US3211660A - Liquid detergent composition - Google Patents

Liquid detergent composition Download PDF

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Publication number
US3211660A
US3211660A US86855A US8685561A US3211660A US 3211660 A US3211660 A US 3211660A US 86855 A US86855 A US 86855A US 8685561 A US8685561 A US 8685561A US 3211660 A US3211660 A US 3211660A
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Prior art keywords
weight
alkyl
polyethoxamer
sulfate
sodium
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US86855A
Inventor
Marion George Francis
Treitler Theodore Leo
Munger Peter Arthur
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Colgate Palmolive Co
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Colgate Palmolive Co
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Priority to IT650470D priority Critical patent/IT650470A/it
Priority to BE617969D priority patent/BE617969A/xx
Priority to CA689791A priority patent/CA689791A/en
Priority to NL276377D priority patent/NL276377A/xx
Priority to BE613165D priority patent/BE613165A/xx
Priority to CA704966A priority patent/CA704966A/en
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to US86855A priority patent/US3211660A/en
Priority to US99696A priority patent/US3231504A/en
Priority to DEC26022A priority patent/DE1287245B/en
Priority to CH64762A priority patent/CH414908A/en
Priority to SE838/62A priority patent/SE302498B/xx
Priority to GB3513/62A priority patent/GB978575A/en
Priority to FR887238A priority patent/FR1314689A/en
Priority to GB20227/62A priority patent/GB948240A/en
Priority to OA50933A priority patent/OA00847A/en
Application granted granted Critical
Publication of US3211660A publication Critical patent/US3211660A/en
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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
    • C11D3/16Organic compounds
    • C11D3/34Organic compounds containing sulfur
    • C11D3/3418Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • 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
    • C11D1/37Mixtures of compounds all of which are anionic
    • 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
    • C11D3/02Inorganic 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/34Organic compounds containing sulfur
    • C11D3/3409Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
    • 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
    • C11D1/02Anionic 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
    • 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 heavy-duty liquid detergent composition
  • a heavy-duty liquid detergent composition comprising in combination a higher alkyl aryl sulfonate detergent, a higher alkyl phenoxy polyethoxamer sulfate detergent, a potassium polyphosphate salt and a sulfonated solubilizing or hydrotropic agent in an aqueous medium, as hereinafter described and claimed.
  • a heavyduty liquid detergent composition of superior qualities can be formulated which comprises essentially about to 18% by weight of a mixture of an alkali metal higher alkyl mononuclear aryl sulfonate salt, said higher alkyl group having about 8 to carbon atoms, an alkali metal higher alkyl phenoxy polyethoxamer sulfate salt material, said higher alkyl group having about 8 to 13 carbon atoms and said polyethoxamer sulfate material having an average of about 4 to about 10 ethylene oxide groups per mole of alkyl phenol, said polyethoxamer sulfate salt material having a purity of at least about 75% by weight based on the total organic solids in said material, the ratio of said alkyl aryl sulfonate to polyethoxamer sulfate being from about 6.5:1 to about 1:4 by weight; a total of about 10 to by Weight of water-soluble inorgan
  • the liquid containing the above ingredients in solution exhibits many desirable characteristics with regard to both physical properties and performance in use.
  • the composition is homogeneous, pourable, and free-flowing from the container as manufactured and after aging. It exhibits a high degree of stability upon storage at normal room temperature of the order of about 70 F. over a period of many months without any appreciable precipitation or formation of immiscible layers. It can be subjected to elevated temperatures of the order of 120 F. or cooled to 40 F. and the liquid is in a clear, homogeneous form when returned to room temperature. As a result, the consumer can utilize it conveniently by the addition of small portions to a dishpan or a laundering bath and the detergent and builder salts will be present in constant composition in each portion.
  • the liquid may be employed in any suitable container or packaging material such as metal, plastic, or glass in the form of bottles, bags, cans or drums.
  • the product exhibits a particularly high level of washing power and foaming action during dishwashing, laundering and in other cleansing operations.
  • a particular advantage of this composition is its high detergent and emulsification power for the cleaning of soiled surfaces containing fats and greases including soiled aluminum and other metals, ceramic materials, Wearing apparel and the like.
  • the product exhibits a good volume of foam initially and during the cleansing operation.
  • the aryl nucleus has at least one alkyl substituent having an average number of about 8 to 15 carbons and preferably between 12 and 1S carbons.
  • the alkyl group may be branched such as nonyl, dodecyl and pentadecyl groups including mixtures thereof which are derived from polymers of mono-olefins, e.g., polypropylene.
  • the alkyl group may be straightchained such as the decyl, keryl and dodecyl groups.
  • the suitable sulfated higher alkyl phenoxy polyethoxamer material has a characteristic chemical structure also.
  • the phenyl group may have additional substituents, e.g., alkyl groups, thereon provided that they do not adversely affect the desired properties. It has a pre-determined number of ethylene oxide groups in order to obtain the desired physical properties and performance characteristics.
  • the polyethoxamer sulfate material is commonly prepared by reaction of the appropriate alkyl phenol with sufficient ethylene oxide followed by sulfation of the reaction product in known manner, such as by the use of oleum or chlorsulfonic acid. If desired, the poly ethoxamer may be sulfated after the sulfonation of the alkyl aryl hydrocarbon using the same sulfonating agent to produce the mixed detergents.
  • the purity of the desired reaction product is a consideration for the manufacture of a product having optimum properties.
  • organic impurities comprise unreacted nonionic (unsulfated) higher alkyl phenoxy ethylene oxide materials, ring sulfonated materials such as alkyl phenoxy ethoxamers wherein the phenyl ring is sulfonated, and possibly very small amounts of degradation products such as higher alkyl phenols and partially de-ethoxylated products.
  • organic impurities should be maintained at a minimum since an excessive amount has been found to adversely affect the physical properties and performance of the product. More particularly, an excessive amount, particularly of the unreacted non-ironic polyethoxamer, has a tendency to raise the cloud point, inhibit foam and decrease the efficiency of the product as an emulsifier of greasy soil in washing operations.
  • the product may contain a minor amount of such organic unreacted or byproduct materials provided that the amount is insufficient to substantially adversely affect the properties of the product.
  • the alkyl phenoxy polyethoxamer sulfate material should have a purity of at least about 75% by weight of the total organic solids in said material with up to about 25% of said other organic solids.
  • the organic solids of the commercial polyethoxamer sulfate should contain not substantially in excess of about unsulfated organic ethoxamer material and not in excess of about ring sulfonated material .by weight of the organic solids in the polyethoxamer sulfate material.
  • a typical product may contain about 10% of each on said organic solids basis.
  • the said impurities are maintained at said low levels by any suitable technique. The careful control of the conditions in the sulfation procedure including the time of reaction and the choice of sulfonating agent will produce materials of desired purity.
  • the reaction product may be purified to remove said organic impurities also, such as by the use of an ion-exchange technique.
  • alkyl aryl sulfonate and sulfated alkyl phenoxy polyethoxamer materials are employed in the form of their alkali metal salts such as the sodium and potassium salts. It is understood that there may be small amounts of inorganic salts such as sodium or potassium sulfate in the sulfonated and sulfated detergents resulting from the method of manufacture. In general, these inorganic sulfate salts should be maintained at as low a iconcentration as practicable.
  • the potassium polyphosphate salts have the property of inhibiting precipitation of calcium and magnesium material in aqueous solution and of contributing to the heavy-duty performance of the liquid detergent product in washing operations. While they may be considered as derived from orthophosphoric acid or the like by the removal of molecularly bound water, any suitable means of manufacture may be employed if desired.
