US3066104A - Heavy duty liquid synthetic detergent composition - Google Patents

Heavy duty liquid synthetic detergent composition Download PDF

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US3066104A
US3066104A US714013A US71401358A US3066104A US 3066104 A US3066104 A US 3066104A US 714013 A US714013 A US 714013A US 71401358 A US71401358 A US 71401358A US 3066104 A US3066104 A US 3066104A
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potassium
composition
weight
sodium
liquid
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US714013A
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Dasch Lawrence
Paul R Cutter
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Diamond Shamrock Corp
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Diamond Alkali Co
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Priority to US714013A priority patent/US3066104A/en
Priority to GB4293/59A priority patent/GB852941A/en
Priority to DED29975A priority patent/DE1081589B/en
Priority to FR786169A priority patent/FR1228110A/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
    • 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/044Hydroxides or bases
    • 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
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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

Definitions

  • This invention relates to synthetic heavy-duty liquid detergents, and more particularly to synthetic heavy-duty liquid detergent compositions wherein the principal building and sequestering agent is sodium tripolyphosphate.
  • the synthetic detergents have, for the most part, been marketed in the form of a powder, which powder is generally made up of an anionic detergent, such as a sodium alkyl aryl sulfonate, a foam stabilizer, such as a condensed alkanolamide of a fatty acid, a building or sequestering agent, such as sodium tripolyphosphate or tetrasodium pyrophosphate, a rust or corrosion inhibitor, such as sodium metasilicate, a soil suspending agent, such as sodium carboxy methyl cellulose and minor amounts of an optical bleach and a dye.
  • anionic detergent such as a sodium alkyl aryl sulfonate
  • a foam stabilizer such as a condensed alkanolamide of a fatty acid
  • a building or sequestering agent such as sodium tripolyphosphate or tetrasodium pyrophosphate
  • a rust or corrosion inhibitor such as sodium metasilicate
  • such a composition does have several disadvantages. Foremost, is the fact that the potassium polyphosphates are about twice :as expensive as the corresponding sodium polyphosphate, thus causing a considerable increase in price of such a liquid heavy-duty detergent over that of the corresponding powder.
  • the building and sequestering action, on an equal weight basis, of the potassium polyphosphates are somewhat less than those of the corresponding sodium polyphosphates, hence making it necessary to use a greater amount of the potassium polyphosphates to achieve results comparable to those achieved when using the sodium polyphosphates.
  • a further object of this invention is to provide a synthetic heavy-duty liquid detergent of the above composition, which detergent is equal in cleaning per- .formance to both the heavy-duty detergent powders and the heavy-duty liquid detergents which use a potassium polyphosphate as the building or sequestering agent.
  • a heavy-duty liquid detergent composition can be made utilizing sodium tripolyphosphate as the major building or sequestering agent, and which composition is equal in cleaning performance to both heavyduty powdered detergents and heavy-duty liquid detergents which utilize potassium polyphosphates as the building or sequestering agent.
  • heavy-duty detergent refers to a product which is alkaline and is suitable for laundry use.
  • light-duty detergent refers to a product that has a pH of about 7 and which is suitable for light household cleaning, such as dishes, etc.
  • the liquid heavy-duty detergent composition of the present invention includes up to about 20%, preferably about 16%, by weight of the total constituents of the composition of a synthetic detergent, having the general formula R,,RSO HN(R wherein x is a number from 1 to 5, R is selected from alkyl groups having from 1 to 18 carbon atoms, at least one of which has at least 8 carbon atoms, R is benzene, and R" is selected from the group consisting of hydrogen, alkyl groups and alkanol groups, said alkyl and alkanol groups containing from 1 to 8 carbon atoms.
  • the synthetic detergent may consist entirely of the above detergent or it may be a mixture consisting of at least 11% by weight of the total constituents in the composition of the above synthetic detergent combined with a sufiicient amount to bring the total synthetic detergent percentage to 16% by weight of the total constituents in the composition of a synthetic detergent having the following general formula RCH OSO R wherein R is an alkyl group having 10 to 18 carbon atoms and R is selected from the group of alkali metals, i.e., sodium, potassium, lithium, rubidium, cesium and francium.
  • the liquid heavyduty detergent composition of the present invention includes up to about 20%, preferably about 16%, of sodium tripolyphosphate as the primary building or sequestering agent, up to about 2%, preferably about 1.5%, SiO as a sodium or potassium silicate as a corrosion inhibitor, up to about 6%, preferably about of a solubilizing agent, such as an alkali metal aryl sulfonate, as for example, potassium xylene sulfonate or potassium toluene sulfonate, and from 0.25 to 0.5%, preferably about 0.36%, lithium added as a water-soluble lithium compound, as for example, lithium hydroxide monohydrate.
