EP0509608A2 - Light duty liquid detergent compositions - Google Patents
Light duty liquid detergent compositions Download PDFInfo
- Publication number
- EP0509608A2 EP0509608A2 EP92201089A EP92201089A EP0509608A2 EP 0509608 A2 EP0509608 A2 EP 0509608A2 EP 92201089 A EP92201089 A EP 92201089A EP 92201089 A EP92201089 A EP 92201089A EP 0509608 A2 EP0509608 A2 EP 0509608A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- composition
- sodium
- sulfosuccinate
- ethylene oxide
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 102
- 239000003599 detergent Substances 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 title claims abstract description 22
- 239000004094 surface-active agent Substances 0.000 claims abstract description 50
- 239000006260 foam Substances 0.000 claims abstract description 49
- -1 sodium alkyl benzene Chemical class 0.000 claims abstract description 49
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 38
- 239000002689 soil Substances 0.000 claims abstract description 35
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 229940077388 benzenesulfonate Drugs 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims description 14
- 238000005187 foaming Methods 0.000 claims description 13
- TYLSDQJYPYQCRK-UHFFFAOYSA-N sulfo 4-amino-4-oxobutanoate Chemical compound NC(=O)CCC(=O)OS(O)(=O)=O TYLSDQJYPYQCRK-UHFFFAOYSA-N 0.000 claims description 13
- 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 11
- 230000006641 stabilisation Effects 0.000 claims description 11
- 238000011105 stabilization Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000003752 hydrotrope Substances 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 8
- 229940048842 sodium xylenesulfonate Drugs 0.000 claims description 8
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002304 perfume Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229940079842 sodium cumenesulfonate Drugs 0.000 claims description 7
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 claims description 7
- JHIXEZNTXMFXEK-UHFFFAOYSA-N N-(tetradecanoyl)ethanolamine Chemical compound CCCCCCCCCCCCCC(=O)NCCO JHIXEZNTXMFXEK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 238000004851 dishwashing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- ZZNDQCACFUJAKJ-UHFFFAOYSA-N 1-phenyltridecan-1-one Chemical compound CCCCCCCCCCCCC(=O)C1=CC=CC=C1 ZZNDQCACFUJAKJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 239000003899 bactericide agent Substances 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 239000003352 sequestering agent Substances 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims description 2
- 229940098691 coco monoethanolamide Drugs 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000417 fungicide Substances 0.000 claims description 2
- 239000002085 irritant Substances 0.000 claims description 2
- 231100000021 irritant Toxicity 0.000 claims description 2
- SKDZEPBJPGSFHS-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)N(CCO)CCO SKDZEPBJPGSFHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003605 opacifier Substances 0.000 claims description 2
- 239000006179 pH buffering agent Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000000516 sunscreening agent Substances 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims 1
- 125000004395 glucoside group Chemical group 0.000 claims 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 11
- 239000003381 stabilizer Substances 0.000 abstract description 3
- 239000004519 grease Substances 0.000 description 37
- 229930182478 glucoside Natural products 0.000 description 16
- 150000008131 glucosides Chemical class 0.000 description 10
- 159000000003 magnesium salts Chemical class 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000002671 adjuvant Substances 0.000 description 5
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 239000013065 commercial product Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- 235000019864 coconut oil Nutrition 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052564 epsomite Inorganic materials 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229930182470 glycoside Natural products 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000008390 olive oil Nutrition 0.000 description 2
- 239000004006 olive oil Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- YNDGLMYLSGEDHX-UHFFFAOYSA-N 1,2,4,3-trioxathiane 3,3-dioxide Chemical compound O=S1(=O)OCCOO1 YNDGLMYLSGEDHX-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- UBLAMKHIFZBBSS-UHFFFAOYSA-N 3-Methylbutyl pentanoate Chemical compound CCCCC(=O)OCCC(C)C UBLAMKHIFZBBSS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000206575 Chondrus crispus Species 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical compound CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 description 1
- ZRURXONDQPKTDP-UHFFFAOYSA-N [2-chloro-6-(phenylcarbamoyl)phenyl] hypobromite Chemical compound ClC1=CC=CC(C(=O)NC=2C=CC=CC=2)=C1OBr ZRURXONDQPKTDP-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940047662 ammonium xylenesulfonate Drugs 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000008365 aqueous carrier Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079886 disodium lauryl sulfosuccinate Drugs 0.000 description 1
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- KHIQYZGEUSTKSB-UHFFFAOYSA-L disodium;4-dodecoxy-4-oxo-3-sulfobutanoate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O.CCCCCCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O KHIQYZGEUSTKSB-UHFFFAOYSA-L 0.000 description 1
- 229960000878 docusate sodium Drugs 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002338 glycosides Chemical group 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- ACGUYXCXAPNIKK-UHFFFAOYSA-N hexachlorophene Chemical compound OC1=C(Cl)C=C(Cl)C(Cl)=C1CC1=C(O)C(Cl)=CC(Cl)=C1Cl ACGUYXCXAPNIKK-UHFFFAOYSA-N 0.000 description 1
- 229960004068 hexachlorophene Drugs 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- HESSGHHCXGBPAJ-UHFFFAOYSA-N n-[3,5,6-trihydroxy-1-oxo-4-[3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyhexan-2-yl]acetamide Chemical compound CC(=O)NC(C=O)C(O)C(C(O)CO)OC1OC(CO)C(O)C(O)C1O HESSGHHCXGBPAJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SLBXZQMMERXQAL-UHFFFAOYSA-M sodium;1-dodecoxy-4-hydroxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].CCCCCCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O SLBXZQMMERXQAL-UHFFFAOYSA-M 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDOBMVIEWHZYDL-UHFFFAOYSA-N tetrachlorosalicylanilide Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(=O)NC1=CC=CC=C1 BDOBMVIEWHZYDL-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- ICUTUKXCWQYESQ-UHFFFAOYSA-N triclocarban Chemical compound C1=CC(Cl)=CC=C1NC(=O)NC1=CC=C(Cl)C(Cl)=C1 ICUTUKXCWQYESQ-UHFFFAOYSA-N 0.000 description 1
- 229960001325 triclocarban Drugs 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940071104 xylenesulfonate Drugs 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
-
- 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
- C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
-
- 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
-
- 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
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
-
- 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
- C11D1/662—Carbohydrates or derivatives
Definitions
- This invention relates to light duty liquid detergents having particular utility in the hand washing of dishware, including dishes, pots, pans, glassware and silverware/flatware. More particularly, it relates to a liquid dishwashing detergent composition which provides stable, persistent foaming characteristics combined with good rinseability, mildness to the skin and effectiveness in removing greasy soils from dishware.
- Foam generation by detergent compositions is associated by the consumer with good detersive ability. However, it is apparent that long lasting foam, whether considered copious or medium to medium-low foam content is, by itself, not a sufficient measure of cleaning ability. Nevertheless, much effort has been extended to optimize foaming characteristics, without necessarily improving cleaning ability.
- Greasy soils are generally considered to be one of the most difficult soil types to be removed by hand washing. Effective grease removal is nearly always associated with requiring high temperature water to help dissolve and remove the grease.
- Another important characteristic to the consumer for hand dishwashing formulations is the ability to easily wash away the copious foam which is associated with good cleaning performance.
- Surfactant systems providing APG generated foams are not always acceptable in terms of rinseability.
- compositions which avoid the elevated problems and accomplish the foregoing objectives.
- the compositions although prepared from otherwise known ingredients, but in unique combinations and proportions, is capable of achieving a new and beneficial result.
- the liquid dishwashing detergent composition comprises, as essential ingredients:
- the present invention is based, in part, on the quite unexpected discovery that the foam stabilizing, foam boosting combination of the alkyl polyglucoside (APG) and alkanolamide components has a significant impact on the grease removal performance of the composition at a constant level of total surfactant/foam stabilization components. More specifically, it has now been found that while some enhanced grease removal benefits may be provided with the foam stabilizing alkanolamide alone, as compared to existing top of the line commercial products, the improvement in grease removal performance is further dramatically improved in the system containing both foam stabilizing alkanolamide and APG. Furthermore, by employing the alkyl ether sulfate (AEOS) with less than 3 moles ethylene oxide, e.g.
- AEOS alkyl ether sulfate
- AEOS-1EO or AEOS-2EO a more copious foam can be obtained as compared to the same composition containing AEOS-3EO (i.e. 3 moles ethylene oxide) while still retaining acceptable mildness.
- AEOS-3EO i.e. 3 moles ethylene oxide
- good rinseability of the dishware is achieved without impairing cleaning performance.
- Liquid Palmolive® (17% NaLAS, 13% AEOS-3EO, 4% LMMEA, 3.3% SCS+SXS, 0.5% inorganic salts; balance perfume, color, ethanol, water), removed about 25 milligrams (mg), of greasy soil (lard) as compared to only 5 mg for the same formula with 0% LMMEA.
- a composition according to this invention containing APG grease removal increases by about 80 mg over the level of LMMEA between about 1% and about 4% by weight of the composition.
- the foam stabilization system which may also itself contribute to the foaming capacity as well as foam stabilizing effect is comprised of the lower alkanolamide of higher alkanoic acid which is the reaction product of a lower alkanol of 2 to 3 carbon atoms and an alkanoic acid of 10 to 16 carbon atoms, preferably with 80% or more of the lower alkanol being ethanol and a similar proportion of the alkanoic acid being of 12 to 14 carbon atoms.
- Other lower alkanols that are also useful are n-propanol and isopropanol.
- the preferred alkanoic acid is a mixture of lauric and myristic acids, generally in proportions of 1:2 to 2:1, with about 50% of each being preferable.
- coconut oil or hydrogenated coconut oil may be used as a source of the alkanoic acids.
