US3156655A - Heavy duty liquid detergent composition - Google Patents
Heavy duty liquid detergent composition Download PDFInfo
- Publication number
- US3156655A US3156655A US46897A US4689760A US3156655A US 3156655 A US3156655 A US 3156655A US 46897 A US46897 A US 46897A US 4689760 A US4689760 A US 4689760A US 3156655 A US3156655 A US 3156655A
- Authority
- US
- United States
- Prior art keywords
- weight
- heavy duty
- liquid detergent
- ethylene oxide
- mixture
- 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 - Lifetime
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- 239000000203 mixture Substances 0.000 title claims description 50
- 239000003599 detergent Substances 0.000 title claims description 30
- 239000007788 liquid Substances 0.000 title claims description 19
- 239000000344 soap Substances 0.000 claims description 20
- 239000000839 emulsion Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 15
- -1 flakes Substances 0.000 description 13
- 239000011734 sodium Substances 0.000 description 10
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 239000012263 liquid product Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 150000001340 alkali metals Chemical group 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 6
- 229940049964 oleate Drugs 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 6
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical group [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 6
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 5
- 229920001983 poloxamer Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 4
- 229940070765 laurate Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 3
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- GHVNFZFCNZKVNT-UHFFFAOYSA-M decanoate Chemical compound CCCCCCCCCC([O-])=O GHVNFZFCNZKVNT-UHFFFAOYSA-M 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-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
- 239000005977 Ethylene Substances 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-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
- 239000002671 adjuvant Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- QCZAWDGAVJMPTA-RNFRBKRXSA-N ClC1=CC=CC(=N1)C1=NC(=NC(=N1)N[C@@H](C(F)(F)F)C)N[C@@H](C(F)(F)F)C Chemical compound ClC1=CC=CC(=N1)C1=NC(=NC(=N1)N[C@@H](C(F)(F)F)C)N[C@@H](C(F)(F)F)C QCZAWDGAVJMPTA-RNFRBKRXSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OVXYGICQHQNTFU-UHFFFAOYSA-N octadecanoic acid;tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O OVXYGICQHQNTFU-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- PYJBVGYZXWPIKK-UHFFFAOYSA-M potassium;tetradecanoate Chemical compound [K+].CCCCCCCCCCCCCC([O-])=O PYJBVGYZXWPIKK-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
-
- 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
- C11D1/40—Monoamines or polyamines; 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
- C11D1/66—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
Definitions
- the present invention relates to cleansers, and more particularly to liquid detergent compositions.
- washday products were sold primarily in particulate form, such as powders, flakes, granules, beads, and the like.
- particulate form such as powders, flakes, granules, beads, and the like.
- major drawbacks to such washday products are the difiiculty in obtaining uniform specific gravity of the particles so that measured amounts of the products will have constant detergent power and the likelihood of wastage due to spilling of an opened carton containing the particulate product.
- liquid detergent products have been replaced to a large extent by liquid detergent products. While liquid detergent compositions do not suffer from the major drawbacks of particulate detergent compositions, they nevertheless introduce problems of their own. Thus, while it is relatively easy to prepare a light duty liquid detergent composition which is homogeneous and hence appealing to the consumer, such products are only useful for light duty work, such as the cleaning of dishes. When one attempts to prepare heavy duty liquid detergent compositions, it is diflicult to obtain products which have homogeneity, because the components of the compositions have a great tendency to separate out from the liquid medium.
- homogeneous heavy duty liquid detergent compositions While some homogeneous heavy duty liquid detergent compositions have been successfully prepared heretofore, they too sulfer from at least two serious drawbacks. For example, some homogeneous heavy duty liquid detergent compositions are only homogeneous because of their high viscosity. The high viscosity, however, renders them difficult to pour and wasteful so that the product tends to adhere to the cap of the container used as a measuring cup or to cling to the inner walls of the container. Moreover, most homogeneous heavy duty liquid detergent compositions generally have high sudsing power so that they cause suds-lock, especially in a front loading or horizontal washing machine, which is injurious to the motor of the machine.
- the prodnet of the invention is a liquid detergent composition which is substantially homogeneous, is readily pourable, and has heavy duty detergent properties. It is also a low sudsing or intermediate sudsing product so that suds-loo is avoided.
- the product of the invention contains seven essential components in order to achieve these highly desirable properties.
- One component is water which serves as a dissolving, suspending, or emulsifying medium for the remaining components in the composition.
- Two further components constitute a synthetic organic nonionic non-soap detergent mixture. This mixture is used in an amount from about 7% to about 10% by weight of the composition.
- One such suitable mixture contains as one component thereof from about to about 9% by weight of an alkyl phenol-ethylene oxide condensate having an alkyl group containing from nine to twelve carbon atoms and containing nine to fifteen oxyethylene units.
