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US3101324A - Liquid detergent composition - Google Patents

Liquid detergent composition Download PDF

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US3101324A
US3101324A US75114A US7511460A US3101324A US 3101324 A US3101324 A US 3101324A US 75114 A US75114 A US 75114A US 7511460 A US7511460 A US 7511460A US 3101324 A US3101324 A US 3101324A
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detergent
liquid
product
alcohol
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US75114A
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Wixon Harold Eugene
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Colgate Palmolive Co
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Colgate Palmolive Co
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    • 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
    • C11D3/06Phosphates, including polyphosphates
    • 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
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/38Cationic compounds
    • C11D1/65Mixtures of anionic with cationic compounds
    • C11D1/655Mixtures of sulfonated products with alkylolamides of carboxylic acids
    • 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
    • C11D3/43Solvents
    • 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
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group

Definitions

  • the present invention relates to a pourable, concentrated liquid detergent composition which comprises an alkali metal higher alkyl aryl sulfonate detergent and a potassium polyphosphate in an aqueous alcoholic medium in homogeneous form, as hereinafter described and claimed.
  • heavy-duty liquid detergent compositions which consist essentially of about 5 to 25% by weight of alkali metal alkyl mononuclear aryl sulfonate detergent having an alkyl group of 8 to 15 carbon atoms and 10 to 50% by weight of a potassium polyphosphate selected from the group consisting of pyrophosphate rand tripolyphosphate, the total content of organic detergent and potassium polyphosphate being a maximum of about 55% by weight, and an aqueous solubilizing medium in admixture therewith suiiicient to [form a liquid pourable in homogeneous form, said aqueous medium containing a saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms in an amount from about /2 to by weight.
  • alkali metal alkyl mononuclear aryl sulfonate detergent having an alkyl group of 8 to 15 carbon atoms and 10 to 50% by weight of a potassium polyphosphate selected from the group consisting of pyrophosphate rand tripoly
  • a feature of the present invention relates to a liquid consisting essentially of the following ingredients propontioned within the stated ranges to form a pourable, substantial-1y homogeneous aqueous liquid which consists essentially of about 5 to by weight of said higher alkyl aryl sulfonate detergent, about 10- to 35% by weight of said potassium polyphosphate, the total amount of detergent and polyphosphate being at least about 20% by weight, about 4 to 12% by weight of an alkali metal lower alkyl aryl sulfonated hydrotropic salt, and preferably about 2 to 15% ofya higher fatty acid alkylolamide, the total solids content being less than about 65% by weight, and
  • the organic detergent and polyphosphate salts are em ployed in substantial amount such that the addition of p a small portion of the liquid product to a washing bath will result in effective detergency and washing power.
  • the proportions of these two ingredients are variable and should be suitably selected and proportioned so that there is termed a pourable, substantially homogeneous product by the solubilizing medium.
  • the amount of detergent is selected from the range of 5 to 25% and usually up to 20% by weight.
  • the amount of polyphosphate is within the range of 10 to 50% and usually up to 35% by weight with the preferred amount being about 15 to
  • the total amount of organic detergent and polyphospha-te should be a maximum of about 55 by weight. It is preferred that the total concentration be at least about 20% by weight.
  • Amounts of detergent and polyphosphate totalling at least 20% by weight are incompatible in water resulting in a' product which genenally separates rapidly, usually within a few minutes.
  • proportions of detergent and phosphate within the stated ranges, pour-able and substantially homogeneous liquids may be formed using an aqueous alcoholic solubilizing medium as described herein.
  • alkyl group' which it is preferred to use is alkyl benzene sulfonate, though other similar detergents having a mononuclear aryl nucleus, such as alkyl toluene and alkyl xylene sulfonates, may be used.
  • the alkyl substituent may be branched such as nonyl, dodecyl land pentadecyl groups including mixtures thereof which are derived from polymers of lower mono-olefins.
  • the alkyl group may be straightchained in structure such as the decyl, keryl anddodecy-l groups.
  • Preferred examples of this class are the alkyl benzene sulfonates having an average of'about 12 to 15 carbons in the alkyl group.
  • These sulfona-te detergents are used in the form of their water-soluble alkali metal salts such as the sodium or potassium salts.
  • the potassium polyphosphate salts have the property of inhibiting precipitation of calcium and magnesium material normal room temperatures (e.g., about 20 C. to 25 C.).
  • the liquid product may be of variable viscosity. It may be highly fluid and free-flowing, or fairly viscous when at rest but pourable freely from the container upon I light shaking.
  • the liquid may be packaged in any suitable container, however, such as metal, glass'or plastic in the form of bottles, cans, drums, packets yor bags.
  • homogeneous as used herein means that the product has a satisfactory degree of stability during storage life against separation orformation of a plurality of distinct. layers which either cannot be re-dispersed by light shaking or which separate rapidly after shaking.
  • Suchcornpositions include liquids which are clear, trans- Y lucent or opaque depending upon the type and proportions of the various solids present therein. Any solid material present in the composition in excess of its solubility in the particular systemis maintained in a noncaking suspension. It is'characteristic that in such cases, upon light shaking, the product is readily converted to a substantially homogeneous liquid which is stable for a sufiicient period of time, e.g., at least about 1 hour, so that each small portion added to a laundering bath or the like will have practically the same composition. The product exhibits a washing power which is comparable to the same quantity of commercial heavy-duty detergents in powdered form.
  • the aqueous alcoholic solubilizing medium should contain a saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms such as ethanol, propanol or isopropanol so as .to provide for desired physical properties of the liquid composition.
  • the alcohol may serve a multiplicity of functions. Using selected proportions of detergent and phosphate within the ranges indicated, the alcohol in sufficient amount renders the detergent and phosphate more compatible in water.
  • the appearance of the liquid such as a clear or opaque product is controllable by the proportions of detergent and phosphate employed in the aqueous medium using a suflicient amount of the alcohol.
  • the alcohol permits desired modification of the viscosity, such as to make the product less viscous where high solids are employed and improve pourability thereby. It can provide for improved low temperature aging of the product such as the prevention of a precipitate at moderately low temperatures, e.g., about 40 E, which does not redisperse upon recovery to room temperature.