  • Such complex or molecularly dehydrated polyphosphate salts are used usually in the form of the normal or completely neutralized salts, e.g., tetrapotassium pyrophosphate and pentapotassium tripolyphosphate.
  • the phosphate may be a partially neutralized salts, e.g., potassium acid tripolyphosphate. Any suitable mixture of polyphosphate materials may be employed. It is preferred to use at least in part tetrapotassium pyrophosphate.
  • the organic detergents and polyphosphate are employed in substantial amount in the composition such that the addition of a small portion of the liquid product to a washing bath will result in effective detergency and washing power.
  • the amount and types of said mixture of organic detergents influence the maximum amount of phosphate that can be incorporated in the composition and yet obtain a composition wit-h the desired properties. It has been found that suitable amounts within the range of about 10 to 1 8%, by weight, preferably 14 to 16%, of
  • the ratio of the alkyl benzene sulfonate to the sulfated polyethoxamer is variable and ratios selected from the range of 6.5 :1 to about 1:4 by weight have been found to be most practicable. It is preferred that the ratio of alkyl aryl sulfonate to sulfated polyethoxamer be greater than 1:1, and particularly from about 1.5:1 to about 3:1 for optimum performance characteristic-s, particularly in foaming power.
  • the polyphosphate favorably influences the physical properties of the system when employed within the range of about 10 to 20%, and par-ticularly about 15 by weight.
  • 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.
  • Other water-soluble inorganic builder salts may be substituted for the potassium-polyphosphate in minor amount such as a few percent, e.g., up to 5%, of sodium polyphosphate or sodium or potassium silicate provided that the builder content is primarily the potassium polyphosphate, e.g., at least about 10%, and the total amount is compatible in the liquid.
  • alkyl phenoxy polyethoxamer sulfates should be employed in these products.
  • the average number of ethylene oxide groups in these materials influences the physical properties of the liquid and the amount of inorganic salt, particularly the amount of potassium polyphosphate, which can be dissolved in the solution.
  • a series of liquid detergents were prepared which contained about 7% by weight of sodium tridecyl benzene sulfonate, 7% by weight of 'sodium higher alkyl phenol-ethylene oxide sulfates, 8%
  • each formulation contained a different polyethoxamer sulfate having the alkyl group and average ethylene oxide content as specified in the table below.
  • the compositions contained 20% potassium pyrophosphate except where lesser quantities are specified in the table below, they are the maximum amounts which could be dissolved therein.
  • the cloud and clear points for each composition are set forth in the following table.
  • compositions having 14 to 30 moles of ethylene oxide possess cloud and clear points which are substantially above room temperature. It is apparent that there is a point within the range from about 9.3 up to 14 moles of ethylene oxide, referred to herein as about 10 moles, which results in significant change in properties of the liquid compositions.
  • the physical properties are influenced also by the amount of polyphosphate in the liquid.
  • a series of aqueous compositions were prepared containing 0 to 15 by weight of potassium pyrophosphate, the balance being about 9% by weight of potassium tridecyl benzene sulfonate, 8.5% sodium xylene sulfonate, 6% sodium nonyl phenoxy polyet-hoxamer sulfate with average of about 6 moles ethylene oxide and 6% of a 1:1 mixture by weight of lauric-myristic isopropanolamide and diethanolamide, the lauric and myristic radicals being in a ratio of about 70:30.
  • the following table shows the cloud and clear points-of the liquids containing the specified amount of potassium pyrophosphate:
  • the polyphosphate within certain proportions favorably affects the physical properties of the liquid. There is a minimum or lowest cloud and clear point which is obtained in the presence of appreciable amounts of the polyphosphate which is usually at least about polyphosphate.
  • the inclusion of the water-soluble sulfonated hydrotropic substance is effective in promoting the compatibility of the ingredients so as to form a homogeneous liquid product.
  • Suitable materials are the alkali metal organic sulfonated (including sulfate d) salts having a lower alkyl group up to about 6 carbons. It is preferred to employ an alkyl aryl sulfonate having up to 3 carbons in a lower alkyl group such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene sulfonates.
  • Sulfonates made from xylene include orthoxylene sulfonates, 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, 1035% orthoxylene sulfonate and -30% paraxylene sulfonate with 0-20% ethylbenzene sulfonate. Any suitable isomeric mixture may be employed, however.
  • Suitable lower alkyl sulfate salts having about 5 to 6 carbons in the alkyl group may be employed also such as the alkali metal n-amyl and n-hexyl sulfate.
  • the hydrotropic materials are employed generally in amounts from about 6 to 12% by weight of the composition. The use of an amount in excess of the amount required to effect a single liquid phase is not helpful since it tends to add additional salt to an already concentrated system.
  • the liquid contain a higher fatty acid .alkylolamide material in a suflicient amount to act as a suds builder. It has been found also that the combination of the above ingredients with a suitable amount of the alkylolamide results in a product which exhibits particularly high foaming power in use, particularly in the stability of the foam generated during dishwashing or laundering operations.
  • the alkylolamide may provide an additional solubilizing effect. It should not be employed in an amount sufficient to destroy the desired physical properties since it is considered as part of the total solids content.
  • the acyl radical of the alkylolamide is selected from 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, isopropanolamide and monoethanolamides of fatty acids having about 10 to 14 carbons in the acyl radical. Examples are the lauric, capric, myristic and coconut diethanolamides, monoethanolamides 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 isopropanolamides condensed with one or two moles of ethylene oxide. In general, the alkylolamides should be employed in amounts of about 2 to 10% by weight in the product, and preferably from about 4 to 8%.
  • the solids content of the concentrated liquid product is variable and is usually from about 26 to 50% by Weight 6 of the concentrated liquid, and the balance being primarily water.
  • the ingredients are proportioned in the aqueous solubilizing medium so as to form a substantially homo geneous product of desired physical properties.
  • a further embodiment of the present invention relates to the inclusion of a minor amout of a water-soluble saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms as part of the aqueous solubilizing medium.
  • a water-soluble saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms
  • examples are ethanol, propanol and isopropanol.
  • the alcohol may serve a multiplicity of functions. It can provide for improved physical properties such as a lower cloud point, improve low temperature aging, modify the viscosity, and the like.
  • a small amount of alcohol in combination with the hydrotropic salt will produce a clear liquid which will be otherwise cloudy at room temperature.
  • the suitable amount of alcohol which may be employed varies With the particular formulation since an excessive amount tends to result in separation of the product into two or more phases.
  • the amount of alcohol employed is up to about 3% by weight of the composition, preferably from about 0.1 to 2% by weight, depending upon the elfects desired.
  • the soil-suspending agent is a hydrophilic colloid which is dispersible in water and is maintained in suspension in the liquid product. It is preferred to use the alkali metal salt of a carboxy lower alkyl cellulose having up to 3 carbons in the alkyl group, such as the sodium and potassium salt of carboxymethylcellulose. The commercial grade of sodium carboxymethylcellulose and the like may be employed.
  • Other known water-soluble cellulosic materials are the lower alkyl and hydroxy alkyl ethers such as methylcellulose, ethylcellulose and hydroxy ethylcellulose; and the various cellulose sulfate materials.
  • 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 agent is usually from about 0.1 to about 2% by weight in the liquid product. It has been found that amounts within this range can be used in the preparation 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 materials in suspension or dispersion in the liquid. Suitable mixtures of cellulosic compounds, or a mixture of a cellulosic compound with a vinyl polymer, or a mixture of a cellulosic compound with castor wax, or any combination thereof, may be employed.
  • the liquid detergent product is prepared in any suitable manner.