- Typical examples thereof include dodecyl phenol condensed with an average of ten moles of ethylene oxide sold commercially as 3,156,655 Patented Nov. 10, 1964 Sterox DI, nonyl phenol condensed with an average of nine moles of ethylene oxide sold commercially as Igepal CO-630, nonyl phenol condensed with an average of ten moles of ethylene oxide sold commercially as Tergitol NPX, and dodecyl phenol condensed with an average of fifteen moles of ethylene oxide.
- the remaining component of this mixture is from about 1% to about 3% by weight of a polyoxyalkylene alkanol having the empirical formula HO(C H O) (C H O) ,(C H. ,O),,l-I where b is an integer from 26 to 30 and a plus c is an integer such that the molecule contains from 0% to 20% of ethylene oxide.
- Typical examples thereof include Pluronic L-61 where b is an integer from 26 to 30 and a plus 0 is an integer such that the molecule contains from 10% to 20% of ethylene oxide and Pluronic L-60 where b is an integer from 26 to 30 and a plus 0 is zero so that the molecule contains 0% or no-ethylene oxide.
- This mixture will impart detergent and low sudsing properties to the liquid product.
- Another suitable synthetic organic nonionic non-soap detergent mixture is as follows. This mixture contains from about 5% to about 7.5% by weight of a tridecyloxypolyethoxyethanol having the formula This component is prepared by condensing tridecyl alcohol with an average of ten moles of ethylene oxide and is sold commercially as Sterox AJ-lOO.
- the remaining component of this mixture is from about 1% to about 3% by weight of either the above mentioned dodecylphenoxypolyethoxyethanol having the formula sold as Sterox DJ or the above mentioned polyoxyalkylene alkanol having the empirical formula where b is an integer from 26 to 30 and a plus 0 is an integer such that the molecule contains from 0% to 20% of ethylene oxide as exemplified by the above liluronic L-60 and Pluronic L-6l.
- This mixture will impart detergent and intermediate sudsing properties to the liquid product.
- Another component of the liquid products imparts heavy duty detergent and sequestering properties thereto.
- This component is potassium pyrophosphate which is present in the liquid product in an amount from about 18% to about 30%, and preferably from about 20% to about 25% by weight.
- the remaining three essential components of the liquid product function as ternary solubilizers or stabilizing agents for the other components in the aqueous medium.
- One of these solubilizers is an interpolymer of vinyl methyl ether and maleic anhydride.
- the specific viscosity of a 1% solution of the interpolymer in Z-butanone is from 0.8 to 3.5, and preferably from 1.2 to 1.8.
- the liquid product contains from about 1% to about 3% by weight of the interpolymer which is present in the final product as an alkali metal salt thereof in view of the alkali in the composition.
- Another solubilizer is an alkali metal soap of a fatty acid having at least ten carbon atoms, namely an alkali metal caprate, laurate or oleate.
- the alkali metal oleate can be used as the pure soap or as a mixed soap from fats and oils containing large amounts of oleic acid, such as tallow fatty acid soap and peanut oil fatty acid soap. In general, it is preferred to use the potassium soaps rather than the sodium soaps.
- the soaps are present in the composition in an amount from about 1% to about 4% by weight. These soaps can be added to the liquid product either as soaps or can be formed in situ by adding the fatty acid or mixed fatty acids and then saponifying 2-butanone is 1.21.8.
- the miscellaneous ingredients are with the alkali present in the product. very small amounts of impurities, dyes, colorants, etc.
- the remaining solubilizer is sodium xylene sulfonate
- Various embodiments of the composition of the invenwhich is used in an amount of from about 2% to about tion are illustrated by the examples set forth below in 6% by weight. Table II. All nine of the examples in Table II were If desired, the liquid product of the invention can consubstantially homogeneous, that is, there was either no tain various compatible adjuvants which do not destroy separation of the components at all or only very slight the basic characteristics of the composition. For examseparation of the components after storing the composiple, the product can contain builders, such as alkali metal tions for two weeks at room temperature and at 125 F. silicates, which also function as corrosion inhibitors.
- composition of the invention is readily prepared by merely mixing together the components thereof in the aqueous medium.
- composition must contain the essential components mentioned above in order to impart thereto substantial homogeneity, heavy duty properties, pourability and controlled sudsing. Not only must these components be present, but also they must be used in the approximate amounts set forth above.