  • the alcohol may adjust also the phase relation ship so as to lower the cloud point and insure a clear liquid at a lower temperature if desired.
  • the amount of alcohol which should be employed varies with the particular formulation so as to achieve at least one of the above improvements in physical properties.
  • the alcohol is a solubilizing agent for said organic detergent in water but is relatively incompatible with inorganic salts.
  • There is a critical maximum proportion of alcohol since an excessive amount will result in separation of the product into two or more layers which either separate rapidly or will not redisperse readily.
  • the amount of alcohol used should not adversely affect the homogeneity of the liquid therefore, such as by separation of inorganic salt solution or by excessively thinning a high solids product where relatively high viscosity is desired as an aid in preventing rapid separation.
  • the aqueous medium contain a water-soluble hydrotropic substance as a solubilizing agent in promoting the compatibility of the ingredients so as to form a homogeneous liquid product.
  • the watersoluble organic sulfonated hydrotropes particularly the alkali metal sulfonated salts having a lower alkyl group up to about 6 carbons, are efiective in these products.
  • Sulfonates made from Xylene include orthoxylene sulfonate, metaxylene sulfonate, paraxylene sulfonate and ethylbenzene sulfonate.
  • Commercial Xylene sulfonates usually contain metaxylene sulfonate as the main ingredient.
  • Analyses of typical commercial products show about 40-50% metaxylene sulfonate, 10-35% orthoxylene sulfonate and 15-30% paraxylene sulfonate with 0-20% ethylbenzene sulfonate. Any suitable isomeric mixture may be employed, however. Suitable lower alkyl sulfate salts may be employed also, such as the alkali metal n-amyl and n-hexyl sulfates. The hydrotrope may be employed in variable amounts depending ing suitable proportions of said solubilizing agents.
  • hydrotropic sulfonate salt may be employed in said range to form a clear or opaque liquid at room temperature.
  • medium amounts of detergent and relatively low phosphate it is possible to obtain a clear liquid at room temperature in the presence of suflicient hydrotropic salt in an aqueous medium.
  • the presence of suitable amounts of alcohol in combination is advantageous for such physical characteristics as lowering of the cloud point, improvement in the low temperature aging of the product, etc, in addition to providing a too-solubilizing action with the hydrotrope permitting use of lesser amounts of the latter ingredient depending upon the particular formulation.
  • a lotion-like or opaque liquid using the hydrotropic salt and alcohol in combination.
  • the amount of hydrotropic salt which may be added is limited since it will increase the solids content. Where the solids content is excessive, a non-pourable product will be obtained.
  • the presence of the alcohol in combination will ermit the formulation of the desired liquid product.
  • the liquid contain a higher fatty acid alkylolamide material in a sufiicient amount to act as a suds builder during washing operations.
  • the alkylolamide provides an additional solubilizing client. It should not be employed in an amount sufiicient to destroy the desired physical properties since it is considered as part of the total solids content.
  • the alkylolamides may be employed in amounts of about 2 to 15% by weight in the product, and preferably from about 3 to 8%.
  • the acyl radical of the alkylolarnide is selected fiom the class of fatty acids having 8 to 18 carbons and each alkylol group has up to 3 carbon atoms usually.
  • diethanolamides, isopropanolamides and monoethanolamides of fatty acids having about 10 to 14 carbons in the acyl radical are preferred.
  • examples are the lauric, capric, myristic and coconut diethanol arnides, monoethanolalmides and isopropanolamides, and mixtures thereof.
  • alkylolamides which are substituted by additional alkylol groups, suitable examples being the above monoethanolamides, diethanolamides and isopropanolarnides condensed with one or two moles of ethylene oxide.
  • pourable, homogeneous liquids may be prepared having a solids content of up to about 65% by weight in the aqueous alcoholic medium contain- It is preferred to have a maximum of about 60% solids for opaque liquids and up to about 50% solids for clear solutions.
  • the balance of the liquid content is primarily water since the liquid alcohol is used in small amounts.
  • the amount of water will be suitably proportioned to provide suifioient solubilizing efieots for the phosphates and similar inorganic salts so as to form a substantially homogeneous product.
  • the amount of Water is general- 1y at least about 30% by weight and preferably from 40 to 60% of the liquid.
  • compositions of the present invention are compatible with a suitable soil-suspendineg material which repre sents a further embodiment of the present invention.
  • a soil-suspending material converts the sys which may be used in compositions of the present invention are the lower alkyl and hydroxy alkyl ethers such as methylcellulose, ethylcellulose and hydroxyethylcellulose; I
  • soil-suspending agents may be employed such as the water-soluble vinyl polymers.
  • water-soluble polyvinyl alcohol which may contain minor amounts of polyvinyl acetate as commercially made.
  • Water-soluble polyvinyl polymeric amides such as polyvinylpyrrolidone of suitable molecular weight may be employed also.
  • the amount 'of'the soil-suspending about 2% by weight in the liquid product. It has been found that amounts within this range can be used in thepreparation of substantially homogeneous products which exhibit a high level of soil suspension during washing.
  • Various materials or mixtures may be employed which assist in maintaining the soil-suspending material in suspension or dispersion in the liquid product. Suitable mixtures of cellulosic compounds, or a mixture of acellulosic compound with a vinyl polymer, or a mixture of a cellulosic compound with castor wax may be employed.
  • the liquid detergent product is prepared in any suitable manner.
  • the hydrotropic salts, the polyphosphate and the organic detergent are added in the form of powders, aqueous solutions or slurries-to the aqueous medium as desired.
  • the alkylolarnide is preferably added in molten or liquid form with agitation to form a homo geneous mixture.-
  • the alcohol may be added at any stage during the mixing operations as desired.
  • the tempera ture of admixture is not critical and room temperatures or reasonable elevated temperatures may be employed.
  • invenagent (including mixtures thereof) is usually from about 0.1 to
  • This product remains substantially homogeneous for many days and produces a high degree of washing power inboth soft and hard water for laundering of soiled textile materials.
  • the washing power corresponds to that of a commercially acceptable heavy-duty detergent composition in powder form.
