EP0241073A2 - Liquid detergents containing anionic surfactant, succinate builder and fatty acid - Google Patents
Liquid detergents containing anionic surfactant, succinate builder and fatty acid Download PDFInfo
- Publication number
- EP0241073A2 EP0241073A2 EP87200529A EP87200529A EP0241073A2 EP 0241073 A2 EP0241073 A2 EP 0241073A2 EP 87200529 A EP87200529 A EP 87200529A EP 87200529 A EP87200529 A EP 87200529A EP 0241073 A2 EP0241073 A2 EP 0241073A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- fatty acid
- succinate
- alkyl
- surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 29
- 239000000194 fatty acid Substances 0.000 title claims abstract description 29
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 29
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 29
- 239000003599 detergent Substances 0.000 title claims abstract description 22
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 title claims abstract description 19
- 239000007788 liquid Substances 0.000 title claims abstract description 14
- 239000003945 anionic surfactant Substances 0.000 title claims description 9
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- -1 alkenyl succinate Chemical compound 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 125000000129 anionic group Chemical group 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 2
- YGMVJVGOHBOAKR-UHFFFAOYSA-M sodium;4-dodec-2-enoxy-4-oxobutanoate Chemical compound [Na+].CCCCCCCCCC=CCOC(=O)CCC([O-])=O YGMVJVGOHBOAKR-UHFFFAOYSA-M 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 239000007844 bleaching agent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000013162 Cocos nucifera Nutrition 0.000 description 5
- 244000060011 Cocos nucifera Species 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- 235000019864 coconut oil Nutrition 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XHWHHMNORMIBBB-UHFFFAOYSA-N 2,2,3,3-tetrahydroxybutanedioic acid Chemical compound OC(=O)C(O)(O)C(O)(O)C(O)=O XHWHHMNORMIBBB-UHFFFAOYSA-N 0.000 description 2
- LMYSNFBROWBKMB-UHFFFAOYSA-N 4-[2-(dipropylamino)ethyl]benzene-1,2-diol Chemical compound CCCN(CCC)CCC1=CC=C(O)C(O)=C1 LMYSNFBROWBKMB-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical class OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- FGQUIQAGZLBOGL-UHFFFAOYSA-N 3-non-1-enyloxolane-2,5-dione Chemical compound CCCCCCCC=CC1CC(=O)OC1=O FGQUIQAGZLBOGL-UHFFFAOYSA-N 0.000 description 1
- LWYAUHJRUCQFCX-UHFFFAOYSA-N 4-dodecoxy-4-oxobutanoic acid Chemical compound CCCCCCCCCCCCOC(=O)CCC(O)=O LWYAUHJRUCQFCX-UHFFFAOYSA-N 0.000 description 1
- XDJAHNALPHLVAX-UHFFFAOYSA-N 4-oxo-4-tetradec-2-enoxybutanoic acid Chemical compound CCCCCCCCCCCC=CCOC(=O)CCC(O)=O XDJAHNALPHLVAX-UHFFFAOYSA-N 0.000 description 1
- LSWKXNPXIJXDHU-UHFFFAOYSA-N 4-oxo-4-tetradecoxybutanoic acid Chemical compound CCCCCCCCCCCCCCOC(=O)CCC(O)=O LSWKXNPXIJXDHU-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000005192 alkyl ethylene group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZMUKYBHKAXKIOO-UHFFFAOYSA-L disodium;2-tetradecylbutanedioate Chemical compound [Na+].[Na+].CCCCCCCCCCCCCCC(C([O-])=O)CC([O-])=O ZMUKYBHKAXKIOO-UHFFFAOYSA-L 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen 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
- 239000002540 palm oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 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
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 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
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- 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
- C11D1/04—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—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
- C11D1/75—Amino oxides
Definitions
- the present invention relates to liquid detergent compositions, preferably heavy-duty liquid detergents, containing an anionic synthetic surfactant and a builder system comprising a C 12 -C 14 alkyl or alkenyl succinic acid or salt thereof (hereinafter referred to as a "succinate”) and a C 12 -C 14 fatty acid or salt thereof (hereinafter referred to as a "fatty acid”) in a molar ratio (calculated on an acid basis) of succinate to fatty acid of from about 0.8 to about 2.4.