  • the hydrotropic salts, the polyphosphate and the organic detergents are added successively in the form of powders, aqueous solutions or slurries to the aqueous medium.
  • the alkylolamide and any waxy materials are preferably added in molten or liquid form with agitation to form a homogeneous product.
  • the alcohol may be added at any stage or in combination with a detergent.
  • the soil-suspending agent may be added in the form of an aqueous solution at any stage during the mixing operations.
  • the temperature of admixture should be sufficient to dissolve or melt the ingredients and reasonably elevated temperature conditions such as up to about 200 F. may be employed as required.
  • ingredients may be added as desired 7 including compatible perfumes, Coloring materials, cor-- rosion or tarnish inhibitors, germicides, bleaching agents, optical bleaches or fluorescent dyes, viscosity modifiers or additional solvent materials, and the like.
  • Example 1 Ingredients: Percent Sodium tridecyl benzene sulfonate 9 Sodium nonyl phenoxy polyethoxamer sulfate 6 Potassium pyrophosphate 15 Commercial sodium xylene sulfonate 8.5 Water Balance
  • the higher alkyl benzene sulfonate is a commercial mixture of the propylene tetramer benzene sulfonate and propylene pentamer benzene sulfonate corresponding on the average to a tridecyl benzene sulfonate.
  • the higher alkyl benzene sulfonate is listed on an active ingredient basis, but contains in addition about 1.6 parts of sodium sulfate in the formulation.
  • the polyethoxamer sulfate material has an average of moles ethylene oxide. It is of desired purity and has only minor amounts of less than about 10% non-ionic unsulfated material and less than about ring sulfonated material on an organic solids basis.
  • the sodium xylene sulfonate is on an active basis and is a commercial material of 90% purity. It comprises a mixture of the meta-, para-, and ortho-xylene sulfonates with some toluene sulfonate.
  • the above composition is a clear solution having a cloud point of 53 F. and a clear point of 56 F. and possesses satisfactory cleansing power.
  • Example II the same materials are employed as in Example I.
  • the added alkylolamide materials have a ratio of about 70:30 lauric to myristic groups.
  • the product is a clear solution at room temperature having low cloud and clear points, and has satisfactory aging and cleansing properties.
  • Example 111 The formulation of Example II is repeated with the addition of 0.5% sodium carboxymethylcellulose and 0.3% castor wax.
  • the carboxymethylcellulose is about 65% .pure and hasan average of about 0.6-0.7 carboxy group per anhydroglucose unit. It is understood that the composition may contain a small amount of perfume, color and fluorescent dye as desired.
  • This liquid formulation has a pH of 10.7 and is homo geneous. It exhibits a high degree of stability, foaming power and detergency in use. Aging results show that the product exhibits good stability both at room temperature and at reduced temperature followed by return to normal room temperature.
  • Example IV The formulation of Example III is repeated with the use of 0.25% each on an active ingredient basis of sodium carboxymethylcellulose and polyvinyl alcohol having a viscosity of 1.8-3 centipoises and a polyvinyl acetate content of l030%. This formulation possesses satisfactory physical properties and performance characteristics also.
  • Example V The formulation of Example II is repeated with the omission of the lower alkyl aryl sulfonate hydrotropes and the substitution of 8.5% of sodium n-hexyl sulfate as Example IV and 8.5 of sodium n-amyl sulfate as Example V. Both products were clear liquids having the desired'physical and cleansing power.
  • Example VII Ingredients The above formulation has the ingredients in the purities illustrated in Example I. It is a clear liquid at room temperature having satisfactory aging and cleansing properties. The addition of the ethanol results in improved physical properties.
  • Example VIII The formulation of Example II is repeated using potassium tridecyl benzene sulfonate, 8.5% commercial sodium xylene sulfonate as the total hydrotropic salt and with the potassium pyrophosphate content lowered to 10% and the addition of 5% by weight of sodium silicate having a sodium oxide to silica ratio of about 1:25. The product is a clear liquid at room temperature with satisfactory properties also.
  • Example IX The formulation of Example II is repeated using 15.4% of sodium tridecyl benzene sulfonate free of inorganic salts and 2.6% of said polyethoxamer sulfate.
  • the liquid product is cloudy at room temperature and the addition of about 3% ethanol results in a clear liquid.
  • a liquid detergent composition which consists essentially of about 10 to 18% by weight of a mixture of an alkali metal higher alkyl mononuclear aryl sulfonate detergent salt, said higher alkyl group having about 8 to 15 carbon atoms, an alkali metal alkyl phenoxy polyethoxamer sulfate salt material, said alkyl group having about 8 to 13 carbon atoms and said polyethoxamer sulfate having an average of about 4 to about 10 moles of ethylene oxide, said polyethoxamer sulfate salt material having a purity of at least about by weight based on the total organic solids in said material, the ratio of said alkyl aryl sulfonate to polyethoxamer sulfate being from about 6.5:1 to about 1:4 by weight; a total of about 10 to 20% by weight of water-soluble inorganic builder salts with at least about 10% of potassium polyphosphate by weight of the composition, about 6
  • a liquid detergent composition which consists essent1ally of about 10 to 18% by weight of a mixture of an alkali metal higher alkyl benzene sulfonate detergent,
  • said higher alkyl group having about 8 to 15 carbon atoms, an alkali metal alkyl phenoxy polyethoxamer sulfate salt material, said alkyl group having about 8 to 13 carbon atoms and said polyethoxamer sulfate having an average of about 4 to about 10 moles of ethylene oxide, said polyethoxamer sulfate salt material having a purity of at least about 75% by weight based on the total organic solids in said material, the ratio of said alkyl benzene sulfonate to polyethoxamer sulfate being from about 6.5 :1 to about 1:4 by weight; a total of about 10 to 20% by weight of water-soluble inorganic builder salts with at least about 10% potassium polyphosphate by weight of the composition, about 6 to 12% by weight of an alkali metal hydrotropic salt selected from the group consist ing of alkyl benzene sulfonates having up to about 3 carbons in the al
  • a liquid detergent composition in accordance with claim 2 which contains up to about 3% by weight of water-soluble saturated aliphatic monohydric alcohol of 2 to 3 carbons.
  • a liquid detergent composition in accordance with claim 2 which contains alkylolamide selected from the group consisting of diethanolamides, monoethanolamides and isopropanolamides of fatty acids having 10 to 14 carbons in the acyl radical.
  • a liquid detergent composition in accordance with claim 2 which has incorporated therein about 0.1 to 2% by Weight of material selected from the group consisting of alkali metal carboxymethylcellulose, hydroxyalkyl ether of cellulose and lower alkyl ether of cellulose having up to 3 carbon atoms in the alkyl group, polyvinyl alcohol and polyvinylpyrrolidone soil-suspending agents.
  • a liquid detergent composition which consists essentially of about 10 to 18% by weight of a mixture of an alkali metal higher alkyl benzene sulfonate detergent, said higher alkyl group having about 8 to 15 carbon atoms, an alkali metal alkyl phenoxy polyethoxamer sulfate salt material, said alkyl group having about 8 to 13 carbon atoms and said polyethoxamer sulfate having an average of about 4 to about 10 moles of ethylene oxide, said polyethoxamer sulfate salt material having a purity of at least about 75% by weight based on the total organic solids in said material, the ratio of said alkyl benzene sulfonate to polyethoxamer sulfate being from about 6.5 :l to about 1:4 by weight; a total of about 10 to by weight of water-soluble inorganic builder salts with at least about 10% potassium polyphosphate by Weight of the composition, about 6 to 12%
  • a liquid detergent composition which consists essentially of about 10 to 18% by Weight of a mixture of an alkali metal higher alkyl benzene sulfonate detergent, said higher alkyl group having about 8 to 15 carbon atoms, an alkali metal alkyl phenoxy polyethoxamer sulfate salt material, said alkyl group having about 8 to 13 carbon atoms and said polyethoxamer sulfate having an average of about 4 to about 6 moles of ethylene oxide, said polyethoxamer sulfate material containing not in excess of about 10% unsulfated polyethoxamer material and not in excess of about 15% ring sulfonated material by weight based on the total organic solids in said material, the ratio of said alkyl benzene sulfonate to polyethoxamer sulfate being greater than 1:1 and up to :1 by Weight; a total of about 10 to 20% by Weight of water-soluble inorganic build
  • a liquid detergent in accordance with claim 9 which contains up to about 3% by weight of ethanol.
  • a liquid detergent composition in accordance with claim 9 having the following approximate formulation by weight:

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  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

948,240. Liquid detergent compositions. PROCTER & GAMBLE CO. May 25, 1962 [May 27, 1961], No. 20227/62. Heading C5D. An aqueous non-alcoholic detergent composition comprises by weight (a) 20-40% of a mixture of (i) one or more C9-18-alkyl benzene sulphonates, preferably sodium dodecylbenzene sulphonate, and (ii) one or more C10-18-alkyl polyoxyethylene sulphates having 2-4 ethylene oxide units in the molecule, preferably coconut alcohol tri-(oxyethylene) sulphate, the cations present in (i) and (ii) being sodium and/or potassium and/or ammonium and the weight ratio of (i) to (ii) being preferably 0.5: 1 to 3 : 1 and most suitably about 1:1; (b) 0.5-5% of a C10-16-fatty acyl alkanolamide, preferably coconut monoethanolamide; (c) 6-18% of sodium and/or potassium and/or ammonium toluene and/or xylene sulphonates, a 2:1 mixture by weight of potassium toluene sulphonate and sodium xylene sulphonate being preferred; and (d) the balance being substantially water. Perfume, colour, optical bleach, anti-tarnish agents, opacifiers, oxidizing agents and buffers may also be present.

Description

United States Patent 3,211,660 LIQUID DETERGENT COMPOSITION George Francis Marion, Paramus, Theodore Leo Treitler,
Millburn, and Peter Arthur Munger, Nutley, N.J., assignors to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Feb. 3, 1961, Ser. No. 86,855 11 Claims. (Cl. 252137) The present invention relates to a heavy-duty liquid detergent composition comprising in combination a higher alkyl aryl sulfonate detergent, a higher alkyl phenoxy polyethoxamer sulfate detergent, a potassium polyphosphate salt and a sulfonated solubilizing or hydrotropic agent in an aqueous medium, as hereinafter described and claimed.
More particularly, it has been found that a heavyduty liquid detergent composition of superior qualities can be formulated which comprises essentially about to 18% by weight of a mixture of an alkali metal higher alkyl mononuclear aryl sulfonate salt, said higher alkyl group having about 8 to carbon atoms, an alkali metal higher alkyl phenoxy polyethoxamer sulfate salt material, said higher alkyl group having about 8 to 13 carbon atoms and said polyethoxamer sulfate material having an average of about 4 to about 10 ethylene oxide groups per mole of alkyl phenol, said polyethoxamer sulfate salt material having a purity of at least about 75% by weight based on the total organic solids in said material, the ratio of said alkyl aryl sulfonate to polyethoxamer sulfate being from about 6.5:1 to about 1:4 by weight; a total of about 10 to by Weight of water-soluble inorganic builder salts comprising primarily potassium polyphosphate and about 6 to 12% by weight of a water-soluble sulfonated hydrotropic salt in an aqueous solubilizing medium, the composition containing said ingredients forming a homogeneous, pourable,
clear liquid at room temperature. Various other distinctive aspects of the present invention will be apparent from the following description.
The liquid containing the above ingredients in solution exhibits many desirable characteristics with regard to both physical properties and performance in use. As to its physical properties, the composition is homogeneous, pourable, and free-flowing from the container as manufactured and after aging. It exhibits a high degree of stability upon storage at normal room temperature of the order of about 70 F. over a period of many months without any appreciable precipitation or formation of immiscible layers. It can be subjected to elevated temperatures of the order of 120 F. or cooled to 40 F. and the liquid is in a clear, homogeneous form when returned to room temperature. As a result, the consumer can utilize it conveniently by the addition of small portions to a dishpan or a laundering bath and the detergent and builder salts will be present in constant composition in each portion. While adjuvant materials may be added which render the final product translucent or opaque as desired and described hereinafter, the requirement for a clear solution of the main ingredients insures that effective foam and washing power will be obtained with each portion and promotes the stability and homogeneity of the product. The liquid may be employed in any suitable container or packaging material such as metal, plastic, or glass in the form of bottles, bags, cans or drums.
In performance, the product exhibits a particularly high level of washing power and foaming action during dishwashing, laundering and in other cleansing operations. A particular advantage of this composition is its high detergent and emulsification power for the cleaning of soiled surfaces containing fats and greases including soiled aluminum and other metals, ceramic materials, Wearing apparel and the like. The product exhibits a good volume of foam initially and during the cleansing operation.
In the formulation of the products of the present invention, there are a number of factors which are of consideration. The properties are affected by these factors which are properly selected and correlated to provide the product hereafter claimed. Among such considerations are the chemical constitution of the materials and their purities which are to be integrated with the suitable ratios and/or proportions thereof so as to produce compositions having the desired properties.
With regard to the higher alkyl mononuclear aryl sulfonate detergent, it is preferred to use the higher alkyl benzene sulfonates, though other similar detergents having a mononuclear aryl group derived from toluene or xylene may be used also. The aryl nucleus has at least one alkyl substituent having an average number of about 8 to 15 carbons and preferably between 12 and 1S carbons. The alkyl group may be branched such as nonyl, dodecyl and pentadecyl groups including mixtures thereof which are derived from polymers of mono-olefins, e.g., polypropylene. The alkyl group may be straightchained such as the decyl, keryl and dodecyl groups.
The suitable sulfated higher alkyl phenoxy polyethoxamer material has a characteristic chemical structure also. In general, there should be at least one higher alkyl group having an average number of about 8 to 13 carbon atoms which can be straight or branched chained, suitable examples being octyl, nonyl and dodecyl groups. The phenyl group may have additional substituents, e.g., alkyl groups, thereon provided that they do not adversely affect the desired properties. It has a pre-determined number of ethylene oxide groups in order to obtain the desired physical properties and performance characteristics. In general, it has an average number of about 4 to about 10 moles of ethylene oxide per alkyl phenyl group since the use of materials having a significantly different number of ethylene oxide groups does not result in the desired product. It is preferred to employ materials having an average number from about 4 to 6 moles of ethylene oxide since their use results in optimum effects.
The polyethoxamer sulfate material is commonly prepared by reaction of the appropriate alkyl phenol with sufficient ethylene oxide followed by sulfation of the reaction product in known manner, such as by the use of oleum or chlorsulfonic acid. If desired, the poly ethoxamer may be sulfated after the sulfonation of the alkyl aryl hydrocarbon using the same sulfonating agent to produce the mixed detergents.
The purity of the desired reaction product is a consideration for the manufacture of a product having optimum properties. Depending upon the method of manufacture, there is usually present varying amounts of organic im purities in admixture with the sulfated ethoxamer compounds. The organic impurities comprise unreacted nonionic (unsulfated) higher alkyl phenoxy ethylene oxide materials, ring sulfonated materials such as alkyl phenoxy ethoxamers wherein the phenyl ring is sulfonated, and possibly very small amounts of degradation products such as higher alkyl phenols and partially de-ethoxylated products. These organic impurities should be maintained at a minimum since an excessive amount has been found to adversely affect the physical properties and performance of the product. More particularly, an excessive amount, particularly of the unreacted non-ironic polyethoxamer, has a tendency to raise the cloud point, inhibit foam and decrease the efficiency of the product as an emulsifier of greasy soil in washing operations. The product may contain a minor amount of such organic unreacted or byproduct materials provided that the amount is insufficient to substantially adversely affect the properties of the product. In general, the alkyl phenoxy polyethoxamer sulfate material should have a purity of at least about 75% by weight of the total organic solids in said material with up to about 25% of said other organic solids. The optimum effects, it is preferred that the organic solids of the commercial polyethoxamer sulfate should contain not substantially in excess of about unsulfated organic ethoxamer material and not in excess of about ring sulfonated material .by weight of the organic solids in the polyethoxamer sulfate material. A typical product may contain about 10% of each on said organic solids basis. The said impurities are maintained at said low levels by any suitable technique. The careful control of the conditions in the sulfation procedure including the time of reaction and the choice of sulfonating agent will produce materials of desired purity. The reaction product may be purified to remove said organic impurities also, such as by the use of an ion-exchange technique.
The described alkyl aryl sulfonate and sulfated alkyl phenoxy polyethoxamer materials are employed in the form of their alkali metal salts such as the sodium and potassium salts. It is understood that there may be small amounts of inorganic salts such as sodium or potassium sulfate in the sulfonated and sulfated detergents resulting from the method of manufacture. In general, these inorganic sulfate salts should be maintained at as low a iconcentration as practicable.
The potassium polyphosphate salts have the property of inhibiting precipitation of calcium and magnesium material in aqueous solution and of contributing to the heavy-duty performance of the liquid detergent product in washing operations. While they may be considered as derived from orthophosphoric acid or the like by the removal of molecularly bound water, any suitable means of manufacture may be employed if desired. Such complex or molecularly dehydrated polyphosphate salts are used usually in the form of the normal or completely neutralized salts, e.g., tetrapotassium pyrophosphate and pentapotassium tripolyphosphate. If desired, the phosphate may be a partially neutralized salts, e.g., potassium acid tripolyphosphate. Any suitable mixture of polyphosphate materials may be employed. It is preferred to use at least in part tetrapotassium pyrophosphate.
The organic detergents and polyphosphate are employed in substantial amount in the composition such that the addition of a small portion of the liquid product to a washing bath will result in effective detergency and washing power. The amount and types of said mixture of organic detergents influence the maximum amount of phosphate that can be incorporated in the composition and yet obtain a composition wit-h the desired properties. It has been found that suitable amounts within the range of about 10 to 1 8%, by weight, preferably 14 to 16%, of
