzene sulphonates and derivatives include water-soluble alkali metal salts of organic sulphonates having alkyl radicals typically containing from about 8 to about 22 carbon atoms, preferably 8 to 18 carbon atoms, still more preferably 12 to 15 carbon atoms and may be unsaturated.
- Examples include sodium salt of linear alkylbenzene sulphonate, alkyl toluene sulphonate, alkyl xylene sulphonate, alkyl phenol sulphonate, alkyl naphthalene-sulphonate, ammonium diamylnaphthalene-sulphonate and sodium dinonylnaphthalene-sulphonate and mixtures with olefin sulphonates.
- alkyl sulphates examples include sodium lauryl sulphate, ammonium lauryl sulphate, diethanolamine(DEA) lauryl sulphate. Suitable examples also includes alkyl sulphates commercially available from natural source with trade names Galaxy 689, Galaxy 780, Galaxy 789, Galaxy 799 SP and from synthetic origin with trade names Safol 23, Dobanol 23A or 23S, Lial 123 S, Alfol 1412S, Empicol LC3, Empicol 075SR.
- Preferred secondary surfactants are sodium salt of linear alkylbenzene sulphonate and sodium lauryl sulphate.
- Most preferred secondary surfactant is sodium salt of linear alkylbenzene sulphonate.
- Secondary surfactant may be present in a concentration of 5 to 95 %, preferably at least 12%, more preferably at least 20%, still more preferably at least 30% but typically not more than 85%, preferably not more than 75%, more preferably not more than 65%, still more preferably not more than 55% by weight of the surfactant system.
- the surfactant system of the present invention may further comprise an amphoteric surfactant.
- Suitable surfactants include cocoamidopropyl betaine (CAPB), coco amido propyl amine oxide (CAPAO), cocodiethanol amide (CDEA) and cocomonoethanol amide (CMEA).
- amphoteric surfactant is cocoamidopropyl betaine.
- the amphoteric surfactant is in a concentration of 0.1 to 20%, preferably at least 0.5%, more preferably at least 3%, still more preferably atleast 6% or even more preferably at least 8% but typically not more than 18%, preferably not more than 16%, more preferably not more than 13%, still more preferably not more than 10% by weight of the surfactant system.
- the surfactant system is present in the composition in a concentration of 8 to 30%, preferably not less than 15%, more preferably not less than 18%, still more preferably not less than 20% but typically not more than 28%, preferably not more than 27% or even not more than 26% by weight of the composition.
- the liquid detergent composition of the present invention comprises a combination of fatty acids.
- the combination of fatty acids used in present invention is selected from lauric (C 12 ) and stearic acid (C 18 ).
- C 12 and C 18 fatty acids are used in combination, the chain lengths of these fatty acids have a crucial role on the flash foam and the antifoam activity during rinse.
- C 12 ensures there is no adverse effect on the flash foam of surfactant solution while C 18 triggers the antifoam activity only during rinse.
- Individual fatty acids are found to either kill the surfactant's flash foam or have poor antifoaming activity.
- Fatty acids used in the present invention are saturated fatty acids. Saturated lauric (C 12 ) and stearic acid (C 18 ) are preferred. Unsaturated fatty acids are not preferred in the present invention.
- Lauric and stearic acid are present in the composition in a ratio of 1:1.
- the fatty acids are present in the composition in a concentration of 0.1 to 1 % by weight, preferably at least 0.5% but typically not more than 0.9%, more preferably not more than 0.8% by weight of the composition.
- the liquid detergent composition of the present invention comprises a non-ionic surfactant.
- the nonionic surfactant of the present invention includes the condensation products of a higher alcohol (e.g., an alkanol containing about 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
- a higher alcohol e.
- Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-C 10 -C 20 alkanoic acid esters having a HLB of 8 to 15 also may be employed as the nonionic surfactant.
- These surfactants are well known and are available from Imperial Chemical Industries under the Tween trade name. Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.
- Preferred non-ionic surfactants of the present invention are Laureth 5, Laureth 7 and Laureth 9.
- the non-ionic surfactant is present in the composition in a concentration of 0.1 to to 3% by weight, preferably at least 0.5%, still more preferably at least 1% but typically not more than 2.5%, more preferably not more than 2% by weight of the composition.
- the composition further comprises water. Preferably 60 to 92%, more preferably not less than 62%, still more preferably not less than 65% but typically not more than 85%, more preferably not more than 80%, still more preferably not more than 75% by weight of the composition.
- compositions according to the invention may contain other ingredients which aid in the cleaning or sensory performance.
- Compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as thickeners, colorants, preservatives, polymers, anti microbial agents, perfumes, pH adjusters, sequesterants, alkalinity agents and hydrotropes.
- pH of the composition of the present invention is between 4.5 and 6.5, preferably between 5 and 6.5, more preferably between 5.5 and 6.
- composition may be used neat or diluted.
- the composition is typically applied neat directly to the surface.
- the composition is preferably diluted with water in a ratio of between 1:1 to 1:10
- composition may be packaged in the form of any commercially available bottle for storing the liquid.