- succinate and fatty acid mixture surprisingly provides a minimum of sudsing in otherwise high sudsing detergents containing a significant amount of anionic synthetic surfactant.
- Example 10 is a low-sudsing detergent containing 2% dodecyl benzene sulfonate, 6% of an 80:20 mixture of tallow:coconut soap, and 6% disodium hexadecane-1,2-dicarboxylate. This results in a molar ratio of dicarboxylate to C 12 -C 14 fatty acid of about 2.7.
- Examples D-M contain 0-1% LAS, 5.5-6% nonenyl succinic anhydride and 1.2-3% coconut fatty acid. The lowest ratio of succinate to fatty acid present is about 1.7.
- the present invention relates to a liquid detergent composition
- a liquid detergent composition comprising, by weight:
- the detergent compositions of the present invention contain anionic synthetic surfactant and succinate and fatty acid builders in a molar ratio (calculated on an acid basis) of succinate to fatty acid of from about 0.8 to about 2.4, preferably from about 0.9 to about 1.8, more preferably from about 1.0 to about 1.4. - Within these ratios, the succinate and fatty acid provide a minimum of suds in otherwise high sudsing detergents containing a significant amount (e.g., greater than 10% by weight) of anionic synthetic surfactant. This is particularly surprising given that one would have expected that sudsing would gradually increase with increasing levels of succinate and decrease with increasing levels of fatty acid.
- the detergent compositions herein contain from about 10% to about 50%, preferably from about 13% to about 40%, more preferably from about 16% to about 30%, by weight, on an acid basis, of an anionic synthetic surfactant.
- Anionic synthetic surfactants are disclosed in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent 3,919,678, Laughlin et al, issued December 30, 1975, both incorporated herein by reference.
- Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- water-soluble salts particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of aryl groups.
- alkyl sulfates especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in United States Patents 2,220,099 and 2,477,383.
- anionic surfactants herein are the water-soluble salts of: paraffin sulfonates containing from about 8 to about 24 (preferably about 12 to 18) carbon -atoms; alkyl glyceryl ether sulfonates, especially those ethers of. C 8-18 alcohols (e.g., those derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; and alkyl ethylene oxide ether sulfates containing about 1 to about 4 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyl group.
- Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane- 1-sutfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
- Preferred anionic surfactants herein are the alkyl sulfates of the formula wherein R is an alkyl chain having from about 12 to about 18 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x is from 0 to about 4.
- R is a C12-C16 alkyl or hydroxyalkyl group, especially a C 12 -C 15 alkyl, and x is from about 0 to about 3.
- anionic surfactants are the linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 12 to about 13, and the C 12-15 alcohol sulfates containing from 0 to about 3 ethylene oxide units, as described above. Also preferred are mixtures of these surfactants in a weight ratio of from about 3:1 to about 1:3, preferably from about 2:1 to about 1:2. These anionics form hardness, preferably magnesium, surfactants that are particularly effective at lowering interfacial tension and removing greasy/oily soils.
- the detergent compositions herein also contain from about 2% to about 25%, preferably from about 3% to about 20%, more preferably from about 5% to about 15%, by weight of a succinate builder of the general formula R-CH ⁇ COOH)CH 2 (COOH), wherein R is C 12 -C 14 alkyl or alkenyl group.
- succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts (e.g., mono-, di-, or tri-ethanolammonium) .
- succinate builders include: lauryl succinate, myristyl succinate, 2-dodecenyt succinate (preferred) and 2-tetradecenyl succinate.