'said mixture of deter-gents and 10 to 20% by weight of potassium polyphosphate may be selected so as to produce suitable products. The ratio of the alkyl benzene sulfonate to the sulfated polyethoxamer is variable and ratios selected from the range of 6.5 :1 to about 1:4 by weight have been found to be most practicable. It is preferred that the ratio of alkyl aryl sulfonate to sulfated polyethoxamer be greater than 1:1, and particularly from about 1.5:1 to about 3:1 for optimum performance characteristic-s, particularly in foaming power. In addition to improved washing power, the polyphosphate favorably influences the physical properties of the system when employed within the range of about 10 to 20%, and par-ticularly about 15 by weight. 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. Other water-soluble inorganic builder salts may be substituted for the potassium-polyphosphate in minor amount such as a few percent, e.g., up to 5%, of sodium polyphosphate or sodium or potassium silicate provided that the builder content is primarily the potassium polyphosphate, e.g., at least about 10%, and the total amount is compatible in the liquid.
It has been found that certain alkyl phenoxy polyethoxamer sulfates should be employed in these products. The average number of ethylene oxide groups in these materials influences the physical properties of the liquid and the amount of inorganic salt, particularly the amount of potassium polyphosphate, which can be dissolved in the solution. For example, a series of liquid detergents were prepared which contained about 7% by weight of sodium tridecyl benzene sulfonate, 7% by weight of 'sodium higher alkyl phenol-ethylene oxide sulfates, 8%
sodium commercial xylene sulfonate, 3% coconut isopropanolamide, and a quantity of potassium pyrophosphate in water. Each formulation contained a different polyethoxamer sulfate having the alkyl group and average ethylene oxide content as specified in the table below. The compositions contained 20% potassium pyrophosphate except where lesser quantities are specified in the table below, they are the maximum amounts which could be dissolved therein. The cloud and clear points for each composition are set forth in the following table.
TABLE I Alkyl Phcnoxy Polyethoxamer Sulfate Percent Potassium Cloud Clear Pyrophos- Point, F. Point, F. Moles phate Alkyl Group Ethylene Oxide 4 20 65 67 5 20 44 64 6 20 42 61 6 20 43 63 9. 3 17. 7 56 64 14 12. 2 87 93 20 10. 6 77 79 Dodecyl 30 7. 7 106 The above data illustrates that it is necessary to select polyethoxamer sulfates having a particular average ethylene oxide content in order to obtain the best combination of properties in the liquid compositions. The compositions having from 4 to 9.3 moles ethylene oxide in the polyethoxamer sulfate exhibit cloud and clear points below normal room temperature. In contrast, the compositions having 14 to 30 moles of ethylene oxide possess cloud and clear points which are substantially above room temperature. It is apparent that there is a point within the range from about 9.3 up to 14 moles of ethylene oxide, referred to herein as about 10 moles, which results in significant change in properties of the liquid compositions.
The physical properties are influenced also by the amount of polyphosphate in the liquid. A series of aqueous compositions were prepared containing 0 to 15 by weight of potassium pyrophosphate, the balance being about 9% by weight of potassium tridecyl benzene sulfonate, 8.5% sodium xylene sulfonate, 6% sodium nonyl phenoxy polyet-hoxamer sulfate with average of about 6 moles ethylene oxide and 6% of a 1:1 mixture by weight of lauric-myristic isopropanolamide and diethanolamide, the lauric and myristic radicals being in a ratio of about 70:30. The following table shows the cloud and clear points-of the liquids containing the specified amount of potassium pyrophosphate:
The above data disclose that the polyphosphate within certain proportions favorably affects the physical properties of the liquid. There is a minimum or lowest cloud and clear point which is obtained in the presence of appreciable amounts of the polyphosphate which is usually at least about polyphosphate.
The inclusion of the water-soluble sulfonated hydrotropic substance is effective in promoting the compatibility of the ingredients so as to form a homogeneous liquid product. Suitable materials are the alkali metal organic sulfonated (including sulfate d) salts having a lower alkyl group up to about 6 carbons. It is preferred to employ an alkyl aryl sulfonate having up to 3 carbons in a lower alkyl group such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene sulfonates. Sulfonates made from xylene include orthoxylene sulfonates, 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, 1035% orthoxylene sulfonate and -30% paraxylene sulfonate with 0-20% ethylbenzene sulfonate. Any suitable isomeric mixture may be employed, however. Suitable lower alkyl sulfate salts having about 5 to 6 carbons in the alkyl group may be employed also such as the alkali metal n-amyl and n-hexyl sulfate. The hydrotropic materials are employed generally in amounts from about 6 to 12% by weight of the composition. The use of an amount in excess of the amount required to effect a single liquid phase is not helpful since it tends to add additional salt to an already concentrated system.
It is preferred that the liquid contain a higher fatty acid .alkylolamide material in a suflicient amount to act as a suds builder. It has been found also that the combination of the above ingredients with a suitable amount of the alkylolamide results in a product which exhibits particularly high foaming power in use, particularly in the stability of the foam generated during dishwashing or laundering operations. In certain formulations, the alkylolamide may provide an additional solubilizing effect. It should not be employed in an amount sufficient to destroy the desired physical properties since it is considered as part of the total solids content. The acyl radical of the alkylolamide is selected from 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, isopropanolamide and monoethanolamides of fatty acids having about 10 to 14 carbons in the acyl radical. Examples are the lauric, capric, myristic and coconut diethanolamides, monoethanolamides 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 isopropanolamides condensed with one or two moles of ethylene oxide. In general, the alkylolamides should be employed in amounts of about 2 to 10% by weight in the product, and preferably from about 4 to 8%.
The solids content of the concentrated liquid product is variable and is usually from about 26 to 50% by Weight 6 of the concentrated liquid, and the balance being primarily water. The ingredients are proportioned in the aqueous solubilizing medium so as to form a substantially homo geneous product of desired physical properties.
A further embodiment of the present invention relates to the inclusion of a minor amout of a water-soluble saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms as part of the aqueous solubilizing medium. Examples are ethanol, propanol and isopropanol. The alcohol may serve a multiplicity of functions. It can provide for improved physical properties such as a lower cloud point, improve low temperature aging, modify the viscosity, and the like. In certain cases, a small amount of alcohol in combination with the hydrotropic salt will produce a clear liquid which will be otherwise cloudy at room temperature. The suitable amount of alcohol which may be employed varies With the particular formulation since an excessive amount tends to result in separation of the product into two or more phases. In general, the amount of alcohol employed is up to about 3% by weight of the composition, preferably from about 0.1 to 2% by weight, depending upon the elfects desired.
It has been found that a suitable soil-suspending material may be incorporated in these formulations. The addition of a soil-suspending material converts the system to a more complex one which has improved performance characteristics in washing operations and will usually render the final product translucent or opaque, though the detergent and builder salts are advantageously in solution. In general, the soil-suspending agent is a hydrophilic colloid which is dispersible in water and is maintained in suspension in the liquid product. It is preferred to use the alkali metal salt of a carboxy lower alkyl cellulose having up to 3 carbons in the alkyl group, such as the sodium and potassium salt of carboxymethylcellulose. The commercial grade of sodium carboxymethylcellulose and the like may be employed. Other known water-soluble cellulosic materials are the lower alkyl and hydroxy alkyl ethers such as methylcellulose, ethylcellulose and hydroxy ethylcellulose; 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.
In general, the amount of the soil-suspending agent (including mixtures thereof) is usually from about 0.1 to about 2% by weight in the liquid product. It has been found that amounts within this range can be used in the preparation 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 materials in suspension or dispersion in the liquid. Suitable mixtures of cellulosic compounds, or a mixture of a cellulosic compound with a vinyl polymer, or a mixture of a cellulosic compound with castor wax, or any combination thereof, may be employed.
The liquid detergent product is prepared in any suitable manner. The hydrotropic salts, the polyphosphate and the organic detergents are added successively in the form of powders, aqueous solutions or slurries to the aqueous medium. The alkylolamide and any waxy materials are preferably added in molten or liquid form with agitation to form a homogeneous product. The alcohol may be added at any stage or in combination with a detergent. The soil-suspending agent may be added in the form of an aqueous solution at any stage during the mixing operations. The temperature of admixture should be sufficient to dissolve or melt the ingredients and reasonably elevated temperature conditions such as up to about 200 F. may be employed as required.
Various other ingredients may be added as desired 7 including compatible perfumes, Coloring materials, cor-- rosion or tarnish inhibitors, germicides, bleaching agents, optical bleaches or fluorescent dyes, viscosity modifiers or additional solvent materials, and the like.
The following examples are further illustrative of the nature of the present invention, and it will be understood that the invention is not limited thereto. All amounts are by weight unless otherwise specified.
Example 1 Ingredients: Percent Sodium tridecyl benzene sulfonate 9 Sodium nonyl phenoxy polyethoxamer sulfate 6 Potassium pyrophosphate 15 Commercial sodium xylene sulfonate 8.5 Water Balance In the above formulation, the higher alkyl benzene sulfonate is a commercial mixture of the propylene tetramer benzene sulfonate and propylene pentamer benzene sulfonate corresponding on the average to a tridecyl benzene sulfonate. The higher alkyl benzene sulfonate is listed on an active ingredient basis, but contains in addition about 1.6 parts of sodium sulfate in the formulation. The polyethoxamer sulfate material has an average of moles ethylene oxide. It is of desired purity and has only minor amounts of less than about 10% non-ionic unsulfated material and less than about ring sulfonated material on an organic solids basis. The sodium xylene sulfonate is on an active basis and is a commercial material of 90% purity. It comprises a mixture of the meta-, para-, and ortho-xylene sulfonates with some toluene sulfonate.