- the bottle containing the liquid can be of different sizes and shapes to accommodate different volumes of the liquid; preferably between 0.25 and 2 L, more preferably between 0.25 and 1.5 L or even between 0.25 and 1 L.
- the bottle is preferably provided with a dispenser, which enables the consumer an easier mode of dispersion of the liquid. Spray or pump-dispensers may also be used.
- the invention in a second aspect, relates to a process of reducing foam during rinse in dishwashing comprising the steps of applying onto the hard surface in neat or diluted form a liquid composition according to the invention, cleaning the hard surface with a cleaning implement; and rinsing the hard surface.
- the composition may be applied by any known ways such as by using a scrub, sponge paper, cloth, wipes or any other direct application.
- the applied composition may be cleaned using a cleaning implement such as a scrub, sponge, paper, cloth or wipes.
- the invention relates to use of a composition according to the invention for providing anti-foaming activity upon rinse.
- compositions were prepared in a batch size of 30 grams each.
- a mixture of the primary and the secondary surfactant was taken in a 50 mL Tarson tube (the concentrations of the surfactants in the examples have been calculated taking into account the purity of the material).
- De-mineralized water was added to this mixture and vortexed till the surfactants had dissolved completely.
- the fatty acid(s) was then added to the mixture and heated to a temperature of 60°C in a water bath (maintained at 65°C). The mixture was stirred in between to ensure homogenous mixing. After complete solubilization of the fatty acid, the mixture was cooled to a temperature of 25 to 30°C, to which the non-ionic surfactant was added and stirred for about 2 to 3 minutes.
- the amphoteric surfactant was added along with the non-ionic surfactant. The final mixture was allowed to cool before using it for foam volume studies.
- test solution 6.25 g/L of the test solution was prepared in 24 FH water. 50 mL of the test solution was taken in a 250 mL graduated glass cylinder. The solution was shook by covering the opening of the cylinder and inverting it 10 times. Then the cylinder was placed on a flat surface of a table for 1 minute for the aqueous layer to separate and it was shook once again to even out the foam level. The volume of foam (excluding aliquote water), in mL was measured and recorded as the initial foam volume.
- the aliquote water was decanted along the sides of the cylinder retaining foam in the cylinder. 50 mL of fresh 24 FH water was added along the sides of the cylinder and the solution was shook and the foam volume measured as mentioned for initial foam measurement above. The cycles were repeated till the foam volume was ⁇ 10 mL.
- the volume of foam generated in the initial wash and the antifoaming effect during rinse by the composition according to the invention is compared to comparative compositions (C2 to C15) comprising various other fatty acids and their combinations.
- Table 2 Set *S urfactant wt % Non-Ionic Surfactant wt % Fatty acid Water wt % Foam volume per rinse cycle, ml wt % Type Initial foam 1 2 3 4 5 6 C1 18 - - - 82 160 160 145 110 60 30 12 C2 18 0.5 0.5 C8 81 147 137 123 83 40 12 ⁇ 1 0 C3 18 0.5 0.5 C12 81 147 130 110 55 19 ⁇ 1 0 - C4 18 0.5 0.5 C14 81 120 110 80 40 12 - ⁇ 1 0 - C5 18 0.5 0.5 C16 81 130 110 60 ⁇ 10 - - - C6 18 0.5 0.5 C18 81 133 113 47 ⁇ 10
- Ex1 performs best when compared to any other compositions comprising fatty acids outside the scope of the present invention (C2 to C15). It is noted that Ex1 maintains the same initial foam as the control (C1) and requires lesser rinse cycles compared to other compositions.
- Example 1 the volume of foam generated in the initial wash and the antifoaming effect during rinse by the composition according to the invention (Ex1) is compared to comparative combinations (C16 and C17) comprising only one component of the composition.
- Table 3 Set *Surfactant wt % Non-Ionic Surfactant wt % Fatty acid Water wt % Foam volume per rinse cycle, ml wt % Type Initial foam 1 2 3 4 5 6 C16 18 - 0.5 C12+C18 81.5 120 100 80 30 ⁇ 10 - - C17 18 0.5 - - 81.5 157 143 127 83 37 18 ⁇ 10 Ex 1 18 0.5 0.5 C12+C18 81 160 150 97 15 ⁇ 10 - - *13.50% LAS + 3.94% SLES 2EO + 0.56% CAPB
- the table shows that the composition according to the invention performs better with respect to the number of rinse cycles and initial foam volume than the compositions with one of the components missing.
- This example demonstrates the effect of concentration of the fatty acid combination on the volume of foam generated in the initial wash and the antifoaming effect during rinse.
- the example compositions Ex1 and Ex2 are compared with comparative compositions C18 and C19 comprising the fatty acid combination in a concentration outside the scope of the invention.
- the table above shows that best results for initial foam and an antifoaming effect during rinse are obtained at a fatty acid combination concentration within the scope of the present invention.
- the table also shows that at higher fatty acid combination concentrations, the initial foam is compromised (C18 and C19).
- compositions according to the invention comprising different concentrations of non-ionic surfactant (Ex1 and Ex3 to Ex5) are compared with comparative compositions having non-ionic surfactant in a concentration outside the scope of the present invention (C20 and C21).
