CA2063264C - Liquid detergent composition - Google Patents
Liquid detergent composition Download PDFInfo
- Publication number
- CA2063264C CA2063264C CA002063264A CA2063264A CA2063264C CA 2063264 C CA2063264 C CA 2063264C CA 002063264 A CA002063264 A CA 002063264A CA 2063264 A CA2063264 A CA 2063264A CA 2063264 C CA2063264 C CA 2063264C
- Authority
- CA
- Canada
- Prior art keywords
- nonionic
- composition according
- weight
- fatty
- detergent
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 239000003599 detergent Substances 0.000 title claims abstract description 27
- 239000007788 liquid Substances 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 44
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 20
- 239000000194 fatty acid Substances 0.000 claims abstract description 20
- 229930195729 fatty acid Natural products 0.000 claims abstract description 20
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- -1 pentose sugars Chemical class 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 7
- 150000002402 hexoses Chemical class 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 235000000346 sugar Nutrition 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- 150000002193 fatty amides Chemical class 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract 2
- 235000019256 formaldehyde Nutrition 0.000 claims abstract 2
- 229920000642 polymer Polymers 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 125000001165 hydrophobic group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 238000005191 phase separation Methods 0.000 claims description 3
- 150000001720 carbohydrates Chemical group 0.000 claims description 2
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 claims description 2
- 150000002972 pentoses Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 abstract description 5
- 229920005862 polyol Polymers 0.000 abstract description 4
- 150000003077 polyols Chemical class 0.000 abstract description 4
- 150000005690 diesters Chemical class 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 12
- 239000011149 active material Substances 0.000 description 8
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 8
- 229920001983 poloxamer Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 229910021538 borax Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000004328 sodium tetraborate Substances 0.000 description 7
- 235000010339 sodium tetraborate Nutrition 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229930182478 glucoside Natural products 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- 229960001790 sodium citrate Drugs 0.000 description 4
- 235000011083 sodium citrates Nutrition 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000003752 hydrotrope Substances 0.000 description 3
- 238000005185 salting out Methods 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XDAVBNHKLPHGGU-UHFFFAOYSA-N 2-methylpentadec-2-enoic acid Chemical compound CCCCCCCCCCCCC=C(C)C(O)=O XDAVBNHKLPHGGU-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 125000001589 carboacyl group Chemical group 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 125000003703 phosphorus containing inorganic group Chemical group 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- FKOKUHFZNIUSLW-UHFFFAOYSA-N 2-Hydroxypropyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(C)O FKOKUHFZNIUSLW-UHFFFAOYSA-N 0.000 description 1
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- VUJGKADZTYCLIL-YHPRVSEPSA-L disodium;5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfonatophenyl]ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S([O-])(=O)=O)C(S(=O)(=O)[O-])=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 VUJGKADZTYCLIL-YHPRVSEPSA-L 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 229940045996 isethionic acid Drugs 0.000 description 1
- 229940099367 lanolin alcohols Drugs 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical class [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940093625 propylene glycol monostearate Drugs 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
-
- 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
- C11D1/38—Cationic compounds
- C11D1/42—Amino alcohols or amino ethers
- C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
-
- 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
-
- 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
- C11D1/667—Neutral esters, e.g. sorbitan esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
-
- 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
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
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- Crystallography & Structural Chemistry (AREA)
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- Cosmetics (AREA)
Abstract
An aqueous detergent-active structured liquid detergent composition comprising: (a) a first nonionic surfactant having an HLB of 12.0 or more; (b) a second nonionic material selected from: (i) C6-C20 aliphatic alcohols; (ii) alkoxylated C8-C24 fatty alcohols, fatty acids; fatty amides or fatty amines, containing from 1-3 alkoxy groups of 2-4 C atoms; (iii) nonionics of the following formula: RO(C n H 2n O)x(CH2CH(OH)CH2O)y H, wherein R is an alkyl or alkenyl group having from 9 to 25 car-bon atoms, n is 2 to 4, x is from 0 to 3, y is from 1-3, the alkylene oxide and glycerol groups are arranged in random or block formation, preferably the molecule is terminated with at least one glycerol group; (iv) mono- or diesters of fatty acids and C2-4 polyols, or esters of fatty acids with reducing hexose or pentose sugars;
or mixtures therof; (c) optionally an anionic surfactant material up to a level of 50 weight % of the total of components a, b and c.
or mixtures therof; (c) optionally an anionic surfactant material up to a level of 50 weight % of the total of components a, b and c.
Description
V1'O 91/00331 _ 1 _ PCT/EP90/00971 LIOUID DETERGENT COMPOSITION
The present invention is concerned with liquid detergent compositions of the kind containing a structure formed from detergent active material, the detergent-active structure existing as a separate phase dispersed within a predominantly aqueous phase. This aqueous phase usually contains dissolved electrolyte. In particular the present invention relates to liquid detergent-active structured compositions containing significant levels of nonionic detergent materials.
The present invention is concerned with liquid detergent compositions which are "internally structured" in that the structure is formed by primary detergent active ingredients.
Such structuring is very well known in the art and may be deliberately brought about to endow properties such as consumer preferred flow properties and/or turbid appearance. Many detergent-active structured liquids are also capable of suspending particulate solids such as detergency builders and abrasive particles.
Some of the different kinds of detergent-active structuring which are possible are described in the reference H.A. Barnes, "Detergents", Ch.2. in K. Walters (Ed), "Rheometry: Industrial Applications", J. Wiley &
Sons, Letchworth 1980. In general, the degree of ordering of such systems increases with increasing surfactant and/or electrolyte concentrations. At very low concentrations, the surfactant can exist as a molecular solution. or as a solution of spherical SUBSTITUTE SHEET
V4'O 91/00331 PCT/EP90/00971 micelles, both of these being isotropic. With the addition of further surfactant and/or electrolyte, structured (anisotropic) systems can form. They are referred to respectively, by various terms such as rod-s micelles, planar lamellar structures, lamellar droplets and liquid crystalline phases. Often, different workers have used different terminology to refer to the detergent-active structures which are really the same.
For instance, in European patent specification EP-A-151 884, lamellar droplets are called "spherulites". The presence and identity of a surfactant structuring system in a liquid may be determined by means known to those skilled in the art for example, optical techniques, various rheometrical measurements, x-ray or neutron diffraction, and sometimes, electron microscopy.
Electrolyte may be only dissolved in the aqueous continuous phase or may also be present as suspended solid particles. Particles of solid materials which are insoluble in the aqueous phase may be suspended alternatively or in addition to any solid electrolyte particles.
Three common product forms in this type are liquids for heavy duty fabrics washing and liquid abrasive and general purpose cleaners. In the first class, the suspended solid can comprise suspended solids which are substantially the same as the dissolved electrolyte, being an excess of same beyond the solubility limit.
This solid is usually present as a detergency builder, i.e. to counteract the effects of calcium ion water hardness in the wash. In the second class, the suspended solid usually comprises a particulate abrasive, insoluble in the system. In that case the electrolyte, present to contribute to the structuring of the active SUBSTITUTE SHEET
N'O 91 /00331 PCT/EP90/00971 from the abrasive compounds. In certain cases, the abrasive can however comprise partially soluble salts which dissolve when the product is diluted. In the third class, the structure is usually used for thickening the product to give consumer-preferred flow properties, and sometimes to suspend pigment particles.
Compositions of the first kind are described in for example our patent specification EP-A-38,101 whilst examples of those in the second category are described in our specification EP-104,452. Those in the third category are for example, described in US 4,244,840.
The dispersed detergent-active structure in these liquids is generally believed to consist of an onion-like configuration comprising concentric bilayers of detergent active molecules, between which is trapped water (aqeuous phase). These configurations of detergent-active material are sometimes referred to as lamellar droplets. It is believed that the close-packing of these droplets enables the solid materials to be kept in suspension. The lamellar droplets are themselves a sub-set of lamellar structures which are capable of being formed in detergent active/aqueous electrolyte systems. Lamellar droplet systems in general, are a preferred category of structures which can exist in detergent liquids.