  • Example 11 The same formulation is used except that the coconut diethanolamide is reduced fnom 10% to 5% by weight,
  • Example III A similar composition is formed by using theformulation of Example I but substituting an equivalent quantity of tetrapotassium pyrophosphate for the tripolyphosphate.
  • Example IV A satisfactory composition is prepared according to the Percent Ingredient:
  • tion is not limited thereto. All parts ace in approximate the balance being minor amounts of perfume, coloring material, and optical bleach. v
  • This product is prepared by the preferred method whereby the potassium tripolyphosphate is added slowly to the water,fo1lowed by introduction of the toluene sulfonate, the dodecyl benzene sulfonate, the coconut diethanolamide and the bleach and coloring material, each material being mixed thoroughly in the aqueous mixture before the next material is introduced.
  • the perfume and ethanol are added followed by the slow addition of the carboxymethylcellulose with continued mixing until there is obtained a relatively thick gelatinous liquid.
  • the mixture is transferred to a water-cooled colloid mill where his homogenized for about 8 minutes.
  • the pH is 9.3, specific gravity 1.3, and viscosity [of about 1500 centipoises.
  • the finished product has a final solvent analysis
  • the sodium tridecyl benzene sulfonate is of about purity,"the balancebeing sodium sulfate formed in its manufacture.
  • the alkyl group of the detergent is derived from a mixture of pnopylene polymers corresponding on the average to a tridecyl group.
  • Example I modified to an ethanol content of 15% with a corresponding reduction in the Water content results in a product which separates rapidly.
  • Example XXII Ingredients Percent Sodium tridecyl benzene sulfonate 19 Potassium pyrophosphate 15 Sodium Xylene sulfonate 7 Coconut diethanolamide 13 Ethanol 4 Water (q.s. to 100%).
  • the alkylolamide is a 1:1 mixture of isopropanolamides and diethanolamides having about a 70: 30 ratio of lauric to myristie radicals.
  • the above formulations are pourable homogeneous liquids and exhibit improved physical properties after aging at 40 F. compared to products free of the alcohol.
  • ingredients may be added or substituted if desired.
  • the individual solubility characteristics of added materials may influence the physical properties of the liquid. It is understood therefore that such ingredients will be suitably selected and the proportions of the various components controlled as'described herein so as to form a liquid product having the desired physical qualities.
  • suitable amounts of various anionic sulfate or sulfonate or non-ionic organic detergents include compatible perfumes, coloring materials, corrosion inhibitors, anti-tarnishing agents, germicides, bleaching agents, optical bleaches or fluorescent dyes, and the like.
  • phosphate materials or similar builder salts such as silicates in the product provided that they do not substantially adversely altect the product.
  • An improved liquid detergent composition consisting essentially of about to 25% by weight of alkali metal alkyl mononuclear aryl sulronate detergent having an alkyl group of 8 to 15 carbon atoms and 10 to 50% by Weight of a potassium polyphosphate selected from the group consisting of pyrophosphate and tripolyphospha'te, the total content of organic detergent and potassium polyphosphate being a maximum of about 55% by weight, and having a saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms in an amount from about /2 to 15% by weight of the composition, the balance being substantially water in admixture therewith sufficient to form a liquid composition pourable in homogeneous form.
  • alkali metal alkyl mononuclear aryl sulronate detergent having an alkyl group of 8 to 15 carbon atoms and 10 to 50% by Weight of a potassium polyphosphate selected from the group consisting of pyrophosphate and tripolyphospha'te, the total content of organic detergent
  • An improved liquid detergent composition consisting essentially of about 5 to 25% by weight of alkali metal alkyl benzene sulfonate detergent having an alkyl group of 8 to 15 carbon atoms and 10 to 50% by weight of a potassium polyphosphate selected from the group consisting of pyrophosphate and tripolyphosphate, the total content of organic detergent and potassium polyphosphate being Within the range of about 20 to 55% by weight, and having ethanol in an amount from about /2 to 15% by Weight of the composition, the balance being substantially water in admixture therewith sufficient to form a pourable, substantially homogeneous liquid composition.
  • a liquid detergent composition consisting essentially of about 5 to 20% by weight of alkali metal :alkyl benzene sulfonate detergent having an :alkyl group of 8 to l5 carbon atoms, about 10 to 35 by Weight of potassium polyphosphate selected from the group consisting 10f pyrophosiphateand tripolyphosphate, the total content ol rganic detergent and potassium polyphosphate being within the range of 20 to 55 by weight, about 4 to 12% y weight of an alkali metal organic sulfionated hydrotropic salt selected from the group consisting of alkali metal allkyl substituted benzene sulfonates having up to 2 carbon atoms in said salkyl substituent and alkyl sulfates having 5-6 canbon atoms, said aqueous alcoholic medium having about /2 to 15% by weight of a saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms, the balance being substantially Water in admixture therewith sufficient to form
  • a liquid detergent composition as set'forth in claim 3 which contains about 2 to 15% of a'higher fatty acid alkylolamide having about 2 to 3 carbons in each alkylol group and about 8 to 18 carbons in the fatty acyl group.
  • a liquid detergent composition consisting essentially of the following ingredients proportioned within the stated ranges to (form a pourable, substantially homogeneous product: about 5 to 20% by weight of alkali metal alkyl benzene sulfonate having an alkyl group of 8 to 15 carbon atoms, about 10 to 35% by weight of potassium polyphosphate selected from the group consisting of pyrophosphate and tripolyphosphate, the total content of organic detergent and potassium polyphosphate being within the range of 20 to 55% by weight, about 4 to 12% by weight of an alkali metal sulfonated hydrotropic salt selected from the group consisting of toluene and xylene sulfon-ates, about 2 to 15% by weight of a higher fatty acid alkylolamide having about 10 to 14 carbon atoms in the fatty acyl radical and 2 to 3 carbon atoms in the alkylol radical, about /2 to 15% by weight of a saturated aliphatic monohydric alcohol of 2 to 3 carbon atom
  • a liquid detergent composition as set forth in claim 5 which contains about 0.1 to 2% by Weight of hydrophilic colloid material selected from the group consisting of alkali metal carboxymethylcellulose, methylcellulose, ethylccllulose, hydnoxyethylcellulose, polyvinylpyrrolidone and ⁇ polyvinyl alcohol.