- compositions comprising the non-ionic surfactant in a concentration according to the invention. At concentrations outside the scope of the invention, the compositions appear to result in phase separation.
- Example 1 the specific combination of fatty acids according to the invention (Ex1) is compared to a composition comprising commercially available mixtures of natural and distilled fatty acids such as coconut fatty acid and palm kernel fatty acid (C22).
- Table 6 Set *S urfactant wt % Non-Ionic Surfactant wt % Fatty acid Water wt % Foam volume per rinse cycle, ml wt % Type Initial foam 1 2 3 4 5 6 Ex1 18 0.5 0.5 C12+ C18 81 160 150 97 15 ⁇ 10 - - C22 18 0.5 0.5 Prifac 5908 81 157 147 117 57 25 ⁇ 1 0 - *13.50% LAS + 3.94% SLES 2EO + 0.56% CAPB
- a composition comprising the anionic surfactant system (Ex6) is compared to a surfactant system additionally comprising an amphoteric surfactant (Ex1).
- Table 7 Set Surfactant wt % No n-Ionic Surfactant wt % Fatty acid (C12 + C18) wt % Water wt % Foam volume per rinse cycle, ml Initial foam 1 2 3 4 5 6 Ex1 18* 0.5 0.5 81 160 150 97 15 ⁇ 10 - - Ex 6 18** 0.5 0.5 81 150 128 87 12 ⁇ 10 - - * 13.50% LAS + 3.94% SLES 2EO + 0.56% CAPB ** 9% LAS + 9% SLES 2EO
- composition comprising the fatty acid combination according to the invention is compared to verify if the same initial foam volume and antifoaming effect as in Ex1 are obtained with the same unsaturated fatty acid or with a combination having one of unsaturated fatty acid (C23 and C24).
Description
- The present invention is in the field of hard surface cleaning compositions; in particular liquid detergent compositions having foaming and cleaning characteristics in the main wash, yet significant foam reduction during rinse.
- Water is becoming a more and more scarcely available commodity, especially in developing countries, where it is not unusual that people have to walk many kilometres to arrive at a water source. As a result of which, there is an increasing need to save water.
- One way of saving water is to reuse the water and another way is to reduce the amount of water being used.
- Washing processes, including laundry, dishwashing and other household cleaning processes, require large amounts of water throughout the world. These are daily chores in which the use of water and a detergent cannot be avoided. Consumers usually like to see a lot of foam while washing as they associate foaming with detergent efficiency. However, it's rinsing that often takes a lot of effort and uses excess of water.
- The amount of water required for rinse is entirely dependent on the detergent used. Therefore, the use of water can be reduced or controlled based on the detergent.
- Thus, it has been a challenge to provide consumers with a cleaning composition that maintains the initial foam while exhibiting an antifoaming effect during rinse.
-
WO 98/27189 WO98/27189 -
JP 2004-203989 -
US 6090764 discloses a manual dishwashing detergent composition containing 0.2 to 10% by weight of a glycerol sulfate, 1 to 50% by weight of a C6-22 alkyl sulfate, C6-22 alkyl ether sulfate, C9-13 alkyl benzene sulfonate or a mixture thereof and 1 to 20% by weight based on the detergent as a whole of an alkyl glucoside. The composition ofUS 6090764 does not include fatty acids, however very small quantities of soap may be present. -
CN 102876483 discloses a low foam easy bleaching liquid detergent composition and its preparation method. The liquid detergent composition comprises 0.1 to 20% unsaturated fatty acid, 0.1 to 5% saturated fatty acids, 0.1 to 5% alkali neutralizing agent, 1 to 25% non-ionic surfactant, 1 to 25% anionic surfactant, 0.5 to 20% of other additives and water. This formulation uses saturated and unsaturated fatty acids to reduce the amount of the liquid detergent wash foam, to solve the problem of difficulty in rinsing. However, there is no disclosure that a specific combination of saturated stearic acid and saturated lauric acid is preferred. -
WO 2013/038750 discloses a liquid detergent composition which contains one or more kinds of anionic surfactant selected from the group consisting of polyoxyalkylene alkyl ether sulfuric acid ester salts and alkylbenzene sulfonic acid salts, a fatty acid and/or a salt thereof, an alkanol amine, a carbonate, a nonionic surfactant and water. However, there is no disclosure about the specific combination of saturated fatty acids selected from stearic and lauric acid. - It is therefore an object of the present invention to provide water saving in household process, especially hand dish wash processes.
- It is another object of the present invention to provide a liquid detergent that has an antifoaming effect during rinse while maintaining foaming characteristics in the mainwash.
- It is a further object of the present invention to provide a liquid detergent composition that uses less water during rinsing in hand dish wash processes.
- Surprisingly, it has been found that an antifoaming effect may be obtained only during rinse in hard surface cleaning processes by a liquid detergent comprising a surfactant system of a primary and a secondary surfactant, a combination of saturated fatty acids selected from lauric and stearic acid and a non-ionic surfactant.