  • a solubilizing agent such as an alkali metal aryl sulfonate, as for example, potassium xylene sulfonate or potassium toluene sulfonate, and from 0.25 to 0.5%, preferably about 0.36%, lithium added as a water-soluble lithium compound, as for example,
  • sufiicient potassium hydroxide or sodium hydroxide to bring the pH of the solution within the range of 11 to 12.5 is also added, with about 60% water being added to make 100%.
  • a soil suspending agent such as potassium carboxy methyl cellulose may also be added as well as minor amounts of an optical bleach, a dye, and a perfume.
  • lithium in the form of a water-soluble lithium compound, such as lithium hydroxide monohydrate, is indispensible in the above formulation, if the formulation is to remain stable and not separate into solid and liquid phases.
  • a water-soluble lithium compound such as lithium hydroxide monohydrate
  • the desired amount of lithium may be added to the detergent formulation in the form of any water-soluble lithium compound, it will be understood that the compound used is limited to those compounds, the anion of which will not produce a deleterious effect on either the detergent composition itself, or in any cleaning process in which it is used.
  • the detergent formulation have an initial pH of between 11 and 12.5. It has been found that this pH may be advantageously reached by adding the lithium in the form of lithium hydroxide monohydrate in the amount of from about 1.5 to 3%, preferably about 2.2%, by weight of the total constituents of the detergent composition.
  • the major synthetic detergent compounds may be referred to generally as amine alkyl aryl sulfonates of which the following are specific examples of these compounds: tetrapropylene benzene triethanolamine sulfonate, tetrapropylene benzene diethanolamine sulfonate, tertiary octyl benzene triethanolamine sulfonate, keryl (C H to C H benzene triethanolamine sulfonate, monyl benzene triethanolamine sulfonate, monyl toluene triethanolamine sulfonate, dodecyl toluene triethanolamine sulfonate, dodecyl benzene triethanolamine sulfonate, as well as various other amine derivatives of the above compound, such as for example, the diethaneamine derivatives.
  • excellent results have been produced when using tetrapropylene benzene triethanolamine sul
  • the second synthetic detergent compounds may be re ferred to generally as alkali metal salts of sulfuric acid esters of higher alcohols.
  • these compounds which are suitable for use in the composition of the present invention are: sodium lauryl sulfate, potassium, lauryl sulfate, sodium myristyl sulfate, potassium myristyl sulfate, sodium palmityl sulfate, potassium palmityl sulfate, sodium stearyl sulfate, potassium stearyl sulfate, as well as various other alkali metal salts of the above compounds.
  • excellent results have been produced when using sodium or potassium lauryl sulfate and hence, these compounds are preferred in the composition of the present invention.
  • liquid detergent composition of this invention good results have been obtained by mixing the solid ingredients with the aqueous medium with heating where necessary to aid in the dissolving of the solid ingredients. It is understood however, that the ingredients may be combined in any other order which is found to be satisfactory.
  • Example I A liquid synthetic detergent formulation is prepared having the following composition in parts by Weight:
  • Alkyl benzene triethanolamine sulfonate 1 (50% active ingredients, 2% impurities, 48% H O) 73.2 Potassium xylene sulfonate (96% active ingredients,
  • the alkyl group is a. branched carbon chain having about 12 carbon atoms and designated by the manufacturer, The nqrviessee Corporation of tlanta, Georgia, as Sul-Fon-Ate
  • the above composition is liquid having a pH of 12.6 and is stable, there being no layering, i.e., formation of liquid and solid phases, after more than 12 months.
  • Example II A synthetic detergent formulation is made having the following composition in parts by weight:
  • Alkyl benzene triethanolamine sulfonate (50% active ingredients, 4% impurities, 12% trieth-
  • the alkyl group is a straight carbon chain containing about 12 carbon atoms and designated by the manufacturer, 'lhe National Aniline Division of the Allied Chemical Compap yl has igalcconol 60-5.
  • the above composition is liquid having a pH of 12.3 and 1s stable, there being no layering, i.e., formation of liquid and solid phases after more than 12 months.
  • Example III A synthetic detergent formulation is made having the following composition in parts by weight:
  • Alkyl benzene triethanolamine sulfonate (50% active ingredients, 4% impurities, 12% triethanolamine sulfonate and 34% E 0) 50.18
  • the alkyl group is a non-branched chain containing about 12 carbon atoms and designated by the manufacturer, The American Alcolac Corporation as Sipex K.
  • This composition is liquid, having a pH of 12.4 and exhibits no layering after standing for more than 12 months.