The present invention is related to detergent-active structured detergent compositions comprising a significant level of nonionic surfactants.
It has been suggested in GB 2 123 846 (Albright and Wilson) examples 49 to 55, to formulate detergent-active structured detergent compositions with high levels of SUBSTITUTE SHEET
~~,3~~'~~ 4 compositions suggested in these examples are not satisfactory in that they suffer from instability.
It has now been found that stable detergent-active structured detergent compositions containing significant levels of nonionic detergent surfactants can be formulated, provided that a specific mixture of nonionic materials is used.
Accordingly the present invention is related to an aqueous detergent-active structured liquid detergent composition, comprising:
(a) a first nonionic surfactant having an HLB of 12.0 or more;
(b) a second nonionic material selected from:
(i) C6-C20 aliphatic alcohols;
(ii) alkoxylated Cg-C24 fatty alcohols, fatty acids, fatty amides or fatty amines, containing from 1-3 alkoxy groups of 2-4 C atoms;
(iii) nonionics of the folllowing formula:
RO(CnH2n0)x(CH2CH(OH)CH20)yH
wherein R is an alkyl or alkenyl group having from 9 to 25 carbon atoms, n is 2 to 4, x is from 0 to 3, y is from 1-3, the alkylene oxide and glycerol groups are arranged in random or block formation, preferably the molecule is SUBSTITUTE SHEET
N'O 91/00331 PCT/E P90/00971 group;
(iv) mono- or di esters of fatty acids and C2_4 polyols, or esters of fatty acids 5 with reducing hexose or pentose sugars;
or mixtures therof;
(c) optionally an anionic surfactant material up to a level of 50 weight ~ of the total of components a,b and c.
Suitable first nonionic materials having an HLB of more than 12 include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. The number of alkylene oxide groups together with the chain length of the hydrophobic groups are selected to provide an HLB of above 12Ø
Examples of nonionic materials having an HLB value above 12 are given in table 1. From this table it is clear that nonionic materials of an HLB above 12.0 generally are characterised by the presence of relative high numbers of alkoxy groups. For the purpose of this invention preferably high HLB nonionics are used which comprise between 5 and 15, more preferred between 6 and 12 EO groups. The HLB of the first nonionic material is preferably between 12.0 and 18.0, more preferred between 12.0 and 16.0, especially preferred between 12.0 and 14Ø
SUBSTITUTE SHEET
WO 91/00331 fCT/EP90/00971 table 1 COMPOUND HLB VALUE
stearyl alcohol 10 EO 12.4 tridecyl alcohol 8 EO 12.7 cetyl alcohol 10 EO 12.9 nonylphenol 10 EO 13.3 tallow fatty acid 15 EO 13.4 lanolin alcohols 16 EO 15.0 propylene glycol monostearate 25 EO 16.0 stearic acid 40 EO 16.9 The second nonionic material for use in compositions according to the present invention generally comprises a relatively long hydrophobic group in combination with no or a relatively small hydrophilic group. For the purpose of the present invention these nonionic materials are selected from fatty alcohols, alkoxylated compounds comprising from 1 to 3 alkoxy groups, glycerol terminated nonionic compounds comprising from 0-3 alkoxy groups, and esters of fatty acids and short chain polyols or reducing hexose or pentose sugars.
Suitable fatty alcohols include the C8-C20 aliphatic alcohols, such as primary or secondary, linear or branched alcohols. Preferably linear, primary alcohols are used. Preferably the C10-Clg alcohols are used, especially the C12-C15 alcohols are preferred, these alcohols have been found to enhance the cleaning performance of detergent compositions according to the present invention. Partucularly preferred is the use of dodecanol. Also, polyhydric alcohols such as fatty alcohol diols, preferably dodecanediol may be used.
SUBSTITUTE SHEET
N'O 91/00331 PCT/EP90/00971 Suitable alkoxylated materials which may be used are the reaction products of a hydrophobic group such as a Cg-C24 fatty alcohol, fatty acid, fatty amide or fatty amine with 1-3 alkylene oxide groups, especially ethylene oxide eventually in combination with propylene oxide. Preferably fatty alcohol adducts are used.
Particularly advantageous in the use of stearyl alcohol 3 EO.
l0 Glycerol terminated nonionic materials may be prepared by optionally subjecting a Cg-C25 higher alcohol to an addition reaction with alkylene oxide, especially ethylene oxide followed by epichlorhydrin or glycerol in an inert atmosphere using an acid or alkali catalyst. In the case of epichlorin, the alcohol is ethoxylated with 0 to 3 moles of ethylene oxide per molecule according to well-known methods. The product is subsequently reacted with 1 to 1.5 moles of epichlorohydrin in the presence of an acid catalyst and the product is treated with potassium hydroxide acetylated and hydrolysed.
Alternatively, after eventual ethoxylation of the alcohol as already described, the ethoxylate is treated with 1 to 1.5 moles of glycidol in the presence of either an alkaline or acidic catalyst. After the reaction the catalyst is neutralised, dehydrated in vacuum and solids produced by neutralisation filtered off to leave the desired nonionic.
When an acid catalyst is used, this may be sodium hydroxide, potassium hydroxide, sodium or potassium metal or sodium methoxide, the reaction temperature being between 30°C and 90°C.
Preferably glycerol terminated nonionics are used which SUBSTITUTE SHEET
V1'O 91 /00331 f CT/ E P9(1/00971 4 ~"
group . ~~
Preferred fatty acid esters of polyols are mono- or diglycerides of C10-20 fatty acids. Preferred fatty acid esters of reducing hexose or pentose sugars are described in WO 89/01480 (NOVO INDUSTRI) and are of the formula:
(R-COO)nX-OR1 wherein R is an alkyl or alkenyl group having from 7 to 18 carbon atoms, R1 is hydrogen or an alkyl group having from 1 to 4 carbon atoms, n is preferably 1, and X is a carbohydrate moiety containing one hexose or pentose unit.
Also mixtures of the nonionic materials listed above may be used.
Preferably the weight ratio of the first nonionic material to the second nonionic material is between 10:1 to 1:10, more preferred from 10:1 to 1:1, especially preferred from 8:1 to 2:1, most preferred from 6:1 to 3:1.
Preferably the level of the first nonionic material is more than 1% by weight, more preferred more than 5%, especially preferred more than 10%. Typical levels are from 1- 35 %, more preferred 5-25% by weight, especially from 10 to 15%.
Preferably the level of the second nonionic material is more than 1 % by weight, more preferred more than 2%, especially preferred more than 3%. Typical levels are from 1- 35 0, more preferred 2-10%, especially from 3 to 8% by weight.
SUBSTITUTE SHEET
N'O 91 /00331 PCT/EP90/00971 ~~ ~3~~~
The total level of nonionic surfactant materials in the composition is preferably more than 5% by weight, more preferred more than 7 %, typically from 10 to 35%, especially preferred from 10 to 25 % by weight.
It has been found advantageous to use combinations of nonionic materials containing materials of which the hydrophobic chain length is about the same. Preferably the ratio of the number of carbon atoms in the hydrophobic group of the first nonionic material to the number of carbon atoms in the hydrophobic group of the second nonionisc material is between 1.5:1 and 1:1.5.
more preferred between 1.2:1 and 1:1.2.
Compositions according to the invention may optionally comprise small amounts of anionic materials. These materials when present are included at a level of less than 50% by weight of the total of surfactant active materials, more preferably less than 40%, especially preferred less than 30%. Particularly preferred are formulations which contain less than 10% on active of anionic surfactants, most preferred are compositions comprising substantially no anionic surfactants.
Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals.containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-Clg) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (Cg-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) SUBSTITUTE SHEET
N'O 91/00331 PCT/EP90/00971 sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and 5 sulphonates; sodium and potassium salts of sulphuric acid esters of higher (Cg-Clg) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products;
the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and 10 neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (Cg-C20) with sodium bisulphite and those derived from reacting paraffins with S02 and C12 and then hydrolysing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly C10-C20 alpha-olefins, with S03 and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (C11-C15) alkyl benzene sulphonates and primary sodium or potassium (C16-Clg) alkyl sulphates.