  • a liquid detergent composition consisting essentially of the fiollowing ingredients proportioned within the stated ranges to form a poura-ble, substantially homogeneous product; about 5 to 20% of alkali metal alkyl benzene sulfonate having an alkyl group of about 12 to 15 carbon atoms, about 15 to 30% by weight of potassium polyphosphate selected from the group consisting of pynopbosphate and txipolyphosphate, about 4 to 12% by weight of an alkali metal sulfonated ⁇ hydrotropic salt selected from the gnoup consisting of toluene and Xylene sulforrates, about 2 to 15% by Weight of a higher fatty acid alkylolamide having about 10 to 14 carbon atoms in the fatty acyl radical and selected from the group consisting of diethanolamides, monoethanolamides and isopnopianolamides, about /2 to 15% by weight of ethanol, and the balance being substantially water, the total solid
  • a liquid detergent composition as set forth in claim 7 which contains about 0.1 to 2% by Weight of sodium carboxymethylcellulose.

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Description

United States Patent 3,101,324 LIQUID DETERGENT QGMPOSHKQN Harold Eugene Wixon, .lersey (Iity, NJL, assignor to Colgate-Palmolive Company, New York, N.Y., a cor poration of Delaware No Drawing. Filed Dec. 12, 1960, SenNo. 75,114
3 Claims. (Cl. 252-138) g The present invention relates to a pourable, concentrated liquid detergent composition which comprises an alkali metal higher alkyl aryl sulfonate detergent and a potassium polyphosphate in an aqueous alcoholic medium in homogeneous form, as hereinafter described and claimed.
In the detergent art, it has been common practice "to prepare detergent compositions in powdered form, as obtained by spray-drying a slurry of the detergent composition for example. In these powdered products, alkaline builder salts such as sodium tripolyphosphate and pyrophosphate have been incorporated in significant amounts to improve the detergency or washing power for the laundering of soiled textile materials. Other. salts such as sodium silicate, carbonate, carboxymethylcellulose and the like have been employed also in the preparation of powdered heavy-duty detergent compositions.
In accordance with the present invention, there are prepared heavy-duty liquid detergent compositions which consist essentially of about 5 to 25% by weight of alkali metal alkyl mononuclear aryl sulfonate detergent having an alkyl group of 8 to 15 carbon atoms and 10 to 50% by weight of a potassium polyphosphate selected from the group consisting of pyrophosphate rand tripolyphosphate, the total content of organic detergent and potassium polyphosphate being a maximum of about 55% by weight, and an aqueous solubilizing medium in admixture therewith suiiicient to [form a liquid pourable in homogeneous form, said aqueous medium containing a saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms in an amount from about /2 to by weight.
A feature of the present invention relates to a liquid consisting essentially of the following ingredients propontioned within the stated ranges to form a pourable, substantial-1y homogeneous aqueous liquid which consists essentially of about 5 to by weight of said higher alkyl aryl sulfonate detergent, about 10- to 35% by weight of said potassium polyphosphate, the total amount of detergent and polyphosphate being at least about 20% by weight, about 4 to 12% by weight of an alkali metal lower alkyl aryl sulfonated hydrotropic salt, and preferably about 2 to 15% ofya higher fatty acid alkylolamide, the total solids content being less than about 65% by weight, and
. of the composition.
airless Patented Aug. 20, 1963 "Ice tetrapotassium pyrophosphate, including any desired combination thereof.
The organic detergent and polyphosphate salts are em ployed in substantial amount such that the addition of p a small portion of the liquid product to a washing bath will result in effective detergency and washing power. The proportions of these two ingredients are variable and should be suitably selected and proportioned so that there is termed a pourable, substantially homogeneous product by the solubilizing medium. As indicated the amount of detergent is selected from the range of 5 to 25% and usually up to 20% by weight. The amount of polyphosphate is within the range of 10 to 50% and usually up to 35% by weight with the preferred amount being about 15 to The total amount of organic detergent and polyphospha-te should be a maximum of about 55 by weight. It is preferred that the total concentration be at least about 20% by weight. Amounts of detergent and polyphosphate totalling at least 20% by weight are incompatible in water resulting in a' product which genenally separates rapidly, usually within a few minutes. With proportions of detergent and phosphate within the stated ranges, pour-able and substantially homogeneous liquids may be formed using an aqueous alcoholic solubilizing medium as described herein. As a general guiding principle, it is advisable to vary the detergent and polyphosphate contents conversely, i.e., relatively low amounts of one are used when relatively high amounts of the other are desired in the product.
1 of the product to flow as aliquid from a container at a lower monohydric alcohol in tan amount sufiicient to I tergent having about 8 to 15 carbon atoms in the alkyl group'which it is preferred to use is alkyl benzene sulfonate, though other similar detergents having a mononuclear aryl nucleus, such as alkyl toluene and alkyl xylene sulfonates, may be used. The alkyl substituent may be branched such as nonyl, dodecyl land pentadecyl groups including mixtures thereof which are derived from polymers of lower mono-olefins. The alkyl group may be straightchained in structure such as the decyl, keryl anddodecy-l groups. Preferred examples of this class are the alkyl benzene sulfonates having an average of'about 12 to 15 carbons in the alkyl group. These sulfona-te detergents are used in the form of their water-soluble alkali metal salts such as the sodium or potassium salts.
The potassium polyphosphate salts have the property of inhibiting precipitation of calcium and magnesium material normal room temperatures (e.g., about 20 C. to 25 C.). The liquid product may be of variable viscosity. It may be highly fluid and free-flowing, or fairly viscous when at rest but pourable freely from the container upon I light shaking. The liquid may be packaged in any suitable container, however, such as metal, glass'or plastic in the form of bottles, cans, drums, packets yor bags. The term homogeneous as used herein means that the product has a satisfactory degree of stability during storage life against separation orformation of a plurality of distinct. layers which either cannot be re-dispersed by light shaking or which separate rapidly after shaking. Suchcornpositions include liquids which are clear, trans- Y lucent or opaque depending upon the type and proportions of the various solids present therein. Any solid material present in the composition in excess of its solubility in the particular systemis maintained in a noncaking suspension. It is'characteristic that in such cases, upon light shaking, the product is readily converted to a substantially homogeneous liquid which is stable for a sufiicient period of time, e.g., at least about 1 hour, so that each small portion added to a laundering bath or the like will have practically the same composition. The product exhibits a washing power which is comparable to the same quantity of commercial heavy-duty detergents in powdered form.