- Suitable alkanoic acid alkanolamides include the monoethanolamides. diethanolamides and the monoisopropanolamides.
- Specific examples include mixed lauric/myristic diethanolamide, lauric/myristic monoethanolamide, lauric monoethanolamide, lauric diethanolamide, coco diethanolamide, coco monoethanolamide, and the like.
- the amount of the alkanoic acid alkanolamide may be up to about 6% of the composition, such as 0.5 to 6%, preferably 1 to 5%, more preferably 1 to 4%, such as 1.5, 2, 3 or 4%, of the composition.
- compositions of this invention which include the salt surfactants (A)(1), (A)(3), (A)(4) and, optionally, (A)(2) and foam stabilization system (B), in the specified proportions, as essential ingredients are formulated in an aqueous carrier to provide mild, stable foaming liquid compositions especially effective in cleaning, by hand washing, dishware, such as dishes, glasses, flatware, pots, pans, etc., at ambient wash water temperature, as well, of course, at warm or hot wash water temperatures.
- the invention formulations are mild to the hands and are clear and homogeneous. Clarity and homogeneity may often, however, be improved by inclusion of, for example, organic solvents and/or hydrotropes, and these and other optional additives may also be included in the compositions in amounts which do not adversely influence the desirable properties.
- Cosmetically acceptable organic solvents usually lower alcohols, such as ethanol, propanol, isopropanol, propylene glycol, or mixtures thereof, may be included in the composition for its thinning effect, lowering of clear point, and for its solubilizing effect for any components which may not be readily soluble in the main aqueous medium.
- the amount of solvent, when present, will usually be limited to about 10%, preferably 8%, especially no more than about 6% of the composition, such as from 2 to 5%.
- Ethanol is the prefeed organic solvent.
- hydrotropes include primarily urea and the lower alkyl aryl sulfonate salts, such as sodium xylene sulfonate, potassium xylene sulfonate, sodium cumene sulfonate, ammonium xylene sulfonate, and the like. Mixtures of two or more hydrotropes may also be used.
- the hydrotrope when used, is generally present in amounts below about 8%, preferably below about 6%, such as from 1 or 2 to 6%.
- opacifying agents e.g. behenic acid
- a pearlescent or pearlizing composition such as an approximately equal mixture of high fatty acid ester of polyethoxy ethanol, coconut oil fatty acid alkanolamide and sodium lauryl ether sulfate.
- the higher fatty acid will usually be of 10 to 18 carbon atoms and the polyethoxy content will be of 1 to 20, preferably 1 to 10 ethoxy groups.
- the alkanolamide will preferably be ethanolamide, but can be mixed with isopropanolamide, too.
- Additional adjuvant components of the present compositions include perfumes; sequestrants, e.g. monohydrogen ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate, trisodium nitrilotriacetate; bactericides, e.g. trichlorocarbanilide, tetrachlorosalicylanilide, hexachlorophene, chlorobromosalicylanilide; antioxidants; thickeners, e.g. sodium carboxymethyl cellulose, polyacrylamide, Irish moss; dyes; water dispersible pigments; salts, e.g. sodium sulfate, magnesium sulfate, as the heptahydrate or anhydrous, sodium chloride; preservatives, such as formaldehyde or hydrogen peroxide, pH modifiers, etc.
- sequestrants e.g. monohydrogen ethylene diamine tetraacetate, tetraso
- the total amount of the additional additives is usually no more than about 20% of the composition, preferably not exceeding 15%, while the amount of any individual ingredient will not generally exceed 10%, especially 5%, and usually no more than 2 or 3%.
- compositions of this invention and the various adjuvants employable therein, and in the claims, although individual constituents are mentioned for various classes or types of components it is within the invention that mixtures thereof be employed, such as mixtures of two or three anionic detergents or mixtures with the nonionic detergents, both possibly with other anionic and nonionic detergents known in the art, mixtures of skin treating materials and mixtures of solvents, among others.
- paraffin sulfonate surfactants such as sodium or magnesium (C12-C18) paraffin sulfonate
- Amphoteric surfactants such as the betaines, e.g. acylamidopropyl dimethyl ammonium betaines, can also often provide improvements in overall performance.
- the viscosities of the detergent compositions may be further varied by the addition of thickening agents, such as gums and cellulose derivatives.
- the product viscosity and flow properties should be such as to make it pourable from a bottle and not so thin as to tend to splash or pour too readily, since usually only small quantities of the liquid detergent are to be utilized in use.
- Viscosities from 20 to 1000 centipoise (Brookfield Viscometer spindle no. 1, 12 r.p.m.) are found useful with those from 100 to 500 cps. being preferred and a viscosity of about 200 centipoise being considered best by most consumers, although at somewhat lower viscosities, e.g. 100 cps., consumer acceptance is almost the same.
- the detergent constituents usually it is preferred to heat the detergent constituents to a somewhat elevated temperature, e.g. 40° to 50°C and then admix them with the water and, optionally, all or a portion of the ethanol. Thereafter, other anionic and nonionic detergents, urea, amide, protein and other adjuvants are added with the more volatile materials, such as perfumes, preferably being added last and after cooling of the composition to about room temperature. Normally when making opaque or pearlescent detergents, the pearlizing mixture will also be added near last at about room temperature.
- various other known techniques may also be employed, depending upon the particular detergent composition.
- the pH of the formulation will generally be near neutral, e.g. about 5 to 8, preferably about 6.5 to 7.5.
- compositions L and L' were prepared: Component L Active Ingredients (wt%) L' Active Ingredients (wt%) Mg linear dodecyl benzene sulfonate [Mg(LDBS)2]11.5 9.6 9.6 Alkyl polyglycoside1) 6.0 6.0 C12-C16 alkyl ether sulfate (1E.O.) 11.8 11.8 Lauric/myristic monoethanolamide (LMMEA)/Sodium Xylene Sulfonate (SXS) (5:3 Blend) 2.0 2) 2.0 2) Ethanol (3A) 4.1 4.1 Sodium cumene sulfonate (SCS) 2.1 2.1 Disodium lauryl sulfosuccinate (Minarol LSS) 4.6 Disodium laureth (3EO) sulfosuccinate 1.5 MgSO4 ⁇ 7H2O 1.0 1.0 Monohydrogen ethylene diamine tetraacetate, trisodium salt (HEDTA) 0.1 0.1 NaCl
- compositions WJ' and WJ'' were prepared: WJ' Active Ingredient wt. % WJ'' Active Ingredient wt. % Na (LDBS) 10.0 10.0 APG 625 9.0 6.0 LMMEA/SXS (5:3) 1.6 1) 4.0 1) AEOS-1EO 14.0 14.0 Ethanol (3A) 0.5 1.3 SCS 0.9 0.9 MgSO4 ⁇ 7H2O 1.0 1.0 NaCl 1.0 1.0 HEDTA 0.1 0.1 Perfume 0.3 0.3 Colorant 0.1 0.1 0.1 Water, deionized q.s. to 100 q.s. to 100 1) Based on LMMEA
- compositions A-E were prepared in the same manner as compositions WJ' and WJ'' except that the amounts of APG-625 and LMMEA were changed as follows: A B C D E (wt %) APG-625 10.0 5.0 10.0 5.0 7.5 LMMEA 4.0 1.0 1.0 4.0 2.5
- compositions from Examples II and III were tested in the Shake-Foam Test, Shell Foam Test and Baumgartner grease (lard) removal test as described below.
- This test measures the ability of a diluted (1%) solution in 150 ppm hardness water to remove a greasy soil (lard) from a test surface (a cleaned glass slide 2.5 cm x 0.1 cm).
- the soil is applied by spreading about 0.2 to about 0.3 gram lard onto each cleaned glass slide.
- the soiled slides are cleaned in a 1% product solution by dipping the soiled slide into the solution 600 times.
- the solution is maintained at ambient temperature (75°F).
- the slides are dried in a desiccator for two hours.
- the difference in weight of the lard before and after the cleaning process is taken as a measure of grease removal, the greater the difference the more effective is the detergent composition.
- test solution An 0.04% concentration of the test solution in 250 ml of water (150 ppm hardness, 45°C) is filled into a water jacketed vessel with baffles and having a constant speed agitation (300 rpm mixing). Stirring is continued until the generated foam covers the entire surface of the test solution.
- a mixed soil (olive oil, milk, Crisco®, and potato buds) is slowly injected at a constant rate sufficient to uniformly disperse the soil below the surface of the solution. The soil interacts first with the surfactant in the solution until the surfactant is depleted and thereafter begins to deplete surfactant from the foam. The amount of soil (in grams) added until the foam quickly collapses is determined. The results (end point) are reported in Table 2 in grams.
- compositions WJ' and L had excellent rinsing characteristics as compared to Liquid Palmolive® and a commercial product containing a high level of magnesium for grease removal, but which is not believed to include any alkyl polyglucoside
- compositions A-E were statistically analyzed to identify main and interaction effects of LMMEA and APG on grease removal. Only LMMEA level was found to affect grease cleaning performance. All other formula factors (surfactants) did not significantly affect grease removal.
- Compositions A and D having 4% LMMEA, removed a high level of grease versus regular Liquid Palmolive® which would remove 25 to 30 mg of soil.
- Another leading commercial product containing a high level of magnesium for grease removal effectiveness would remove 120 mg of soil.
- the L and L' formulas also contain higher Mg levels and also remove more grease. These formulas are clinically milder than the commercial high Mg product.
- the product WJ'' containing 6% APG and 4% LMMEA which provided comparable grease removal performance to formulas A and D was clinically tested and found to be as mild as Liquid Palmolive®.