It is also possible, and sometimes preferred, to include other anionic materials in the composition such as alkali metal soaps of a fatty acid, especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof. The sodium or potassium soaps of these acids can be used.
In many (but not all) cases, the total detergent active material may be present at from 2% to 60% by weight of the total composition, for example from 5% to 40% and SUBSTITUTE SHEET
N'O 91/00331 PCT/EP9(1/00971 m ~d~~~~:~
The liquid compositions according to the present invention preferably have a pH of above 7.0, more preferred from 7.5 to 12.0, ideally between 8.5 and 11.0 at 25 °C.
Compositions according to the invention are preferably physically stable in that they yield no more than 2% by volume phase separation when stored at 25°C for 21 days from the time of preparation.
The viscosity of compositions according to the present is preferably less than 2500 mPas, more preferred less than 1500 mPas, especially preferred between 30 and 1000 mPas at 21 s-1.
One way of regulating the viscosity and stability of compositions according to the present invention is to include viscosity regulating polymeric materials.
Viscosity and/or stability regulating polymers which are preferred for incorporation in compositions according to the invention include deflocculating polymers having a hydrophilic backbone and at least one hydrophobic side chain. Such polymers are for instance described in our copending European application 346 995.
Deflocculation polymers for use in detergent formulations according to the present invention may be of anionic, nonionic or cationic nature. Nonionic deflocculation polymers are preferred.
The hydrophilic backbone of the polymer is typically a homo-, co- or ter-polymer containing carboxylic acid groups (or more preferably) salt forms thereof), e.g.
SUBSTITUTE SKEET
VVO 91/00331 f'CT/Ef9(1/00971 ~~;~
together or with other monomer units such as vinyl ethers, styrene etc. The hydrophobic chain or chains typically are selected from saturated and unsaturated alkyl chains, e.g. having from 5 to 24 carbon atoms and are optionally bonded to the backbone via an alkoxylene or polyalkoxylene linkage, for example a polyethoxy, polypropoxy or butyloxy (or mixtures of same) linkage having from 1 to 50 alkoxylene groups. Thus, in some forms, the side chains) will essentially have the character of a nonionic surfactant. Preferred polymers are disclosed in our copending European patent application 346 995.
Preferably the amount of viscosity regulating polymer is from 0.1 to 5o by weight of the total composition, more preferred from 0.2 to 2%.
In many cases it is preferred for the aqueous continuous phase to contain dissolved electrolyte. As used herein, the term electrolyte means any ionic water soluble material. However, in lamellar droplet dispersions, not all the electrolyte is necessarily dissolved but may be suspended as particles of solid because the total electrolyte concentration of the liquid is higher than the solubility limit of the electrolyte. Mixtures of electrolytes also may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being substantially only in the suspended solid phase. Two or more electrolytes may also be distributed approximately proportionally, between these two phases. In part, this may depend on processing, e.g.
the order of addition of components. On the other hand, the term "salts" includes all organic and inorganic materials which may be included, other than surfactants and water, whether or not they are ionic, and this term SUBSTITUTE SHEET
N'O 91 /00331 PCT/ E P9(1/00971 soluble materials).
The only restriction on the total amount of detergent active material and electrolyte (if any) is that in the lamellar droplet compositions embraced in the present invention, together they must result in formation of an aqueous lamellar dispersion. Thus, within the ambit of the present invention, a very wide variation in surfactant types and levels is possible. The selection of surfactant types and their proportions, in order to obtain a stable liquid with the required structure will be fully within the capability of those skilled in the art. However, it can be mentioned that an important sub-class of useful compositions is those where the detergent active material comprises blends of different surfactant types.
In the case of blends of surfactants, the precise proportions of each component which will result in such stability and viscosity will depend on the types) and amounts) of the electrolytes, as is the case with conventional detergent-active structured liquids.
The compositions optionally also contain electrolyte in an amount sufficient to bring about structuring of the detergent active material. Preferably though, the compositions contain from 1% to 60%, especially from 10 to 45% of a salting-out electrolyte. Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646, that is all electrolytes having a lyotropic number of less than 9.5. Optionally, some salting-in electrolyte (as defined in the latter specification) may also be included, provided it is of a kind and in an amount compatible with the other components and the composition is still in accordance with the definition SUBSTITUTE SHEET
V1'O 91/00331 PCT/EP9(1/00971 electrolyte~~hether salting-in or salting-out), or any substantially water insoluble salt which may be present, may have detergency builder properties. In any event, it is preferred that compositions according to the present invention include detergency builder material, some or all of which may be electrolyte. The builder material is any capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the dispersion of the fabric softening clay material.
Examples of phosphorus-containing inorganic detergency builders, when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used.
Examples of non-phosphorus-containing inorganic detergency builders, when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
In the context of inorganic builders, we prefer to include electrolytes which promote the solubility of other electrolytes, for example use of potassium salts to promote the solubility of sodium salts. Thereby, the amount of dissolved electrolyte can be increased SUBSTITUTE SHEET
N'O 91/00331 PCT/EP90/00971 patent specification GB 1 302 543.
Examples of organic detergency builders, when present, include the alkaline metal, ammonium and substituted 5 ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates.
Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, 10 oxydisuccinic acid, CMOS, melitic acid, benzene polycarboxylic acids and citric acid.
Preferably the levl of non-soap builder material is from 0-50 %, more preferably 2-40 %, most preferably 5-30 15 by weight of the composition.
In the context of organic builders, it is also desirable to incorporate polymers which are only partly dissolved, in the aqueous continuous phase as described in EP
301.882. This allows a viscosity reduction (due to the polymer which is dissolved) whilst incorporating a sufficiently high amount to achieve a secondary benefit, especially building, because the part which is not dissolved does not bring about the instability that would occur if substantially all were dissolved.
Typical amounts are from 0.5 to 4.5% by weight.
It is further possible to include in the compositions of the present invention, alternatively, or in addition to the partly dissolved polymer, yet another polymer which is substantially totally soluble in the aqueous phase and has an electrolyte resistance of more than 5 grams sodium nitrilotriacetate in 100m1 of a 5% by weight aqueous solution of the polymer, said second polymer also having a vapour pressure in 20% aqueous solution, SUBSTITUTE SHEET
V1'O 91/00331 PCT/EP90/00971 2% by weight or greater aqueous solution of polyethylene glycol having an average molecular weight of 6000; said second polymer having a molecular weight of at least 1000. Use of such polymers is generally described in our EP 301,883.
The incorporation of the soluble polymer permits formulation with improved physical stability at the same viscosity (relative to the composition without the soluble polymer) or lower viscosity with the same stability. The soluble polymer can also reduce viscosity drift, even when it also brings about a viscosity reduction. Here, improved stability and lower viscosity mean over and above any such effects brought about by the deflocculating polymer.
It is especially preferred to incorporate the soluble polymer with a partly dissolved polymer which has a large insoluble component. That is because although the building capacity of the partly dissolved polymer will be good (since relatively high quantities can be stably incorporated), the viscosity reduction will not be optimum (since little will be dissolved). Thus, the soluble polymer can usefully function to reduce the viscosity further, to an ideal level. The soluble polymer can, for example, be incorporated at from 0.05 to 20% by weight, although usually, from 0.1 to 2.5% by weight of the total composition is sufficient, and especially from 0.2 to 1.5 by weight. Often, levels above these can cause instability.
Although it is possible to incorporate minor amounts of hydrotropes other than water-miscible solvents, we prefer that the compositions of the present invention are substantially free from hydrotropes. By hydrotrope SUBSTITUTE SHEET
'~'O 91/00331 PCT/EP9(1/00971 m the solubility of surfactants in aqueous solution.
Apart from the ingredients already mentioned, a number of optional ingredients may also be present, for example lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases, amylases and lipases (including Lipolase (Trade Mark) ex Novo), germicides and colourants.