- Accordingly, in a first aspect, the present invention provides a liquid detergent composition comprising 8 to 30% by weight of a surfactant system comprising a primary surfactant of the formula R1-OR')n-SO3 - M+, wherein: R1 is saturated or unsaturated C8-C16 alkyl chain; R' is ethylene; n is from 1 to 18; M+ is a suitable cation which provides charge neutrality selected from sodium, calcium, potassium and magnesium; and a secondary surfactant selected from alkylbenzene sulphonate and derivatives; and alkyl sulphates; less than or equal to 1 % by weight of a combination of saturated fatty acids selected from lauric and stearic acid; less than or equal to 3% by weight of a non-ionic surfactant; and water.
- In a second aspect, the invention provides a process of reducing foam during rinse in dishwashing comprising the steps of applying onto the hard surface in neat or diluted form a liquid composition according to the invention; cleaning the hard surface with a cleaning implement; and rinsing the hard surface.
- In a third aspect, the invention provides use of a composition according to the invention for providing anti-foaming activity upon rinse.
- In the context of the present invention, the reference to "hard surface" typically means utensils or kitchenware, kitchen tops, kitchen floors, sinks and platforms, floors and bathrooms.
- These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be utilised in any other aspect of the invention. The word "comprising" is intended to mean "including" but not necessarily "consisting of" or "composed of." In other words, the listed steps or options need not be exhaustive. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about". Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated.
- In a first aspect, the invention relates to a liquid detergent composition comprising a surfactant system, a combination of fatty acids, a non-ionic surfactant and water.
- The liquid detergent composition of the present invention comprises a surfactant system.
- The surfactant system comprises a primary and a secondary surfactant. Both the primary and the secondary surfactants are selected from anionic surfactants.
- The primary surfactant of the present invention is a surfactant of the formula:
- R1-(OR')nO-SO3 - M+, wherein:
- R1 is saturated or unsaturated C8-C16, preferably C12-C14 alkyl chain; preferably, R1 is a saturated C8-C16, more preferably a saturated C12-C14 alkyl chain;
- R' is ethylene;
- n is from 1 to 18; preferably from 1 to 15, more preferably from 1 to 10 ,still more preferably from 1 to 5.
- M+ is a suitable cation which provides charge neutrality, preferably sodium, calcium, potassium, or magnesium, more preferably a sodium cation.
- Preferred primary surfactants are sodium lauryl ether sulphate having 1 to 3 ethylene oxide units per molecule.
- Most preferred primary surfactant of the present invention is sodium lauryl ether sulphate having 1 to 2 ethylene oxide units per molecule.
- Primary surfactant may be present in a concentration of 5 to 95 %, preferably at least 12%, more preferably at least 20%, still more preferably at least 30% but typically not more than 85%, preferably not more than 75%, more preferably not more than 65% , still more preferably not more than 55% by weight of the surfactant system.
- The secondary surfactant of the present invention may be selected from alkylbenzene sulphonates and derivatives; and alkyl sulphates.
- Alkylbenzene sulphonates and derivatives include water-soluble alkali metal salts of organic sulphonates having alkyl radicals typically containing from about 8 to about 22 carbon atoms, preferably 8 to 18 carbon atoms, still more preferably 12 to 15 carbon atoms and may be unsaturated.
- Examples include sodium salt of linear alkylbenzene sulphonate, alkyl toluene sulphonate, alkyl xylene sulphonate, alkyl phenol sulphonate, alkyl naphthalene-sulphonate, ammonium diamylnaphthalene-sulphonate and sodium dinonylnaphthalene-sulphonate and mixtures with olefin sulphonates.
- Examples of alkyl sulphates include sodium lauryl sulphate, ammonium lauryl sulphate, diethanolamine(DEA) lauryl sulphate. Suitable examples also includes alkyl sulphates commercially available from natural source with trade names Galaxy 689, Galaxy 780, Galaxy 789, Galaxy 799 SP and from synthetic origin with trade names Safol 23, Dobanol 23A or 23S, Lial 123 S, Alfol 1412S, Empicol LC3, Empicol 075SR.
- Preferred secondary surfactants are sodium salt of linear alkylbenzene sulphonate and sodium lauryl sulphate.
- Most preferred secondary surfactant is sodium salt of linear alkylbenzene sulphonate.
- Secondary surfactant may be present in a concentration of 5 to 95 %, preferably at least 12%, more preferably at least 20%, still more preferably at least 30% but typically not more than 85%, preferably not more than 75%, more preferably not more than 65%, still more preferably not more than 55% by weight of the surfactant system.
- The surfactant system of the present invention may further comprise an amphoteric surfactant. Suitable surfactants include cocoamidopropyl betaine (CAPB), coco amido propyl amine oxide (CAPAO), cocodiethanol amide (CDEA) and cocomonoethanol amide (CMEA).
- Most preferred amphoteric surfactant is cocoamidopropyl betaine.
- When present, the amphoteric surfactant is in a concentration of 0.1 to 20%, preferably at least 0.5%, more preferably at least 3%, still more preferably atleast 6% or even more preferably at least 8% but typically not more than 18%, preferably not more than 16%, more preferably not more than 13%, still more preferably not more than 10% by weight of the surfactant system.