The aqueous alcoholic solubilizing medium should contain a saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms such as ethanol, propanol or isopropanol so as .to provide for desired physical properties of the liquid composition. Depending upon the proportions of the other ingredients in a particular composition, the alcohol may serve a multiplicity of functions. Using selected proportions of detergent and phosphate within the ranges indicated, the alcohol in sufficient amount renders the detergent and phosphate more compatible in water. The appearance of the liquid such as a clear or opaque product is controllable by the proportions of detergent and phosphate employed in the aqueous medium using a suflicient amount of the alcohol. For example, in products containing about 10 to 20% phosphate and about to 25% detergent where minimum amounts of both are employed or where the amounts vary conversely, the presence of a suitable amount of alcohol, e.g., usually about to can provide for a clear liquid at room temperature. In other instances, such as where medium to high amounts of both detergent and phosphate are employed, the resulting products tend to be translucent to opaque with the alcohol preventing unduly rapid separation or formation of non-redispersible phases.
In addition, the alcohol permits desired modification of the viscosity, such as to make the product less viscous where high solids are employed and improve pourability thereby. It can provide for improved low temperature aging of the product such as the prevention of a precipitate at moderately low temperatures, e.g., about 40 E, which does not redisperse upon recovery to room temperature. The alcohol may adjust also the phase relation ship so as to lower the cloud point and insure a clear liquid at a lower temperature if desired. In general, it tends also to minimize foaming and aeration of the product during manufacture and upon shaking of the container so as to permit pouring of uniform portions thereofl These improvements may be edected with relatively small amounts of alcohol, e.g., up to about 10% and usually up to 5% by weight, Where the aqueous medium contains supplemental solubilizing agents such as the hydrotrope described herein to promote the stability of the system.
The amount of alcohol which should be employed varies with the particular formulation so as to achieve at least one of the above improvements in physical properties. In general, the alcohol is a solubilizing agent for said organic detergent in water but is relatively incompatible with inorganic salts. There is a critical maximum proportion of alcohol since an excessive amount will result in separation of the product into two or more layers which either separate rapidly or will not redisperse readily. The amount of alcohol used should not adversely affect the homogeneity of the liquid therefore, such as by separation of inorganic salt solution or by excessively thinning a high solids product where relatively high viscosity is desired as an aid in preventing rapid separation.
It is advantageous that the aqueous medium contain a water-soluble hydrotropic substance as a solubilizing agent in promoting the compatibility of the ingredients so as to form a homogeneous liquid product. The watersoluble organic sulfonated hydrotropes, particularly the alkali metal sulfonated salts having a lower alkyl group up to about 6 carbons, are efiective in these products.
It is preferred to employ an aryl sulfonate such as the sodium and potassium toluene and xylene sulfonate salts. Sulfonates made from Xylene include orthoxylene sulfonate, metaxylene sulfonate, paraxylene sulfonate and ethylbenzene sulfonate. Commercial Xylene sulfonates usually contain metaxylene sulfonate as the main ingredient. Analyses of typical commercial products show about 40-50% metaxylene sulfonate, 10-35% orthoxylene sulfonate and 15-30% paraxylene sulfonate with 0-20% ethylbenzene sulfonate. Any suitable isomeric mixture may be employed, however. Suitable lower alkyl sulfate salts may be employed also, such as the alkali metal n-amyl and n-hexyl sulfates. The hydrotrope may be employed in variable amounts depending ing suitable proportions of said solubilizing agents.
upon the proportions of other ingredients but ordinarily it will be present in a suitable amount from about 4% to about 12%, preferably about 4 to 10%, by weight of the composition.
The presence of a combination of the hydrotropic sulfonate salt and the lower aliphatic alcohol permits increased flexibility for variation in formulation so as to obtain a range of physical properties which is not possible by the use of these ingredients individually. The hydrotropic salt may be employed in said range to form a clear or opaque liquid at room temperature. In certain formulations containing medium amounts of detergent and relatively low phosphate, it is possible to obtain a clear liquid at room temperature in the presence of suflicient hydrotropic salt in an aqueous medium. The presence of suitable amounts of alcohol in combination is advantageous for such physical characteristics as lowering of the cloud point, improvement in the low temperature aging of the product, etc, in addition to providing a too-solubilizing action with the hydrotrope permitting use of lesser amounts of the latter ingredient depending upon the particular formulation. In systems containing medium to high amounts of detergent and phosphate within the ranges described, there is produced a lotion-like or opaque liquid using the hydrotropic salt and alcohol in combination. There may be obtained homogeneous liquids with this combination using amounts of the alcohol and hydrotropic salt which individually do not provide a product of sufiicient homogeneity or pourability. For example, Where the solids concentration is at a high level, the amount of hydrotropic salt which may be added is limited since it will increase the solids content. Where the solids content is excessive, a non-pourable product will be obtained. The presence of the alcohol in combination will ermit the formulation of the desired liquid product.
It is preferred that the liquid contain a higher fatty acid alkylolamide material in a sufiicient amount to act as a suds builder during washing operations. In certain formulations, the alkylolamide provides an additional solubilizing client. It should not be employed in an amount sufiicient to destroy the desired physical properties since it is considered as part of the total solids content. In general, the alkylolamides may be employed in amounts of about 2 to 15% by weight in the product, and preferably from about 3 to 8%. The acyl radical of the alkylolarnide is selected fiom the class of fatty acids having 8 to 18 carbons and each alkylol group has up to 3 carbon atoms usually. It is preferred to use the diethanolamides, isopropanolamides and monoethanolamides of fatty acids having about 10 to 14 carbons in the acyl radical. Examples are the lauric, capric, myristic and coconut diethanol arnides, monoethanolalmides and isopropanolamides, and mixtures thereof. There may be employed also the alkylolamides which are substituted by additional alkylol groups, suitable examples being the above monoethanolamides, diethanolamides and isopropanolarnides condensed with one or two moles of ethylene oxide.