Amongst these optional ingredients, as mentioned previously, are agents to which lamellar dispersions without deflocculating polymer are highly stability-sensitive and by virtue of the present invention, can be incorporated in higher, more useful amounts. These agents cause a problem because they tend to promote flocculation of the lamellar droplets. Examples of such agents are fluorescers like Blankophor RKH, Tinopal LMS, and Tinopal DMS-X and Blankophor BBM as well as metal chelating agents, especially of the phosphonate type, for example the bequest range sold by Monsanto.
The compositions according to the invention may be prepared by methods well known in the art. A
particularly preferred method for preparing the compositions involves the formation of a non-aqueous pre-mix comprising at least the two nonionic materials, followed by dispersing this premix in water. This method is particularly advantageous in that it avoids difficulties in dissolving the second less water soluble nonionic material.
The invention will now be illustrated by way of the following Examples. In all Examples, unless stated to the contrary, all percentages are by weight.
SUBSTITUTE SHEET
V'O 91/00331 PCT/Ef90/009'1 The following compositions were prepared by premixing the active materials followed by dispersing the mix in water containing the electrolyte.
The following stable compositions were obtained:
EXAMPLE I II III
l0 Component weight ~ercentacre dodecanol 3.8 3.2 3.2 C13-C15 7E0 15.2 12.8 12.8 Glycerol -- -- 5.0 borax -- -- 3.5 sodiumcitrate.2H20 4.8 4.0 --water ------balan ce-----viscosity (mPas 21 s-1) 845 1024 966 The following composition was prepared by a method as described in example 1:
INGREDIENT %(WT) Synperonic A7 12.5 Dodecanol 3.1 Glycerol 2.7 Borax 1.9 silicone (DB100) 0.2 zeolite(WessalithP) 15.6 water balance This composition was stable and showed no phase separation upon storage. The pH of the composition was 7.2.
SUBSTITUTE SHEET
V1'O 91/00331 PCT/EP9(1/00971 The following composition was prepared as in the previous examples:
INGREDIENT %(wtl Synperonic A7 12.9 Dodecanol 3.2 LAS (Marlon AS-3) 10.7 NaOH 1.4 sodiumcitrate.2H20 9.0 silicone (DB100) 0.2 polymer(a) 0.5 water balance (a) deflocculating polymer being a copolymer of acrylic acid and laurylmethacrylic acid in a ratio of 25 :1, and a molecular weight of from 3,000 to 4,000.
The following composition was prepared as described hereabove:
2 5 I NGRED I ENT %~ WT1 Synperonic A7 19.5 LAS (Marlon AS-3) 3.2 Oleic acid 7.4 Dobanol-2E0-Glycerol 4.9 Glycerol 4.9 Borax 3.4 sodium citrate.2H20 9.9 NaOH 1.4 polymer (a) 1.0 water balance SUBSTITUTE SHEET
V1'O 91 /00331 PCT/EY9(1/00971 c~ ~' ~~ ~~~3~ ~~
Examt~le 7 The following composition was prepared by heating the water to 50 °C and adding the ingredients in the listed order under stirring, whereby the glucoside, borax and 5 Glycerol were added sequentially with 2 minutes mixing/stirring between each addition. STP was added gradually over a 10 minute period followed by further stirring for 10 minutes before the addition of Synperonic A7.
l0 Component %wt demin water 56.0 alkanoyl glucosidel) 9.9 borax 3.2 15 glycerol 5.0 STPP 23.6 Synpreonic A7 2.3 1) ethyl 6-0-dodecanoyl glucoside ex NOVO
Example 8 The following composition was made as in example I
Component % wt sodiumcitrate.2H20 2.7 Glycerol 5.4 Borax 4.3 Zeolite (Wessalith P) 27.0 alkanoyl glucosidel) 7.6 Synperonic A3 1.3 Synperonic A7 3.8 Sokolan PA50 (BASF) 0.4 water balance 1) ethyl 6-0-dodecanoyl glucoside ex NOVO
SUBSTITUTE SHEET
f1'O 91/00331 PCT/EY90/00971 Example ~ "~~ ~9 The following composition was made as in example 1 Component % wt Glycerol 5.0 borax 3.5 Na-citrate.2aq 10.0 NaOH 2.3 LAS (Marlon AS-3) 18.7 polymerl) 1.0 Synperonic A7 8.0 dodecanediol 12.0 water balance 1) deflocculating polymer being a copolymer of acrylic acid and laurylmethacrylic acid in a ratio of 25 :1, and a molecular weight of from 3,000 to 4,000.
Examples 10-12 The following formulations were made as in example 1.
Component (% wt) 10 11 12 Synperonic A7 15.2 13.3 13.3 Nacitrate.2aq 4.8 4.8 4.8 dodecanediol 3.8 -- --Cg_11 glycerol ether -- 5.7 --glucosidel) -- -- 5.7 water -----balance-----1) ethyl 6-0-dodecanoyl glucoside ex NOVO
SUBSTITUTE SHEET
The present invention is concerned with liquid detergent compositions of the kind containing a structure formed from detergent active material, the detergent-active structure existing as a separate phase dispersed within a predominantly aqueous phase. This aqueous phase usually contains dissolved electrolyte. In particular the present invention relates to liquid detergent-active structured compositions containing significant levels of nonionic detergent materials.
The present invention is concerned with liquid detergent compositions which are "internally structured" in that the structure is formed by primary detergent active ingredients.
Such structuring is very well known in the art and may be deliberately brought about to endow properties such as consumer preferred flow properties and/or turbid appearance. Many detergent-active structured liquids are also capable of suspending particulate solids such as detergency builders and abrasive particles.
Some of the different kinds of detergent-active structuring which are possible are described in the reference H.A. Barnes, "Detergents", Ch.2. in K. Walters (Ed), "Rheometry: Industrial Applications", J. Wiley &
Sons, Letchworth 1980. In general, the degree of ordering of such systems increases with increasing surfactant and/or electrolyte concentrations. At very low concentrations, the surfactant can exist as a molecular solution. or as a solution of spherical SUBSTITUTE SHEET
V4'O 91/00331 PCT/EP90/00971 micelles, both of these being isotropic. With the addition of further surfactant and/or electrolyte, structured (anisotropic) systems can form. They are referred to respectively, by various terms such as rod-s micelles, planar lamellar structures, lamellar droplets and liquid crystalline phases. Often, different workers have used different terminology to refer to the detergent-active structures which are really the same.
For instance, in European patent specification EP-A-151 884, lamellar droplets are called "spherulites". The presence and identity of a surfactant structuring system in a liquid may be determined by means known to those skilled in the art for example, optical techniques, various rheometrical measurements, x-ray or neutron diffraction, and sometimes, electron microscopy.
Electrolyte may be only dissolved in the aqueous continuous phase or may also be present as suspended solid particles. Particles of solid materials which are insoluble in the aqueous phase may be suspended alternatively or in addition to any solid electrolyte particles.
Three common product forms in this type are liquids for heavy duty fabrics washing and liquid abrasive and general purpose cleaners. In the first class, the suspended solid can comprise suspended solids which are substantially the same as the dissolved electrolyte, being an excess of same beyond the solubility limit.
This solid is usually present as a detergency builder, i.e. to counteract the effects of calcium ion water hardness in the wash. In the second class, the suspended solid usually comprises a particulate abrasive, insoluble in the system. In that case the electrolyte, present to contribute to the structuring of the active SUBSTITUTE SHEET
N'O 91 /00331 PCT/EP90/00971 from the abrasive compounds. In certain cases, the abrasive can however comprise partially soluble salts which dissolve when the product is diluted. In the third class, the structure is usually used for thickening the product to give consumer-preferred flow properties, and sometimes to suspend pigment particles.
Compositions of the first kind are described in for example our patent specification EP-A-38,101 whilst examples of those in the second category are described in our specification EP-104,452. Those in the third category are for example, described in US 4,244,840.