  • Example IV A synthetic detergent formulation having the following composition in parts by weight is made: Alkyl benzene triethanolamine sulfonate (60% active ingredients, 2% triethanolamine sulfonate, 38% H O) 61.00
  • - 'Ihe alkyl group is a branched chain containing about 12 carbon atoms and designated by the manufacturer, The Atlantic Refining Company of Philadelphia, Pennsylvania, as -Ultrawet 60-L.
  • the above formulation is a liquid having a pH of 12.4 and shows no sign of layering after standing for more than 12 months.
  • Example V A synthetic detergent formulation is made up having the following composition in parts by weight: Alkyl benzene triethanolamine sulfonate (60% active ingredients, 2% triethanolamine sulfonate, 38% H O) 61.00
  • the above composition is liquid, having a pH of 11.8 and exhibits no layering after standing for more than 12 months.
  • the above composition is liquid, having a pH of 11.5 and exhibits no layering after standing for more than 12 months.
  • Example VII A synethic detergent formulation is made up as in Example VI except that 3.5 parts by weight LiOH-H O, 2.01 parts by weight KOH and 69.36 parts by weight water are used. This formulation is liquid having a pH of 11.4 and exhibits no layering after standing for 12 months.
  • Example VIII A synthetic detergent formulation as in Example VI is made up except that 3 parts by weight LiOH-H O, 2.68
  • Example IX A synthetic detergent is made having the following composition in parts by weight:
  • the alkyl group is a branched hydrocarbon chain containing about 12 carbon atoms and is designated by the rraalnpfacturer, Ninol Labs. of Chicago, Illinois as Ninex This formulation has a pH of 12.3 but is very unstable, forming solid and liquid layers upon standing overnight.
  • Example X A synthetic detergent formulation is made as in Example IX except that 5.7 parts by weight NaOH is used instead of KOH and 75.87 parts by weight water are used. This formulation has a pH of 12.6 and like the formulation of Example VIII is very unstable, separating into solid and liquid layers upon standing overnight.
  • Example XI A synthetic detergent formulation is made having the following composition in parts by weight:
  • Alkyl benzene triethanolamine sulfonate (60% active ingredients, 2% triethanolamine sulfonate,
  • the above formulation has a pH of 12.0 and is very unstable, forming liquid and solid layers upon standing overnight.
  • the resulting detergent product is unstable. Moreover, it is also seen that the corresponding sodium and potassium compounds cannot be substituted for the ithium compound in the formulation and still obtain a stable composition.
  • Example XII A synthetic detergent formulation is made having the following composition in parts by weight: Alkyl benzene triethanolamine sulfonate 1 (60% active ingredients, 2% triethanolamine sulfonate,
  • the above formulation has a pH of 12.2 and is stable, there being no layering after standing for more than 6 months.
  • Example XIII A synthetic detergent formulation is made as in Example XII with the exception that 46 parts by weight of sodium tripolyphosphate, 42.6 parts by weight of Ultrawet 60-L and 77.27 parts by weight of water are used. This formulation is a liquid, having a pH of 12.3, and is found to be unlayered after standing for more than 6 months.
  • washing tests are made comparing the formulation of the present invention with a standard heavy-duty synthetic powder and a synthetic heavy-duty potassium polyphosphate built liquid detergent.
  • the apparatus used in these tests is a Launder-Ometer, the standard laboratory washing machine of the American Association of Textile Chemists and-Colorists, manufactured by The Atlas Electric Devices Company of Chicago, Illinois. This machine consists of a water bath, having positioned herein a rotor which carries 20 glass jars or similar sample holders. The rotor is driven in the water bath at a speed of 42 rpm, the temperature of the water bath being thermostatically controlled at 120 F.
  • wheat starch and a mixture of vegetable and mineral oils, are placed in each glass .jar with ml. of water and 0.5 g.-1 g. of the detergent to be tested, the water having a known hardness.
  • Ten rubber balls are placed in each jar to provide mechanical agitation for the samples and the jars are closed and placed in the Launder-Ometer.
  • the jars are rotated in the Launder- Ometer for a period of 30 minutes at a temperature of 120 F after which time the fabric specimens are rinsed, by agitation, for 30 seconds in 6 liters of distilled water at a temperature of F.
  • the patches are then placed between two cotton towels and ironed with an electric iron until dry.
  • the amount of light reflected from the patches is measured both before and after the washing test with a standard photometer, the gain in the amount of reflectance after washing being used as the measure of the effectiveness of the detergent.