- compositions WJ' and WJ'' were both evaluated to have equal mildness to Liquid Palmolive® and superior mildness to the high Mg-containing commercial product.
- the surfactants which were tested were the sodium monolauryl sulfosuccinate used in L, the sodium monolauryl (3E.O.) sulfosuccinate used in L' (laureth), sodium dioctyl sulfosuccinate, and mono-C16 alkyl sulfosuccinamate, monoethanolamine salt (ris). All of these surfactants were obtained from Rhone Poulenc (France).
- Grease cleaning results of the various sulfosuccinates tested at 0%, 1.5%, and 3% in the L formula (MgLAS) indicate all four sulfosuccinates produce a high and comparable level of baumgartner performance at all levels tested.
- the Dioctyl SS appears to give a peak in performance higher than the other materials at 1.5%.
- dioctyl sulfosuccinate is not believed to provide the same degree of mildness as the higher chain length alkyl esters.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Abstract
Description
- This invention relates to light duty liquid detergents having particular utility in the hand washing of dishware, including dishes, pots, pans, glassware and silverware/flatware. More particularly, it relates to a liquid dishwashing detergent composition which provides stable, persistent foaming characteristics combined with good rinseability, mildness to the skin and effectiveness in removing greasy soils from dishware.
- Foam generation by detergent compositions is associated by the consumer with good detersive ability. However, it is apparent that long lasting foam, whether considered copious or medium to medium-low foam content is, by itself, not a sufficient measure of cleaning ability. Nevertheless, much effort has been extended to optimize foaming characteristics, without necessarily improving cleaning ability.
- Greasy soils are generally considered to be one of the most difficult soil types to be removed by hand washing. Effective grease removal is nearly always associated with requiring high temperature water to help dissolve and remove the grease.
- Clearly, there would be a great advantage to formulate a mild, foaming, liquid hand dishwashing composition, which is capable of and effective in removing greasy soils as well as other soil types from dishware using water at ambient or warm to high temperature.
- It has been known that among the anionic surfactants, those based on magnesium as the counterion (i.e. cation) can improve grease cutting performance. However, grease cutting performance is generally associated with increased irritation to the skin, e.g. hands, of the consumer.
- It has also been known to use generally milder types of surfactants to ameliorate the somewhat harsh effects of the magnesium based anionic surfactants. Alkyl polyglucoside (APG) nonionic surfactants have been suggested for this purpose. However, although providing some foaming characteristics, the APG type surfactant has generally poorer foaming performance than other conventional foaming surfactants.
- Another important characteristic to the consumer for hand dishwashing formulations is the ability to easily wash away the copious foam which is associated with good cleaning performance. Surfactant systems providing APG generated foams are not always acceptable in terms of rinseability.
- Accordingly, it is an object of this invention to provide hand dishwashing aqueous compositions which combine acceptable mildness, foaming and grease cleaning performance.
- It is another object of the invention to provide such compositions with good foam rinseability.
- The present invention provides compositions which avoid the elevated problems and accomplish the foregoing objectives. The compositions, although prepared from otherwise known ingredients, but in unique combinations and proportions, is capable of achieving a new and beneficial result.
- In accordance with the present invention, the liquid dishwashing detergent composition comprises, as essential ingredients:
- (A) a surfactant system comprising: (1) from about 7.5 to 20% of a C₁₀-C₁₆ alkyl benzene sulfonate anionic surfactant; (2) from 0 to 8% of an alkali metal salt of a monoalkyl C₈-C₁₈ sulfosuccinate or sulfosuccinamate anionic surfactant, wherein the alkyl group may be ethoxylated with up to about 8 moles of ethylene oxider (3) from about 8 to about 20% of anionic C₁₂-C₂₀ alkyl ether sulfate having from about 1 to less than 3 ethylene oxide groups, on average; and, (4) from about 3 to 12% of an alkyl glucoside having from 12 to 16 carbon atoms, on average, in the alkyl chain, and an average degree of polymerization in the range of from about 1 to 3; and (B) from about 0.5 to 6% of a foam stabilization system comprising at least one lower alkanolamide of higher alkanoic acid, and the balance water. The total actives (A) + (B) will usually range from about 25 to about 54% or more of the total composition.
Optional, but often beneficial adjuvants which can, and often are included in the composition include: - (C) a low irritant organic solvent, up to about 10%;
- (D) hydrotrope, up to about 8%;
- (E) other adjuvants, such as, chelating or sequestering agents, coloring agents, dyes, perfumes, bactericides, fungicides, preservatives, sunscreening agents, pH modifiers, pH buffering agents, opacifiers, antioxidants, thickeners, proteins, and the like, up to about 20%, in total, with a maximum of any individual component being about 10%.
- Unless indicated otherwise all percents and percentages given herein are on a by weight basis.
- The components of the invention compositions will now be described in greater detail.
- The present invention is based, in part, on the quite unexpected discovery that the foam stabilizing, foam boosting combination of the alkyl polyglucoside (APG) and alkanolamide components has a significant impact on the grease removal performance of the composition at a constant level of total surfactant/foam stabilization components. More specifically, it has now been found that while some enhanced grease removal benefits may be provided with the foam stabilizing alkanolamide alone, as compared to existing top of the line commercial products, the improvement in grease removal performance is further dramatically improved in the system containing both foam stabilizing alkanolamide and APG. Furthermore, by employing the alkyl ether sulfate (AEOS) with less than 3 moles ethylene oxide, e.g. AEOS-1EO or AEOS-2EO, a more copious foam can be obtained as compared to the same composition containing AEOS-3EO (i.e. 3 moles ethylene oxide) while still retaining acceptable mildness. Also, by employing low levels of the foam boosting alkanolamide component (B), in conjunction with the specified surfactant system (A), good rinseability of the dishware is achieved without impairing cleaning performance. For example, the assignee's current commercially available liquid light duty hand washing product, Liquid Palmolive® (17% NaLAS, 13% AEOS-3EO, 4% LMMEA, 3.3% SCS+SXS, 0.5% inorganic salts; balance perfume, color, ethanol, water), removed about 25 milligrams (mg), of greasy soil (lard) as compared to only 5 mg for the same formula with 0% LMMEA. However, in a composition according to this invention containing APG, grease removal increases by about 80 mg over the level of LMMEA between about 1% and about 4% by weight of the composition. These observations were based on surfactant systems in which the counterion of the anionic surfactant(s) was sodium. In systems in which magnesium salts of the anionic ABS surfactant are used, both the concentration of the Mg ion and the alkanolamide strongly influence grease removal. For example, when tested in the Baumgartner grease soil removal test with a surfactant system containing 10 wt % linear dodecyl benzene sulfonate (LAS)/12 wt % fatty C₁₂-C₁₆ alcohol ethoxylate (1 mole ethylene oxide (1EO))/6wt % APG (C₁₂ to C₁₆ alkyl; D.P.=1.6) the grease removal performance obtained at the Mg and LMMEA levels indicated in the following Table 1 were obtained.
Table 1 Mg ion % LMMEA % Grease Removal, mg 0.1 4 37 0.1 2 8 0.4 2 61 0.25 3 60 0.4 4 80 - The components of the inventions's compositions will now be described.
-
- (1) The first essential surfactant ingredient is the anionic salt of an alkyl benzene sulfonic acid (ABS), preferably a linear C₁₀ to C₁₆ alkyl benzene sulfonate (LAS).
Furthermore, when the magnesium salt is used, it may be, for example, a magnesium oxide neutralized linear dodecyl benzene sulfonic acid, or alternatively, the magnesium salt may be formed by adding an electrolyte magnesium salt, such as magnesium chloride, magnesium sulfate, etc. to sodium alkyl benzene sulfonate. In the latter alternative, an excess of the magnesium salt electrolyte could raise the cloud/clear point of the composition. This undesirable effect can, however, be compensated for by addition of hydrotrope, as described below.
The anionic surfactant (1) is present in an amount of from about 7.5% to about 20%, based on the total composition, or in an amount of from about 28 to 40%, based on the total surfactants (A)(1), (2), (3) and (4). The more preferred range of amounts of the anionic ABS salt surfactant is from about 8 to 12 or 15%, especially about 9 to 11%, e.g. about 10%, based on the total composition, or about 29 to 35%, especially about 30 to 33%, based on the sum of the surfactants (A)(1), (2), (3) and (4).
At below the 7.5% (total) level the improvement in low temperature grease removal becomes insufficient, while at amounts above 20% (total) the composition containing the magnesium salt tends to be mildly irritating to the hands.
The anionic ABS in the surfactant system may be in the form of the alkali metal or alkaline earth metal salts, or mixtures thereof. The preferred alkali metals are sodium and potassium, preferably sodium. The preferred alkaline earth metals are calcium and magnesium preferably magnesium. The linear alkyl group preferably contains from 10 to 13 carbon atoms, especially 11 carbon atoms, approximately, on average, e.g. sodium and/or magnesium linear dodecyl benzene sulfonate. The sodium salt anionic is generally considered to be a milder detergent than the magnesium salt but is less effective for greasy soil removal and is also less effective in generating foam, especially in the presence of soil. However, when used in combination with APG, AEOS-1 to 2 EO, and alkanolamide foam stabilizer, satisfactory foam generation, grease removal and mildness can be simultaneously exhibited.
On the other hand, enhanced grease removal performance can be achieved with the Mg salt anionic. However, since the level of Mg ion can be lowered for any particular level of grease removal performance, it is still possible to achieve levels of mildness which are acceptable to the consumer. This appears to be especially so, in terms of perceived mildness effects, reported by small test panels of consumers, in compositions also containing the below described sulfosuccinate or sulfosuccinamate anionic surfactants. - (2) In accordance with one embodiment of the invention, a mono-alkyl C₈-C₁₈ sulfosuccinate or sulfosuccinamate anionic surfactant may be incorporated in the compositions of this invention, especially when the magnesium salt of ABS is used as, or as part of, component (1).