The dispersed detergent-active structure in these liquids is generally believed to consist of an onion-like configuration comprising concentric bilayers of detergent active molecules, between which is trapped water (aqeuous phase). These configurations of detergent-active material are sometimes referred to as lamellar droplets. It is believed that the close-packing of these droplets enables the solid materials to be kept in suspension. The lamellar droplets are themselves a sub-set of lamellar structures which are capable of being formed in detergent active/aqueous electrolyte systems. Lamellar droplet systems in general, are a preferred category of structures which can exist in detergent liquids.
The present invention is related to detergent-active structured detergent compositions comprising a significant level of nonionic surfactants.
It has been suggested in GB 2 123 846 (Albright and Wilson) examples 49 to 55, to formulate detergent-active structured detergent compositions with high levels of SUBSTITUTE SHEET
~~,3~~'~~ 4 compositions suggested in these examples are not satisfactory in that they suffer from instability.
It has now been found that stable detergent-active structured detergent compositions containing significant levels of nonionic detergent surfactants can be formulated, provided that a specific mixture of nonionic materials is used.
Accordingly the present invention is related to an aqueous detergent-active structured liquid detergent composition, comprising:
(a) a first nonionic surfactant having an HLB of 12.0 or more;
(b) a second nonionic material selected from:
(i) C6-C20 aliphatic alcohols;
(ii) alkoxylated Cg-C24 fatty alcohols, fatty acids, fatty amides or fatty amines, containing from 1-3 alkoxy groups of 2-4 C atoms;
(iii) nonionics of the folllowing formula:
RO(CnH2n0)x(CH2CH(OH)CH20)yH
wherein R is an alkyl or alkenyl group having from 9 to 25 carbon atoms, n is 2 to 4, x is from 0 to 3, y is from 1-3, the alkylene oxide and glycerol groups are arranged in random or block formation, preferably the molecule is SUBSTITUTE SHEET
N'O 91/00331 PCT/E P90/00971 group;
(iv) mono- or di esters of fatty acids and C2_4 polyols, or esters of fatty acids 5 with reducing hexose or pentose sugars;
or mixtures therof;
(c) optionally an anionic surfactant material up to a level of 50 weight ~ of the total of components a,b and c.
Suitable first nonionic materials having an HLB of more than 12 include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. The number of alkylene oxide groups together with the chain length of the hydrophobic groups are selected to provide an HLB of above 12Ø
Examples of nonionic materials having an HLB value above 12 are given in table 1. From this table it is clear that nonionic materials of an HLB above 12.0 generally are characterised by the presence of relative high numbers of alkoxy groups. For the purpose of this invention preferably high HLB nonionics are used which comprise between 5 and 15, more preferred between 6 and 12 EO groups. The HLB of the first nonionic material is preferably between 12.0 and 18.0, more preferred between 12.0 and 16.0, especially preferred between 12.0 and 14Ø
SUBSTITUTE SHEET
WO 91/00331 fCT/EP90/00971 table 1 COMPOUND HLB VALUE
stearyl alcohol 10 EO 12.4 tridecyl alcohol 8 EO 12.7 cetyl alcohol 10 EO 12.9 nonylphenol 10 EO 13.3 tallow fatty acid 15 EO 13.4 lanolin alcohols 16 EO 15.0 propylene glycol monostearate 25 EO 16.0 stearic acid 40 EO 16.9 The second nonionic material for use in compositions according to the present invention generally comprises a relatively long hydrophobic group in combination with no or a relatively small hydrophilic group. For the purpose of the present invention these nonionic materials are selected from fatty alcohols, alkoxylated compounds comprising from 1 to 3 alkoxy groups, glycerol terminated nonionic compounds comprising from 0-3 alkoxy groups, and esters of fatty acids and short chain polyols or reducing hexose or pentose sugars.
Suitable fatty alcohols include the C8-C20 aliphatic alcohols, such as primary or secondary, linear or branched alcohols. Preferably linear, primary alcohols are used. Preferably the C10-Clg alcohols are used, especially the C12-C15 alcohols are preferred, these alcohols have been found to enhance the cleaning performance of detergent compositions according to the present invention. Partucularly preferred is the use of dodecanol. Also, polyhydric alcohols such as fatty alcohol diols, preferably dodecanediol may be used.
SUBSTITUTE SHEET
N'O 91/00331 PCT/EP90/00971 Suitable alkoxylated materials which may be used are the reaction products of a hydrophobic group such as a Cg-C24 fatty alcohol, fatty acid, fatty amide or fatty amine with 1-3 alkylene oxide groups, especially ethylene oxide eventually in combination with propylene oxide. Preferably fatty alcohol adducts are used.
Particularly advantageous in the use of stearyl alcohol 3 EO.
l0 Glycerol terminated nonionic materials may be prepared by optionally subjecting a Cg-C25 higher alcohol to an addition reaction with alkylene oxide, especially ethylene oxide followed by epichlorhydrin or glycerol in an inert atmosphere using an acid or alkali catalyst. In the case of epichlorin, the alcohol is ethoxylated with 0 to 3 moles of ethylene oxide per molecule according to well-known methods. The product is subsequently reacted with 1 to 1.5 moles of epichlorohydrin in the presence of an acid catalyst and the product is treated with potassium hydroxide acetylated and hydrolysed.
Alternatively, after eventual ethoxylation of the alcohol as already described, the ethoxylate is treated with 1 to 1.5 moles of glycidol in the presence of either an alkaline or acidic catalyst. After the reaction the catalyst is neutralised, dehydrated in vacuum and solids produced by neutralisation filtered off to leave the desired nonionic.
When an acid catalyst is used, this may be sodium hydroxide, potassium hydroxide, sodium or potassium metal or sodium methoxide, the reaction temperature being between 30°C and 90°C.
Preferably glycerol terminated nonionics are used which SUBSTITUTE SHEET
V1'O 91 /00331 f CT/ E P9(1/00971 4 ~"
group . ~~
Preferred fatty acid esters of polyols are mono- or diglycerides of C10-20 fatty acids. Preferred fatty acid esters of reducing hexose or pentose sugars are described in WO 89/01480 (NOVO INDUSTRI) and are of the formula:
(R-COO)nX-OR1 wherein R is an alkyl or alkenyl group having from 7 to 18 carbon atoms, R1 is hydrogen or an alkyl group having from 1 to 4 carbon atoms, n is preferably 1, and X is a carbohydrate moiety containing one hexose or pentose unit.
Also mixtures of the nonionic materials listed above may be used.
Preferably the weight ratio of the first nonionic material to the second nonionic material is between 10:1 to 1:10, more preferred from 10:1 to 1:1, especially preferred from 8:1 to 2:1, most preferred from 6:1 to 3:1.
Preferably the level of the first nonionic material is more than 1% by weight, more preferred more than 5%, especially preferred more than 10%. Typical levels are from 1- 35 %, more preferred 5-25% by weight, especially from 10 to 15%.
Preferably the level of the second nonionic material is more than 1 % by weight, more preferred more than 2%, especially preferred more than 3%. Typical levels are from 1- 35 0, more preferred 2-10%, especially from 3 to 8% by weight.
SUBSTITUTE SHEET
N'O 91 /00331 PCT/EP90/00971 ~~ ~3~~~
The total level of nonionic surfactant materials in the composition is preferably more than 5% by weight, more preferred more than 7 %, typically from 10 to 35%, especially preferred from 10 to 25 % by weight.
It has been found advantageous to use combinations of nonionic materials containing materials of which the hydrophobic chain length is about the same. Preferably the ratio of the number of carbon atoms in the hydrophobic group of the first nonionic material to the number of carbon atoms in the hydrophobic group of the second nonionisc material is between 1.5:1 and 1:1.5.
more preferred between 1.2:1 and 1:1.2.
Compositions according to the invention may optionally comprise small amounts of anionic materials. These materials when present are included at a level of less than 50% by weight of the total of surfactant active materials, more preferably less than 40%, especially preferred less than 30%. Particularly preferred are formulations which contain less than 10% on active of anionic surfactants, most preferred are compositions comprising substantially no anionic surfactants.
Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals.containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-Clg) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (Cg-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) SUBSTITUTE SHEET
N'O 91/00331 PCT/EP90/00971 sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and 5 sulphonates; sodium and potassium salts of sulphuric acid esters of higher (Cg-Clg) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products;
the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and 10 neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (Cg-C20) with sodium bisulphite and those derived from reacting paraffins with S02 and C12 and then hydrolysing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly C10-C20 alpha-olefins, with S03 and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (C11-C15) alkyl benzene sulphonates and primary sodium or potassium (C16-Clg) alkyl sulphates.
It is also possible, and sometimes preferred, to include other anionic materials in the composition such as alkali metal soaps of a fatty acid, especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof. The sodium or potassium soaps of these acids can be used.
In many (but not all) cases, the total detergent active material may be present at from 2% to 60% by weight of the total composition, for example from 5% to 40% and SUBSTITUTE SHEET
N'O 91/00331 PCT/EP9(1/00971 m ~d~~~~:~
The liquid compositions according to the present invention preferably have a pH of above 7.0, more preferred from 7.5 to 12.0, ideally between 8.5 and 11.0 at 25 °C.
Compositions according to the invention are preferably physically stable in that they yield no more than 2% by volume phase separation when stored at 25°C for 21 days from the time of preparation.
The viscosity of compositions according to the present is preferably less than 2500 mPas, more preferred less than 1500 mPas, especially preferred between 30 and 1000 mPas at 21 s-1.
One way of regulating the viscosity and stability of compositions according to the present invention is to include viscosity regulating polymeric materials.
Viscosity and/or stability regulating polymers which are preferred for incorporation in compositions according to the invention include deflocculating polymers having a hydrophilic backbone and at least one hydrophobic side chain. Such polymers are for instance described in our copending European application 346 995.
Deflocculation polymers for use in detergent formulations according to the present invention may be of anionic, nonionic or cationic nature. Nonionic deflocculation polymers are preferred.
The hydrophilic backbone of the polymer is typically a homo-, co- or ter-polymer containing carboxylic acid groups (or more preferably) salt forms thereof), e.g.
SUBSTITUTE SKEET
VVO 91/00331 f'CT/Ef9(1/00971 ~~;~
together or with other monomer units such as vinyl ethers, styrene etc. The hydrophobic chain or chains typically are selected from saturated and unsaturated alkyl chains, e.g. having from 5 to 24 carbon atoms and are optionally bonded to the backbone via an alkoxylene or polyalkoxylene linkage, for example a polyethoxy, polypropoxy or butyloxy (or mixtures of same) linkage having from 1 to 50 alkoxylene groups. Thus, in some forms, the side chains) will essentially have the character of a nonionic surfactant. Preferred polymers are disclosed in our copending European patent application 346 995.
Preferably the amount of viscosity regulating polymer is from 0.1 to 5o by weight of the total composition, more preferred from 0.2 to 2%.
In many cases it is preferred for the aqueous continuous phase to contain dissolved electrolyte. As used herein, the term electrolyte means any ionic water soluble material. However, in lamellar droplet dispersions, not all the electrolyte is necessarily dissolved but may be suspended as particles of solid because the total electrolyte concentration of the liquid is higher than the solubility limit of the electrolyte. Mixtures of electrolytes also may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being substantially only in the suspended solid phase. Two or more electrolytes may also be distributed approximately proportionally, between these two phases. In part, this may depend on processing, e.g.
the order of addition of components. On the other hand, the term "salts" includes all organic and inorganic materials which may be included, other than surfactants and water, whether or not they are ionic, and this term SUBSTITUTE SHEET
N'O 91 /00331 PCT/ E P9(1/00971 soluble materials).
The only restriction on the total amount of detergent active material and electrolyte (if any) is that in the lamellar droplet compositions embraced in the present invention, together they must result in formation of an aqueous lamellar dispersion. Thus, within the ambit of the present invention, a very wide variation in surfactant types and levels is possible. The selection of surfactant types and their proportions, in order to obtain a stable liquid with the required structure will be fully within the capability of those skilled in the art. However, it can be mentioned that an important sub-class of useful compositions is those where the detergent active material comprises blends of different surfactant types.
In the case of blends of surfactants, the precise proportions of each component which will result in such stability and viscosity will depend on the types) and amounts) of the electrolytes, as is the case with conventional detergent-active structured liquids.
The compositions optionally also contain electrolyte in an amount sufficient to bring about structuring of the detergent active material. Preferably though, the compositions contain from 1% to 60%, especially from 10 to 45% of a salting-out electrolyte. Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646, that is all electrolytes having a lyotropic number of less than 9.5. Optionally, some salting-in electrolyte (as defined in the latter specification) may also be included, provided it is of a kind and in an amount compatible with the other components and the composition is still in accordance with the definition SUBSTITUTE SHEET
V1'O 91/00331 PCT/EP9(1/00971 electrolyte~~hether salting-in or salting-out), or any substantially water insoluble salt which may be present, may have detergency builder properties. In any event, it is preferred that compositions according to the present invention include detergency builder material, some or all of which may be electrolyte. The builder material is any capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the dispersion of the fabric softening clay material.
Examples of phosphorus-containing inorganic detergency builders, when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used.
Examples of non-phosphorus-containing inorganic detergency builders, when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
In the context of inorganic builders, we prefer to include electrolytes which promote the solubility of other electrolytes, for example use of potassium salts to promote the solubility of sodium salts. Thereby, the amount of dissolved electrolyte can be increased SUBSTITUTE SHEET
N'O 91/00331 PCT/EP90/00971 patent specification GB 1 302 543.
Examples of organic detergency builders, when present, include the alkaline metal, ammonium and substituted 5 ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates.
Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, 10 oxydisuccinic acid, CMOS, melitic acid, benzene polycarboxylic acids and citric acid.
Preferably the levl of non-soap builder material is from 0-50 %, more preferably 2-40 %, most preferably 5-30 15 by weight of the composition.
In the context of organic builders, it is also desirable to incorporate polymers which are only partly dissolved, in the aqueous continuous phase as described in EP
301.882. This allows a viscosity reduction (due to the polymer which is dissolved) whilst incorporating a sufficiently high amount to achieve a secondary benefit, especially building, because the part which is not dissolved does not bring about the instability that would occur if substantially all were dissolved.
Typical amounts are from 0.5 to 4.5% by weight.
It is further possible to include in the compositions of the present invention, alternatively, or in addition to the partly dissolved polymer, yet another polymer which is substantially totally soluble in the aqueous phase and has an electrolyte resistance of more than 5 grams sodium nitrilotriacetate in 100m1 of a 5% by weight aqueous solution of the polymer, said second polymer also having a vapour pressure in 20% aqueous solution, SUBSTITUTE SHEET
V1'O 91/00331 PCT/EP90/00971 2% by weight or greater aqueous solution of polyethylene glycol having an average molecular weight of 6000; said second polymer having a molecular weight of at least 1000. Use of such polymers is generally described in our EP 301,883.
The incorporation of the soluble polymer permits formulation with improved physical stability at the same viscosity (relative to the composition without the soluble polymer) or lower viscosity with the same stability. The soluble polymer can also reduce viscosity drift, even when it also brings about a viscosity reduction. Here, improved stability and lower viscosity mean over and above any such effects brought about by the deflocculating polymer.
It is especially preferred to incorporate the soluble polymer with a partly dissolved polymer which has a large insoluble component. That is because although the building capacity of the partly dissolved polymer will be good (since relatively high quantities can be stably incorporated), the viscosity reduction will not be optimum (since little will be dissolved). Thus, the soluble polymer can usefully function to reduce the viscosity further, to an ideal level. The soluble polymer can, for example, be incorporated at from 0.05 to 20% by weight, although usually, from 0.1 to 2.5% by weight of the total composition is sufficient, and especially from 0.2 to 1.5 by weight. Often, levels above these can cause instability.
