US2970963A - Opaque liquid detergent composition - Google Patents

Opaque liquid detergent composition Download PDF

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Publication number
US2970963A
US2970963A US730260A US73026058A US2970963A US 2970963 A US2970963 A US 2970963A US 730260 A US730260 A US 730260A US 73026058 A US73026058 A US 73026058A US 2970963 A US2970963 A US 2970963A
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United States
Prior art keywords
sodium
composition
alkyl
detergent
glyceryl ether
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Expired - Lifetime
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US730260A
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English (en)
Inventor
Richard D Walker
Blinka Joseph
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Procter and Gamble Co
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Procter and Gamble Co
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Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to US730260A priority Critical patent/US2970963A/en
Priority to FR789721A priority patent/FR1242862A/fr
Priority to DEP22569A priority patent/DE1095975B/de
Priority to AT290059A priority patent/AT227856B/de
Priority to GB13225/59A priority patent/GB877155A/en
Priority to BE589857D priority patent/BE589857A/xx
Application granted granted Critical
Publication of US2970963A publication Critical patent/US2970963A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • C11D3/048Nitrates or nitrites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0089Pearlescent compositions; Opacifying agents

Definitions

  • This invention relates to an opaque liquid detergent characterized by improved viscosity characteristics and stability against gravitational separation.
  • an opaque liquid detergent composition c'als ranging in chain length from C to C
  • This alkyl glyceryl ether sulfonate is readily soluble in the aqueous vehicle as compared to. the C to C alkyl glyceryl ether sulfonate used as the substantially insoluble opacifier.
  • the C to C alkyl glyceryl ether sulfonate is an excellent detergent and a particular attribute is the ability to produce stable suds in the use of the liquid detergent composition.
  • Suds stabilization i.e., prolonging of the life of the suds, is very important in a light duty liquid detergent which is used for dish washing and the like since the user gauges the detergency capacity of the washing solution by the amount of suds present and will be likely to be misled if the suds do not persist for a reasonable length of time.
  • the C to C alkyl glyceryl ether sulfonate has still another desirable function.
  • the presence of this solubilized homologue with the C to C alkyl glyceryl ethersulfonate opacifying crystals promotes a slight crystal growth and orientation of the suspended opacifier. crystals and causes the opacity of the composition to be a highly desirable opalescent sheen rather than merely a milky white opacity.
  • the preferred method of improving stability is to make the specific gravity of the liquid phase close to that of the solid opacifying agent phase. Since the specific gravity of the solid phase of the opaque compositions herein concerned is greater than that of the liquid phase, the
  • Dissolved electrolyte salts tend to reduce the viscosity of the opaque liquid compositions described herein by reducing the tendency of the opacifier crystals to group together or to form gels. This is a result of the electrolytic activity of the ions of the salts reducing the solubility of the opacifier ingredient, tending to keep the opacifier crystals apart in the suspension and keeping them in a finer form. This phenomenon is referred to herein as a graining action.
  • the use of electrolyte salts as graining agents generally reduces the amounts of the solvents and hydrotropes required to obtain the desired viscosity in opaque liquid compositions.
  • Sodium chloride is more soluble than sodium sulfate (about 10% at F.), but is not sufiiciently soluble to obtain as high range of specific gravities of the liquid phase as is desirable. Sodium chloride also tends to precipitate on chilling the compositions. Sodium .chloride. is also a powerful graining agent and tends to grain the C to C alkyl glyceryl ether sulfonate out of solution which, as described above, tends to increase the viscosity of the composition.
  • Sodium acetate is more soluble than sodium chloride (about 14% at 80 F.) but, being the salt of an organic acid, is a very weak graining agenn It is expensive and does not increase the specific gravity of the liquid phase of the opaque composition nearly as much as the same concentration of an inorganic salt. It is rather ineffective toward improving the stability against gravitational separation of the opaque liquid compositions.
  • the solution of the problem of finding an effective method of increasing stability without an undesirable increase in viscosity in the opaque alkyl glyceryl ether sulfonate compositions herein defined demands an electrolyte salt which is highly soluble in the compositions, effective in increasing the specific gravity of the liqiud phase, and has a suitable graining action on the C to C alkyl glyceryl ether sulfonate but does not have an undesirable graining action on the C to C alkyl glyceryl ether sulfonate.