It is disclosed in U.S. Patent 4,839,098 to Wisotski, et al. to incorporate in an APG (alkyl of C₁₀ to C₁₈, D.P.=1 to 5) containing liquid diswashing detergent composition from 10 to 80 parts by weight of a C₇ to C₉ dialkyl sulfosuccinate, based on a total surfactant content of 15 to 50% by weight, to enhance foaming and cleaning power. This patent suggests that such compositions should be free from petroleum-based anionic surfactants, such as alkyl benzene sulfonates and alkane sulfonates. However, other anionic surfactants such as alkyl ether sulfate or alkyl sulfate may replace a portion of the APG or dialkyl sulfosuccinate. The di(C₇-C₉) alkyl sulfosuccinate are not considered to be mild surfactants and can contribute to harshness or irritation to the consumer.
In the compositions of this invention, the sulfosuccinate or sulfosuccinamate is present as the monoalkylsuccinate (MAS) or monoalkylsulfosuccinamate (MASA) where R is an aliphatic radical, preferably alkyl, of from 10 to 18 carbon atoms, especially from 12 to 16 carbon atoms, and preferably lauryl (C₁₂), and M is a cation, such as an alkali metal, e.g. sodium or potassium, preferably sodium, ammonium, alkanolamine, e.g. ethanolamine, or magnesium. The alkyl radical may be ethoxylated with up to about 8 moles, preferably up to about 6 moles, on average, e.g. 2, 3 or 4 moles, of ethylene oxide, per mole of alkyl group.
Minor amounts, e.g. up to about 5% of dialkyl sulfosuccinates may be present with the monoalkyl sulfosuccinate or monoalkyl sulfosuccinamate. The mono-alkyl ester substantially free of dialkyl ester, and especially sodium mono-lauryl ester which may be ethoxylated with up to 4 moles of ethylene oxide and the mono- C₁₆ alkyl sulfosuccinamate monoethanolamine salt are preferred.
When present, the sulfosuccinate or sulfosuccinamate, anionic surfactant is used in amounts ranging from about 2 to 20% by weight, preferably from about 3 to 15 % by weight, based on the total surfactants (A)(1)-(4). Based on the total composition, the preferred amounts of the sulfosuccinate anionic surfactant ranges from about 0.5 to 8 wt %, more preferably 0.8 to 7 wt %. - (3) The compositions of this invention also include an anionic alkyl ether sulfate (also commonly referred to as fatty alcohol ether ethyleneoxy sulfate AEOS·nEO where n represents the number of moles, on average, of ethylene oxide (EO)) containing from about 10 to 20 carbon atoms in the alkyl moiety, preferably from about 12 to 14 or 16 carbon atoms and from 1 to less than 3 moles, preferably 1 to 2 moles, especially 1 mole, ethylene oxide, on average, per mole of the alkyl sulfate. The alkyl ether sulfate, which may be represented by the formula R(OC₂H₄)nOSO₃M, where R is the residue of a fatty alcohol of from about 10 to 20 carbon atoms, n is a number of from 1 to less than 3, and M is a cation, is usually present as the alkali metal salt, especially the sodium salt, but may also be present as the potassium salt, ammonium salt, alkanolamine salt or magnesium salt.
The amount of the alkyl ether sulfate will usually be in the range of from about 32 to about 50% by weight, preferably from about 34 to 48% by weight, based on the total weight of surfactants (A)(1)-(4) or from about 8 to 20%, preferably 9 to 18%, and more preferably 10 to 16% by weight of the total composition. - (4) Another essential surfactant in the invention composition is (4) an alkyl glucoside, preferably an alkyl polyglucoside, although alkyl monoglucoside may also be used.
The alkyl mono- and polysaccharides have received much attention recently for their beneficial detergent, foaming and viscosity modifying properties. Examples of patent literature relating to light duty liquid compositions containing alkyl monosaccharides include U.S. Patents 4,732,704 and 4,732,696. The alkyl polysaccharides are used in the liquid detergent compositions disclosed, for example, in U.S. Patents 4,396,520, 4,536,318, 4,565,647, 4,599,177, 4,663,069 and 4,668,422 (including monoglucosides), as well as many of the patents and literature cited in these patents.
In the present invention, a narrow subgenus of the alkyl saccharides has been found to effectively enhance grease removal with acceptable mildness when used in combination with the other surfactants (A)(1)-(3) and the foam stabilizer (B).
The alkyl glycosides used in this invention are those having an alkyl group of from 12 to 16 carbon atoms, on average, and a glucoside hydrophilic group containing from about 1 to about 3, preferably from about 1.2 to about 3, and most preferably from about 1.3 to 2.7, glucoside units, such as 1.3, 1.4, 1.5, 1.6, 2.0 or 2.6 glucoside units. Of course, the number of glucoside units in any particular surfactant molecule will be a whole number (i.e. an integer), however, for any actual physical sample of alkyl glucoside surfactants there will, in general, be a range of glucoside units, and it is the average value which characterizes a particular surfactant product. The alkyl glycosides with lower D.P. values tend to provide more copious foaming whereas those with higher D.P. values tend to be more soluble, for the same alkyl chain length. If the alkyl group contains less than 12 carbon atoms, satisfactory mildness is difficult to achieve.
The alkyl group is preferably attached at the 1-position of the sugar molecule, but may be attached at the 1-, 3- or 4-positions, thus giving a glucosyl rather than a glucoside. Furthermore, in the polyglucosides, the additional glucoside units are predominantly attached to the previous glucoside at the 2-position, but attachment at the 3-, 4- and 6-positions can also occur.
Optionally, and less desirably, there may be a polyalkylene oxide chain (e.g. polyethylene oxide) joining the alkyl moiety and the glucoside units).
The preferred alkyl glucosides have the formula
R²O(CmH2mO)t(Z)x
wherein Z is derived from glucose, R² is an alkyl group containing from 12 to about 16 carbon atoms, m is 2 or 3, preferably 2, t is from 0 to about 6, preferably 0, and x is from 1 to 3 (on average), preferably from 1.2 to 3, most preferably from 1.3 to 2.7. To prepare these compounds a long chain alcohol (R²OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol (C₁-C₆) is reacted with glucose or a polyglucoside (x=2 to 3) to yield a short chain alkyl glucoside (x=1 to 3) which can in turn be reacted with a longer chain alcohol (R²OH) to displace the short chain alcohol and obtain the desired alkyl glucoside. If this two step procedure is used, the short chain alkyl glucoside content of the final alkyl glucoside material should be less than 50%, preferably less than 10%, more preferably less than 5%, most preferably 0% of the alkyl glucoside.
The amount of unreacted alcohol (the free fatty alcohol content) in the desired alkyl polyglucoside surfactant is preferably less than about 2%, more preferably less than about 0.5% by weight of the total of the alkyl polyglucoside plus unreacted alcohol. The amount of alkyl monoglucoside, if present, is preferably no more than about 40%, more preferably no more than about 20% by weight of the total of the alkyl polyglucoside. For some uses it is desirable to have the alkyl monoglucoside content less than about 10%, especially less than about 5%.
The amount of the alkyl glucoside surfactant to achieve the desired foam and detersive properties is in the range of from about 14 to 32%, preferably from about 16 to 30%, based on the sum of the surfactants (A)(1), (2), (3) and (4). The preferred amounts range from 3 to 12%, especially from 4 or 5 to 10%, based on the total composition.
Within these ranges the relative amounts of the alkyl benzene sulfonate (ABS) surfactant and alkyl glucoside (APG) surfactant is not particularly critical, but will generally be within the range of ABS:APG of from about 2.5:1 to 1:2, preferably from about 2:1 to 1:1.2.
In the invention compositions, the total amount of active surfactant components (A) plus (B) will be in the range of from about 25% to 54% of the total composition, preferably from about 28 to 50%, more preferably from about 28% to 42%, such as 30%, 32%, 34%, 35% or 40%. - The foam stabilization system which may also itself contribute to the foaming capacity as well as foam stabilizing effect is comprised of the lower alkanolamide of higher alkanoic acid which is the reaction product of a lower alkanol of 2 to 3 carbon atoms and an alkanoic acid of 10 to 16 carbon atoms, preferably with 80% or more of the lower alkanol being ethanol and a similar proportion of the alkanoic acid being of 12 to 14 carbon atoms. Other lower alkanols that are also useful are n-propanol and isopropanol. The preferred alkanoic acid is a mixture of lauric and myristic acids, generally in proportions of 1:2 to 2:1, with about 50% of each being preferable. Alternatively, coconut oil or hydrogenated coconut oil may be used as a source of the alkanoic acids. Suitable alkanoic acid alkanolamides include the monoethanolamides. diethanolamides and the monoisopropanolamides.
- Specific examples include mixed lauric/myristic diethanolamide, lauric/myristic monoethanolamide, lauric monoethanolamide, lauric diethanolamide, coco diethanolamide, coco monoethanolamide, and the like.
- The amount of the alkanoic acid alkanolamide may be up to about 6% of the composition, such as 0.5 to 6%, preferably 1 to 5%, more preferably 1 to 4%, such as 1.5, 2, 3 or 4%, of the composition.
- The compositions of this invention which include the salt surfactants (A)(1), (A)(3), (A)(4) and, optionally, (A)(2) and foam stabilization system (B), in the specified proportions, as essential ingredients are formulated in an aqueous carrier to provide mild, stable foaming liquid compositions especially effective in cleaning, by hand washing, dishware, such as dishes, glasses, flatware, pots, pans, etc., at ambient wash water temperature, as well, of course, at warm or hot wash water temperatures. The invention formulations are mild to the hands and are clear and homogeneous. Clarity and homogeneity may often, however, be improved by inclusion of, for example, organic solvents and/or hydrotropes, and these and other optional additives may also be included in the compositions in amounts which do not adversely influence the desirable properties.