It has been found that pourable, homogeneous liquids may be prepared having a solids content of up to about 65% by weight in the aqueous alcoholic medium contain- It is preferred to have a maximum of about 60% solids for opaque liquids and up to about 50% solids for clear solutions. The balance of the liquid content is primarily water since the liquid alcohol is used in small amounts. The amount of water will be suitably proportioned to provide suifioient solubilizing efieots for the phosphates and similar inorganic salts so as to form a substantially homogeneous product. The amount of Water is general- 1y at least about 30% by weight and preferably from 40 to 60% of the liquid.
It has been found that these formulations are compatible with a suitable soil-suspendineg material which repre sents a further embodiment of the present invention. The addition of a soil-suspending material converts the syswhich may be used in compositions of the present invention are the lower alkyl and hydroxy alkyl ethers such as methylcellulose, ethylcellulose and hydroxyethylcellulose; I
and the various cellulose sulfate materials.
Other types of soil-suspending agents may be employed such as the water-soluble vinyl polymers. Examples are water-soluble polyvinyl alcohol which may contain minor amounts of polyvinyl acetate as commercially made. Water-soluble polyvinyl polymeric amides such as polyvinylpyrrolidone of suitable molecular weight may be employed also. i
In general, the amount 'of'the soil-suspending about 2% by weight in the liquid product. It has been found that amounts within this range can be used in thepreparation of substantially homogeneous products which exhibit a high level of soil suspension during washing. Various materials or mixtures may be employed which assist in maintaining the soil-suspending material in suspension or dispersion in the liquid product. Suitable mixtures of cellulosic compounds, or a mixture of acellulosic compound with a vinyl polymer, or a mixture of a cellulosic compound with castor wax may be employed.
The liquid detergent product is prepared in any suitable manner. The hydrotropic salts, the polyphosphate and the organic detergent are added in the form of powders, aqueous solutions or slurries-to the aqueous medium as desired. The alkylolarnide is preferably added in molten or liquid form with agitation to form a homo geneous mixture.- The alcohol may be added at any stage during the mixing operations as desired. The tempera ture of admixture is not critical and room temperatures or reasonable elevated temperatures may be employed.
The following examples are illustrative of the nature of the invention and it will be understood that the invenagent, (including mixtures thereof) is usually from about 0.1 to
'following formulation. H
of 45% of ethyl alcohol and 2.740% water due to some loss of solvent during processing. 7
This product remains substantially homogeneous for many days and produces a high degree of washing power inboth soft and hard water for laundering of soiled textile materials. The washing power corresponds to that of a commercially acceptable heavy-duty detergent composition in powder form.
' Example 11 The same formulation is used except that the coconut diethanolamide is reduced fnom 10% to 5% by weight,
with a corresponding increase in the water content. This product is satisfactory also, and exhibits no apparent sep aration after about 8 hours. 2
Example III A similar composition is formed by using theformulation of Example I but substituting an equivalent quantity of tetrapotassium pyrophosphate for the tripolyphosphate.
Example IV A satisfactory composition is prepared according to the Percent Ingredient:
' Sodium dodecyl benzene sulfonate 12 Potassium tripolyphosphate .Q. 36 Potassium toluene sulfionate 6 Coconut diethanola'mide 9 Sodium carboxymethylcellulose 0.8 Ethanol -a 6 Water (q.s. to 100% t I Examples V-X [Percent] Ingredients v VI VII VIII IX- )X Sodium trideeyl benzene sulfODiLlZG 5 5 25 5 20 25 10 20 10 35 15 Ethanol 14. 11 12 14 15 10 Water (q.s. to 100%).
tion is not limited thereto. All parts ace in approximate the balance being minor amounts of perfume, coloring material, and optical bleach. v
This product is prepared by the preferred method whereby the potassium tripolyphosphate is added slowly to the water,fo1lowed by introduction of the toluene sulfonate, the dodecyl benzene sulfonate, the coconut diethanolamide and the bleach and coloring material, each material being mixed thoroughly in the aqueous mixture before the next material is introduced. The perfume and ethanol are added followed by the slow addition of the carboxymethylcellulose with continued mixing until there is obtained a relatively thick gelatinous liquid. The mixture is transferred to a water-cooled colloid mill where his homogenized for about 8 minutes. The pH is 9.3, specific gravity 1.3, and viscosity [of about 1500 centipoises. The finished product has a final solvent analysis In the above formulations, the sodium tridecyl benzene sulfonate is of about purity,"the balancebeing sodium sulfate formed in its manufacture. The alkyl group of the detergent is derived from a mixture of pnopylene polymers corresponding on the average to a tridecyl group.
All of. the above products are pourable homogeneous liquids in use. The product of Examples V-VII are clear solutions at 77 F. The use of lesser amounts of alcohol results in a higher cloud point. The products of Examples VIII-X are opaque liquidswhich upon aging separate into two re-dispersible liquid phases and upon light shaking are converted to homogeneous products having satisfactory stabi1i-ty.-- As indicative of the adverse effect of excessive alcohol in a particular formulation, Example I modified to an ethanol content of 15% with a corresponding reduction in the Water content results in a product which separates rapidly.
Water (q.s. to Y The above formulation ispourable as a homogeneous liquid upon light shaking due to some separation upon aging. The absence ofalcohol and an increase of hydrotrope to 8% results in a non-pourable product. Theuse of insufficient alcohol, e.g., 7%, in the above formula results in a liquid product which separates rapidly into two layers.
Example XXII Ingredients Percent Sodium tridecyl benzene sulfonate 19 Potassium pyrophosphate 15 Sodium Xylene sulfonate 7 Coconut diethanolamide 13 Ethanol 4 Water (q.s. to 100%).
I The above formulation is a pourable, clear solution at room temperature whereas the omission of the alcohol results in a turbid liquid product. I
1 The alkylolamide is a 1:1 mixture of isopropanolamides and diethanolamides having about a 70: 30 ratio of lauric to myristie radicals.
The above formulations are clear solutions with low cloud points whereas in the absence of the alcohol the resulting products have two phases with cloud points above room temperature.