- The surfactant system is present in the composition in a concentration of 8 to 30%, preferably not less than 15%, more preferably not less than 18%, still more preferably not less than 20% but typically not more than 28%, preferably not more than 27% or even not more than 26% by weight of the composition.
- The liquid detergent composition of the present invention comprises a combination of fatty acids.
- The combination of fatty acids used in present invention is selected from lauric (C12) and stearic acid (C18).
- Without wishing to be bound by a theory, it is thought that when C12 and C18 fatty acids are used in combination, the chain lengths of these fatty acids have a crucial role on the flash foam and the antifoam activity during rinse. C12 ensures there is no adverse effect on the flash foam of surfactant solution while C18 triggers the antifoam activity only during rinse. Individual fatty acids are found to either kill the surfactant's flash foam or have poor antifoaming activity.
- Fatty acids used in the present invention are saturated fatty acids. Saturated lauric (C12) and stearic acid (C18) are preferred. Unsaturated fatty acids are not preferred in the present invention.
- Lauric and stearic acid are present in the composition in a ratio of 1:1.
- The fatty acids are present in the composition in a concentration of 0.1 to 1 % by weight, preferably at least 0.5% but typically not more than 0.9%, more preferably not more than 0.8% by weight of the composition.
- The liquid detergent composition of the present invention comprises a non-ionic surfactant.
- The nonionic surfactant of the present invention includes the condensation products of a higher alcohol (e.g., an alkanol containing about 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol. Particularly preferred is Lauryl alcohol condensed with 5, 7 and 9 moles of ethylene oxide (Laureth 5, Laureth 7 and Laureth 9).
- Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-C10-C20 alkanoic acid esters having a HLB of 8 to 15 also may be employed as the nonionic surfactant. These surfactants are well known and are available from Imperial Chemical Industries under the Tween trade name. Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.
- Preferred non-ionic surfactants of the present invention are Laureth 5, Laureth 7 and Laureth 9.
- The non-ionic surfactant is present in the composition in a concentration of 0.1 to to 3% by weight, preferably at least 0.5%, still more preferably at least 1% but typically not more than 2.5%, more preferably not more than 2% by weight of the composition.
- The composition further comprises water. Preferably 60 to 92%, more preferably not less than 62%, still more preferably not less than 65% but typically not more than 85%, more preferably not more than 80%, still more preferably not more than 75% by weight of the composition.
- The composition according to the invention may contain other ingredients which aid in the cleaning or sensory performance. Compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as thickeners, colorants, preservatives, polymers, anti microbial agents, perfumes, pH adjusters, sequesterants, alkalinity agents and hydrotropes.
- pH of the composition of the present invention is between 4.5 and 6.5, preferably between 5 and 6.5, more preferably between 5.5 and 6.
- The composition may be used neat or diluted.
- For hard surface cleaning or for dishwashing purposes, the composition is typically applied neat directly to the surface. When applied in a diluted form, the composition is preferably diluted with water in a ratio of between 1:1 to 1:10
- Both manual dishwashing and machine dishwashing are considered in the context of the present invention.
- The composition may be packaged in the form of any commercially available bottle for storing the liquid.
- The bottle containing the liquid can be of different sizes and shapes to accommodate different volumes of the liquid; preferably between 0.25 and 2 L, more preferably between 0.25 and 1.5 L or even between 0.25 and 1 L. The bottle is preferably provided with a dispenser, which enables the consumer an easier mode of dispersion of the liquid. Spray or pump-dispensers may also be used.
- In a second aspect, the invention relates to a process of reducing foam during rinse in dishwashing comprising the steps of applying onto the hard surface in neat or diluted form a liquid composition according to the invention, cleaning the hard surface with a cleaning implement; and rinsing the hard surface.
- The composition may be applied by any known ways such as by using a scrub, sponge paper, cloth, wipes or any other direct application. The applied composition may be cleaned using a cleaning implement such as a scrub, sponge, paper, cloth or wipes.
- In a third aspect, the invention relates to use of a composition according to the invention for providing anti-foaming activity upon rinse.
- The invention will now be illustrated by means of the following non-limiting examples.
-
Materials :Table 1 Name Chemical /Material Grade Manufacturer/ Supplier Fatty Acids Caprylic acid Lab Grade Sigma Lauric acid Lab Grade SD Fine Chem Myristic acid Lab Grade Fluka Palmitic acid Lab Grade Sigma Stearic acid Lab Grade SDFine Chem Oleic acid Lab Grade Sigma Prifac 5908 (Hydrogenated topped palm kernel fatty acids) Lab Grade CRODA Non-ionic Surfactant Laureth 7 (Lauryl alcohol ethoxylates) Commercial Galaxy Surfactants Anionic Surfactant LAS powder (Linear alkyl benzene suphonate) (97% active content) Commercial Advance Surfactants India Limited SLES 2EO (Sodium Lauryl ether sulfonate) (70% active content) Commercial Galaxy Amphoteric Surfactant CAPB (Cocoamidopropyl betaine) (29-31% active content) Commercial Galaxy - The compositions were prepared in a batch size of 30 grams each. A mixture of the primary and the secondary surfactant was taken in a 50 mL Tarson tube (the concentrations of the surfactants in the examples have been calculated taking into account the purity of the material). De-mineralized water was added to this mixture and vortexed till the surfactants had dissolved completely. The fatty acid(s) was then added to the mixture and heated to a temperature of 60°C in a water bath (maintained at 65°C). The mixture was stirred in between to ensure homogenous mixing. After complete solubilization of the fatty acid, the mixture was cooled to a temperature of 25 to 30°C, to which the non-ionic surfactant was added and stirred for about 2 to 3 minutes. In compositions with amphoteric surfactant, the amphoteric surfactant was added along with the non-ionic surfactant. The final mixture was allowed to cool before using it for foam volume studies.