- Cosmetically acceptable organic solvents, usually lower alcohols, such as ethanol, propanol, isopropanol, propylene glycol, or mixtures thereof, may be included in the composition for its thinning effect, lowering of clear point, and for its solubilizing effect for any components which may not be readily soluble in the main aqueous medium. The amount of solvent, when present, will usually be limited to about 10%, preferably 8%, especially no more than about 6% of the composition, such as from 2 to 5%. Ethanol is the prefeed organic solvent.
- In order to assist in solubilizing various components of the composition, maintain a low clear point, and possibly modify viscosity, it is customary to include a hydrotropic substance in the composition. Typical hydrotropes include primarily urea and the lower alkyl aryl sulfonate salts, such as sodium xylene sulfonate, potassium xylene sulfonate, sodium cumene sulfonate, ammonium xylene sulfonate, and the like. Mixtures of two or more hydrotropes may also be used. The hydrotrope, when used, is generally present in amounts below about 8%, preferably below about 6%, such as from 1 or 2 to 6%.
- Various other materials may also be included in the present compositions for their desirable functional or aesthetic effects. Among these, those materials employed to increase the mildness of the detergent composition to the human hands, such as the water soluble proteins, are often very useful.
- Although solvents, including water, tend to make the products clear liquids, it is sometimes desirable to opacify them or make them appear pearly. For such purpose there may be employed opacifying agents, e.g. behenic acid, or a pearlescent or pearlizing composition, such as an approximately equal mixture of high fatty acid ester of polyethoxy ethanol, coconut oil fatty acid alkanolamide and sodium lauryl ether sulfate. The higher fatty acid will usually be of 10 to 18 carbon atoms and the polyethoxy content will be of 1 to 20, preferably 1 to 10 ethoxy groups. The alkanolamide will preferably be ethanolamide, but can be mixed with isopropanolamide, too.
- Additional adjuvant components of the present compositions include perfumes; sequestrants, e.g. monohydrogen ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate, trisodium nitrilotriacetate; bactericides, e.g. trichlorocarbanilide, tetrachlorosalicylanilide, hexachlorophene, chlorobromosalicylanilide; antioxidants; thickeners, e.g. sodium carboxymethyl cellulose, polyacrylamide, Irish moss; dyes; water dispersible pigments; salts, e.g. sodium sulfate, magnesium sulfate, as the heptahydrate or anhydrous, sodium chloride; preservatives, such as formaldehyde or hydrogen peroxide, pH modifiers, etc.
- The total amount of the additional additives is usually no more than about 20% of the composition, preferably not exceeding 15%, while the amount of any individual ingredient will not generally exceed 10%, especially 5%, and usually no more than 2 or 3%.
- In the above description of the compositions of this invention and the various adjuvants employable therein, and in the claims, although individual constituents are mentioned for various classes or types of components it is within the invention that mixtures thereof be employed, such as mixtures of two or three anionic detergents or mixtures with the nonionic detergents, both possibly with other anionic and nonionic detergents known in the art, mixtures of skin treating materials and mixtures of solvents, among others.
- For example, under certain circumstances paraffin sulfonate surfactants, such as sodium or magnesium (C₁₂-C₁₈) paraffin sulfonate, can be used to replace part or all of the ABS surfactant, achieve good foam and grease removal characteristics. Amphoteric surfactants, such as the betaines, e.g. acylamidopropyl dimethyl ammonium betaines, can also often provide improvements in overall performance.
- The viscosities of the detergent compositions may be further varied by the addition of thickening agents, such as gums and cellulose derivatives. The product viscosity and flow properties should be such as to make it pourable from a bottle and not so thin as to tend to splash or pour too readily, since usually only small quantities of the liquid detergent are to be utilized in use. Viscosities from 20 to 1000 centipoise (Brookfield Viscometer spindle no. 1, 12 r.p.m.) are found useful with those from 100 to 500 cps. being preferred and a viscosity of about 200 centipoise being considered best by most consumers, although at somewhat lower viscosities, e.g. 100 cps., consumer acceptance is almost the same.
- In manufacturing the described formulations, usually it is preferred to heat the detergent constituents to a somewhat elevated temperature, e.g. 40° to 50°C and then admix them with the water and, optionally, all or a portion of the ethanol. Thereafter, other anionic and nonionic detergents, urea, amide, protein and other adjuvants are added with the more volatile materials, such as perfumes, preferably being added last and after cooling of the composition to about room temperature. Normally when making opaque or pearlescent detergents, the pearlizing mixture will also be added near last at about room temperature. Although the described method of making the compositions is preferred, various other known techniques may also be employed, depending upon the particular detergent composition.
- The pH of the formulation will generally be near neutral, e.g. about 5 to 8, preferably about 6.5 to 7.5.
- The following representative non-limiting examples will help to further understand the present invention.
- The following compositions L and L' were prepared:
Component L Active Ingredients (wt%) L' Active Ingredients (wt%) Mg linear dodecyl benzene sulfonate [Mg(LDBS)₂]11.5 9.6 9.6 Alkyl polyglycoside¹) 6.0 6.0 C₁₂-C₁₆ alkyl ether sulfate (1E.O.) 11.8 11.8 Lauric/myristic monoethanolamide (LMMEA)/Sodium Xylene Sulfonate (SXS) (5:3 Blend) 2.02) 2.02) Ethanol (3A) 4.1 4.1 Sodium cumene sulfonate (SCS) 2.1 2.1 Disodium lauryl sulfosuccinate (Minarol LSS) 4.6 Disodium laureth (3EO) sulfosuccinate 1.5 MgSO₄·7H₂O 1.0 1.0 Monohydrogen ethylene diamine tetraacetate, trisodium salt (HEDTA) 0.1 0.1 NaCl 2.0 2.0 Perfume 0.4 0.4 Color 0.1 0.1 Water, deionized qs qs 1) APG 625 from Henkel Corp., hydrophobe chain length of C₁₂/C₁₄/C₁₆ = 68/26/6, average of 1.6 glycoside units. 2) Based on LMMEA; SXS=1.2 wt% - The following compositions WJ' and WJ'' were prepared:
WJ' Active Ingredient wt. % WJ'' Active Ingredient wt. % Na (LDBS) 10.0 10.0 APG 625 9.0 6.0 LMMEA/SXS (5:3) 1.61) 4.01) AEOS-1EO 14.0 14.0 Ethanol (3A) 0.5 1.3 SCS 0.9 0.9 MgSO₄·7H₂O 1.0 1.0 NaCl 1.0 1.0 HEDTA 0.1 0.1 Perfume 0.3 0.3 Colorant 0.1 0.1 Water, deionized q.s. to 100 q.s. to 100 1) Based on LMMEA - Compositions A-E were prepared in the same manner as compositions WJ' and WJ'' except that the amounts of APG-625 and LMMEA were changed as follows:
A B C D E (wt %) APG-625 10.0 5.0 10.0 5.0 7.5 LMMEA 4.0 1.0 1.0 4.0 2.5 - The compositions from Examples II and III were tested in the Shake-Foam Test, Shell Foam Test and Baumgartner grease (lard) removal test as described below.
- This test measures the ability of a diluted (1%) solution in 150 ppm hardness water to remove a greasy soil (lard) from a test surface (a cleaned glass slide 2.5 cm x 0.1 cm). The soil is applied by spreading about 0.2 to about 0.3 gram lard onto each cleaned glass slide. The soiled slides are cleaned in a 1% product solution by dipping the soiled slide into the solution 600 times. The solution is maintained at ambient temperature (75°F). After washing, the slides are dried in a desiccator for two hours. The difference in weight of the lard before and after the cleaning process is taken as a measure of grease removal, the greater the difference the more effective is the detergent composition.
- 100 ml of a diluted (1%) test solution in 150 ppm hardness water (113°F) is filled into a 500ml graduated cylinder with a stopper. The stoppered cylinder is placed on an agitating machine which rotates the cylinder for 20 cycles at 30 rpm. The height of the foam in the cylinder is observed. A sugar cube having adsorbed thereon 0.01 ± 0.001 grams of a mixed soil (potato buds, Crisco®, milk, olive oil and water) is then added to the cylinder and the test repeated. This procedure is continued until a total of 0.03 grams of soil have been added.
- An 0.04% concentration of the test solution in 250 ml of water (150 ppm hardness, 45°C) is filled into a water jacketed vessel with baffles and having a constant speed agitation (300 rpm mixing). Stirring is continued until the generated foam covers the entire surface of the test solution. A mixed soil (olive oil, milk, Crisco®, and potato buds) is slowly injected at a constant rate sufficient to uniformly disperse the soil below the surface of the solution. The soil interacts first with the surfactant in the solution until the surfactant is depleted and thereafter begins to deplete surfactant from the foam. The amount of soil (in grams) added until the foam quickly collapses is determined. The results (end point) are reported in Table 2 in grams.
- Each of these tests were performed in triplicate and the reported results represent the average of the three tests.
- The results of the tests are shown in Table 2.