  • the standard soil used in these tests consists of 3 gms. of Germantown lampblack, 6 gms. of wheat starch and 9 gms. of a vegetable shortening, which materials are warmed to 100 F. and mulled into a paste. To this paste is added 12.9 grns. of a high grade, impurity free mineral oil, designated by the manufacturer as Nujol, and the mixture is stirred at a temperature of 100 F. until homogeneous.
  • the heavy-duty powder synthetic detergent which is used is a commercial product containing about 20% of a synthetic detergent which is a combination of a sodium alkyl aryl sulfonate and a sodium alcohol sulfate about 2% of a condensed alkanol amide of a fatty acid as a foam stabilizer, about 45% of sodium tripolyphosphate as the alkaline builder, about 7% of sodium metasilicate as the corrosion inhibitor, about 18% of sodium sulfate to increase the bulk of the product, about 1% sodium carboxy methyl cellulose as the soil suspending agent and the remainder (about7%) water.
  • the synthetic heavy-duty liquid detergent used is, likewise, a commercial product containing about 10% of potassium alkyl aryl sulfonate as the synthetic detergent, about 7% of a condensed alkanol amide of a fatty acid as the foam stabilizer, about 20% of tetrapotassium pyrophosphate as the alkaline builder, about 7.5% sodium xylene sulfonate as the solubilizing agent, about 12% liquid potassium silicate (30% solution) as the corrosion inhibitor, about 3% potassium hydroxide, about 1% sodium carboxy methyl cellulose as the soil suspending agent, and the remainder (about 40%) water.
  • Example XI V Detergent Cone Soiled Washed (Name of H20 Hardness Cloth Cloth Gain Detergent (ppm. of 02.00;) Reflec- Reflecon 100 m1. tance tanee Heavy Duty Powder 0.5 Distilled H20"-.- 38. 3 76. 5 38.2 K Built Liquid 0.5 Distilled H10---" 38. 3 71.2 32.9
  • the' synthetic liquid heavy-duty detergents .of the present invention are at least comparable in washing effectiveness to the heavy-duty powder and the potassium built heavy-duty liquid.
  • the formulations of the present invention contain only about 40% active ingredients as compared to the potassium built liquid which contains 50% active ingredients or the heavy-duty powder which contains almost 100% active ingredients. It can thus be seen that when quantities of the detergents are used containing equivalent amounts of active ingredients, i.e., .7 gm. of the formulation of the present invention and .5 gm. of the potassium built liquid, the washing effectiveness of the formulation of the present invention are equal to or better than that of the potassium built liquid.
  • the heavy-duty powder it would be necessary to use better than 1 gm. of the present formulation to have active ingredients equivalent to those in a half a gram of a heavy-duty powder and similar washing elfectivene'ss would result.
  • a stable heavy-duty liquidsynthetic detergent composition comprising 11% to 20% of a synthetic detergent, at least 11% of which is an amine alkyl aryl sulfonate having the general formula:
  • R is selected from alkyl groups having 1 to 18 carbon atoms, at least one of which has at least 8 carbon atoms, R is benzene
  • R" is selected from the group consisting of hydrogen, alkyl groups and alkanol groups, said alkyl and alkanol groups containing from 1 to 8 carbon atoms, and up to of which is an alkali metal salt of a sulfuric acid ester of a higher alcohol, 15% to 20% of sodium tripolyphosphate as the alkaline builder, l% to 2% of SiO-,, as an alkali metal silicate as the corrosion inhibitor, 4% to 6% of an alkali metal aryl sulfonate, the aryl group of which is selected from the group consisting of xylene and toluene, as the solubilizing agent, and in addition to said alkali metal silicate, from 0.25 to 0.5% lithium as a lithium hydroxide, up to about 1% of potassium carboxy
  • a stable heavy duty liquid synthetic detergent formulation having the following composition in percent by weight:
  • a stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:
  • a stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:
  • a stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:
  • a stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:
  • a stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:

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Abstract

A heavy duty homogeneous aqueous synthetic detergent composition comprises (a) an alkylaryl amine sulphonate; (b) an alkali metal silicate; (c) an alkali metal aryl sulphonate; (d) sodium tripolyphosphate; and (e) at least 0.25% by weight of the total composition of lithium as a water soluble lithium compound. (a) preferably comprises up to 20% by weight of the composition, and has the general formula (R)x-R1-SO3HN(R11)3 where x is 1-5, R is selected from alkyl groups of 1-18 carbon atoms at least one of which has at least 8 carbon atoms, R1 is benzene, R11 is selected from alkyl or alkanol groups containing 1-8 carbon atoms; tetrapropylene benzene triethanolamine sulphonate is the preferred compound. (b) is a sodium or potassium silicate wherein generally the ratio SiO2:Na2O is 3.3:1 and that of SiO2:K2O is 2.2:1, and the amount incorporated is up to 2% of the composition by weight, calculated as SiO2. (c) is used in amounts up to 6% by weight and is usually potassium xylene or toluene sulphonate (d) comprises up to 20% of the composition and (e), which is invariably lithium hydroxide monohydrate, from 0.25-0.5%, calculated as lithium. In one embodiment, ingredient (a) is in part replaced by up to 5% of an alkali metal alkyl sulphate having 10-18 carbon atoms, preferably sodium lauryl sulphate, the amount of (a) then incorporated being at least 11%. The compositions generally also contain up to 1% potassium carboxymethyl cellulose, and optical bleach, dye, and perfume.