The above composition is a clear solution having a cloud point of 53 F. and a clear point of 56 F. and possesses satisfactory cleansing power.
In the above formulation, the same materials are employed as in Example I. The added alkylolamide materials have a ratio of about 70:30 lauric to myristic groups. The product is a clear solution at room temperature having low cloud and clear points, and has satisfactory aging and cleansing properties.
Example 111 The formulation of Example II is repeated with the addition of 0.5% sodium carboxymethylcellulose and 0.3% castor wax. The carboxymethylcellulose is about 65% .pure and hasan average of about 0.6-0.7 carboxy group per anhydroglucose unit. It is understood that the composition may contain a small amount of perfume, color and fluorescent dye as desired.
This liquid formulation has a pH of 10.7 and is homo geneous. It exhibits a high degree of stability, foaming power and detergency in use. Aging results show that the product exhibits good stability both at room temperature and at reduced temperature followed by return to normal room temperature.
Example IV The formulation of Example III is repeated with the use of 0.25% each on an active ingredient basis of sodium carboxymethylcellulose and polyvinyl alcohol having a viscosity of 1.8-3 centipoises and a polyvinyl acetate content of l030%. This formulation possesses satisfactory physical properties and performance characteristics also.
8 Examples V-Vl The formulation of Example II is repeated with the omission of the lower alkyl aryl sulfonate hydrotropes and the substitution of 8.5% of sodium n-hexyl sulfate as Example IV and 8.5 of sodium n-amyl sulfate as Example V. Both products were clear liquids having the desired'physical and cleansing power.
Example VII Ingredients The above formulation has the ingredients in the purities illustrated in Example I. It is a clear liquid at room temperature having satisfactory aging and cleansing properties. The addition of the ethanol results in improved physical properties.
Example VIII The formulation of Example II is repeated using potassium tridecyl benzene sulfonate, 8.5% commercial sodium xylene sulfonate as the total hydrotropic salt and with the potassium pyrophosphate content lowered to 10% and the addition of 5% by weight of sodium silicate having a sodium oxide to silica ratio of about 1:25. The product is a clear liquid at room temperature with satisfactory properties also.
Example IX The formulation of Example II is repeated using 15.4% of sodium tridecyl benzene sulfonate free of inorganic salts and 2.6% of said polyethoxamer sulfate. The liquid product is cloudy at room temperature and the addition of about 3% ethanol results in a clear liquid.
Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications can be substituted therefor without departing from the principles and true spirit of the inventlon.
Having thus described the invention, what is claimed is:
1. A liquid detergent composition which consists essentially of about 10 to 18% by weight of a mixture of an alkali metal higher alkyl mononuclear aryl sulfonate detergent salt, said higher alkyl group having about 8 to 15 carbon atoms, an alkali metal alkyl phenoxy polyethoxamer sulfate salt material, said alkyl group having about 8 to 13 carbon atoms and said polyethoxamer sulfate having an average of about 4 to about 10 moles of ethylene oxide, said polyethoxamer sulfate salt material having a purity of at least about by weight based on the total organic solids in said material, the ratio of said alkyl aryl sulfonate to polyethoxamer sulfate being from about 6.5:1 to about 1:4 by weight; a total of about 10 to 20% by weight of water-soluble inorganic builder salts with at least about 10% of potassium polyphosphate by weight of the composition, about 6 to 12% by weight of water-soluble hydrotropic salt selected from the group consisting of alkyl benzene sulfonates having up to about 3 carbons in the alkyl group and alkyl sulfates having about 5 to 6 carbons in said alkyl group, and the balance containing primarily Water, the composition containing said ingredients having a solid content of up to about 50% by weight and forming a homogeneous, pourable, clear liquid at room temperature.
2. A liquid detergent composition which consists essent1ally of about 10 to 18% by weight of a mixture of an alkali metal higher alkyl benzene sulfonate detergent,
said higher alkyl group having about 8 to 15 carbon atoms, an alkali metal alkyl phenoxy polyethoxamer sulfate salt material, said alkyl group having about 8 to 13 carbon atoms and said polyethoxamer sulfate having an average of about 4 to about 10 moles of ethylene oxide, said polyethoxamer sulfate salt material having a purity of at least about 75% by weight based on the total organic solids in said material, the ratio of said alkyl benzene sulfonate to polyethoxamer sulfate being from about 6.5 :1 to about 1:4 by weight; a total of about 10 to 20% by weight of water-soluble inorganic builder salts with at least about 10% potassium polyphosphate by weight of the composition, about 6 to 12% by weight of an alkali metal hydrotropic salt selected from the group consist ing of alkyl benzene sulfonates having up to about 3 carbons in the alkyl group and alkyl sulfates having about to 6 carbons in said alkyl group, about 2 to by weight of a higher fatty acid alkylolamide having about 8 to 18 carbon atoms in the fatty acyl group and up to 3 carbon atoms in each alkylol group, and the balance being primarily water, the composition containing said ingredients having a solid content of up to about 50% by weight and forming a homogeneous, pourable, clear liquid at room temperature.
3. A liquid detergent composition in accordance with claim 2 wherein said polyethoxamer sulfate salt material has an average of about 4 to 6 moles of ethylene oxide and contains not in excess of about 10% unsulfated polyethoxamer and not in excess of about ring sulfonated materials by weight of organic solids.
4. A liquid detergent composition in accordance with claim 2 wherein said hydrotropic salt is selected from the group consisting of sodium and potassium toluene and xylene sulfonates.
5. A liquid detergent composition in accordance with claim 2 which contains up to about 3% by weight of water-soluble saturated aliphatic monohydric alcohol of 2 to 3 carbons.
6. A liquid detergent composition in accordance with claim 2 which contains alkylolamide selected from the group consisting of diethanolamides, monoethanolamides and isopropanolamides of fatty acids having 10 to 14 carbons in the acyl radical.
7. A liquid detergent composition in accordance with claim 2 which has incorporated therein about 0.1 to 2% by Weight of material selected from the group consisting of alkali metal carboxymethylcellulose, hydroxyalkyl ether of cellulose and lower alkyl ether of cellulose having up to 3 carbon atoms in the alkyl group, polyvinyl alcohol and polyvinylpyrrolidone soil-suspending agents.
8. A liquid detergent composition which consists essentially of about 10 to 18% by weight of a mixture of an alkali metal higher alkyl benzene sulfonate detergent, said higher alkyl group having about 8 to 15 carbon atoms, an alkali metal alkyl phenoxy polyethoxamer sulfate salt material, said alkyl group having about 8 to 13 carbon atoms and said polyethoxamer sulfate having an average of about 4 to about 10 moles of ethylene oxide, said polyethoxamer sulfate salt material having a purity of at least about 75% by weight based on the total organic solids in said material, the ratio of said alkyl benzene sulfonate to polyethoxamer sulfate being from about 6.5 :l to about 1:4 by weight; a total of about 10 to by weight of water-soluble inorganic builder salts with at least about 10% potassium polyphosphate by Weight of the composition, about 6 to 12% by Weight of an alkali metal hydrotropic salt selected from the group consisting of sulfonates of xylene, toluene, ethyl benzene, isopropyl benzene and suitable mixtures thereof and alkyl sulfates having about 5 to 6 carbons in said alkyl group, about 2 to 10% 70 by weight of a higher fatty acid alkylolamide having about 8 to 18 carbon atoms in the fatty acyl group and up to 3 carbon atoms in each alkylol group, and the balance being primarily water with about 0.1 to 3% by Weight of a water-soluble saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms, the composition containing said ingredients having a solids content of up to about 50% by weight and forming a homogeneous, pourable, clear liquid at room temperature.
9. A liquid detergent composition which consists essentially of about 10 to 18% by Weight of a mixture of an alkali metal higher alkyl benzene sulfonate detergent, said higher alkyl group having about 8 to 15 carbon atoms, an alkali metal alkyl phenoxy polyethoxamer sulfate salt material, said alkyl group having about 8 to 13 carbon atoms and said polyethoxamer sulfate having an average of about 4 to about 6 moles of ethylene oxide, said polyethoxamer sulfate material containing not in excess of about 10% unsulfated polyethoxamer material and not in excess of about 15% ring sulfonated material by weight based on the total organic solids in said material, the ratio of said alkyl benzene sulfonate to polyethoxamer sulfate being greater than 1:1 and up to :1 by Weight; a total of about 10 to 20% by Weight of water-soluble inorganic builder salts with at least about 10% potassium pyrophosphate by weight of the composition, about 6 to 12% by Weight of a hydrotropic salt selected from the group consisting of alkali metal toluene and xylene sulfonates, about 4 to 8% by weight of a higher fatty acid alkylolamide having about 10 to 14 carbon atoms in the acyl group and up to 3 carbon atoms in each alkylol group, and the balance being primarily water, the composition containing said ingredients having a solids content of up to about 50% by Weight and forming a homogeneous, pourable, clear liquid at room temperature.
10. A liquid detergent in accordance with claim 9 which contains up to about 3% by weight of ethanol.
11. A liquid detergent composition in accordance with claim 9 having the following approximate formulation by weight:
Ingredients- Percent Sodium higher alkyl benzene sulfonate 9 Sodium alkyl phenoxy polyethoxamer sulfate 6 Higher fatty acid alkylolamide 4- 8 Potassium pyrophosphate 15 Alkali metal lower alkyl aryl sulfonate 6-12 said alkyl benzene sulfonate having an average of about 12-15 carbons in the alkyl group, the alkyl phenoxy polyethoxamer sulfate having about 9 to 12 carbons in the alkyl group and an average of about 4 to 6 moles of ethylene oxide, said higher fatty alkylolamide having about 8 to 18 carbon atoms in the acyl group and being selected from the group consisting of diethanolamides, monoethanolamides and isopropanolamides, said alkali metal lower alkyl aryl sulfonate being selected from the group consisting of sodium and potassium toluene sulfonates and xylene sulfonates.
References Cited by the Examiner UNITED STATES PATENTS 2,859,182 11/58 Carroll 252137 wuss 3/59 Krumrei et al. 252-137 2,994,665 8/61 Reich et a1. 252137 2,999,068 9/61 Pilcher et al. 252-437 3,000,830 9/61 Fong et a1 252137 XR FOREIGN PATENTS 855,893 12/60 Great Britain.
JULIUS GREENWALD, Primary Examiner. ALBERT T. MEYERS, Examiner.