  • sodium nitrate has the heretofore unobserved properties for solving problems such as those here confronted and for accomplishing the above mentioned objects. It is highly soluble and can be dissolved in the concentrated detergent compositions in amounts sufiicient to give a desired specific gravity. It has the heretofore undisclosed characteristics of having a suitable graining action which affects the C to C alkyl glyceryl ether sulfonate (opacifier) without undesirably affecting the C to C homologue, whereby lower'viscosities at higher concentrations are achieved. It thus enables a reduction in the use of expensive hydrotropes and solvents.
  • composition of the present invention is an opaque liquid detergent which contains in solution a water soluble anionic synthetic detergent alkali metal salt at least part of which is an alkyl glyceryl ether sulfonate salt having alkyl radicals C to C in chain length and suspended therein as a crys-tallizing opacifying agent an alkyl glyceryl ether sulfonate salt having alkyl radicals C to C in chain length and being substantially insoluble in the composition at room temperature.
  • a water soluble anionic synthetic detergent alkali metal salt at least part of which is an alkyl glyceryl ether sulfonate salt having alkyl radicals C to C in chain length and suspended therein as a crys-tallizing opacifying agent an alkyl glyceryl ether sulfonate salt having alkyl radicals C to C in chain length and being substantially insoluble in the composition at room temperature.
  • the invention lies in the use, in this composition, of an amount of dissolved sodium nitrate sufiicient to increase the specific gravity of the aqueous vehicle whereby the stability against gravitational separation is increased and sufficient to provide a graining action on the opacifying crystalsthereby reducing the viscosity of the composition..
  • small amounts of hydrotropes. and solvents can also be advantageously used in the aqueous vehicle of the composition of this invention as more fully hereinafter described.
  • the opacifier is suspended in the detergent solution by first dissolving a suitable C to C alkyl glyceryl ether sulfonate salt in the detergent solution containing dissolved C to C alkyl glyceryl ether sulfonate and sodium nitrate at a temperature at which the said C to C alkyl glyceryl ether sulfonate salt is substantially completely soluble, and then cooling the solution to a temperature, preferably room temperature, at which C to C alkyl glyceryl ether sulfonate salt is substantially insoluble.
  • insoluble alkyl glyceryl ether sulfonate salt precipitates in the form of fine crystals which remain suspended in the detergent solution and which cause the product to have an over-all pearly white opacity;
  • the presence of dissolved C to C alkyl glyceryl ether sulfonate salt in the detergent promotes a very slight crystal growth and orientation of the precipitated crystals resulting in an opalescent sheen which enhances the opaque appearance.
  • the crystal growth is probably a result of some C to C alkyl glyceryl ether sulfonate coming out of solution; although on heatingand chillingof the composition there is also a small amount of digestion and recrystallization of C to C alkyl glyceryl ether sulfonate.
  • the dissolved sodium nitrate through its graining action promotes the precipitation of the opacifier crystals in a very fine form, and this fine form also tends to increase the stability of the opacifier crystals against gravitational separation.
  • the opacifier is substantially insoluble in the concentrated detergent solution at room temperatures, it becomes dissolved when the detergent solution is diluted to the concentrations normally used in forming a washing solution.
  • substantially insoluble alkyl glyceryl ether sulfonates are those sodium salts with alkyl chain lengths of about C to about C
  • Sodium alkyl glyceryl ether sulfo-nates with alkyl chain lengths of C to C are too soluble to be used as opacifiers but .are, of course, used as all or part of the substantially completely dissolved anionic synthetic detergent in the present compositions.
  • Alkyl glyceryl ether sulfonates can be produced, for example, by sulfonating with sodium sulfite the reaction product of a higher fatty alcohol and a slightmolar excess of epichlorohydrin.
  • Single, sodium alkyl glyceryl ether sulfonates with an alkyl radical of 16 or 18 carbon atoms, for example, can be employed as the opacifier of the compositions of this invention; but it is ordinarily more convenient and less.
  • the higher alcohols derived by the high pressure hydrogenation of tallow or by the sodium reduction of substantially completely hydrogenated tallow are preferred for the production of the opacifier used in the composition of this invention because they contain predominantly l6 and 18 carbon atoms in the alkyl chain.
  • Another .source is the separated higher molecular weight alcohol fraction from a fatty alcohol.