- compositions of the present invention further contain from about 1% to about 15%, preferably from 2% to about 10%, more preferably from about 3% to about 6%, by weight of a C 12 -C 14 fatty acid, or salt thereof.
- Suitable fatty acids can be obtained from natural sources such as plant or animal esters (e.g., palm kernel oil, palm oil and coconut oil) or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process).
- suitable fatty acids for use in the compositions of this invention include lauric, myristic, coconut and palm kernel fatty acid.
- Preferred are saturated coconut fatty acids, from about 5: 1 to 1:1 (preferably about 3:1) weight ratio mixtures of lauric and myristic acid, and palm kernel fatty acid.
- the succinate and fatty acid builders herein are calcium-selective builders, which means they preferentially control calcium ion in the wash solution, rather than magnesium or other hardness ions. It is believed that these calcium-selective builders adequately control wash water hardness, preventing excessive interactions with the anionic surfactant herein and with soils, while allowing sufficient free hardness to complex some of the anionic surfactant to produce a hardness surfactant (such as magnesium linear alkylbenzene sulfonate) that is highly effective at removing greasy and oily soils. Such hardness-surfactants pack at the oil/water interface where they lower interfacial tension and enhance removal of greasyloily soils.
- a hardness surfactant such as magnesium linear alkylbenzene sulfonate
- the liquid detergent compositions herein can optionally contain any of the auxiliary ingredients known for use in detergent compositions. These include cosurfactants, cobuilders, neutralizing agents, buffering agents, phase regulants, solvents, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, antioxidants, bactericides, dyes, perfumes, and brighteners, such as those described in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, incorporated herein by reference.
- compositions herein include those described in U.S. Patent 4,561,998, Wertz et al, issued December 31, 1985, and U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both incorporated herein by reference.
- compositions herein preferably contain from about 1% to about 20%, more preferably from about 3% to about 15%, most preferably from about 5% to about 10%, by weight of an ethoxylated nonionic surfactant of the formula R (OC 2 H 4 ) n OH, wherein R is a C 10 -C 16 alkyl group (preferred) or a C 8- C 12 alkyl phenyl group, n is from about 3 to about 9, and said nonionic surfactants has an HLB (hydrophile-lipophile balance) of from about 9 to about 13, preferably from about 10 to about 13.
- HLB hydrophile-lipophile balance
- compositions herein can be formulated to have a pH of from about 7.5 to about 12, more preferably from about 8 to about 11.
- Certain preferred compositions herein are alkaline compositions that are particularly useful in combination with peroxyacid bleach compositions, which generally have a pH of from about 2 to about 5 for best bleach stability.
- Such alkaline compositions have a pH of from about 9 to about 12, preferably from about 9.5 to about 11.5, more preferably from about 10 to about 11. They preferably contain from about 2% to about 15%, more preferably from about 4% to about 10%, by weight of monoethanolamine.
- the combination of such an alkaline composition and peroxyacid bleach preferably delivers a wash water pH of from about 7.8 to about 9, preferably from about 7.9 to about 8.5, which is desired for good bleaching performance, a minimum of fabric yellowing, and a minimum of bleach decomposition by the monoethanolamine.
- composition was prepared by adding the components to a mixing tank in the order listed with continuous mixing.
- the above composition is preferably used in combination with the following liquid diperoxyacid bleach composition.
- the liquid bleach composition was prepared by high shear mixing of the components in an Eppenbach mixer while in an ice bath.
- the DPDA and water were added to the mixer before turning the mixer on.
- the suds suppressor was added to minimize foaming while mixing and to minimize air entrapment in the finished composition.
- the other components were added in the order listed at the indicated times after turning on the mixer.
- the pH of the composition was determined to be 3.20 at 20°C. After 4 hr. 10 min., the pH was again determined to be 3.20 at 20°C and the mixer was turned off.
- the composition was a stable suspension of the ingredients and had a viscosity of about 350 cps at about 20°C.