- For the measurement of foam volume, standard cylinder shake method was used.
- 6.25 g/L of the test solution was prepared in 24 FH water. 50 mL of the test solution was taken in a 250 mL graduated glass cylinder. The solution was shook by covering the opening of the cylinder and inverting it 10 times. Then the cylinder was placed on a flat surface of a table for 1 minute for the aqueous layer to separate and it was shook once again to even out the foam level. The volume of foam (excluding aliquote water), in mL was measured and recorded as the initial foam volume.
- To measure the foam in the first and further rinse cycles, the aliquote water was decanted along the sides of the cylinder retaining foam in the cylinder. 50 mL of fresh 24 FH water was added along the sides of the cylinder and the solution was shook and the foam volume measured as mentioned for initial foam measurement above. The cycles were repeated till the foam volume was <10 mL.
- Initial foam volume equal to the control or upto 10 mL lesser than the control is considered to be good. Foam volume reduction of <10 mL in the fourth or lower cycles are considered to be good.
- In this example, the volume of foam generated in the initial wash and the antifoaming effect during rinse by the composition according to the invention (Ex1) is compared to comparative compositions (C2 to C15) comprising various other fatty acids and their combinations.
Table 2 Set *S urfactant wt % Non-Ionic Surfactant wt% Fatty acid Water wt% Foam volume per rinse cycle, ml wt% Type Initial foam 1 2 3 4 5 6 C1 18 - - - 82 160 160 145 110 60 30 12 C2 18 0.5 0.5 C8 81 147 137 123 83 40 12 <1 0 C3 18 0.5 0.5 C12 81 147 130 110 55 19 <1 0 - C4 18 0.5 0.5 C14 81 120 110 80 40 12 - <1 0 - C5 18 0.5 0.5 C16 81 130 110 60 <10 - - - C6 18 0.5 0.5 C18 81 133 113 47 <10 - - - C7 18 0.5 0.5 C8+C12 81 130 130 140 70 30 12 - <1 0 C8 18 0.5 0.5 C8+C14 81 135 130 110 50 18 - <1 0 - C9 18 0.5 0.5 C8+C16 81 140 140 110 70 30 <1 0 - C10 18 0.5 0.5 C8+C18 81 130 130 110 60 30 <1 0 - C11 18 0.5 0.5 C12+ C14 81 140 120 110 70 30 <1 0 - C12 18 0.5 0.5 C12+ C16 81 130 130 100 50 16 - - Ex1 18 0.5 0.5 C12+ C18 81 160 150 97 15 <10 - - C13 18 0.5 0.5 C14+ C16 81 130 110 70 26 - <10 - - C14 18 0.5 0.5 C14+ C18 81 130 120 50 <10 - - - C15 18 0.5 0.5 C16+ C18 81 110 100 40 <10 - - - *13.50% LAS + 3.94% SLES 2EO + 0.56% CAPB - The table above shows that the composition according to the invention (Ex1) performs best when compared to any other compositions comprising fatty acids outside the scope of the present invention (C2 to C15). It is noted that Ex1 maintains the same initial foam as the control (C1) and requires lesser rinse cycles compared to other compositions.
- In this example, the volume of foam generated in the initial wash and the antifoaming effect during rinse by the composition according to the invention (Ex1) is compared to comparative combinations (C16 and C17) comprising only one component of the composition.
Table 3 Set *Surfactant wt% Non-Ionic Surfactant wt% Fatty acid Water wt% Foam volume per rinse cycle, ml wt % Type Initial foam 1 2 3 4 5 6 C16 18 - 0.5 C12+C18 81.5 120 100 80 30 <10 - - C17 18 0.5 - - 81.5 157 143 127 83 37 18 <10 Ex 1 18 0.5 0.5 C12+C18 81 160 150 97 15 <10 - - *13.50% LAS + 3.94% SLES 2EO + 0.56% CAPB - The table shows that the composition according to the invention performs better with respect to the number of rinse cycles and initial foam volume than the compositions with one of the components missing.
- This example demonstrates the effect of concentration of the fatty acid combination on the volume of foam generated in the initial wash and the antifoaming effect during rinse. The example compositions Ex1 and Ex2 are compared with comparative compositions C18 and C19 comprising the fatty acid combination in a concentration outside the scope of the invention.