Description

United States Patent 3,066,104 HEAVY DUTY LIQUID SYNTHETIC DETERGENT COMPOSITION Lawrence Dasch and Paul R. Cutter, Painesville, Ohio, assignors to Diamond Alkali Company, Cleveland, Ohio, a corporation of Delaware No Drawing. Filed Feb. 10, 1958, Ser. No. 714,013 11 Claims. (0 252-137) This invention relates to synthetic heavy-duty liquid detergents, and more particularly to synthetic heavy-duty liquid detergent compositions wherein the principal building and sequestering agent is sodium tripolyphosphate.
In recent years, the natural detergents, such as the various soaps, have been replaced to a considerable extent by synthetic detergents, particularly in the laundry field, both home and commercial. This has come about primarily because the synthetic detergents, unlike the natural detergents are resistant to both acids and hard water. Thus, synthetic detergents can be used both in cleaning processes where the pH is below 8, in which processes the soaps dissociate and can not be used, as well as in hard water wherein the soaps form insoluble calcium and magnesium compounds, which compounds are deleterious to the cleaning action of the soap.
The synthetic detergents have, for the most part, been marketed in the form of a powder, which powder is generally made up of an anionic detergent, such as a sodium alkyl aryl sulfonate, a foam stabilizer, such as a condensed alkanolamide of a fatty acid, a building or sequestering agent, such as sodium tripolyphosphate or tetrasodium pyrophosphate, a rust or corrosion inhibitor, such as sodium metasilicate, a soil suspending agent, such as sodium carboxy methyl cellulose and minor amounts of an optical bleach and a dye. These ingredients make up about 70% of the composition, the remaining 30% being an inert electrolyte, such as sodium sulfate, which although added mainly to increase the bulk of the finished detergent product, does itself have some detergent value.
More recently, synthetic heavy-duty detergents in liquid form have begun to be preferred over the powders. The liquids have been found to be more convenient to use, i.e., they can be easily poured from their containers and resealed therein by means of a replaceable cap, while the powders have a tendency to spill out of their cartons. Moreover, the liquids are instantly soluble in either hot or cold water, while powders, in a laundering operation, may fold into the dry clothes and not get completely into solution until the wash cycle is half over. However, since these detergent compositions are in solution rather than in the dry state, a radical change in their formulation over that of the dry powder formulation has been necessary.
The primary departure in a liquid heavy-duty synthetic detergent formulation from that of a dry formulation is the use of a potassium polyphosphate as the alkaline builder or sequestering agent instead of a sodium polyphosphate. This change is necessary because of the limited solubility of the sodium polyphosphates in water, hence making it impossible to incorporate the necessary amount of detergent composition and builder or sequestering agent in the solution without causing it to break up into a solid-liquid phase. In addition, it is necessary to incorporate a solubilizing agent such as sodium xylene sulfonate into the composition, which agent aids in dispersing the organic detergent constituents in the solution. Finally, the sodium sulfate filler used in the powder is replaced in the liquid detergent by water.
"ice
Although such a liquid composition, utilizing a potassium polyphospha-te as the building agent or sequestering agent, gives cleaning results comparable to those obtained by using a heavy-duty detergent powder, such a composition does have several disadvantages. Foremost, is the fact that the potassium polyphosphates are about twice :as expensive as the corresponding sodium polyphosphate, thus causing a considerable increase in price of such a liquid heavy-duty detergent over that of the corresponding powder. In addition, the building and sequestering action, on an equal weight basis, of the potassium polyphosphates are somewhat less than those of the corresponding sodium polyphosphates, hence making it necessary to use a greater amount of the potassium polyphosphates to achieve results comparable to those achieved when using the sodium polyphosphates.
It is, therefore, an object of this invention to provide a vsynthetic heavy-duty liquid detergent composition, which composition utilizes sodium tripolyphosphate as the principal building or sequestering agent.