- a substantially homogeneous, readily pourable, heavy duty liquid detergent composition consisting essen- 45 tially of an aqueous emulsion of (1) from about 7% to about 10% by weight of a synthetic organic nonionic non-soap detergent mixture, said mixture being selected from the group consisting of (A) from about 5% to about 9% by weight of an alkyl penol-ethylene oxide condensate having an alkyl group containing from nine to twelve carbon atoms and containing nine to fifteen oxyethylene units Table I Examples A B Sterox DJ 9 Pluronie L-61 1 Sterox All-100. 7 Potassium Pyrophosphate 25 25 25 25 25 25 20 5 Sodium Pyrophospl1ate 5 PVM/MA- 2 2 2 2 2 Sodium Xylene Sulionate 7 3. 5 2 2 zeq Hen
- PVM/ MA is an abbreviation for the interpolymer of vinyl methyl ether and maleic anhydride wherein the HO (C2H4O)(C3HO)b(C2HO)cH specific viscosity of a 1% solution of the interpolymer in where b is an inte er from 26 to 30 and a plus 0 is an plus from about 1% to about 3% by weight of a polyoxyinteger such that the molecule contains from to 20% of ethylene oxide and (B) from about to about 7.5 by Weight of a tridecyloxypolyethoxyethanol having the formula C H O(CH CH O) CH CH OH plus from about 1% to about 3% by Weight of a material selected from the group consisting of (a) a dodecylphenoxypolyethoxyethanol having the formula and (b) a poly
- a substantially homogeneous, readily pourable, heavy duty liquid detergent composition consisting essentially of an aqueous emulsion of (1) from about 7% to about by weight of a synthetic organic nonionic non-soap detergent mixture, said mixture being made up of from about 5% to about 9% by Weight of an alkyl phenol-ethylene oxide condensate having an alkyl group containing from nine to twelve carbon atoms and containing nine to fifteen oxyethylene units plus from about 1% to about 3% by weight of a polyoxyalkylene alkanol having the emp rical formula where b is an integer from 26 to 30 and a plus 0 is an integer such that the molecule contains from 0% to 20% of ethylene oxide, (2) from about 18% to about 30% by weight of potassium pyrophosphate, (3) from about 2% to about 3% by weight of an alkali metal salt of an interpolymer of vinyl methyl ether and maleic anhydride, (4) from about 1% to about 4% by weight of an alkali metal soap selected from
- composition as defined by claim 2 which also con tains about 3 by weight of an alkali metal silicate.
- a substantially homogeneous, readily pourable, heavy duty liquid detergent composition consisting essentially of an aqueous emulsion of (1) from about 7% to about 10% by weight of a synthetic organic nonionic nonsoap detergent mixture, said mixture being made up of from about 5% to about 7.5% by weight of a tridecyloxypolyethoxyethanol having the formula plus from about 1% to about 3% by weight of a material selected from the group consisting of (a) a dodecylphenoxypolyethoxyethanol having the formula and (b) a polyoxyalkylene alkanol having the empirical formula HO(8 1-1 0) (C H O) (C I-I O) H Where b is an integer from 26 to 30 and a plus 0 is an integer such that the molecule contains from 0% to 20% of ethylene oxide, (2) from about 18% to about 30% by weight of potassium pyrophosphate, (3) from about 2% to about 3% by weight of an alkali metal salt of an interpolymer of vinyl
- composition as defined by claim 5 which also contains about 3% by weight of an alkali metal silicate.
- a substantially homogeneous, readily pourable, heavy duty liquid detergent composition consisting essentially of an aqueous emulsion of (1) about 7% by Weight of dodecylphenoxypolyethoxyethanol having the formula o Hu-o onron,0 01120112011 (2) about 2% by weight of a polyoxyalkylene alkanol having the empirical formula where b is an integer from 26 to 30 and a plus c is an integer such that the molecule contains from 10% to 20% of ethylene oxide (3) about 20% by weight of potassium pyrophosphate, (4) about 5% by weight of sodium pyrophosphate, (5) about 2% by weight of an alkali metal salt of an interpolymer of vinyl methyl ether and maleic anhydride, (6) about 2% by Weight of an alkali metal oleate, (7) about 1% by weight of an alkali metal soap of tallow fatty acids, and (8) about 2% by weight of sodium xylene sulfonate; the alkali metal cations of
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Description
United States Patent Ofiice 3,156,655 HEAVY DUTY LIQUID DETERGENT COMPOSITION Willard M. Bright, Ridgewood, N.J., assignor to Lever Brothers Company, New York, N.Y., a corporation of Maine No Drawing. Filed Aug. 2, 1960, Ser. No. 46,897
8 Claims. (Cl. 252-409) The present invention relates to cleansers, and more particularly to liquid detergent compositions.
Until recently washday products were sold primarily in particulate form, such as powders, flakes, granules, beads, and the like. Among the major drawbacks to such washday products are the difiiculty in obtaining uniform specific gravity of the particles so that measured amounts of the products will have constant detergent power and the likelihood of wastage due to spilling of an opened carton containing the particulate product.
Recently particulate washday products have been replaced to a large extent by liquid detergent products. While liquid detergent compositions do not suffer from the major drawbacks of particulate detergent compositions, they nevertheless introduce problems of their own. Thus, while it is relatively easy to prepare a light duty liquid detergent composition which is homogeneous and hence appealing to the consumer, such products are only useful for light duty work, such as the cleaning of dishes. When one attempts to prepare heavy duty liquid detergent compositions, it is diflicult to obtain products which have homogeneity, because the components of the compositions have a great tendency to separate out from the liquid medium.