Claims (1)

1. A LIQUID DETERGENT COMPOSITION WHICH CONSISTS ESSENTIALLY OF ABOUT 10 TO 18% BY WEIGHT OF A MIXTURE OF AN ALKALI METAL HIGHER ALKYL MONONUCLEAR ARYL SULFONATE DETERGENT SALT, SAID HIGHER ALKYL GROUP HAVING ABOUT 8 TO 15 CARBONATOMS, AN ALKALI METAL ALKYL PHENOXY POLYETHOXAMER SULFATE SALT MATERIAL, SAID ALKYL GROUP HAVING ABOUT 8 TO 13 CARBON ATOMS AND SAID POLYETHOXAMER SULFATE HAVING AN AVERAGE OF ABOUT 4 TO ABOUT 10 MOLES OF ETHYLENE OXIDE, SAID POLYETHOXAMER SULFATE SALT MATERIAL HAVING A PURITY OF AT LEAST ABOUT 75% BY WEIGHT BASED ON THE TOTAL ORGANIC SOLIDS IN SAID MATERIAL, THE RATIO OF SAID ALKYL ARYL SULFONATE TO POLYETHOXAMER SULFATE BEING FROM ABOUT 6.5:1 TO ABOUT 1:4 BY WEIGHT; TOTAL OF ABOUT 10 TO 20% BY WEIGHT OF WATER-SOLUBLE INORGANIC BUILDER SALTS WITH AT LEAST ABOUT 10% OF POTASSIUM POLYPHOSPHATE BY WEIGHT OF THE COMPOSITION, ABOUT 6 TO 12% BY WEIGHT OF WATER-SOLUBLE HYDROTROPIC SALT SELECTED FROM THE GROUP CONSISTING OF ALKYL BENZENE SULFONATES HAVING UP TO ABOUT 3 CARBONS IN THE ALKYL GROUP AND ALKYL SULFATES HAVING ABOUT 5 TO 6 CARBONS IN SAID ALKYL GROUP, AND THE BALANCE CONTAINING PRIMARILY WATER, THE COMPOSITION CONTAINING SAID INGREDIENTS HAVING A SOLID CONTENT OF UP TO ABOUT 50% BY WEIGHT AND FORMING A HOMOGENEOUS, POURABLE, CLEAR LIQUID AT ROOM TEMPERATURE.
US86855A 1961-02-03 1961-02-03 Liquid detergent composition Expired - Lifetime US3211660A (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
IT650470D IT650470A (en) 1961-02-03
BE617969D BE617969A (en) 1961-02-03
CA689791A CA689791A (en) 1961-02-03 Liquid detergent composition
NL276377D NL276377A (en) 1961-02-03
BE613165D BE613165A (en) 1961-02-03
CA704966A CA704966A (en) 1961-02-03 Non-alcoholic liquid detergent composition containing anionic detergent surface active agents
US86855A US3211660A (en) 1961-02-03 1961-02-03 Liquid detergent composition
US99696A US3231504A (en) 1961-02-03 1961-03-31 Liquid detergent compositions
DEC26022A DE1287245B (en) 1961-02-03 1962-01-18 Liquid cleaning agent
CH64762A CH414908A (en) 1961-02-03 1962-01-19 Liquid detergent
SE838/62A SE302498B (en) 1961-02-03 1962-01-25
GB3513/62A GB978575A (en) 1961-02-03 1962-01-30 Liquid detergent compositions
FR887238A FR1314689A (en) 1961-02-03 1962-02-07 Liquid detergent composition
GB20227/62A GB948240A (en) 1961-02-03 1962-05-25 Non-alcoholic liquid detergent composition containing anionic detergent surface active agents
OA50933A OA00847A (en) 1961-02-03 1964-12-19 Liquid detergent composition.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US86855A US3211660A (en) 1961-02-03 1961-02-03 Liquid detergent composition
US99696A US3231504A (en) 1961-02-03 1961-03-31 Liquid detergent compositions
IT972161 1961-05-27