A further object of this invention is to provide a synthetic heavy-duty liquid detergent of the above composition, which detergent is equal in cleaning per- .formance to both the heavy-duty detergent powders and the heavy-duty liquid detergents which use a potassium polyphosphate as the building or sequestering agent.
These and other objects will become apparent to those skilled in the art from the description of the invention which follows.
Pursuant to the above objects, it has been found that by incorporating a small amount of a water-soluble lithium compound into the heavy-duty liquid detergent formulation, a heavy-duty liquid detergent composition can be made utilizing sodium tripolyphosphate as the major building or sequestering agent, and which composition is equal in cleaning performance to both heavyduty powdered detergents and heavy-duty liquid detergents which utilize potassium polyphosphates as the building or sequestering agent.
The term heavy-duty detergent as used in the specification and claims refers to a product which is alkaline and is suitable for laundry use. This is contrasted with the term light-duty detergent, which term refers to a product that has a pH of about 7 and which is suitable for light household cleaning, such as dishes, etc.
The liquid heavy-duty detergent composition of the present invention includes up to about 20%, preferably about 16%, by weight of the total constituents of the composition of a synthetic detergent, having the general formula R,,RSO HN(R wherein x is a number from 1 to 5, R is selected from alkyl groups having from 1 to 18 carbon atoms, at least one of which has at least 8 carbon atoms, R is benzene, and R" is selected from the group consisting of hydrogen, alkyl groups and alkanol groups, said alkyl and alkanol groups containing from 1 to 8 carbon atoms. The synthetic detergent may consist entirely of the above detergent or it may be a mixture consisting of at least 11% by weight of the total constituents in the composition of the above synthetic detergent combined with a sufiicient amount to bring the total synthetic detergent percentage to 16% by weight of the total constituents in the composition of a synthetic detergent having the following general formula RCH OSO R wherein R is an alkyl group having 10 to 18 carbon atoms and R is selected from the group of alkali metals, i.e., sodium, potassium, lithium, rubidium, cesium and francium.
In addition to the synthetic detergent, the liquid heavyduty detergent composition of the present invention includes up to about 20%, preferably about 16%, of sodium tripolyphosphate as the primary building or sequestering agent, up to about 2%, preferably about 1.5%, SiO as a sodium or potassium silicate as a corrosion inhibitor, up to about 6%, preferably about of a solubilizing agent, such as an alkali metal aryl sulfonate, as for example, potassium xylene sulfonate or potassium toluene sulfonate, and from 0.25 to 0.5%, preferably about 0.36%, lithium added as a water-soluble lithium compound, as for example, lithium hydroxide monohydrate. In addition, sufiicient potassium hydroxide or sodium hydroxide to bring the pH of the solution within the range of 11 to 12.5 is also added, with about 60% water being added to make 100%. If it is desired, about 1% by weight of the total constituents of a soil suspending agent such as potassium carboxy methyl cellulose may also be added as well as minor amounts of an optical bleach, a dye, and a perfume.
It has been found that 0.25 to 0.5% lithium, in the form of a water-soluble lithium compound, such as lithium hydroxide monohydrate, is indispensible in the above formulation, if the formulation is to remain stable and not separate into solid and liquid phases. Although it is not known how the lithium functions in this formulation, nor even what its function is, it has been found that similar results can not be obtained by using sodium or potassium. When equivalent amounts of the corresponding sodium and potassium compounds are substituted for the lithium in the above formulation, the mixture separates almost at once, forming liquid and solid phases. It is only when lithium is present, in the amounts indicated above, i.e., 0.25 to 0.5 by weight of the total composition, that a stable mixture is formed.
Although, as set forth above, the desired amount of lithium may be added to the detergent formulation in the form of any water-soluble lithium compound, it will be understood that the compound used is limited to those compounds, the anion of which will not produce a deleterious effect on either the detergent composition itself, or in any cleaning process in which it is used. Inasmuch as the best laundering results are achieved when the cleaning is done in a solution having a pH between 9 and 10, to achieve this pH, it is desirable that the detergent formulation have an initial pH of between 11 and 12.5. It has been found that this pH may be advantageously reached by adding the lithium in the form of lithium hydroxide monohydrate in the amount of from about 1.5 to 3%, preferably about 2.2%, by weight of the total constituents of the detergent composition.
The major synthetic detergent compounds may be referred to generally as amine alkyl aryl sulfonates of which the following are specific examples of these compounds: tetrapropylene benzene triethanolamine sulfonate, tetrapropylene benzene diethanolamine sulfonate, tertiary octyl benzene triethanolamine sulfonate, keryl (C H to C H benzene triethanolamine sulfonate, monyl benzene triethanolamine sulfonate, monyl toluene triethanolamine sulfonate, dodecyl toluene triethanolamine sulfonate, dodecyl benzene triethanolamine sulfonate, as well as various other amine derivatives of the above compound, such as for example, the diethaneamine derivatives. Of these compounds, excellent results have been produced when using tetrapropylene benzene triethanolamine sulfonate and keryl benzene triethanolamine sulfonate, and for this reason these compounds are preferred.