While some homogeneous heavy duty liquid detergent compositions have been successfully prepared heretofore, they too sulfer from at least two serious drawbacks. For example, some homogeneous heavy duty liquid detergent compositions are only homogeneous because of their high viscosity. The high viscosity, however, renders them difficult to pour and wasteful so that the product tends to adhere to the cap of the container used as a measuring cup or to cling to the inner walls of the container. Moreover, most homogeneous heavy duty liquid detergent compositions generally have high sudsing power so that they cause suds-lock, especially in a front loading or horizontal washing machine, which is injurious to the motor of the machine.
There is provided in accordance with the present invention a liquid detergent composition which does not suffer from these drawbacks mentioned above. The prodnet of the invention is a liquid detergent composition which is substantially homogeneous, is readily pourable, and has heavy duty detergent properties. It is also a low sudsing or intermediate sudsing product so that suds-loo is avoided.
The product of the invention contains seven essential components in order to achieve these highly desirable properties. One component is water which serves as a dissolving, suspending, or emulsifying medium for the remaining components in the composition.
Two further components constitute a synthetic organic nonionic non-soap detergent mixture. This mixture is used in an amount from about 7% to about 10% by weight of the composition.
One such suitable mixture contains as one component thereof from about to about 9% by weight of an alkyl phenol-ethylene oxide condensate having an alkyl group containing from nine to twelve carbon atoms and containing nine to fifteen oxyethylene units. Typical examples thereof include dodecyl phenol condensed with an average of ten moles of ethylene oxide sold commercially as 3,156,655 Patented Nov. 10, 1964 Sterox DI, nonyl phenol condensed with an average of nine moles of ethylene oxide sold commercially as Igepal CO-630, nonyl phenol condensed with an average of ten moles of ethylene oxide sold commercially as Tergitol NPX, and dodecyl phenol condensed with an average of fifteen moles of ethylene oxide. The remaining component of this mixture is from about 1% to about 3% by weight of a polyoxyalkylene alkanol having the empirical formula HO(C H O) (C H O) ,(C H. ,O),,l-I where b is an integer from 26 to 30 and a plus c is an integer such that the molecule contains from 0% to 20% of ethylene oxide. Typical examples thereof include Pluronic L-61 where b is an integer from 26 to 30 and a plus 0 is an integer such that the molecule contains from 10% to 20% of ethylene oxide and Pluronic L-60 where b is an integer from 26 to 30 and a plus 0 is zero so that the molecule contains 0% or no-ethylene oxide. This mixture will impart detergent and low sudsing properties to the liquid product.
Another suitable synthetic organic nonionic non-soap detergent mixture is as follows. This mixture contains from about 5% to about 7.5% by weight of a tridecyloxypolyethoxyethanol having the formula This component is prepared by condensing tridecyl alcohol with an average of ten moles of ethylene oxide and is sold commercially as Sterox AJ-lOO. The remaining component of this mixture is from about 1% to about 3% by weight of either the above mentioned dodecylphenoxypolyethoxyethanol having the formula sold as Sterox DJ or the above mentioned polyoxyalkylene alkanol having the empirical formula where b is an integer from 26 to 30 and a plus 0 is an integer such that the molecule contains from 0% to 20% of ethylene oxide as exemplified by the above liluronic L-60 and Pluronic L-6l. This mixture will impart detergent and intermediate sudsing properties to the liquid product.
Another component of the liquid products imparts heavy duty detergent and sequestering properties thereto. This componentis potassium pyrophosphate which is present in the liquid product in an amount from about 18% to about 30%, and preferably from about 20% to about 25% by weight.
The remaining three essential components of the liquid product function as ternary solubilizers or stabilizing agents for the other components in the aqueous medium. One of these solubilizers is an interpolymer of vinyl methyl ether and maleic anhydride. The specific viscosity of a 1% solution of the interpolymer in Z-butanone is from 0.8 to 3.5, and preferably from 1.2 to 1.8. The liquid product contains from about 1% to about 3% by weight of the interpolymer which is present in the final product as an alkali metal salt thereof in view of the alkali in the composition.
Another solubilizer is an alkali metal soap of a fatty acid having at least ten carbon atoms, namely an alkali metal caprate, laurate or oleate. The alkali metal oleate can be used as the pure soap or as a mixed soap from fats and oils containing large amounts of oleic acid, such as tallow fatty acid soap and peanut oil fatty acid soap. In general, it is preferred to use the potassium soaps rather than the sodium soaps. The soaps are present in the composition in an amount from about 1% to about 4% by weight. These soaps can be added to the liquid product either as soaps or can be formed in situ by adding the fatty acid or mixed fatty acids and then saponifying 2-butanone is 1.21.8. The miscellaneous ingredients are with the alkali present in the product. very small amounts of impurities, dyes, colorants, etc.