- the DPDA had an average particle size of about 2-5 microns.
- the compositions are preferably used in a volume ratio of detergent composition to liquid bleach of about 5.5:1.
- the detergent composition is designed for a usage level of about 0.55 cups in a typical U.S. laundering process. This delivers a concentration of product in the wash water of about 0.22% by weight. Usage of about 0.1 cups (i.e., about 25 ml) of the liquid bleach- delivers about 10 ppm of available oxygen to the wash water.
- the detergent composition and liquid bleach are preferably simultaneously codispersed from a dual compartment bottle at a volume ratio of detergent to bleach of about 5.5:1.
- the mixture of the succinate and fatty acid builders in the above detergent composition is preferred because it causes less fabric yellowing and measuring cup residue than an all fatty acid formula when used with the above liquid bleach.
- compositions of the invention which can be prepared by adding the components to a mixing tank in the order listed with continuous mixing, are as follows.
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Abstract
Description
- The present invention relates to liquid detergent compositions, preferably heavy-duty liquid detergents, containing an anionic synthetic surfactant and a builder system comprising a C12-C14 alkyl or alkenyl succinic acid or salt thereof (hereinafter referred to as a "succinate") and a C12-C14 fatty acid or salt thereof (hereinafter referred to as a "fatty acid") in a molar ratio (calculated on an acid basis) of succinate to fatty acid of from about 0.8 to about 2.4. Within this range, the succinate and fatty acid mixture surprisingly provides a minimum of sudsing in otherwise high sudsing detergents containing a significant amount of anionic synthetic surfactant.
- British Patent 1,293,753, Evans et a1, published October 25, 1972, discloses dicarboxylate builders, including alkyl and alkenyl succinates. Example 10 is a low-sudsing detergent containing 2% dodecyl benzene sulfonate, 6% of an 80:20 mixture of tallow:coconut soap, and 6% disodium hexadecane-1,2-dicarboxylate. This results in a molar ratio of dicarboxylate to C12-C14 fatty acid of about 2.7.
- European Patent Application 28,850, van der Griend, published May 20, 1981, discloses liquid detergents containing nonionic surfactant, a small amount of C10-C15 alkylbenzene sulfonate, builder and C7-C12 alkyl or alkenyl succinate as a hydrotrope. Examples D-M contain 0-1% LAS, 5.5-6% nonenyl succinic anhydride and 1.2-3% coconut fatty acid. The lowest ratio of succinate to fatty acid present is about 1.7.
- U.S. Patent 3,776,851, Cheng, issued December 4, 1973, discloses detergents containing 5-70% tetrahydroxysuccinic acid builders. Example 4 contains 20% tetrahydroxysuccinic acid and 1.8% 80:20 tallow:coconut soap as a suds suppressor.
- U.S. Patent 3,707,511, Lamberti et al, issued December 26, 1972, discloses that C10-C16 alkyl or alkenyl succinates are useful as suds boosters and stabilizers for detergents, particularly those containing alkylaryl sulfonates. There are no examples of compositions containing succinate and fatty acid.
- The present invention relates to a liquid detergent composition comprising, by weight:
- (a) from about 10% to about 50% of an anionic synthetic surfactant;
- (b) from about 2% to about 25% of a C12-C14 alkyl or alkenyl succinic acid, or salt thereof; and
- (c) from about 1% to about 15% of a C12-C14 fatty acid, or salt thereof;
- The detergent compositions of the present invention contain anionic synthetic surfactant and succinate and fatty acid builders in a molar ratio (calculated on an acid basis) of succinate to fatty acid of from about 0.8 to about 2.4, preferably from about 0.9 to about 1.8, more preferably from about 1.0 to about 1.4. - Within these ratios, the succinate and fatty acid provide a minimum of suds in otherwise high sudsing detergents containing a significant amount (e.g., greater than 10% by weight) of anionic synthetic surfactant. This is particularly surprising given that one would have expected that sudsing would gradually increase with increasing levels of succinate and decrease with increasing levels of fatty acid.