The second synthetic detergent compounds may be re ferred to generally as alkali metal salts of sulfuric acid esters of higher alcohols. Examples of these compounds which are suitable for use in the composition of the present invention are: sodium lauryl sulfate, potassium, lauryl sulfate, sodium myristyl sulfate, potassium myristyl sulfate, sodium palmityl sulfate, potassium palmityl sulfate, sodium stearyl sulfate, potassium stearyl sulfate, as well as various other alkali metal salts of the above compounds. Of these compounds, excellent results have been produced when using sodium or potassium lauryl sulfate and hence, these compounds are preferred in the composition of the present invention.
In forming the liquid detergent composition of this invention, good results have been obtained by mixing the solid ingredients with the aqueous medium with heating where necessary to aid in the dissolving of the solid ingredients. It is understood however, that the ingredients may be combined in any other order which is found to be satisfactory.
In order that those skilled in the art may better understand the compositions of the present invention, the following examples are offered.
Example I A liquid synthetic detergent formulation is prepared having the following composition in parts by Weight:
Alkyl benzene triethanolamine sulfonate 1 (50% active ingredients, 2% impurities, 48% H O) 73.2 Potassium xylene sulfonate (96% active ingredients,
4% H O) 9.2 N21 SiO -5H O Sodium tripolyphosphate 35.0 LiOH'H O 4.0 Potassium carboxy methyl cellulose (5% Water solution) 36.0 Water 59.8
Bleach 0.2 Dye (0.75% water solution) 2.0
1 The alkyl group is a. branched carbon chain having about 12 carbon atoms and designated by the manufacturer, The geknqrviessee Corporation of tlanta, Georgia, as Sul-Fon-Ate The above composition is liquid having a pH of 12.6 and is stable, there being no layering, i.e., formation of liquid and solid phases, after more than 12 months.
Example II A synthetic detergent formulation is made having the following composition in parts by weight:
Alkyl benzene triethanolamine sulfonate (50% active ingredients, 4% impurities, 12% trieth- The alkyl group is a straight carbon chain containing about 12 carbon atoms and designated by the manufacturer, 'lhe National Aniline Division of the Allied Chemical Compap yl has igalcconol 60-5. b h d 11 e a '57 group 15 a nonranc e c ain contalnin abo 12 carbon atoms and designated by the manufacture r, TE; American Alcolac Corporation, as Sipex SD.
The above composition is liquid having a pH of 12.3 and 1s stable, there being no layering, i.e., formation of liquid and solid phases after more than 12 months.
Example III A synthetic detergent formulation is made having the following composition in parts by weight:
Alkyl benzene triethanolamine sulfonate (50% active ingredients, 4% impurities, 12% triethanolamine sulfonate and 34% E 0) 50.18
Potassium xylene sulfonate (96% active ingredients and 4% H O) 1 Nacconol 60-8.
Example III-Continued Potassium alkyl sulfonate (28% active ingredients, 2% fatty alcohols, 2% inorganic salts and 68% H O) 50.40 Na- SiO -5H O 10.60 Sodium tripolyphosphate 35.00 LiOH-H O 4.00 Potassium carboxy methyl cellulose (5% water solution) 36.00 Water 32.39 Bleach 0.23 Dye (0.75% water solution) 2.00
2 The alkyl group is a non-branched chain containing about 12 carbon atoms and designated by the manufacturer, The American Alcolac Corporation as Sipex K.
This composition is liquid, having a pH of 12.4 and exhibits no layering after standing for more than 12 months.
Example IV A synthetic detergent formulation having the following composition in parts by weight is made: Alkyl benzene triethanolamine sulfonate (60% active ingredients, 2% triethanolamine sulfonate, 38% H O) 61.00
Potassium xylene sulfonate (96% active ingredients, 4% H O) 9.20 Sodium tripolyphosphate 35.00 LiOH-H O 6.00 K SiO (SiO :K O ratio=2. 2 :1) 17.70 Potassium carboxy methyl cellulose (5% water solution) 36.00 Water 62.87 Bleach 0.23 Dye (0.75% water solution) 2.00
- 'Ihe alkyl group is a branched chain containing about 12 carbon atoms and designated by the manufacturer, The Atlantic Refining Company of Philadelphia, Pennsylvania, as -Ultrawet 60-L.