The remaining solubilizer is sodium xylene sulfonate Various embodiments of the composition of the invenwhich is used in an amount of from about 2% to about tion are illustrated by the examples set forth below in 6% by weight. Table II. All nine of the examples in Table II were If desired, the liquid product of the invention can consubstantially homogeneous, that is, there was either no tain various compatible adjuvants which do not destroy separation of the components at all or only very slight the basic characteristics of the composition. For examseparation of the components after storing the composiple, the product can contain builders, such as alkali metal tions for two weeks at room temperature and at 125 F. silicates, which also function as corrosion inhibitors. In Also all nine of the examples in Table II were readily general, the product would contain about 3% by weight pourable and had heavy duty properties. They were furof sodium or potassium silicate. Other suitable comther characterized by being either low sudsing or interpatible adjuvants include very small amounts of fluorescent mediate sudsing so that suds-lock was avoided.
Table II Examples 1 2 3 4 6 6 7 8 9 Sterox DJ 7 7 7 2 2 5 2 5 Pluronic L-fil 2 2 3 2 2 Pluronic L-60 2 Sterox AJ-lOO 6 6 7 7. 5 Dodecyl phenol condensed with an average of moles of ethylene oxide 7 Potassium Pyrophosphate 25 20 2O 20 20 20 20 Sodium Pyronhosnh'ite 5 5 5 5 5 5 5 PVM/MA 2 2 2 2 2 2 2 Oapric Acid 2 Laurie Acid 2 Oleic Acid. 2 2 2 2 2 2 Tallow Fatty Acids 1 1 1 1 2 1 Potassium Hydroxide 2. 28 2. 2. 1 1. 82 1.73 2 3 2. 3 2 2. 28 Sodium Silicate (Na OzsiOz ta 5) 3 3 3 I Water and Miscellaneous 56. 72 53. 45 56. 9 56. 18 56. 27 58. 7 56. 7 57. 0 56. 72
dyes, colorants, perfumes and soil suspending agents, such as sodium carboxymethylcellulose.
The composition of the invention is readily prepared by merely mixing together the components thereof in the aqueous medium.
The composition must contain the essential components mentioned above in order to impart thereto substantial homogeneity, heavy duty properties, pourability and controlled sudsing. Not only must these components be present, but also they must be used in the approximate amounts set forth above.
This is readily demonstrated by the examples set forth below in Table I wherein various essential components were omitted from some formulations and wherein other soaps were used, such as potassium myristate and potassium stearate. All of the seven products set forth in Table I below were not substantially homogeneous in that they were unstable after two weeks storage at room temperature and at 125 F., and generally marked separation of these products into layers was observed immediately upon completion of the formulations.
In the examples in Table II above, Sterox DJ, Pluronic L-61, Pluronic L-60, Sterox Ali-100, PVM/ MA and miscellaneous ingredients have been identified hereinabove.
It will be appreciated that various modifications and changes may be made in the liquid detergent compositions of the invention in addition to those discussed and illustrated above without departing from the spirit of the 0 invention and accordingly the invention is to be limited only within the scope of the appended claims.
What is claimed is:
l. A substantially homogeneous, readily pourable, heavy duty liquid detergent composition consisting essen- 45 tially of an aqueous emulsion of (1) from about 7% to about 10% by weight of a synthetic organic nonionic non-soap detergent mixture, said mixture being selected from the group consisting of (A) from about 5% to about 9% by weight of an alkyl penol-ethylene oxide condensate having an alkyl group containing from nine to twelve carbon atoms and containing nine to fifteen oxyethylene units Table I Examples A B Sterox DJ 9 Pluronie L-61 1 Sterox All-100. 7 Potassium Pyrophosphate 25 25 25 25 25 20 5 Sodium Pyrophospl1ate 5 PVM/MA- 2 2 2 2 Sodium Xylene Sulionate 7 3. 5 2 2 zeq Hen
Oapric Acid 2 Myristic Acid Stearic Acid 2 Oleie Acid 4. 66 2. 33 Tallow Fatty Acids. 2. 34 1. 17 Potassium Hydroxide 1. 5 0. 09 1- 82 2. 2 O. 91 1. 82 1. 9 Sodium Silicate (Na;0:SiOz ratio of 1:2.5)- 3 Water and Miscellaneous 61. 5 58. 91 57. 18 58.8 59. 09 56. 18 57. 1
In the examples of Table I above, Sterox DJ, Sterox AI-100 and Pluronic L61 have been identified hereinalkylene alkanol having the empirical formula above. PVM/ MA is an abbreviation for the interpolymer of vinyl methyl ether and maleic anhydride wherein the HO (C2H4O)(C3HO)b(C2HO)cH specific viscosity of a 1% solution of the interpolymer in where b is an inte er from 26 to 30 and a plus 0 is an plus from about 1% to about 3% by weight of a polyoxyinteger such that the molecule contains from to 20% of ethylene oxide and (B) from about to about 7.5 by Weight of a tridecyloxypolyethoxyethanol having the formula C H O(CH CH O) CH CH OH plus from about 1% to about 3% by Weight of a material selected from the group consisting of (a) a dodecylphenoxypolyethoxyethanol having the formula and (b) a polyoxyalkylene alkanol having the empirical formula HO((3 1-1 0),,(C H O) (C H O) H where b is an integer from 26 to 30 and a plus 0 is an integer such that the molecule contains from 0% to 20% of ethylene oxide, (2) from about 18% to about 30% by weight of postassium pyrophosphate, (3) from about 1% to about 3% by weight of an alkali metal salt of an interpolymer of vinyl methyl ether and maleic anhydride, (4) from about 1% to about 4% by weight of mi alkali metal soap selected from the group consisting of caprate, laurate and oleate, and (5) from about 2% to about 6% by weight of sodium xylene sulfonate; the alkali metal cations of components (3) and (4) being selected from the group consisting of sodium and potassium.