Examples X VI-X VII [Percent] Ingredients Sodium dodecyl benzene sull'onate Tetrapotassium pyrophosphate Sodium xylene sullonate Coconut diethanolamide. Coconut isopropauolamide. Ethanol Sodium carboxymethyleellulose- Castor Wax Water (q. .to 100%).
The above formulations are pourable homogeneous liquids and exhibit improved physical properties after aging at 40 F. compared to products free of the alcohol.
Various other ingredients may be added or substituted if desired. In a liquid containing a plurality of components, the individual solubility characteristics of added materials may influence the physical properties of the liquid. It is understood therefore that such ingredients will be suitably selected and the proportions of the various components controlled as'described herein so as to form a liquid product having the desired physical qualities. Thus, there may be included suitable amounts of various anionic sulfate or sulfonate or non-ionic organic detergents. Other adjuvant materials include compatible perfumes, coloring materials, corrosion inhibitors, anti-tarnishing agents, germicides, bleaching agents, optical bleaches or fluorescent dyes, and the like. If desired, there may be included other phosphate materials or similar builder salts such as silicates in the product provided that they do not substantially adversely altect the product.
This application is a continuation-in-part of my prior application Serial No. 532,735, filed September 6, 1955, and now abandoned.
Although the present invention has been described and illustrated with reference to specific examples, it is understood that modifications and variations of composition are contemplated within the scope of the appended claims.
What is desired to be claimed is:
1. An improved liquid detergent composition consisting essentially of about to 25% by weight of alkali metal alkyl mononuclear aryl sulronate detergent having an alkyl group of 8 to 15 carbon atoms and 10 to 50% by Weight of a potassium polyphosphate selected from the group consisting of pyrophosphate and tripolyphospha'te, the total content of organic detergent and potassium polyphosphate being a maximum of about 55% by weight, and having a saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms in an amount from about /2 to 15% by weight of the composition, the balance being substantially water in admixture therewith sufficient to form a liquid composition pourable in homogeneous form.
2. An improved liquid detergent composition consisting essentially of about 5 to 25% by weight of alkali metal alkyl benzene sulfonate detergent having an alkyl group of 8 to 15 carbon atoms and 10 to 50% by weight of a potassium polyphosphate selected from the group consisting of pyrophosphate and tripolyphosphate, the total content of organic detergent and potassium polyphosphate being Within the range of about 20 to 55% by weight, and having ethanol in an amount from about /2 to 15% by Weight of the composition, the balance being substantially water in admixture therewith sufficient to form a pourable, substantially homogeneous liquid composition.
3. A liquid detergent composition consisting essentially of about 5 to 20% by weight of alkali metal :alkyl benzene sulfonate detergent having an :alkyl group of 8 to l5 carbon atoms, about 10 to 35 by Weight of potassium polyphosphate selected from the group consisting 10f pyrophosiphateand tripolyphosphate, the total content ol rganic detergent and potassium polyphosphate being within the range of 20 to 55 by weight, about 4 to 12% y weight of an alkali metal organic sulfionated hydrotropic salt selected from the group consisting of alkali metal allkyl substituted benzene sulfonates having up to 2 carbon atoms in said salkyl substituent and alkyl sulfates having 5-6 canbon atoms, said aqueous alcoholic medium having about /2 to 15% by weight of a saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms, the balance being substantially Water in admixture therewith sufficient to form a pourable, substantially homogeneous liquid, the total solids content being less than about 65% by weight of the composition.
4. A liquid detergent composition as set'forth in claim 3 which contains about 2 to 15% of a'higher fatty acid alkylolamide having about 2 to 3 carbons in each alkylol group and about 8 to 18 carbons in the fatty acyl group.
5. A liquid detergent composition consisting essentially of the following ingredients proportioned within the stated ranges to (form a pourable, substantially homogeneous product: about 5 to 20% by weight of alkali metal alkyl benzene sulfonate having an alkyl group of 8 to 15 carbon atoms, about 10 to 35% by weight of potassium polyphosphate selected from the group consisting of pyrophosphate and tripolyphosphate, the total content of organic detergent and potassium polyphosphate being within the range of 20 to 55% by weight, about 4 to 12% by weight of an alkali metal sulfonated hydrotropic salt selected from the group consisting of toluene and xylene sulfon-ates, about 2 to 15% by weight of a higher fatty acid alkylolamide having about 10 to 14 carbon atoms in the fatty acyl radical and 2 to 3 carbon atoms in the alkylol radical, about /2 to 15% by weight of a saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms, and the balance being substantially water, the total solids content being less than 65% by weight of the composition.
6. A liquid detergent composition as set forth in claim 5 which contains about 0.1 to 2% by Weight of hydrophilic colloid material selected from the group consisting of alkali metal carboxymethylcellulose, methylcellulose, ethylccllulose, hydnoxyethylcellulose, polyvinylpyrrolidone and \polyvinyl alcohol.
7. A liquid detergent composition consisting essentially of the fiollowing ingredients proportioned within the stated ranges to form a poura-ble, substantially homogeneous product; about 5 to 20% of alkali metal alkyl benzene sulfonate having an alkyl group of about 12 to 15 carbon atoms, about 15 to 30% by weight of potassium polyphosphate selected from the group consisting of pynopbosphate and txipolyphosphate, about 4 to 12% by weight of an alkali metal sulfonated \hydrotropic salt selected from the gnoup consisting of toluene and Xylene sulforrates, about 2 to 15% by Weight of a higher fatty acid alkylolamide having about 10 to 14 carbon atoms in the fatty acyl radical and selected from the group consisting of diethanolamides, monoethanolamides and isopnopianolamides, about /2 to 15% by weight of ethanol, and the balance being substantially water, the total solids content being less than 60% by weight of the composition.
'8. A liquid detergent composition as set forth in claim 7 which contains about 0.1 to 2% by Weight of sodium carboxymethylcellulose.
10 References Cited in the file of this patent UNITED STATES PATENTS 2,477,383 Lewis July 26, 1949 2,581,677 M alClhlis Jan. 8, 1952 2,607,740 Vitale Aug. 19, 1952 2,615,847 Thompson Oct. 28, 1952 2,746,931 Vitaie May 22, 1956 2,947,702 Ooskie Aug. 2, :1'9-60 FOREIGN PATENTS 650,222 Great Britain Feb. 21, 1951 OTHER REFERENCES Trexler: Soap and Sanitary Chemicals, July 1950, pp. 39-41, 82.