- The detergent compositions herein contain from about 10% to about 50%, preferably from about 13% to about 40%, more preferably from about 16% to about 30%, by weight, on an acid basis, of an anionic synthetic surfactant. Anionic synthetic surfactants are disclosed in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent 3,919,678, Laughlin et al, issued December 30, 1975, both incorporated herein by reference.
- Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of aryl groups.) Examples of this group of synthetic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in United States Patents 2,220,099 and 2,477,383.
- Other anionic surfactants herein are the water-soluble salts of: paraffin sulfonates containing from about 8 to about 24 (preferably about 12 to 18) carbon -atoms; alkyl glyceryl ether sulfonates, especially those ethers of. C8-18 alcohols (e.g., those derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; and alkyl ethylene oxide ether sulfates containing about 1 to about 4 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyl group.
- Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane- 1-sutfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
- Preferred anionic surfactants herein are the alkyl sulfates of the formula
- Highly preferred anionic surfactants are the linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 12 to about 13, and the C12-15 alcohol sulfates containing from 0 to about 3 ethylene oxide units, as described above. Also preferred are mixtures of these surfactants in a weight ratio of from about 3:1 to about 1:3, preferably from about 2:1 to about 1:2. These anionics form hardness, preferably magnesium, surfactants that are particularly effective at lowering interfacial tension and removing greasy/oily soils.
- The detergent compositions herein also contain from about 2% to about 25%, preferably from about 3% to about 20%, more preferably from about 5% to about 15%, by weight of a succinate builder of the general formula R-CH{COOH)CH2(COOH), wherein R is C12-C14 alkyl or alkenyl group.
- These succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts (e.g., mono-, di-, or tri-ethanolammonium) .
- Specific examples of succinate builders include: lauryl succinate, myristyl succinate, 2-dodecenyt succinate (preferred) and 2-tetradecenyl succinate.
- The compositions of the present invention further contain from about 1% to about 15%, preferably from 2% to about 10%, more preferably from about 3% to about 6%, by weight of a C12-C14 fatty acid, or salt thereof.
- Suitable fatty acids can be obtained from natural sources such as plant or animal esters (e.g., palm kernel oil, palm oil and coconut oil) or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process). Examples of suitable fatty acids for use in the compositions of this invention include lauric, myristic, coconut and palm kernel fatty acid. Preferred are saturated coconut fatty acids, from about 5: 1 to 1:1 (preferably about 3:1) weight ratio mixtures of lauric and myristic acid, and palm kernel fatty acid.
- The succinate and fatty acid builders herein are calcium-selective builders, which means they preferentially control calcium ion in the wash solution, rather than magnesium or other hardness ions. It is believed that these calcium-selective builders adequately control wash water hardness, preventing excessive interactions with the anionic surfactant herein and with soils, while allowing sufficient free hardness to complex some of the anionic surfactant to produce a hardness surfactant (such as magnesium linear alkylbenzene sulfonate) that is highly effective at removing greasy and oily soils. Such hardness-surfactants pack at the oil/water interface where they lower interfacial tension and enhance removal of greasyloily soils.
- The liquid detergent compositions herein can optionally contain any of the auxiliary ingredients known for use in detergent compositions. These include cosurfactants, cobuilders, neutralizing agents, buffering agents, phase regulants, solvents, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, antioxidants, bactericides, dyes, perfumes, and brighteners, such as those described in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, incorporated herein by reference.
- Preferred compositions herein include those described in U.S. Patent 4,561,998, Wertz et al, issued December 31, 1985, and U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both incorporated herein by reference.