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US3211660A true US3211660A (en) 1965-10-12

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US86855A Expired - Lifetime US3211660A (en) 1961-02-03 1961-02-03 Liquid detergent composition
US99696A Expired - Lifetime US3231504A (en) 1961-02-03 1961-03-31 Liquid detergent compositions

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Application Number Title Priority Date Filing Date
US99696A Expired - Lifetime US3231504A (en) 1961-02-03 1961-03-31 Liquid detergent compositions

Country Status (11)

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US (2) US3211660A (en)
BE (2) BE613165A (en)
CA (2) CA689791A (en)
CH (1) CH414908A (en)
DE (1) DE1287245B (en)
FR (1) FR1314689A (en)
GB (2) GB978575A (en)
IT (1) IT650470A (en)
NL (1) NL276377A (en)
OA (1) OA00847A (en)
SE (1) SE302498B (en)

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US3928213A (en) * 1973-03-23 1975-12-23 Procter & Gamble Fabric softener and soil-release composition and method
US4018720A (en) * 1975-07-14 1977-04-19 The Procter & Gamble Company Laundry detergent compositions in emulsion/suspension
WO2000027958A1 (en) * 1998-11-06 2000-05-18 The Procter & Gamble Company Hydrophilic index for aqueous, liquid laundry detergent compositions containing las

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DE1467572A1 (en) * 1964-07-22 1969-01-23 Continental Oil Co Detergent compositions
FR2082249A5 (en) * 1970-03-09 1971-12-10 Colgate Palmolive Co
GB1437089A (en) * 1972-05-26 1976-05-26 Albright & Wilson Detergent concentrates
US4152306A (en) * 1976-02-26 1979-05-01 LDMJ Limited Windshield cleaning solvent
US4113638A (en) * 1976-08-04 1978-09-12 Atlantic Richfield Company Frothing composition for gypsum dispersions
US4692271B1 (en) * 1977-12-09 1997-07-22 Albright & Wilson Concentrated aqueous surfactant compositions
US4753754B1 (en) * 1977-12-09 1997-05-13 Albright & Wilson Concentrated aqueous surfactant compositions
US4487710A (en) * 1982-03-01 1984-12-11 The Procter & Gamble Company Granular detergents containing anionic surfactant and ethoxylated surfactant solubility aid
US4537708A (en) * 1983-08-30 1985-08-27 Fmc Corporation Homogeneous laundry detergent slurries containing nonionic surface-active agents
US4597889A (en) * 1984-08-30 1986-07-01 Fmc Corporation Homogeneous laundry detergent slurries containing polymeric acrylic stabilizers
US4687593A (en) * 1984-12-17 1987-08-18 Monsanto Company Alkylaryl sulfonate compositions
US4645623A (en) * 1984-12-17 1987-02-24 Monsanto Company Alkylaryl sulfonate compositions
US4671895A (en) * 1985-11-15 1987-06-09 Colgate-Palmolive Company Liquid detergent compositions
US4854969A (en) * 1986-07-02 1989-08-08 Sun Chemical Corporation Lithographic fountain solutions
DE4008919A1 (en) * 1990-03-20 1991-09-26 Benckiser Gmbh Joh A Aq. cleaning compsn. for microwave oven - contg. alkane sulphonate or alkyl:benzene sulphonate and alcohol polyglycol ether sulphate and thickener, free from ionic surfactant(s)

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US2877185A (en) * 1956-06-29 1959-03-10 Procter & Gamble Clear liquid detergent composition
GB855893A (en) * 1958-07-10 1960-12-07 Unilever Ltd Improvements in or relating to liquid detergent compositions
US2994665A (en) * 1959-04-15 1961-08-01 Lever Brothers Ltd Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents
US2999068A (en) * 1959-04-27 1961-09-05 Procter & Gamble Personal use detergent lotion
US3000830A (en) * 1952-12-05 1961-09-19 Fong Willie Use of polyvinylpyrrolidone as a soil-suspending agent

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US2950254A (en) * 1955-04-25 1960-08-23 Dehydag Gmbh Method of producing a pearly luster in shampoo concentrates
US2877187A (en) * 1955-08-10 1959-03-10 Lever Brothers Ltd Detergent containing beta, beta'-decylaminobisethanolpropionamide
DE1047973B (en) * 1956-09-21 1958-12-31 Willi Maurer K G Resistant detergent pastes
DE1072348B (en) * 1956-10-01 1960-06-02 The Procter & Gamble Company, Cincinnati, Ohio (V. St. A.) laundry detergent

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US3000830A (en) * 1952-12-05 1961-09-19 Fong Willie Use of polyvinylpyrrolidone as a soil-suspending agent
US2877185A (en) * 1956-06-29 1959-03-10 Procter & Gamble Clear liquid detergent composition
US2859182A (en) * 1956-11-02 1958-11-04 Lever Brothers Ltd Heavy duty liquid detergent composition
GB855893A (en) * 1958-07-10 1960-12-07 Unilever Ltd Improvements in or relating to liquid detergent compositions
US2994665A (en) * 1959-04-15 1961-08-01 Lever Brothers Ltd Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents
US2999068A (en) * 1959-04-27 1961-09-05 Procter & Gamble Personal use detergent lotion

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928213A (en) * 1973-03-23 1975-12-23 Procter & Gamble Fabric softener and soil-release composition and method
US4018720A (en) * 1975-07-14 1977-04-19 The Procter & Gamble Company Laundry detergent compositions in emulsion/suspension
WO2000027958A1 (en) * 1998-11-06 2000-05-18 The Procter & Gamble Company Hydrophilic index for aqueous, liquid laundry detergent compositions containing las

Also Published As

Publication number Publication date
OA00847A (en) 1967-11-15
CA689791A (en) 1964-06-30
SE302498B (en) 1968-07-22
BE617969A (en)
FR1314689A (en) 1963-01-11
GB948240A (en) 1964-01-29
GB978575A (en) 1964-12-23
NL276377A (en)
US3231504A (en) 1966-01-25
CH414908A (en) 1966-06-15
BE613165A (en)
CA704966A (en) 1965-03-02
IT650470A (en)
DE1287245B (en) 1969-01-16

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