Although it is possible to incorporate minor amounts of hydrotropes other than water-miscible solvents, we prefer that the compositions of the present invention are substantially free from hydrotropes. By hydrotrope SUBSTITUTE SHEET
'~'O 91/00331 PCT/EP9(1/00971 m the solubility of surfactants in aqueous solution.
Apart from the ingredients already mentioned, a number of optional ingredients may also be present, for example lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases, amylases and lipases (including Lipolase (Trade Mark) ex Novo), germicides and colourants.
Amongst these optional ingredients, as mentioned previously, are agents to which lamellar dispersions without deflocculating polymer are highly stability-sensitive and by virtue of the present invention, can be incorporated in higher, more useful amounts. These agents cause a problem because they tend to promote flocculation of the lamellar droplets. Examples of such agents are fluorescers like Blankophor RKH, Tinopal LMS, and Tinopal DMS-X and Blankophor BBM as well as metal chelating agents, especially of the phosphonate type, for example the bequest range sold by Monsanto.
The compositions according to the invention may be prepared by methods well known in the art. A
particularly preferred method for preparing the compositions involves the formation of a non-aqueous pre-mix comprising at least the two nonionic materials, followed by dispersing this premix in water. This method is particularly advantageous in that it avoids difficulties in dissolving the second less water soluble nonionic material.
The invention will now be illustrated by way of the following Examples. In all Examples, unless stated to the contrary, all percentages are by weight.
SUBSTITUTE SHEET
V'O 91/00331 PCT/Ef90/009'1 The following compositions were prepared by premixing the active materials followed by dispersing the mix in water containing the electrolyte.
The following stable compositions were obtained:
EXAMPLE I II III
l0 Component weight ~ercentacre dodecanol 3.8 3.2 3.2 C13-C15 7E0 15.2 12.8 12.8 Glycerol -- -- 5.0 borax -- -- 3.5 sodiumcitrate.2H20 4.8 4.0 --water ------balan ce-----viscosity (mPas 21 s-1) 845 1024 966 The following composition was prepared by a method as described in example 1:
INGREDIENT %(WT) Synperonic A7 12.5 Dodecanol 3.1 Glycerol 2.7 Borax 1.9 silicone (DB100) 0.2 zeolite(WessalithP) 15.6 water balance This composition was stable and showed no phase separation upon storage. The pH of the composition was 7.2.
SUBSTITUTE SHEET
V1'O 91/00331 PCT/EP9(1/00971 The following composition was prepared as in the previous examples:
INGREDIENT %(wtl Synperonic A7 12.9 Dodecanol 3.2 LAS (Marlon AS-3) 10.7 NaOH 1.4 sodiumcitrate.2H20 9.0 silicone (DB100) 0.2 polymer(a) 0.5 water balance (a) deflocculating polymer being a copolymer of acrylic acid and laurylmethacrylic acid in a ratio of 25 :1, and a molecular weight of from 3,000 to 4,000.
The following composition was prepared as described hereabove:
2 5 I NGRED I ENT %~ WT1 Synperonic A7 19.5 LAS (Marlon AS-3) 3.2 Oleic acid 7.4 Dobanol-2E0-Glycerol 4.9 Glycerol 4.9 Borax 3.4 sodium citrate.2H20 9.9 NaOH 1.4 polymer (a) 1.0 water balance SUBSTITUTE SHEET
V1'O 91 /00331 PCT/EY9(1/00971 c~ ~' ~~ ~~~3~ ~~
Examt~le 7 The following composition was prepared by heating the water to 50 °C and adding the ingredients in the listed order under stirring, whereby the glucoside, borax and 5 Glycerol were added sequentially with 2 minutes mixing/stirring between each addition. STP was added gradually over a 10 minute period followed by further stirring for 10 minutes before the addition of Synperonic A7.
l0 Component %wt demin water 56.0 alkanoyl glucosidel) 9.9 borax 3.2 15 glycerol 5.0 STPP 23.6 Synpreonic A7 2.3 1) ethyl 6-0-dodecanoyl glucoside ex NOVO
Example 8 The following composition was made as in example I
Component % wt sodiumcitrate.2H20 2.7 Glycerol 5.4 Borax 4.3 Zeolite (Wessalith P) 27.0 alkanoyl glucosidel) 7.6 Synperonic A3 1.3 Synperonic A7 3.8 Sokolan PA50 (BASF) 0.4 water balance 1) ethyl 6-0-dodecanoyl glucoside ex NOVO
SUBSTITUTE SHEET
f1'O 91/00331 PCT/EY90/00971 Example ~ "~~ ~9 The following composition was made as in example 1 Component % wt Glycerol 5.0 borax 3.5 Na-citrate.2aq 10.0 NaOH 2.3 LAS (Marlon AS-3) 18.7 polymerl) 1.0 Synperonic A7 8.0 dodecanediol 12.0 water balance 1) deflocculating polymer being a copolymer of acrylic acid and laurylmethacrylic acid in a ratio of 25 :1, and a molecular weight of from 3,000 to 4,000.
Examples 10-12 The following formulations were made as in example 1.
Component (% wt) 10 11 12 Synperonic A7 15.2 13.3 13.3 Nacitrate.2aq 4.8 4.8 4.8 dodecanediol 3.8 -- --Cg_11 glycerol ether -- 5.7 --glucosidel) -- -- 5.7 water -----balance-----1) ethyl 6-0-dodecanoyl glucoside ex NOVO
SUBSTITUTE SHEET
Claims (10)
1. An aqueous detergent-active structured liquid detergent composition, comprising:
(a) a first nonionic surfactant having an HLB of 12.0 or more;
(b) a second nonionic material selected from:
(i) C6-C20 aliphatic alcohols;
(ii) alkoxylated C8-C24 fatty acids or fatty amides containing from 1-3 alkoxy groups of 2-4 C
atoms;
(iii)nonionics of the following formula:
RO(C n H2n O)x(CH2CH(OH)CH2O)y H
wherein R is an alkyl or alkenyl group having from 9 to 25 carbon atoms, n is 2 to 4, x is from 1 to 3, y is from 1-3, the alkylene oxide and glycerol groups are arranged in random or block formation, preferably the molecule is terminated with at least one. glycerol group;
(iv) esters of fatty acids with reducing hexose or pentose sugars of the formula:
wherein R is an alkyl or alkenyl group, R1 is an alkyl group having from 1 to 4 carbon atoms and X is a carbohydrate moiety containing one hexose or pentose unit.
or mixtures thereof:
(c) optionally an anionic surfactant material up to a level of 50 weight % of the total of components a, b and c.
(a) a first nonionic surfactant having an HLB of 12.0 or more;
(b) a second nonionic material selected from:
(i) C6-C20 aliphatic alcohols;
(ii) alkoxylated C8-C24 fatty acids or fatty amides containing from 1-3 alkoxy groups of 2-4 C
atoms;
(iii)nonionics of the following formula:
RO(C n H2n O)x(CH2CH(OH)CH2O)y H
wherein R is an alkyl or alkenyl group having from 9 to 25 carbon atoms, n is 2 to 4, x is from 1 to 3, y is from 1-3, the alkylene oxide and glycerol groups are arranged in random or block formation, preferably the molecule is terminated with at least one. glycerol group;
(iv) esters of fatty acids with reducing hexose or pentose sugars of the formula:
wherein R is an alkyl or alkenyl group, R1 is an alkyl group having from 1 to 4 carbon atoms and X is a carbohydrate moiety containing one hexose or pentose unit.
or mixtures thereof:
(c) optionally an anionic surfactant material up to a level of 50 weight % of the total of components a, b and c.
2. Composition according to claim 1, wherein the weight ratio of the first nonionic material to the second nonionic material is between 10:1 to 1:10.
3. Composition according to claim 1 or 2, wherein the level of the first nonionic material is more than 5%
by weight.
by weight.
4. Composition according to any one of the preceding claims, wherein the level of the second nonionic material is more than 3% by weight.
5. Composition according to any one of the preceding claims wherein the ratio of the number of carbon atoms in the hydrophobic group of the first nonionic material to the number of carbon atoms in the hydrophobic group of the second nonionic material is between 1.5:1 and 1:1.5.