Table 4 Set *Surfactant wt % Non-Ionic Surfactant wt% Fatty acid (C12 + C18) wt% Water wt% Foam volume per rinse cycle, ml Initial foam 1 2 3 4 5 6 Ex1 18 0.5 0.5 81 160 150 97 15 <10 - - Ex2 18 0.5 1 80.5 160 160 90 42 <10 - - C18 18 0.5 2 79.5 110 90 56 26 <10 - - C19 18 0.5 3 78.5 80 60 24 <10 - - - *13.50% LAS + 3.94% SLES 2EO + 0.56% CAPB - The table above shows that best results for initial foam and an antifoaming effect during rinse are obtained at a fatty acid combination concentration within the scope of the present invention. The table also shows that at higher fatty acid combination concentrations, the initial foam is compromised (C18 and C19).
- In this example, compositions according to the invention comprising different concentrations of non-ionic surfactant (Ex1 and Ex3 to Ex5) are compared with comparative compositions having non-ionic surfactant in a concentration outside the scope of the present invention (C20 and C21).
Table 5 Set *Surfactant wt % Non-Ionic Surfactant wt% Fatty acid (C12 + C18) wt% Water wt% Foam volume per rinse cycle, ml Initial foam 1 2 3 4 5 6 Ex1 18 0.5 0.5 81 160 150 97 15 <10 - - Ex3 18 1 0.5 80.5 155 126 80 20 <10 - - Ex4 18 2 0.5 79.5 160 135 70 15 <10 - - Ex5 18 3 0.5 78.5 160 140 80 <10 - - - C20 18 3.5 0.5 78 Phase separation C21 18 4 0.5 77.5 Phase separation *13.50% LAS + 3.94% SLES 2EO + 0.56% CAPB - It is inferred from the results of the above table that good initial foam and reduction in foam during rinse are obtained with compositions comprising the non-ionic surfactant in a concentration according to the invention. At concentrations outside the scope of the invention, the compositions appear to result in phase separation.
- In this example, the specific combination of fatty acids according to the invention (Ex1) is compared to a composition comprising commercially available mixtures of natural and distilled fatty acids such as coconut fatty acid and palm kernel fatty acid (C22).
Table 6 Set *S urfactant wt % Non-Ionic Surfactant wt% Fatty acid Water wt% Foam volume per rinse cycle, ml wt% Type Initial foam 1 2 3 4 5 6 Ex1 18 0.5 0.5 C12+ C18 81 160 150 97 15 <10 - - C22 18 0.5 0.5 Prifac 5908 81 157 147 117 57 25 <1 0 - *13.50% LAS + 3.94% SLES 2EO + 0.56% CAPB - The above table shows that the good initial foam generated by Ex1 and the antifoaming effect during rinse is still not obtained even if the fatty acid combination is replaced by commercially available mixtures having combinations of the same.
- In this example, a composition comprising the anionic surfactant system (Ex6) is compared to a surfactant system additionally comprising an amphoteric surfactant (Ex1).
Table 7 Set Surfactant wt% No n-Ionic Surfactant wt % Fatty acid (C12 + C18) wt% Water wt% Foam volume per rinse cycle, ml Initial foam 1 2 3 4 5 6 Ex1 18* 0.5 0.5 81 160 150 97 15 <10 - - Ex 6 18** 0.5 0.5 81 150 128 87 12 <10 - - * 13.50% LAS + 3.94% SLES 2EO + 0.56% CAPB
** 9% LAS + 9% SLES 2EO - The above table shows that addition of an amphoteric surfactant helps in boosting the initial foam generated by the composition according to the invention.
- In this example, the composition comprising the fatty acid combination according to the invention is compared to verify if the same initial foam volume and antifoaming effect as in Ex1 are obtained with the same unsaturated fatty acid or with a combination having one of unsaturated fatty acid (C23 and C24).
Table 8 Set *S urfactant wt % Non-Ionic Surfactant wt% Fatty acid Water wt% Foam volume per rinse cycle, ml wt% Type Initial foam 1 2 3 4 5 6 Ex1 18 0.5 0.5 C12+ C18 81 160 150 97 15 <10 - - C3 18 0.5 0.5 C12 81 147 130 110 55 19 <1 0 - C23 18 0.5 0.5 C18:1 81 110 110 70 10 - - - C24 18 0.5 0.5 C12+ C18:1 81 110 110 80 30 <10 - - *13.50% LAS + 3.94% SLES 2EO + 0.56% CAPB - The above table clearly shows that use of the same unsaturated fatty acid alone or in combination with a saturated fatty acid in the composition considerably decreases the initial foam volume.
Claims (9)
- A liquid detergent composition comprisinga) 8 to 30% by weight of a surfactant system comprising(i) a primary surfactant of the formula R1-(OR')n-O-SO3 - M+, wherein:R1 is saturated or unsaturated C8-C16 alkyl chain;R' is ethylene;n is from 1 to 18;M+ is a suitable cation which provides charge neutrality selected from sodium, calcium, potassium and magnesium; and (ii) a secondary surfactant selected from alkylbenzene sulphonate and derivatives; and alkyl sulphates;b) 0.1 to 1 %by weight of a combination of saturated fatty acids selected from lauric and stearic acid in a ratio of 1:1;c) 0.1 to 3% by weight of a non-ionic surfactant; andd) water.