2. A substantially homogeneous, readily pourable, heavy duty liquid detergent composition consisting essentially of an aqueous emulsion of (1) from about 7% to about by weight of a synthetic organic nonionic non-soap detergent mixture, said mixture being made up of from about 5% to about 9% by Weight of an alkyl phenol-ethylene oxide condensate having an alkyl group containing from nine to twelve carbon atoms and containing nine to fifteen oxyethylene units plus from about 1% to about 3% by weight of a polyoxyalkylene alkanol having the emp rical formula where b is an integer from 26 to 30 and a plus 0 is an integer such that the molecule contains from 0% to 20% of ethylene oxide, (2) from about 18% to about 30% by weight of potassium pyrophosphate, (3) from about 2% to about 3% by weight of an alkali metal salt of an interpolymer of vinyl methyl ether and maleic anhydride, (4) from about 1% to about 4% by weight of an alkali metal soap selected from the group consisting of caprate, laurate and oleate, and (5) from about 2% to about 6% by Weight of sodium xylene sulfonate; the alkali metal cations of components (3) and (4) being selected from the group consisting of sodium and potassium.
3. A composition as defined by claim 2 wherein the potassium pyrophosphate is present in an amount from about 20% to about 25% by weight.
4. A composition as defined by claim 2 which also con tains about 3 by weight of an alkali metal silicate.
5. A substantially homogeneous, readily pourable, heavy duty liquid detergent composition consisting essentially of an aqueous emulsion of (1) from about 7% to about 10% by weight of a synthetic organic nonionic nonsoap detergent mixture, said mixture being made up of from about 5% to about 7.5% by weight of a tridecyloxypolyethoxyethanol having the formula plus from about 1% to about 3% by weight of a material selected from the group consisting of (a) a dodecylphenoxypolyethoxyethanol having the formula and (b) a polyoxyalkylene alkanol having the empirical formula HO(8 1-1 0) (C H O) (C I-I O) H Where b is an integer from 26 to 30 and a plus 0 is an integer such that the molecule contains from 0% to 20% of ethylene oxide, (2) from about 18% to about 30% by weight of potassium pyrophosphate, (3) from about 2% to about 3% by weight of an alkali metal salt of an interpolymer of vinyl methyl ether and maleic anhydride, (4) from about 1% to about 4% by weight of an alkali metal soap selected from the group consisting of caprate, laurate and oleate, and (5) from about 2% to about 6% by weight of sodium xylene sulfonate; the alkali metal cations of components (3) and (4) being selected from the group consisting of sodium and potassium.
6. A composition as defined by claim 5 wherein the potassium pyrophosphate is present in an amount from about 20% to about 25% by weight.
7. A composition as defined by claim 5 which also contains about 3% by weight of an alkali metal silicate.
8. A substantially homogeneous, readily pourable, heavy duty liquid detergent composition consisting essentially of an aqueous emulsion of (1) about 7% by Weight of dodecylphenoxypolyethoxyethanol having the formula o Hu-o onron,0 01120112011 (2) about 2% by weight of a polyoxyalkylene alkanol having the empirical formula where b is an integer from 26 to 30 and a plus c is an integer such that the molecule contains from 10% to 20% of ethylene oxide (3) about 20% by weight of potassium pyrophosphate, (4) about 5% by weight of sodium pyrophosphate, (5) about 2% by weight of an alkali metal salt of an interpolymer of vinyl methyl ether and maleic anhydride, (6) about 2% by Weight of an alkali metal oleate, (7) about 1% by weight of an alkali metal soap of tallow fatty acids, and (8) about 2% by weight of sodium xylene sulfonate; the alkali metal cations of components (5), (6) and (7) being selected from the group consisting of sodium and potassium.