6. Composition according to any one of the preceding claims, containing less than 10% by weight on active of anionic surfactants.
7. Composition according to any one of the preceding claims, yielding no more than 2% by volume phase separation when stored at 25°C for 21 days from the time of preparation.
8. Composition according to any one of the preceding claims, containing deflocculating polymers having a hydrophilic backbone and at least one hydrophobic side chain.
9. Composition according to claim 8, containing from 0.2 to 2.0% by weight of deflocculating polymer.
10. Method for preparing a detergent composition according to any one of the preceding claims, said method involving the formation of a non-aqueous pre-mix comprising at least the two nonionic materials, followed by dispersing this premix in water.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8914602.1 | 1989-06-26 | ||
GB898914602A GB8914602D0 (en) | 1989-06-26 | 1989-06-26 | Liquid detergent composition |
PCT/EP1990/000971 WO1991000331A1 (en) | 1989-06-26 | 1990-06-12 | Liquid detergent composition |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2063264A1 CA2063264A1 (en) | 1990-12-27 |
CA2063264C true CA2063264C (en) | 2001-10-02 |
Family
ID=10659051
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002063264A Expired - Fee Related CA2063264C (en) | 1989-06-26 | 1990-06-12 | Liquid detergent composition |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0479846B2 (en) |
JP (1) | JPH04506367A (en) |
KR (1) | KR960000200B1 (en) |
AU (1) | AU639243B2 (en) |
BR (1) | BR9007474A (en) |
CA (1) | CA2063264C (en) |
DE (1) | DE69004432T3 (en) |
ES (1) | ES2060182T5 (en) |
GB (1) | GB8914602D0 (en) |
WO (1) | WO1991000331A1 (en) |
ZA (1) | ZA904960B (en) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9025248D0 (en) * | 1990-11-20 | 1991-01-02 | Unilever Plc | Detergent compositions |
GB9102945D0 (en) * | 1991-02-12 | 1991-03-27 | Unilever Plc | Detergent composition |
CA2060698C (en) * | 1991-02-12 | 1997-09-30 | Peter J. Hall | Detergent compositions |
DE4236109A1 (en) * | 1992-10-26 | 1994-04-28 | Henkel Kgaa | Liquid detergent |
ATE172234T1 (en) * | 1992-11-26 | 1998-10-15 | Procter & Gamble | CLEANING AGENT COMPOSITIONS WITH A COMBINATION OF HIGHLY HYDROPHILIC AND HIGHLY HYDROPHOBIC NON-IONIC SURFACTANTS |
SK53294A3 (en) | 1993-05-07 | 1995-04-12 | Albright & Wilson | Concentrated aqueous mixture containing surface active matter and its use |
US6090762A (en) * | 1993-05-07 | 2000-07-18 | Albright & Wilson Uk Limited | Aqueous based surfactant compositions |
US5520839A (en) * | 1993-09-10 | 1996-05-28 | Lever Brothers Company, Division Of Conopco, Inc. | Laundry detergent composition containing synergistic combination of sophorose lipid and nonionic surfactant |
TW294720B (en) * | 1994-09-30 | 1997-01-01 | Unilever Nv | |
DE19517033A1 (en) * | 1995-05-10 | 1996-11-14 | Hoechst Ag | Mixture of surfactants |
JP3556806B2 (en) * | 1996-07-24 | 2004-08-25 | サンスター株式会社 | Detergent composition |
US6194371B1 (en) * | 1998-05-01 | 2001-02-27 | Ecolab Inc. | Stable alkaline emulsion cleaners |
KR100462314B1 (en) * | 2001-05-07 | 2004-12-23 | (주)네오팜 | Deterent compositions for industrial use and preparing method thereof |
EP1747260A4 (en) * | 2004-04-15 | 2008-07-30 | Rhodia | STRUCTURED SURFACTANT COMPOSITIONS |
JP5046714B2 (en) | 2007-04-06 | 2012-10-10 | 花王株式会社 | Detergent composition for clothing |
CN101903510B (en) | 2007-12-28 | 2012-05-23 | 花王株式会社 | Laundry composition for clothing |
WO2012115250A1 (en) * | 2011-02-25 | 2012-08-30 | ライオン株式会社 | Liquid detergent for clothing |
TW202128969A (en) * | 2019-11-25 | 2021-08-01 | 日商花王股份有限公司 | Liquid detergent composition for textile products |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4206070A (en) * | 1975-12-24 | 1980-06-03 | The Procter & Gamble Company | Detergent compositions |
CA1081574A (en) * | 1975-12-24 | 1980-07-15 | Kenneth L. Jones | Detergent compositions |
JPS5920754B2 (en) * | 1980-09-08 | 1984-05-15 | 日産自動車株式会社 | industrial metal cleaning agent |
GB8308263D0 (en) * | 1983-03-25 | 1983-05-05 | Unilever Plc | Aqueous liquid detergent composition |
JPH0678550B2 (en) * | 1986-07-09 | 1994-10-05 | 旭電化工業株式会社 | Rinse aid composition |
DE3626224A1 (en) * | 1986-08-02 | 1988-02-04 | Henkel Kgaa | CLEANING SUPPLIES |
GB8718215D0 (en) * | 1987-07-31 | 1987-09-09 | Unilever Plc | Liquid detergent compositions |
GB8813978D0 (en) * | 1988-06-13 | 1988-07-20 | Unilever Plc | Liquid detergents |
CA1335646C (en) * | 1988-06-13 | 1995-05-23 | Guido Clemens Van Den Brom | Liquid detergent compositions |
ATE156514T1 (en) * | 1989-05-22 | 1997-08-15 | Procter & Gamble | MILD LIQUID OR GEL DISHWASHING DETERGENT CONTAINING AN ALKYL-ETHOXY-CARBOXYLATE AS SURFACE-ACTIVE SUBSTANCE |
-
1989
- 1989-06-26 GB GB898914602A patent/GB8914602D0/en active Pending
-
1990
- 1990-06-12 AU AU58559/90A patent/AU639243B2/en not_active Ceased
- 1990-06-12 DE DE69004432T patent/DE69004432T3/en not_active Expired - Fee Related
- 1990-06-12 WO PCT/EP1990/000971 patent/WO1991000331A1/en active IP Right Grant
- 1990-06-12 ES ES90909723T patent/ES2060182T5/en not_active Expired - Lifetime
- 1990-06-12 KR KR1019910701967A patent/KR960000200B1/en not_active Expired - Fee Related
- 1990-06-12 JP JP2509164A patent/JPH04506367A/en active Pending
- 1990-06-12 BR BR909007474A patent/BR9007474A/en not_active IP Right Cessation
- 1990-06-12 EP EP90909723A patent/EP0479846B2/en not_active Expired - Lifetime
- 1990-06-12 CA CA002063264A patent/CA2063264C/en not_active Expired - Fee Related
- 1990-06-26 ZA ZA904960A patent/ZA904960B/en unknown
Also Published As
Publication number | Publication date |
---|---|
AU639243B2 (en) | 1993-07-22 |
GB8914602D0 (en) | 1989-08-16 |
EP0479846A1 (en) | 1992-04-15 |
EP0479846B1 (en) | 1993-11-03 |
EP0479846B2 (en) | 2003-08-27 |
AU5855990A (en) | 1991-01-17 |
CA2063264A1 (en) | 1990-12-27 |
KR960000200B1 (en) | 1996-01-03 |
BR9007474A (en) | 1992-06-16 |
DE69004432T3 (en) | 2004-03-18 |
WO1991000331A1 (en) | 1991-01-10 |
ES2060182T3 (en) | 1994-11-16 |
DE69004432T2 (en) | 1994-02-24 |
ZA904960B (en) | 1992-02-26 |
DE69004432D1 (en) | 1993-12-09 |
ES2060182T5 (en) | 2004-05-01 |
KR920702718A (en) | 1992-10-06 |
JPH04506367A (en) | 1992-11-05 |
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