  • single sodium alkyl glyceryl ether sulfonates with an alkylradical of .12 or 14 carbon atoms can be employed as the dissolved suds stabilizer detergent in the composition of this invention; but it is ordinarily more convenient and less expensive to use a mixture of. such compounds in which the alkyl radicals are derived from readily available fatty alcohol mixtures.
  • the higher alcohols produced by the reduction of coconut oil, palm kernel oil or other oils of the coconut oil group are a ready source of C to C14 alcohols.
  • the coconut oil group is defined as a group of tropical nutoils characterized by a preponderance ofcombined fatty. acids having ten to fourteen carbon atoms.
  • the separated middle cut fraction from a fatty alcohol mixturederived by the reduction of an oil from the coconut oil group.
  • Such a fraction consists chiefly of C and C alcohols with the C C ,.C and most of the C and C alcchols removed by fractionation.
  • alkali metal salts of organic sul furic reaction products having in their molecular structurealkyl radical but since other constituents of the detergent molecule can be varied to increase the degreeof solubility, the number of carbonatoms in the alkyl radical can also be adjusted upwardly in such instances to as high as 18, for example.
  • the synthetics which may be used in the composition of the present invention are: sodium alkyl benzene sulfonates especially those of the types described in U.S.
  • Patents 2,220,099 and 2,477,383 in which the alkyl groups con tain from about 9 to about 15 carbon atoms; sodium alkyl sulfates, especially those derived by sulfation of higher alcohols produced by reduction of coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium salts of sulfuric acid esters of the reaction product of one mole of coconut oil fatty alcohol and about 3 moles of ethylene oxide or of one mole of tallow fatty alcohol and about 10 moles of ethylene oxide; sodium salts of alkyl (C -C ethylene oxide ether sulfates which have an average of one unit of ethylene oxide per molecule; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fattyacids are derived' from coconut oil; sodium salts of a fatty acid amide of a methyl taurine in which the fatty acids, for example
  • the dissolved anionic synthetic detergent is present in the opaque liquid compositions of this invention in an amount by weightin the range of about 15% to about 40%. Included in these amounts of dissolved anionic. synthetic detergent is at least about 2% of C to C 4 sodium alkyl glyceryl ether sulfonate. This much C to C alkyl glyceryl ether sulfonate is necessary to achieve the desired crystal growth and orientation of opacifying crystals for pearly white opalescence and suds stabilizing properties in the opaque liquid composition of this invention.
  • the entire amount of dissolved anionic synthetic deter gent in the composition can constitute C to C alkyl glyceryl ether sulfonate up to the limit of its solubility although it is preferable to use this detergent in the range of about 2% to about 10% by weight and supplement it with a more soluble anionic synthetic detergent such as sodium alkyl sulfate, 2. sodium alkyl benzene sulfonate or a sodium alkyl ethylene oxide ether sulfate which has an average of three ethylene oxide units per molecule.
  • Suspended in the solution of dissolved anionic synthetic detergent is about 1% to about 9%, preferably about 2% to about 5%, by weight of the C to C sodium alkyl glyceryl ether sulfonate opacifying agent which is substantially insoluble in the solution at room temperature.
  • Solvents also serve to increase, if desirable, the amount of anionic synthetic detergent which can be dissolved in the opaque liquid compositions of this invention.
  • Ethanol, propanol and isopropanol are useful for this purpose and the amounts used are from to about 15% (ordinarily about -10%) by weight of the composition.
  • Ethylene glycol and propylene glycol can also be used but are not as effective as the above mentioned The preferred range is about 20% to about 35%.
  • solvents Up to about 5% sodium toluene, benzene or xylene sulfonate can also be used as a hydrotrope in conjunction with the above mentioned solvents.
  • the dissolved sodium nitrate can be advantageously used up to the limit of its solubility in the opaque liquid compositions of this invention (up to about 20% at F.). At least about 2% dissolved sodium nitrate by Weight of the composition is neededto provide a graining action for the opacifying agent when used in ranges above designated and has a quite noticeable graining effect over a composition containing no dissolved nitrate salt.
  • the specific gravity of the liquid phase increases linearly with increasing amounts of dissolved sodium nitrate.
  • the graining action of the dissolved sodium nitrate on a fixed amount of alkyl glyceryl ether sulfonate increases (decreasing viscosity) with increased amounts of the nitrate salt.
  • compositions of this invention results in products with excellent viscosity characteristics and stability against gravitational separation.
  • About 12% dissolved sodium nitrate also results in an optimum graining action.
  • Example I An opaque liquid detergent composition was prepared from the following ingredients:
  • the mixture was then cooled to about 80 F. in a heat exchanger thereby effecting the precipitation of the crystals of opacifying agent.
  • the resulting composition was an excellent detergent having outstanding sudsing and suds stability characteristics in dishwashing. It poured easily having a viscosity of about 300 cp. at room temperature and had a very stable opacity characterized by an opalescent sheen.
  • Example II An opaque liquid detergent composition was prepared as described in Example I from the following ingredients:
  • suds promoting additives which can be used in the preparation of the detergent compositions of this invention, but which are not necessary, are the monoand diethanolamides and isopropanolamides of coconut oil fatty acids.
  • perfumes and fluorescent brightening agents known in the art can be added to improve product appeal and performance. Since the opalescent sheen is the basic feature of the invention, dyes can be added to produce pastel shades which can greatly enhance the customer attraction to the product.
  • This invention results in a stable, cflicient, light duty detergent with a highly desirable appearance.
  • An opaque liquid detergent composition consisting essentially of an aqueous vehicle containing in solution about% to about 40% of a water soluble anionic nonsoap synthetic detergent sodium salt, said detergent salt comprising in part an amount of sodium alkyl glyceryl ether sulfonate with alkyl radicals ranging in chain length from C to C equivalent to at least 2% by weight of the composition, and suspended therein as a crystalline opacifying agent about 1% to. about 9% of an alkyl lyceryl ether sulfonate. sodium salt with alkylradicals' ranging in chain length from C to C and which is sub.-
  • aqueous vehicle containing in solution from about 2% to about 20% sodium nitrate sufiicient to'pro vide a graining action for said opacifying agent thereby reducing the viscosity of said composition and sufficient to increase the Specific gravity of said aqueous vehicle where-- by the stability of said opacifying agent against gravitational separation is increased, said percentages being'by weight of the composition.
  • An opaque liquid detergent composition consisting essentially of about 15% to about 40% of a dissolved water-soluble anionic synthetic detergent sodium salt selected from the group consisting of anionic sulfate and sulfonate synthetic detergents, said detergent salt comprising in part an amount of sodium alkyl glyceryl ether sulfonate with alkyl radicals ranging in chain length from C to C equivalent to at least 2% by weight of the composition, as an opacifying agent about 1% to about 9% of a suspension of sodium alkyl glyceryl ether sulfonate with alkyl radicals ranging in chain length from C to C and which is substantially insoluble in the composition at room temperature, 0% to about 15% of a water soluble organic solvent selected from the group consisting of ethanol, propanol and isopropanol, and about 2% to of the composition. 7
  • the opacifying agent is sodium alkyl glyceryl ether sulfonate in which the alkyl radicals are derived from a fatty alcohol derived by the reduction of tallow and the anionic synthetic detergent salt is selected from the group consisting of alkyl sulfate, alkyl benzene sulfonate and alkyl ethylene oxide ether sulfate having an average of three ethylene oxide
  • An opaque liquid detergent composition consisting essentially of about 20% to about 35% of dissolved watersoluble anionic synthetic detergent sodium salt selected from the group consisting of anionic sulfate and sulfonate synthetic detergents, said detergent salt comprising in part an amount of sodium alkyl glyceryl ether sulfonate with alkyl radicals ranging in chain length from C to C equivalent to about 2% to about 10% by weight of the composition, as an opacifying agent about 2% to about 5% of a suspension of sodium alkyl glyceryl ether sulfonate with alkyl radicals ranging in chain length from' C to C and which is substantially insoluble in the composition at room temperature, about 5% to about 10% of 'a water soluble organic solvent selected from the group consisting of ethanol, propanol and isopropanol, and about 6% to about 18% dissolved sodium nitrate, said ingredients being in an aqueous vehicle and said percentages being by weight.
  • the opacifying agent is sodium alkyl glyceryl ether sulfonate in which the alkyl radicals are derived from a fatty alcohol derived by the reduction of tallow and the anionic synthetic detergent salt is selected from the group consisting of sodium alkyl sulfate, sodium alkyl benzene sulfonate and sodium alkyl ethylene oxide ether sulfate having an average of three ethylene oxide units per molecule, the alkyl radicalrin said detergent salt having from about 8 to about 18 carbon atoms. 7
  • An opaque liquid detergent composition consisting essentially of about 25% sodium coconut oil alcohol ethylene oxide ether sulfate, about 4% sodium coconut oil alcohol glyceryl ether sulfonate, about 3% sodium tallow alcohol glyceryl ether sulfonate, about 8% coconut oil monoethanol amide, about 2% sodium toluene sulfonate, about 8% ethanol, about 12% sodium nitrate and about 38% water. 7