- A composition according to claim 1, wherein the composition comprises 60 to 92% by weight of water.
- A composition according to claim 1 or 2 wherein the non-ionic surfactant is Laureth 5, Laureth 7 or Laureth 9.
- A composition according to anyone of claims 1 to 3, wherein the primary surfactant is sodium lauryl ether sulphate having 1 to 2 ethylene oxide units per molecule.
- A composition according to anyone of claims 1 to 4, wherein the secondary surfactant is sodium salt of linear alkylbenzene sulphonate or sodium lauryl sulphate.
- A composition according to anyone of claims 1 to 5, wherein the surfactant system further comprises an amphoteric surfactant.
- A composition according to claim 6, wherein the amphoteric surfactant is cocoamidopropyl betaine.
- A process of reducing foam during rinse in dishwashing comprising the steps of:a) applying onto the hard surface in neat or diluted form a liquid composition according to anyone of claims 1 to 7 ;b) cleaning the hard surface with a cleaning implement; andc) rinsing the hard surface.
- Use of a composition according to any one of claims 1 to 8 for providing anti- foaming activity upon rinse.
Applications Claiming Priority (2)
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EP14182852 | 2014-08-29 | ||
PCT/EP2015/068913 WO2016030226A1 (en) | 2014-08-29 | 2015-08-18 | Liquid detergent composition |
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EP3186347A1 EP3186347A1 (en) | 2017-07-05 |
EP3186347B1 true EP3186347B1 (en) | 2017-12-20 |
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EP (1) | EP3186347B1 (en) |
CN (1) | CN106574217B (en) |
AR (1) | AR101702A1 (en) |
BR (1) | BR112017003309B1 (en) |
CL (1) | CL2017000324A1 (en) |
EA (1) | EA032981B1 (en) |
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US11104865B2 (en) | 2016-02-17 | 2021-08-31 | Conopeo, Inc. | Dishwash composition comprising rinse-activatable antifoam |
EP3545062B1 (en) * | 2016-11-24 | 2020-02-19 | Unilever N.V. | Liquid detergent composition |
EP3697884A1 (en) * | 2017-10-19 | 2020-08-26 | The Procter and Gamble Company | Cleaning compositions containing fatty acid blend |
BR112021011742A2 (en) * | 2018-12-17 | 2021-08-31 | Unilever Ip Holdings B.V. | LIQUID DETERGENT COMPOSITION, HARD SURFACE CLEANING METHOD AND USE OF THE COMPOSITION |
EP3670639A1 (en) | 2018-12-17 | 2020-06-24 | Unilever N.V. | Liquid hand dishwash formulation comprising hydroxy fatty acid and polymer |
WO2020126601A1 (en) | 2018-12-17 | 2020-06-25 | Unilever N.V. | Liquid hand dishwash formulation comprising fatty acids and polymer |
WO2022122559A1 (en) * | 2020-12-07 | 2022-06-16 | Unilever Ip Holdings B.V. | A hard surface cleaning composition |
WO2023083995A1 (en) | 2021-11-12 | 2023-05-19 | Clariant International Ltd | Hand dish-washing composition containing ethoxylated glycerol esters |
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DE1692012A1 (en) * | 1968-01-12 | 1971-01-21 | Henkel & Cie Gmbh | laundry detergent |
DE2244665A1 (en) * | 1972-09-12 | 1974-03-21 | Huels Chemische Werke Ag | DETERGENT WITH A FOAM-EMPTY SUBSTANCE |
JPS60204701A (en) * | 1984-03-30 | 1985-10-16 | Toho Chem Ind Co Ltd | Low-foaming wettable dust composition for agricultural purpose |
CN85106704B (en) * | 1985-08-31 | 1988-03-09 | 冯正泽 | Foam depressant |
AU2005300860B2 (en) * | 2004-11-08 | 2008-12-11 | Unilever Plc | Liquid detergent composition |
WO2013064357A1 (en) * | 2011-11-02 | 2013-05-10 | Henkel Ag & Co. Kgaa | Structured detergent or cleaning agent having a flow limit ii |
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2015
- 2015-08-18 EA EA201790493A patent/EA032981B1/en not_active IP Right Cessation
- 2015-08-18 WO PCT/EP2015/068913 patent/WO2016030226A1/en active Application Filing
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- 2015-08-18 CN CN201580042797.4A patent/CN106574217B/en active Active
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CL2017000324A1 (en) | 2017-08-18 |
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SA517380868B1 (en) | 2020-08-26 |
CN106574217A (en) | 2017-04-19 |
BR112017003309B1 (en) | 2022-02-08 |
EP3186347A1 (en) | 2017-07-05 |
BR112017003309A2 (en) | 2018-01-23 |
CN106574217B (en) | 2019-05-31 |
AR101702A1 (en) | 2017-01-04 |
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