- The compositions herein preferably contain from about 1% to about 20%, more preferably from about 3% to about 15%, most preferably from about 5% to about 10%, by weight of an ethoxylated nonionic surfactant of the formula R (OC2H4)nOH, wherein R is a C10-C16 alkyl group (preferred) or a C8-C12 alkyl phenyl group, n is from about 3 to about 9, and said nonionic surfactants has an HLB (hydrophile-lipophile balance) of from about 9 to about 13, preferably from about 10 to about 13. HLB is defined in detail in Nonionic Surfactants, by M.J. Schick, Marcel Dekker, Inc., 1966, pages 607-613-, incorporated herein by reference. These ethoxylated nonionic surfactants suspend hardness-surfactants in the wash water solution. -They are used at a level high enough to prevent excessive precipitation of hardness-surfactants at the oil/water interface (which makes soil removal more difficult), but low enough to allow for the desired adsorption and packing at the interface.
- The compositions herein can be formulated to have a pH of from about 7.5 to about 12, more preferably from about 8 to about 11. Certain preferred compositions herein are alkaline compositions that are particularly useful in combination with peroxyacid bleach compositions, which generally have a pH of from about 2 to about 5 for best bleach stability. Such alkaline compositions have a pH of from about 9 to about 12, preferably from about 9.5 to about 11.5, more preferably from about 10 to about 11. They preferably contain from about 2% to about 15%, more preferably from about 4% to about 10%, by weight of monoethanolamine. The combination of such an alkaline composition and peroxyacid bleach preferably delivers a wash water pH of from about 7.8 to about 9, preferably from about 7.9 to about 8.5, which is desired for good bleaching performance, a minimum of fabric yellowing, and a minimum of bleach decomposition by the monoethanolamine.
- The following examples illustrate the compositions of the present invention.
- All parts, percentages and ratios used herein are by weight unless otherwise specified.
-
- The above composition is preferably used in combination with the following liquid diperoxyacid bleach composition. The liquid bleach composition was prepared by high shear mixing of the components in an Eppenbach mixer while in an ice bath. The DPDA and water were added to the mixer before turning the mixer on. The suds suppressor was added to minimize foaming while mixing and to minimize air entrapment in the finished composition. The other components were added in the order listed at the indicated times after turning on the mixer.
- After 3 hr. 30 min., the pH of the composition was determined to be 3.20 at 20°C. After 4 hr. 10 min., the pH was again determined to be 3.20 at 20°C and the mixer was turned off. The composition was a stable suspension of the ingredients and had a viscosity of about 350 cps at about 20°C. The DPDA had an average particle size of about 2-5 microns.
- The above describes the preferred process for making the composition since high shear mixing of the components in an ice bath, their order of addition and the approximate times of addition have all been found to be important to obtain the desired physical stability.
- The compositions are preferably used in a volume ratio of detergent composition to liquid bleach of about 5.5:1. The detergent composition is designed for a usage level of about 0.55 cups in a typical U.S. laundering process. This delivers a concentration of product in the wash water of about 0.22% by weight. Usage of about 0.1 cups (i.e., about 25 ml) of the liquid bleach- delivers about 10 ppm of available oxygen to the wash water. The detergent composition and liquid bleach are preferably simultaneously codispersed from a dual compartment bottle at a volume ratio of detergent to bleach of about 5.5:1.
- The mixture of the succinate and fatty acid builders in the above detergent composition is preferred because it causes less fabric yellowing and measuring cup residue than an all fatty acid formula when used with the above liquid bleach.
-
the molar ratio of (b) to (c), on an acid basis, being from about 0.8 to about 2.4.