Claims (1)

1. AN IMPROVED LIQUID DETERGENT COMPOSITION CONSISTALKYL MONONUCLEAR ARYL SULFONATE DETERGENT HAVING AN ALKYL GROUP OF 8 TO 15 CARBON ATOMS AND 10 TO 50% BY WEIGHT OF A POTASSIUM POLYPHOSPHATE SELECTED FROM THE GROUP CONSISTING OF PYROPHOSPHATE AND TRIPOLYPHOSPHATE, THE TOTAL CONTENT OF ORGANIC DETERGENT AND POTASSIUM POLYPHOSPHATE BEING A MAXIMUM OF ABOUT 55% BY WEIGHT, AND HAVING A SATURATED ALIPHATIC MONOHYDRIC ALCOHOL OF 2 TO 3 CARBON ATOMS IN AN AMOUNT FROM ABOUT 1/2 TO 15% BY WEIGHT OF THE COMPOSITION, THE BALANCE BEING SUBSTANTIALLY WATER IN ADMIXTURE THEREWITH SUFFICIENT TO FORM A LIQUID COMPOSITION POURABLE IN HOMOGENEOUS FORM. ING ESSENTIALLY OF ABOUT 5 TO 25% BY WEIGHT OF ALKALI METAL
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US3240713A (en) * 1962-08-02 1966-03-15 Benjamin M Hulsh Wood flour rug cleaning composition
US3254028A (en) * 1961-02-06 1966-05-31 Colgate Palmolive Co Liquid detergent composition
US3318816A (en) * 1964-11-12 1967-05-09 Colgate Palmolive Co Detergent composition in solid form containing a synergistic mixture of cmc and pvp
US3320173A (en) * 1964-04-17 1967-05-16 Continental Oil Co Heavy duty liquid detergent
US3346503A (en) * 1963-10-11 1967-10-10 Monsanto Co Heavy-duty liquid detergent emulsion compositions and processes for preparing the same
US3354091A (en) * 1959-12-22 1967-11-21 Colgage Palmolive Company Homogeneous heavy-duty liquid detergent
US3377290A (en) * 1963-07-13 1968-04-09 Henkel & Compagnie G M B H Liquid or paste detergent preparations having sulfofatty acid salts as viscosity reducing agents
US3424689A (en) * 1964-08-28 1969-01-28 Kao Corp Heavy-duty liquid detergent composition
US3522186A (en) * 1966-12-12 1970-07-28 Procter & Gamble Abrasive liquid detergent compositions
US3527707A (en) * 1963-06-05 1970-09-08 Exxon Research Engineering Co Liquid detergent composition
US3755206A (en) * 1970-03-09 1973-08-28 Colgate Palmolive Co Detergent compositions
US4152306A (en) * 1976-02-26 1979-05-01 LDMJ Limited Windshield cleaning solvent

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US2477383A (en) * 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
GB650222A (en) * 1948-04-19 1951-02-21 Frederick Joseph Pollok Improvements in or relating to aqueous solutions containing soapless detergents
US2581677A (en) * 1952-01-08 Phosphate detergent composition in
US2607740A (en) * 1950-05-03 1952-08-19 Colgate Palmolive Peet Co Liquid anionic-dialkylolamide detergent composition
US2615847A (en) * 1950-01-27 1952-10-28 Atlantic Refining Co Alkaryl sulfonate detergents
US2746931A (en) * 1949-10-29 1956-05-22 Colgate Palmolive Co Synthetic detergent compositions
US2947702A (en) * 1957-01-23 1960-08-02 Procter & Gamble Liquid detergent compositions

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US2581677A (en) * 1952-01-08 Phosphate detergent composition in
US2477383A (en) * 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
GB650222A (en) * 1948-04-19 1951-02-21 Frederick Joseph Pollok Improvements in or relating to aqueous solutions containing soapless detergents
US2746931A (en) * 1949-10-29 1956-05-22 Colgate Palmolive Co Synthetic detergent compositions
US2615847A (en) * 1950-01-27 1952-10-28 Atlantic Refining Co Alkaryl sulfonate detergents
US2607740A (en) * 1950-05-03 1952-08-19 Colgate Palmolive Peet Co Liquid anionic-dialkylolamide detergent composition
US2947702A (en) * 1957-01-23 1960-08-02 Procter & Gamble Liquid detergent compositions

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* Cited by examiner, † Cited by third party
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US3354091A (en) * 1959-12-22 1967-11-21 Colgage Palmolive Company Homogeneous heavy-duty liquid detergent
US3254028A (en) * 1961-02-06 1966-05-31 Colgate Palmolive Co Liquid detergent composition
US3240713A (en) * 1962-08-02 1966-03-15 Benjamin M Hulsh Wood flour rug cleaning composition
US3527707A (en) * 1963-06-05 1970-09-08 Exxon Research Engineering Co Liquid detergent composition
US3377290A (en) * 1963-07-13 1968-04-09 Henkel & Compagnie G M B H Liquid or paste detergent preparations having sulfofatty acid salts as viscosity reducing agents
US3346503A (en) * 1963-10-11 1967-10-10 Monsanto Co Heavy-duty liquid detergent emulsion compositions and processes for preparing the same
US3320173A (en) * 1964-04-17 1967-05-16 Continental Oil Co Heavy duty liquid detergent
US3424689A (en) * 1964-08-28 1969-01-28 Kao Corp Heavy-duty liquid detergent composition
US3318816A (en) * 1964-11-12 1967-05-09 Colgate Palmolive Co Detergent composition in solid form containing a synergistic mixture of cmc and pvp
US3522186A (en) * 1966-12-12 1970-07-28 Procter & Gamble Abrasive liquid detergent compositions
US3755206A (en) * 1970-03-09 1973-08-28 Colgate Palmolive Co Detergent compositions
US4152306A (en) * 1976-02-26 1979-05-01 LDMJ Limited Windshield cleaning solvent

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