References (Jited in the file of this patent UNITED STATES PATENTS 2,560,839 Ayo et a1 July 17, 1951 2,621,169 Robinette et al. Dec. 9, 1952 2,859,182 Carroll Nov. 4, 1958 2,894,921 Jones July 14, 1959 2,913,417 Weeks Nov. 17, 1959 FOREIGN PATENTS 783,585 Great Britain Sept. 25, 1957 799,421 Great Britain Aug. 6, 1958 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,156,555 November 10, 1954 Willard M, Bright It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Columns 3 and 4, Table II, first column below line 9 insert Sodium Xylene Sulfonate and insert the numeral "2" all the way across the table in each column; column 4, line 49, for "penol-ethylene" read phenol-ethylene column 5, line 16, for "postassium" read potassium Signed and sealed this 13th day of April 1965.
(SEAL) Altest:
ERNEST W. SWIDER- EDWARD J. BRENNER Attesting Officer Commissioner of Patents
Claims (1)
1. A SUBSTANTIALLY HOMOGENEOUS, READILY POURABLE, HEAVY DUTY LIQUID DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF AN AQUEOUS EMULSION OF (1) FROM ABOUT 7% TO ABOUT 10% BY WEIGHT OF A SYNTHETIC ORGANIC NONIONIC NON-SOAP DETERGENT MIXTURE, SAID MIXTURE BEING SELECTED FROM THE GROUP CONSISTING OF (A) FROM ABOUT 5% TO ABOUT 9% BY WEIGHT OF AN ALKYL PENOL-ETHYLENE OXIDE CONDENSATE HAVING AN ALKYL GROUP CONTAINING FROM NINE TO TWELVE CARBON ATOMS AND CONTAINING NINE TO FIFTEEN OXYTHYLENE UNITS PLUS FROM ABOUT 1% TO ABOUT 3% BY WEIGHT OF A POLYOXYALKYLENE ALKANOL HAVING THE EMPIRICAL FORMULA
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| US46897A US3156655A (en) | 1960-08-02 | 1960-08-02 | Heavy duty liquid detergent composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46897A US3156655A (en) | 1960-08-02 | 1960-08-02 | Heavy duty liquid detergent composition |
| US47043A US3230174A (en) | 1960-08-02 | 1960-08-02 | Synergistic combination of sodium dodecane sulfonate and trietha-nolamine lauryl sulfate |
| US444493A US3267040A (en) | 1960-08-02 | 1965-03-08 | Synergistic combinations of alkane sulfonates and alkoxy hydroxy propane sulfonates |
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| US3156655A true US3156655A (en) | 1964-11-10 |
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Cited By (28)
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| US3297638A (en) * | 1963-04-30 | 1967-01-10 | Monsanto Co | Composition consisting of an admixture of a phenol-aldehyde resin, an alkyl phenol-ethylene oxide condensate and a polyoxypropylene-ethylene oxide reaction product |
| US3304262A (en) * | 1964-06-01 | 1967-02-14 | Colgate Palmolive Co | Cleansing composition and method of manufacture thereof |
| US3346503A (en) * | 1963-10-11 | 1967-10-10 | Monsanto Co | Heavy-duty liquid detergent emulsion compositions and processes for preparing the same |
| US3382177A (en) * | 1963-12-11 | 1968-05-07 | Morton Int Inc | Stabilized opaque detergent composition |
| US3615784A (en) * | 1969-08-04 | 1971-10-26 | John Godfrey | Compositions for producing improved concrete |
| US3619119A (en) * | 1967-12-28 | 1971-11-09 | Henkel & Cie Gmbh | Pasty spot-treating compositions for use on textiles |
| US3619234A (en) * | 1968-03-02 | 1971-11-09 | Hoechst Ag | Process for the optical brightening of fibrous materials of synthetic polyamides or cellulose esters |
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| US3931033A (en) * | 1973-12-14 | 1976-01-06 | Henkel & Cie G.M.B.H. | Liquid foam-regulated nonionic detergent compositions |
| US3953351A (en) * | 1973-03-15 | 1976-04-27 | Lever Brothers Company | Liquid laundry detergent |
| US4082684A (en) * | 1975-04-29 | 1978-04-04 | Lever Brothers Company | Liquid detergent |
| US4126572A (en) * | 1976-03-11 | 1978-11-21 | Lever Brothers Company | Built liquid detergent composition |
| US4136050A (en) * | 1977-02-16 | 1979-01-23 | Betz Laboratories, Inc. | Dust suppression method and composition |
| US4147649A (en) * | 1976-01-02 | 1979-04-03 | The Procter & Gamble Company | Liquid detergent composition |
| US4153571A (en) * | 1974-01-02 | 1979-05-08 | Basf Wyandotte Corporation | Heat dependent alkali gel cleaning compositions and process for cleaning greasy surfaces |