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
US730260A 1958-04-23 1958-04-23 Opaque liquid detergent composition Expired - Lifetime US2970963A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US730260A US2970963A (en) 1958-04-23 1958-04-23 Opaque liquid detergent composition
FR789721A FR1242862A (fr) 1958-04-23 1959-03-18 Composition détersive
DEP22569A DE1095975B (de) 1958-04-23 1959-04-10 Fluessiges, undurchsichtiges Reinigungsmittel
AT290059A AT227856B (de) 1958-04-23 1959-04-17 Undurchsichtiges, flüssiges Reinigungsmittel
GB13225/59A GB877155A (en) 1958-04-23 1959-04-17 Opaque liquid detergent composition
BE589857D BE589857A (enrdf_load_stackoverflow) 1958-04-23 1960-04-19

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US730260A US2970963A (en) 1958-04-23 1958-04-23 Opaque liquid detergent composition

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US2970963A true US2970963A (en) 1961-02-07

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US730260A Expired - Lifetime US2970963A (en) 1958-04-23 1958-04-23 Opaque liquid detergent composition

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US (1) US2970963A (enrdf_load_stackoverflow)
AT (1) AT227856B (enrdf_load_stackoverflow)
BE (1) BE589857A (enrdf_load_stackoverflow)
DE (1) DE1095975B (enrdf_load_stackoverflow)
FR (1) FR1242862A (enrdf_load_stackoverflow)
GB (1) GB877155A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3085067A (en) * 1960-02-10 1963-04-09 Procter & Gamble Sarcosinate shampoo
US3211661A (en) * 1961-12-15 1965-10-12 Procter & Gamble Liquid detergent composition
US3282852A (en) * 1962-05-11 1966-11-01 Colgate Palmolive Co Heavy duty liquid detergents
US3296147A (en) * 1964-06-24 1967-01-03 Dow Chemical Co Cleaner for food residues
US5310508A (en) * 1992-07-15 1994-05-10 Colgate-Palmolive Company Mild personal cleansing compositions containing sodium alcohol ethoxy glyceryl sulfonate

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1205221B (de) * 1961-08-21 1965-11-18 Procter & Gamble Fluessiges Reinigungsmittel

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2094489A (en) * 1937-09-28 Wetting-out
US2527077A (en) * 1947-06-02 1950-10-24 Procter & Gamble Detergent composition
US2766212A (en) * 1952-09-16 1956-10-09 Gen Aniline & Film Corp Detergents
US2770599A (en) * 1953-09-23 1956-11-13 Colgate Palmolive Co Stable liquid shampoos

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2094489A (en) * 1937-09-28 Wetting-out
US2527077A (en) * 1947-06-02 1950-10-24 Procter & Gamble Detergent composition
US2766212A (en) * 1952-09-16 1956-10-09 Gen Aniline & Film Corp Detergents
US2770599A (en) * 1953-09-23 1956-11-13 Colgate Palmolive Co Stable liquid shampoos

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3085067A (en) * 1960-02-10 1963-04-09 Procter & Gamble Sarcosinate shampoo
US3211661A (en) * 1961-12-15 1965-10-12 Procter & Gamble Liquid detergent composition
US3282852A (en) * 1962-05-11 1966-11-01 Colgate Palmolive Co Heavy duty liquid detergents
US3296147A (en) * 1964-06-24 1967-01-03 Dow Chemical Co Cleaner for food residues
US5310508A (en) * 1992-07-15 1994-05-10 Colgate-Palmolive Company Mild personal cleansing compositions containing sodium alcohol ethoxy glyceryl sulfonate

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Publication number Publication date
GB877155A (en) 1961-09-13
DE1095975B (de) 1960-12-29
AT227856B (de) 1963-06-10
BE589857A (enrdf_load_stackoverflow) 1960-05-13
FR1242862A (fr) 1961-01-09

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