Table 2 COMP Total Surfactants and LMMEA (wt %) Wt ratio APG/LMMEA Shake Foam Volume, ml. Shell Foam soil wt, g to EP Grease mg soil removed no soil 0.01 soil 0.02 soil 0.03 soil A 38 (10/4) 403 337 273 217 10.9 79 B 30 (5/1) 418 340 290 242 6.7 3 C 35 (10/1) 417 335 287 235 9.6 7 D 33 (5/4) 393 317 252 193 9.9 91 E 34 (7.5/2.5) 430 353 315 268 10.6 40 WJ' 34.6 (9/1.6) 15 WJ'' 34 (6/4) 98 L 34.0 (6/2) 87 L' 30.9 (6/2) 87 Note: Formulas A-WJ'' have 10 LAS and 14 AEOS-1EO; Formulas L and L' contain 9.6 LAS and 11.8 AEOS-1EO; tests conducted in 150 ppm water. Total surfactants = (A)(1) + (A)(2) + (A)(3) + (A)(4) + (B). - Both Compositions WJ' and L had excellent rinsing characteristics as compared to Liquid Palmolive® and a commercial product containing a high level of magnesium for grease removal, but which is not believed to include any alkyl polyglucoside
- The above formulas A-E were statistically analyzed to identify main and interaction effects of LMMEA and APG on grease removal. Only LMMEA level was found to affect grease cleaning performance. All other formula factors (surfactants) did not significantly affect grease removal. Compositions A and D, having 4% LMMEA, removed a high level of grease versus regular Liquid Palmolive® which would remove 25 to 30 mg of soil. For reference, another leading commercial product containing a high level of magnesium for grease removal effectiveness would remove 120 mg of soil. However, it is significantly more irritating than Liquid Palmolive® in a clinical handsoak test. The L and L' formulas also contain higher Mg levels and also remove more grease. These formulas are clinically milder than the commercial high Mg product. The product WJ'' containing 6% APG and 4% LMMEA, which provided comparable grease removal performance to formulas A and D was clinically tested and found to be as mild as Liquid Palmolive®.
- Compositions WJ' and WJ'' were both evaluated to have equal mildness to Liquid Palmolive® and superior mildness to the high Mg-containing commercial product.
- While the representative composition WJ' (NaLAS) was not as effective as Liquid Palmolive® or the high Mg-containing commercial product in the standard Baumgartner grease (lard) removal test, it appears to be superior in terms of Crisco®-monoglyceride grease soil removal in a sample soaking test.
- Similar compositions containing 17% LAS/13 AEOS-3EO with 0% APG and with 0% LMMEA or 4% LMMEA were tested in the grease removal test. The composition containing 0% LMMEA removed approximately 5 mg of soil while the composition with 4% LMMEA removed 25 mg of soil. This demonstrates the interaction of LMMEA with APG to produce the enhanced performance on grease.
- In order to test the effect of the sulfosuccinate/sulfosuccinamate anionic surfactant in the composition L of Example 1, four different surfactants were tested at 0%, 1.5% and 3% sulfosuccinate/sulfosuccinamate levels in composition L and were compared to Liquid Palmolive® (POL) in the Baumgartner grease removal and Shake Foam tests described above. The surfactants which were tested were the sodium monolauryl sulfosuccinate used in L, the sodium monolauryl (3E.O.) sulfosuccinate used in L' (laureth), sodium dioctyl sulfosuccinate, and mono-C₁₆ alkyl sulfosuccinamate, monoethanolamine salt (ris). All of these surfactants were obtained from Rhone Poulenc (France).
- The results are shown in Table 3.
Table 3 Baumgartner Shake Foam Volume, mls mgs SD Initial SD 0.1 soil SD 0.2 soil SD 0.3 soil SD POL (ref) 37 11 385 10 330 30 260 15 195 15 0% Sulfosuccinate 122 34 387 12 317 25 252 23 184 24 1.5% dioctyl 160 8 365 0 305 5 240 15 195 15 3% dioctyl 118 4 395 30 315 15 270 5 210 15 1.5% laureth 126 25 390 5 315 5 255 20 185 25 3% laureth 104 48 380 10 340 10 270 15 215 15 1.5% lauryl 117 28 380 10 295 15 260 5 215 10 3% lauryl 134 16 405 5 340 20 290 25 235 20 1.5% ris 144 6 390 10 320 10 280 15 210 10 3% ris 110 20 375 10 325 10 275 20 225 25 NOTE: SD = Standard Deviation, based on three replicates. - Grease cleaning results of the various sulfosuccinates tested at 0%, 1.5%, and 3% in the L formula (MgLAS) indicate all four sulfosuccinates produce a high and comparable level of baumgartner performance at all levels tested. The Dioctyl SS appears to give a peak in performance higher than the other materials at 1.5%.
- In general, there is a slight upward trend in foam volume at each level of soil addition as the sulfosuccinate increases from 0% to 3%. Performance is not considered to be significantly different unless a difference in foam volume greater than 50 mls is observed. The lowest to highest foam volume at each condition regardless of sulfosuccinate type or level is typically within 50 ml. Therefore, based on minimal impact on foam volume, any of the four materials could be used. The more important factors are formula mildness and consumer acceptability.
- The dioctyl sulfosuccinate is not believed to provide the same degree of mildness as the higher chain length alkyl esters.
Claims (8)
- A liquid dishwashing detergent composition providing stable foaming characteristics and which is mild to the hands and is effective in removing greasy soils, said composition comprising:(A) a surfactant system comprising(1) from about 7.5 to 20% by weight of a salt of a C₁₀-C₁₆ linear alkyl benzene sulfonate anionic surfactant, said salt being selected from the group consisting of alkali metal salts, alkaline earth metal salts and mixtures thereof;(2) from 0 to about 8% of anionic C₁₀-C₁₈ alkyl sulfosuccinate or sulfosuccinamate, wherein the alkyl group may be ethoxylated with up to 8 moles of ethylene oxide;(3) from about 8 to 20% of anionic C₁₀-C₂₀ alkyl ether sulfate having from 1 to less than 3 moles ethylene oxide per mole of alkyl group; and(4) from about 3 to 12% by weight of an alkyl polyglucoside having from 12 to 16 carbon atoms, on average, in the alkyl chain, and an average degree of polymerization in the range of from about 1 to about 3;(B) from about 0.5 to about 6% by weight of a foam stabilization system comprising at least one lower alkanolamide of higher alkanoic acid;
the total weight of components (A) and (B) ranging from about 25 to 54% by weight of the composition;(C) up to about 10% by weight of a low irritant organic solvent;(D) up to about 8% by weight of hydrotrope;(E) up to about 20% by weight in total of one or more optional additives chosen from chelating or sequestering agents, coloring agents, dyes, perfumes, bactericides, fungicides, preservatives, sunscreening agents, pH modifiers, pH buffering agents, opacifiers, antioxidants, thickeners, and proteins; and,(F) balance, water. - The composition of claim 1 which comprises(A) from about 28 to 50%(B) from about 1 to 5%;(C) from about 2 to 5%;(D) from about 1 to 6%;(E) up to about 10%;(F) balance, water.
- The composition of claim 2 wherein the surfactant system (A) comprises (1) from about 8 to 15% of a of a C₁₀ to C₁₄ alkyl benzene sulfonate, (2) 0 to about 8% of sodium salt of C₁₀ to C₁₄ mono-alkyl sulfosuccinate or sulfosuccinamate, (3) 10 to 16% of sodium salt of C₁₀ to C₁₄ alkyl ether sulfate having from 1 to 2 moles ethylene oxide, and (4) from about 4 to 10% of an alkyl polyglucoside having from about 12 to 16 carbon atoms in the alkyl group and from about 1.2 to 3 glucoside units.
- The composition of claim 3 wherein the foam stabilization system (B) comprises at least one compound selected from the group consisting of lauric diethanolamide, lauric monoethanolamide, myristic diethanolamide, myristic monoethanolamide, coco diethanolamide, and coco monoethanolamide.
- The composition of claim 4 therein the foam stabilization system (B) comprises from about 1 to 5% of the composition.
- The composition of claim 1 which comprises(A) a surfactant system comprising(1) about 8 to 12% C₁₀-C₁₄ linear alkyl benzene sulfonate,(2) about 0 to 6% sodium C₁₀-C₁₆ mono-alkyl sulfosuccinate or sulfosuccinamate,(3) about 9 to about 18% C₁₀-C₁₆ alkyl ether sulfate having from 1 to 2 ethylene oxide groups, and(4) from about 5 to 10% of said alkyl polyglucoside.(B) from about 1 to 5% of said foam stabilization system comprising lauric/myristic monoethanolamide;
the total amount of (A) + (B) ranging from about 28 to 42% of the composition;(C) up to about 5% of ethanol;(D) up to about 4% of hydrotrope;(E) up to about 6% in total of said one or more additives; and,(F) water. - The composition of claim 1 which comprises(A) a surfactant system comprising(1) about 9 to about 11% of sodium dodecyl benzene sulfonate,(2) 0 to about 2% sodium C₁₀-C₁₄ mono-alkyl sulfosuccinate or sulfosuccinamate, the alkyl group of which may be ethoxylated with up to 6 moles of ethylene oxide,(3) about 10 to about 16% C₁₀-C₁₆ alkyl ether sulfate having from 1 to 2 ethylene oxide groups, and(4) about 6 to about 9% of said alkyl polyglucoside;(B) 1 to 3% of said foam stabilization system comprising lauric/myristic monoethanolamide;(C) 0.2 to 2% ethanol;(D) 0.5 to 4% of sodium xylene sulfonate, sodium cumene sulfonate or mixtures thereof;(E) 0.5 to 5% in total of one or more of magnesium sulfate, sodium chloride, color and fragrance; and,(F) water.