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| US4212760A (en) * | 1977-12-07 | 1980-07-15 | Basf Aktiengesellschaft | Solubilized alkaline, aqueous solutions of nonionic surfactants |
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| US4737305A (en) * | 1986-04-25 | 1988-04-12 | Pennzoil Products Company | Dust suppressant composition and method |
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| US5147576A (en) * | 1988-06-13 | 1992-09-15 | Lever Brothers Company, Division Of Conopco, Inc. | Liquid detergent composition in the form of lamellar droplets containing a deflocculating polymer |
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| US20040261887A1 (en) * | 2003-06-26 | 2004-12-30 | William Lewis | Mixing apparatus and methods using the same |
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| US20060223736A1 (en) * | 2005-03-30 | 2006-10-05 | R. Lewis Technologies, Inc. | Dye and scent pouches and methods of making the same |
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| US3297638A (en) * | 1963-04-30 | 1967-01-10 | Monsanto Co | Composition consisting of an admixture of a phenol-aldehyde resin, an alkyl phenol-ethylene oxide condensate and a polyoxypropylene-ethylene oxide reaction product |
| US3346503A (en) * | 1963-10-11 | 1967-10-10 | Monsanto Co | Heavy-duty liquid detergent emulsion compositions and processes for preparing the same |
| US3382177A (en) * | 1963-12-11 | 1968-05-07 | Morton Int Inc | Stabilized opaque detergent composition |
| US3304262A (en) * | 1964-06-01 | 1967-02-14 | Colgate Palmolive Co | Cleansing composition and method of manufacture thereof |
| US3619119A (en) * | 1967-12-28 | 1971-11-09 | Henkel & Cie Gmbh | Pasty spot-treating compositions for use on textiles |
| US3619234A (en) * | 1968-03-02 | 1971-11-09 | Hoechst Ag | Process for the optical brightening of fibrous materials of synthetic polyamides or cellulose esters |
| US3615784A (en) * | 1969-08-04 | 1971-10-26 | John Godfrey | Compositions for producing improved concrete |
| US3870648A (en) * | 1971-01-14 | 1975-03-11 | Gaf Corp | Polyelectrolytes as detergent builders |
| US3953351A (en) * | 1973-03-15 | 1976-04-27 | Lever Brothers Company | Liquid laundry detergent |
| US3931033A (en) * | 1973-12-14 | 1976-01-06 | Henkel & Cie G.M.B.H. | Liquid foam-regulated nonionic detergent compositions |
| US4153571A (en) * | 1974-01-02 | 1979-05-08 | Basf Wyandotte Corporation | Heat dependent alkali gel cleaning compositions and process for cleaning greasy surfaces |
| US4082684A (en) * | 1975-04-29 | 1978-04-04 | Lever Brothers Company | Liquid detergent |
| US4147649A (en) * | 1976-01-02 | 1979-04-03 | The Procter & Gamble Company | Liquid detergent composition |
| US4126572A (en) * | 1976-03-11 | 1978-11-21 | Lever Brothers Company | Built liquid detergent composition |
| US4136050A (en) * | 1977-02-16 | 1979-01-23 | Betz Laboratories, Inc. | Dust suppression method and composition |
| US4171276A (en) * | 1977-02-16 | 1979-10-16 | Betz Laboratories, Inc. | Dust suppression method and composition |
| US4212760A (en) * | 1977-12-07 | 1980-07-15 | Basf Aktiengesellschaft | Solubilized alkaline, aqueous solutions of nonionic surfactants |
| US4774016A (en) * | 1983-01-24 | 1988-09-27 | Crinos Industria Farmacobiologica Spa | Skin cleaning preparations containing an HLB 10-19 nonionic emulsifier and a thickening agent |
| US4657690A (en) * | 1983-04-15 | 1987-04-14 | L'oreal | Washing and foaming composition based on non-ionic surface-active agents and anionic polymers |
| US4588516A (en) * | 1984-12-26 | 1986-05-13 | Schwartz Lenore F | Cleaning liquid and process of using same |
| US4737305A (en) * | 1986-04-25 | 1988-04-12 | Pennzoil Products Company | Dust suppressant composition and method |
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| US8210215B2 (en) | 2003-06-26 | 2012-07-03 | R. Lewis Technologies, Inc. | Mixing apparatus and methods of using the same |
| US8905088B2 (en) | 2003-06-26 | 2014-12-09 | R. Lewis Technologies, Inc. | Mixing apparatus and methods of using the same |
| US20060223736A1 (en) * | 2005-03-30 | 2006-10-05 | R. Lewis Technologies, Inc. | Dye and scent pouches and methods of making the same |
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