Claims (11)
the molar ratio of (b) to (c), on an acid basis, being from about 0.8 to about 2.4.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT87200529T ATE69260T1 (en) | 1986-03-31 | 1987-03-23 | LIQUID DETERGENTS CONTAINING AN ANIONIC SURFACE ACTIVE AGENT, A Succinic Acid Builder SALT AND A FATTY ACID. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US84638286A | 1986-03-31 | 1986-03-31 | |
US846382 | 1986-03-31 |
Publications (4)
Publication Number | Publication Date |
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EP0241073A2 true EP0241073A2 (en) | 1987-10-14 |
EP0241073A3 EP0241073A3 (en) | 1989-03-15 |
EP0241073B1 EP0241073B1 (en) | 1991-11-06 |
EP0241073B2 EP0241073B2 (en) | 1995-03-08 |
Family
ID=25297769
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87200529A Expired - Lifetime EP0241073B2 (en) | 1986-03-31 | 1987-03-23 | Liquid detergents containing anionic surfactant, succinate builder and fatty acid |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0241073B2 (en) |
JP (1) | JPH07113120B2 (en) |
KR (1) | KR950004927B1 (en) |
AT (1) | ATE69260T1 (en) |
AU (1) | AU612317B2 (en) |
CA (1) | CA1332137C (en) |
DE (1) | DE3774312D1 (en) |
GB (1) | GB2188645A (en) |
GR (1) | GR3003069T3 (en) |
HK (1) | HK50294A (en) |
IE (1) | IE60012B1 (en) |
MX (1) | MX169254B (en) |
NZ (1) | NZ219812A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0363763A1 (en) * | 1988-10-07 | 1990-04-18 | Henkel Kommanditgesellschaft auf Aktien | Liquid detergent |
WO1997016263A1 (en) * | 1995-10-30 | 1997-05-09 | Henkel Kommanditgesellschaft Auf Aktien | Ultrasonic cleaning process and cleaning agent suitable therefor |
WO1998027189A1 (en) * | 1996-12-17 | 1998-06-25 | Colgate-Palmolive Company | Mildly acidic laundry detergent composition |
US5916865A (en) * | 1996-08-30 | 1999-06-29 | Clariant Gmbh | Liquid bleaching agent suspension |
CN102803461A (en) * | 2010-03-15 | 2012-11-28 | 花王株式会社 | Liquid detergent composition |
WO2016196555A1 (en) * | 2015-06-02 | 2016-12-08 | Stepan Company | Cold-water cleaning method |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2523341B2 (en) * | 1987-11-09 | 1996-08-07 | 花王株式会社 | Strongly alkaline aqueous solution of nonionic surfactant |
EP0430330A3 (en) * | 1989-11-24 | 1991-12-18 | The Procter & Gamble Company | Suspending liquid detergent compositions |
GB9816377D0 (en) * | 1998-07-29 | 1998-09-23 | Dow Corning Sa | Foam control agents |
US6352966B1 (en) | 2000-05-19 | 2002-03-05 | Albemarle Corporation | Cleansing bars |
EP2130897B1 (en) * | 2008-06-02 | 2011-08-31 | The Procter & Gamble Company | Surfactant concentrate |
JP2013076054A (en) * | 2011-09-15 | 2013-04-25 | Kao Corp | Liquid detergent composition |
PL3101101T3 (en) * | 2015-06-05 | 2018-06-29 | The Procter & Gamble Company | Compacted liquid laundry detergent composition |
US11879110B2 (en) | 2019-11-27 | 2024-01-23 | The Procter & Gamble Company | Alkylbenzenesulfonate surfactants |
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US2220099A (en) | 1934-01-10 | 1940-11-05 | Gen Aniline & Flim Corp | Sulphonic acids |
US2477383A (en) | 1946-12-26 | 1949-07-26 | California Research Corp | Sulfonated detergent and its method of preparation |
GB1293753A (en) | 1968-08-08 | 1972-10-25 | Unilever Ltd | Detergent composition |