- The composition of claim 1 comprising(A) a surfactant system comprising(1) about 9 to about 11% of magnesium C₁₀-C₁₂ alkyl benzene sulfonate,(2) about 0.8 to about 7% of C₁₀-C₁₆ monoalkyl sulfosuccinate or sulfosuccinamate, wherein the alkyl group may be ethoxylated with up to 5 moles ethylene oxide,(3) about 8 to about 14% of C₁₀-C₁₆ alkyl ether sulfate, ethoxylated with from 1 to 2 moles ethylene oxide, and(4) about 4 to about 8% of said alkyl polyglucoside;(B) 1 to 3% of said foam stabilization system comprising lauric/myristic monoethanolamide;(C) 0 to 2% ethanol;(D) 0.5 to 4% of sodium xylene sulfonate, sodium cumene sulfonate or mixtures thereof;(E) 0.5 to 5% in total of one or more of magnesium sulfate, sodium chloride, color and fragrance; and,(F) water.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68511891A | 1991-04-15 | 1991-04-15 | |
| US685118 | 1991-04-15 | ||
| US07/854,048 US5565146A (en) | 1991-04-15 | 1992-03-18 | Light duty liquid detergent compositions |
| US854048 | 1992-03-18 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0509608A2 true EP0509608A2 (en) | 1992-10-21 |
| EP0509608A3 EP0509608A3 (en) | 1993-03-10 |
| EP0509608B1 EP0509608B1 (en) | 1996-07-10 |
Family
ID=27103506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92201089A Revoked EP0509608B1 (en) | 1991-04-15 | 1992-04-15 | Light duty liquid detergent compositions |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0509608B1 (en) |
| JP (1) | JPH05132699A (en) |
| CN (1) | CN1067068A (en) |
| AT (1) | ATE140259T1 (en) |
| AU (1) | AU661682B2 (en) |
| CA (1) | CA2066009A1 (en) |
| DE (1) | DE69212045T2 (en) |
| FI (1) | FI921673A7 (en) |
| GR (1) | GR1001299B (en) |
| HU (1) | HU212050B (en) |
| IE (1) | IE75910B1 (en) |
| MW (1) | MW2192A1 (en) |
| MX (1) | MX9201702A (en) |
| NO (1) | NO300333B1 (en) |
| PH (1) | PH31565A (en) |
| PT (1) | PT100381B (en) |
| RO (1) | RO108359B1 (en) |
| TR (1) | TR25951A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5531939A (en) * | 1994-03-23 | 1996-07-02 | Amway Corporation | Concentrated glass and window cleaning composition and method of use |
| US5575864A (en) * | 1994-03-23 | 1996-11-19 | Haley; Kalliopi S. | Method for cleaning a hard surface with an all-purpose liquid cleaning composition |
| WO1997034973A1 (en) * | 1996-03-21 | 1997-09-25 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| WO1997035947A1 (en) * | 1996-03-25 | 1997-10-02 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| WO1997038073A1 (en) * | 1996-04-08 | 1997-10-16 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| WO1997038072A1 (en) * | 1996-04-08 | 1997-10-16 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| US5703033A (en) * | 1996-02-06 | 1997-12-30 | The Procter & Gamble Company | Low sudsing, low streaking and filming hard surface cleaners |
| WO1997047717A3 (en) * | 1996-06-13 | 1998-01-29 | Colgate Palmolive Co | Light duty liquid cleaning compositions |
| WO1998005743A1 (en) * | 1996-08-06 | 1998-02-12 | Colgate-Palmolive Company | High foaming nonionic surfactant based liquid detergent |
| WO1998006817A1 (en) * | 1996-08-14 | 1998-02-19 | Colgate-Palmolive Company | Light duty liquid microemulsion cleaning compositions |
| WO1998005744A3 (en) * | 1996-08-07 | 1998-06-25 | Colgate Palmolive Co | Light duty liquid cleaning compositions |
| WO1998005745A3 (en) * | 1996-08-08 | 1998-07-09 | Colgate Palmolive Co | Light duty liquid cleaning compositions |
| US5814590A (en) * | 1996-02-06 | 1998-09-29 | The Procter & Gamble Company | Low streaking and filming hard surface cleaners |
| WO1998046713A1 (en) * | 1997-04-16 | 1998-10-22 | Unilever Plc | Light duty cleaning composition |
| WO1998050506A1 (en) * | 1997-05-02 | 1998-11-12 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| WO1998053041A1 (en) * | 1997-05-20 | 1998-11-26 | Colgate-Palmolive Company | Light duty liquid microemulsion cleaning compositions |
| WO1999006508A1 (en) * | 1997-07-31 | 1999-02-11 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| WO1999022943A1 (en) * | 1997-10-30 | 1999-05-14 | Cognis Deutschland Gmbh | Application of alkyl polyglucosides in printing ink cleaners |
| WO2002099024A1 (en) * | 2001-06-01 | 2002-12-12 | Kay Chemical, Inc. | All-purpose, super-concentrated liquid detergent composition |
| WO2003080784A1 (en) * | 2002-03-21 | 2003-10-02 | Colgate-Palmolive Company | Foamstable antimicrobial liquid dish cleaning compositions |
| WO2023285245A1 (en) * | 2021-07-16 | 2023-01-19 | Basf Se | A premix comprising alkyl polyglycoside for use in preparing a liquid detergent formulation |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2824192B2 (en) * | 1993-05-31 | 1998-11-11 | 花王株式会社 | Detergent composition |
| KR20030023394A (en) * | 2001-09-13 | 2003-03-19 | 에스케이케미칼주식회사 | Liquid detergent composition for infant |
| JP4795298B2 (en) * | 2007-04-12 | 2011-10-19 | 花王株式会社 | Liquid detergent composition |
| US7902137B2 (en) * | 2008-05-30 | 2011-03-08 | American Sterilizer Company | Biodegradable scale control composition for use in highly concentrated alkaline hard surface detergents |
| CN101760346B (en) * | 2009-12-17 | 2011-12-21 | 陈政 | Multi-element concentrated tableware detergent |
| JP5642598B2 (en) * | 2010-04-07 | 2014-12-17 | 花王株式会社 | Dishwashing composition for hand washing |
| JP5642599B2 (en) * | 2010-04-08 | 2014-12-17 | 花王株式会社 | Dishwashing composition for hand washing |
| JP5809006B2 (en) * | 2011-10-12 | 2015-11-10 | 花王株式会社 | Dishwashing composition for hand washing |
| JP5602199B2 (en) * | 2011-10-12 | 2014-10-08 | 花王株式会社 | Dishwashing composition for hand washing |
| JP5654537B2 (en) * | 2011-10-12 | 2015-01-14 | 花王株式会社 | Dishwashing composition for hand washing |
| JP5957198B2 (en) * | 2011-10-12 | 2016-07-27 | 花王株式会社 | Dishwashing composition for hand washing |
| US9072919B2 (en) * | 2012-10-12 | 2015-07-07 | L'oreal S.A. | Synergistic antioxidant cosmetic compositions containing at least one of baicalin and taxifolin, at least one of caffeine and nicotinamide, at least one of vitamin C and resveratrol and ferulic acid |
| CN102994254A (en) * | 2012-11-26 | 2013-03-27 | 启东市隆腾电气有限公司 | Automotive glass cleaning agent |
| CN103194321B (en) * | 2013-03-24 | 2015-08-26 | 山西振东家庭健康护理用品有限公司 | antibacterial detergent for tableware and preparation method thereof |
| JP2017119657A (en) * | 2015-12-28 | 2017-07-06 | ライオン株式会社 | Liquid skin cleansing composition |
| WO2017204148A1 (en) * | 2016-05-27 | 2017-11-30 | 花王株式会社 | Method for washing hard surface |
| KR101959815B1 (en) * | 2017-11-14 | 2019-03-20 | 주식회사 제씨콤 | Insulating detergent composition for communication and electric equipment |
| CN111304008B (en) * | 2019-11-28 | 2021-05-28 | 纳爱斯浙江科技有限公司 | A liquid detergent composition with antibacterial function in low hardness water environment |
| CN118126780B (en) * | 2024-03-01 | 2024-11-05 | 江苏爱特福84股份有限公司 | A kind of kitchen disinfection detergent and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ206211A (en) * | 1982-11-16 | 1986-04-11 | Unilever Plc | Foaming liquid detergent compositions containing sulphosuccinic acid esters |
| DE3706015A1 (en) * | 1987-02-25 | 1988-11-17 | Henkel Kgaa | LIQUID DETERGENT |
| NZ230239A (en) * | 1988-08-19 | 1991-05-28 | Colgate Palmolive Co | Dishwashing detergents containing alkyl mono- or poly-glucosides |
| US5015414A (en) * | 1988-09-08 | 1991-05-14 | Kao Corporation | Low-irritant detergent composition containing alkyl saccharide and sulfosuccinate surfactants |
| GB8905551D0 (en) * | 1989-03-10 | 1989-04-19 | Unilever Plc | Detergent compositions |
| JPH0699711B2 (en) * | 1989-07-25 | 1994-12-07 | 花王株式会社 | Liquid detergent composition |
-
1992
- 1992-04-08 AU AU14753/92A patent/AU661682B2/en not_active Ceased
- 1992-04-13 MX MX9201702A patent/MX9201702A/en not_active IP Right Cessation
- 1992-04-13 GR GR920100146A patent/GR1001299B/en unknown
- 1992-04-13 PT PT100381A patent/PT100381B/en not_active IP Right Cessation
- 1992-04-13 PH PH44199A patent/PH31565A/en unknown
- 1992-04-14 NO NO921480A patent/NO300333B1/en unknown
- 1992-04-14 RO RO92-200515A patent/RO108359B1/en unknown
- 1992-04-14 CA CA002066009A patent/CA2066009A1/en not_active Abandoned
- 1992-04-14 MW MW21/92A patent/MW2192A1/en unknown
- 1992-04-14 JP JP4094178A patent/JPH05132699A/en active Pending
- 1992-04-14 HU HU9201274A patent/HU212050B/en not_active IP Right Cessation
- 1992-04-14 FI FI921673A patent/FI921673A7/en not_active Application Discontinuation
- 1992-04-14 IE IE921184A patent/IE75910B1/en not_active IP Right Cessation
- 1992-04-15 TR TR92/0326A patent/TR25951A/en unknown
- 1992-04-15 AT AT92201089T patent/ATE140259T1/en not_active IP Right Cessation
- 1992-04-15 DE DE69212045T patent/DE69212045T2/en not_active Expired - Fee Related
- 1992-04-15 EP EP92201089A patent/EP0509608B1/en not_active Revoked
- 1992-04-15 CN CN92102658A patent/CN1067068A/en active Pending