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US3776851A (en) | 1972-09-25 | 1973-12-04 | Colgate Palmolive Co | Detergents containing tetrahydroxysuccinic acid and salts thereof |
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GB1380390A (en) * | 1970-12-16 | 1975-01-15 | Unilever Ltd | Detergent compositions |
GB2179669B (en) * | 1985-08-15 | 1988-12-29 | Procter & Gamble | Built liquid detergents |
JP3470354B2 (en) * | 1993-07-21 | 2003-11-25 | 大同特殊鋼株式会社 | Dimension measuring device for heating traveling members |
-
1987
- 1987-03-23 DE DE8787200529T patent/DE3774312D1/en not_active Expired - Fee Related
- 1987-03-23 EP EP87200529A patent/EP0241073B2/en not_active Expired - Lifetime
- 1987-03-23 AT AT87200529T patent/ATE69260T1/en not_active IP Right Cessation
- 1987-03-30 IE IE81587A patent/IE60012B1/en not_active IP Right Cessation
- 1987-03-30 CA CA000533361A patent/CA1332137C/en not_active Expired - Fee Related
- 1987-03-30 NZ NZ219812A patent/NZ219812A/en unknown
- 1987-03-30 KR KR1019870002922A patent/KR950004927B1/en active IP Right Grant
- 1987-03-30 GB GB08707572A patent/GB2188645A/en not_active Withdrawn
- 1987-03-30 AU AU70781/87A patent/AU612317B2/en not_active Ceased
- 1987-03-31 MX MX005811A patent/MX169254B/en unknown
- 1987-03-31 JP JP62076555A patent/JPH07113120B2/en not_active Expired - Lifetime
-
1991
- 1991-11-07 GR GR91401150T patent/GR3003069T3/en unknown
-
1994
- 1994-05-19 HK HK50294A patent/HK50294A/en not_active IP Right Cessation
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US2477383A (en) | 1946-12-26 | 1949-07-26 | California Research Corp | Sulfonated detergent and its method of preparation |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0363763A1 (en) * | 1988-10-07 | 1990-04-18 | Henkel Kommanditgesellschaft auf Aktien | Liquid detergent |
WO1990004014A1 (en) * | 1988-10-07 | 1990-04-19 | Henkel Kommanditgesellschaft Auf Aktien | Liquid detergent |
WO1997016263A1 (en) * | 1995-10-30 | 1997-05-09 | Henkel Kommanditgesellschaft Auf Aktien | Ultrasonic cleaning process and cleaning agent suitable therefor |
US5916865A (en) * | 1996-08-30 | 1999-06-29 | Clariant Gmbh | Liquid bleaching agent suspension |
WO1998027189A1 (en) * | 1996-12-17 | 1998-06-25 | Colgate-Palmolive Company | Mildly acidic laundry detergent composition |
CN102803461A (en) * | 2010-03-15 | 2012-11-28 | 花王株式会社 | Liquid detergent composition |
TWI491728B (en) * | 2010-03-15 | 2015-07-11 | Kao Corp | Liquid detergent composition |
WO2016196555A1 (en) * | 2015-06-02 | 2016-12-08 | Stepan Company | Cold-water cleaning method |
Also Published As
Publication number | Publication date |
---|---|
CA1332137C (en) | 1994-09-27 |
GB2188645A (en) | 1987-10-07 |
ATE69260T1 (en) | 1991-11-15 |
JPH07113120B2 (en) | 1995-12-06 |
AU612317B2 (en) | 1991-07-11 |
HK50294A (en) | 1994-05-27 |
EP0241073A3 (en) | 1989-03-15 |
MX169254B (en) | 1993-06-28 |
IE870815L (en) | 1987-09-30 |
DE3774312D1 (en) | 1991-12-12 |
AU7078187A (en) | 1987-10-08 |
JPS63397A (en) | 1988-01-05 |
KR870009007A (en) | 1987-10-22 |
KR950004927B1 (en) | 1995-05-16 |
EP0241073B1 (en) | 1991-11-06 |
NZ219812A (en) | 1989-06-28 |
IE60012B1 (en) | 1994-05-18 |
EP0241073B2 (en) | 1995-03-08 |
GB8707572D0 (en) | 1987-05-07 |
GR3003069T3 (en) | 1993-02-17 |
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