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5531939A (en) * | 1994-03-23 | 1996-07-02 | Amway Corporation | Concentrated glass and window cleaning composition and method of use |
| US5575864A (en) * | 1994-03-23 | 1996-11-19 | Haley; Kalliopi S. | Method for cleaning a hard surface with an all-purpose liquid cleaning composition |
| US5837065A (en) * | 1994-03-23 | 1998-11-17 | Amway Corporation | Concentrated all-purpose light duty liquid cleaning composition and method of use |
| US5814590A (en) * | 1996-02-06 | 1998-09-29 | The Procter & Gamble Company | Low streaking and filming hard surface cleaners |
| US5703033A (en) * | 1996-02-06 | 1997-12-30 | The Procter & Gamble Company | Low sudsing, low streaking and filming hard surface cleaners |
| WO1997034973A1 (en) * | 1996-03-21 | 1997-09-25 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| WO1997035947A1 (en) * | 1996-03-25 | 1997-10-02 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| WO1997038072A1 (en) * | 1996-04-08 | 1997-10-16 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| WO1997038073A1 (en) * | 1996-04-08 | 1997-10-16 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| AU719890B2 (en) * | 1996-04-08 | 2000-05-18 | Colgate-Palmolive Company, The | Light duty liquid cleaning compositions |
| WO1997047717A3 (en) * | 1996-06-13 | 1998-01-29 | Colgate Palmolive Co | Light duty liquid cleaning compositions |
| WO1998005743A1 (en) * | 1996-08-06 | 1998-02-12 | Colgate-Palmolive Company | High foaming nonionic surfactant based liquid detergent |
| WO1998005744A3 (en) * | 1996-08-07 | 1998-06-25 | Colgate Palmolive Co | Light duty liquid cleaning compositions |
| WO1998005745A3 (en) * | 1996-08-08 | 1998-07-09 | Colgate Palmolive Co | Light duty liquid cleaning compositions |
| WO1998006817A1 (en) * | 1996-08-14 | 1998-02-19 | Colgate-Palmolive Company | Light duty liquid microemulsion cleaning compositions |
| WO1998046713A1 (en) * | 1997-04-16 | 1998-10-22 | Unilever Plc | Light duty cleaning composition |
| WO1998050506A1 (en) * | 1997-05-02 | 1998-11-12 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| WO1998053041A1 (en) * | 1997-05-20 | 1998-11-26 | Colgate-Palmolive Company | Light duty liquid microemulsion cleaning compositions |
| WO1999006508A1 (en) * | 1997-07-31 | 1999-02-11 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| WO1999022943A1 (en) * | 1997-10-30 | 1999-05-14 | Cognis Deutschland Gmbh | Application of alkyl polyglucosides in printing ink cleaners |
| US6346156B1 (en) | 1997-10-30 | 2002-02-12 | Cognis Deutschland Gmbh | Application of alkyl polyglucosides in printing ink cleaners |
| WO2002099024A1 (en) * | 2001-06-01 | 2002-12-12 | Kay Chemical, Inc. | All-purpose, super-concentrated liquid detergent composition |
| US6759382B2 (en) | 2001-06-01 | 2004-07-06 | Kay Chemical, Inc. | Detergent composition containing a primary surfactant system and a secondary surfactant system, and a method of using the same |
| WO2003080784A1 (en) * | 2002-03-21 | 2003-10-02 | Colgate-Palmolive Company | Foamstable antimicrobial liquid dish cleaning compositions |
| WO2023285245A1 (en) * | 2021-07-16 | 2023-01-19 | Basf Se | A premix comprising alkyl polyglycoside for use in preparing a liquid detergent formulation |
| US20240287423A1 (en) * | 2021-07-16 | 2024-08-29 | Basf Se | A premix comprising alkyl polyglycoside for use in preparing a liquid detergent formulation |
Also Published As
| Publication number | Publication date |
|---|---|
| MW2192A1 (en) | 1994-01-12 |
| GR1001299B (en) | 1993-07-30 |
| DE69212045D1 (en) | 1996-08-14 |
| FI921673L (en) | 1992-10-16 |
| PT100381B (en) | 2001-05-31 |
| MX9201702A (en) | 1992-10-01 |
| ATE140259T1 (en) | 1996-07-15 |
| IE921184A1 (en) | 1992-10-21 |
| EP0509608A3 (en) | 1993-03-10 |
| EP0509608B1 (en) | 1996-07-10 |
| NO921480D0 (en) | 1992-04-14 |
| NO921480L (en) | 1992-10-16 |
| IE75910B1 (en) | 1997-10-08 |
| TR25951A (en) | 1993-11-01 |
| FI921673A0 (en) | 1992-04-14 |
| DE69212045T2 (en) | 1997-02-27 |
| PT100381A (en) | 1993-06-30 |
| JPH05132699A (en) | 1993-05-28 |
| HU212050B (en) | 1996-01-29 |
| PH31565A (en) | 1998-11-03 |
| HUT60761A (en) | 1992-10-28 |
| AU1475392A (en) | 1992-10-22 |
| FI921673A7 (en) | 1992-10-16 |
| HU9201274D0 (en) | 1992-07-28 |
| AU661682B2 (en) | 1995-08-03 |
| NO300333B1 (en) | 1997-05-12 |
| CN1067068A (en) | 1992-12-16 |
| CA2066009A1 (en) | 1992-10-16 |
| RO108359B1 (en) | 1994-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0509608B1 (en) | Light duty liquid detergent compositions | |
| US5480586A (en) | Light duty liquid detergent compostion comprising a sulfosuccinamate-containing surfactant blend | |
| US5565146A (en) | Light duty liquid detergent compositions | |
| US4595526A (en) | High foaming nonionic surfacant based liquid detergent | |
| US4732704A (en) | Manual dishwashing liquid detergent containing fatty alkylmonogluside | |
| US5476614A (en) | High foaming nonionic surfactant based liquid detergent | |
| EP0554991B1 (en) | Detergent compositions | |
| US5073293A (en) | Mild detergent compositions containing alkylglycoside and dicarboxylic acid surfactants | |
| KR960015369B1 (en) | Washing and cleaning agent in paste form and process for producing it | |
| JP2807088B2 (en) | Light duty liquid dishwashing detergent composition | |
| EP0573341B1 (en) | High foaming nonionic surfactant based liquid detergent | |
| AU634489B2 (en) | Light duty liquid detergent compositions | |
| US5503779A (en) | High foaming light duty liquid detergent | |
| JPH0354156B2 (en) | ||
| AU663186B2 (en) | High foaming nonionic surfactant based liquid detergent | |
| EP0387063B1 (en) | Detergent compositions | |
| US5780411A (en) | High foaming nonionic surfactant based liquid detergent | |
| US5629279A (en) | High foaming nonionic surfactant based liquid detergent | |
| US5756441A (en) | High foaming nonionic surfactant based liquid detergent | |
| JP3428170B2 (en) | Liquid detergent composition | |
| US5789370A (en) | High foaming nonionic surfactant based liquid detergent | |
| NZ242284A (en) | Aqueous dishwashing detergent comprising an alkyl benzene sulphonate | |
| EP0699228B1 (en) | High foaming nonionic surfactant based liquid detergent | |
| US5869439A (en) | High foaming nonionic surfactant based liquid detergent | |
| WO1998050507A1 (en) | High foaming nonionic surfactant based liquid detergent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE |
|
| 17P | Request for examination filed |
Effective date: 19930809 |
|
| 17Q | First examination report despatched |
Effective date: 19941114 |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT Effective date: 19960710 Ref country code: LI Effective date: 19960710 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19960710 Ref country code: AT Effective date: 19960710 Ref country code: DK Effective date: 19960710 Ref country code: ES Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19960710 Ref country code: CH Effective date: 19960710 |
|
| REF | Corresponds to: |
Ref document number: 140259 Country of ref document: AT Date of ref document: 19960715 Kind code of ref document: T |
|
| REF | Corresponds to: |
Ref document number: 69212045 Country of ref document: DE Date of ref document: 19960814 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19961010 |
|
| ET | Fr: translation filed | ||
| NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19970415 |
|
| PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
| PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19970425 Year of fee payment: 6 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970430 |
|
| PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19970521 Year of fee payment: 6 |
|
| 26 | Opposition filed |
Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN Effective date: 19970410 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19970619 Year of fee payment: 6 |
|
| PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
| PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19970415 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19980430 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980430 |
|
| PLBO | Opposition rejected |
Free format text: ORIGINAL CODE: EPIDOS REJO |
|
| APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
| APAE | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOS REFNO |
|
| APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
| BERE | Be: lapsed |
Owner name: COLGATE-PALMOLIVE CY Effective date: 19980430 |
|
| APAE | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOS REFNO |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990202 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
| RDAH | Patent revoked |
Free format text: ORIGINAL CODE: EPIDOS REVO |
|
| RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
| 27W | Patent revoked |
Effective date: 20020927 |
|
| APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