The above formulation is a liquid having a pH of 12.4 and shows no sign of layering after standing for more than 12 months.
Example V A synthetic detergent formulation is made up having the following composition in parts by weight: Alkyl benzene triethanolamine sulfonate (60% active ingredients, 2% triethanolamine sulfonate, 38% H O) 61.00
Potassium xylene sulfonate (96% active ingredients,.4% H O) 9.20
Sodium tripolyphosphate 35.00
Potassium carboxy methyl cellulose (5% water 1 Ultrawet 60-L.
The above composition is liquid, having a pH of 11.8 and exhibits no layering after standing for more than 12 months.
Example VI A synthetic detergent formulation is made up having the following composition in parts by weight: 'Alkyl benzene triethanolamine sulfonate (60% active ingredients, 2% triethanolamine sulfosolution) 36.00 LiOH-H O 5.00 Na SiO (SiO :Na O ratio=3.3:1) 11.70
Water 69.87 Bleach .23 Dye (0.75% water solution) 2.00
6 KOH v 1.34 Na SiO (SiO :Na O ratio=3.3:l) 11.70 Water 69.53 Bleach 0.23 Dye (0.75% water solution) 2.00
The above composition is liquid, having a pH of 11.5 and exhibits no layering after standing for more than 12 months.
Example VII A synethic detergent formulation is made up as in Example VI except that 3.5 parts by weight LiOH-H O, 2.01 parts by weight KOH and 69.36 parts by weight water are used. This formulation is liquid having a pH of 11.4 and exhibits no layering after standing for 12 months.
Example VIII A synthetic detergent formulation as in Example VI is made up except that 3 parts by weight LiOH-H O, 2.68
, parts by weight KOH, and 69.19 parts by Weight water are used. This formulation has a pH of 11.4, but is very unstable, forming liquid and solid phases upon standing for only one day. 7
Example IX A synthetic detergent is made having the following composition in parts by weight:
Alkyl benzene triethanolamine sulfonate active ingredients, 1% triethanolamine sulfoa nate, 24% H O) 49.10 Sodium tripolyphosphate 35.00 Potassium carboxy methyl cellulose (5% water solution) 36.00 Potassium xylene sulfonate (96% active ingrediients, 4% H O) 9.20 K SiO (SiO :K O ratio=2.2:1) 16.90 KOH 8.00 Water 73.57 Bleach 0.23 Dye (0.75% water solution) 2.00
The alkyl group is a branched hydrocarbon chain containing about 12 carbon atoms and is designated by the rraalnpfacturer, Ninol Labs. of Chicago, Illinois as Ninex This formulation has a pH of 12.3 but is very unstable, forming solid and liquid layers upon standing overnight.
Example X A synthetic detergent formulation is made as in Example IX except that 5.7 parts by weight NaOH is used instead of KOH and 75.87 parts by weight water are used. This formulation has a pH of 12.6 and like the formulation of Example VIII is very unstable, separating into solid and liquid layers upon standing overnight.
Example XI A synthetic detergent formulation is made having the following composition in parts by weight:
, Alkyl benzene triethanolamine sulfonate (60% active ingredients, 2% triethanolamine sulfonate,
nate, 38% H 0) 61.00. Potassium xylene sulfonate (96% active ingredients, 4% H O) 9.20 Sodium tripolyphosphate 35.00
Potassium carboxy methyl cellulose (5% water solution) l LiOH-H O- 1 Ultrawet 60-L.
1 Ultrawet 60-L.
The above formulation has a pH of 12.0 and is very unstable, forming liquid and solid layers upon standing overnight.
From Examples VIII-XI, it can be seen that when less than 0.25% Li, i.e., less than 1.5% LiOH-H O, is
used in the formulations of the present invention, the resulting detergent product is unstable. Moreover, it is also seen that the corresponding sodium and potassium compounds cannot be substituted for the ithium compound in the formulation and still obtain a stable composition.
Example XII A synthetic detergent formulation is made having the following composition in parts by weight: Alkyl benzene triethanolamine sulfonate 1 (60% active ingredients, 2% triethanolamine sulfonate,
1 Ultrawet 60-L.
The above formulation has a pH of 12.2 and is stable, there being no layering after standing for more than 6 months.
Example XIII A synthetic detergent formulation is made as in Example XII with the exception that 46 parts by weight of sodium tripolyphosphate, 42.6 parts by weight of Ultrawet 60-L and 77.27 parts by weight of water are used. This formulation is a liquid, having a pH of 12.3, and is found to be unlayered after standing for more than 6 months.
To determine the effectiveness of the liquid synthetic heavy-duty detergent formulations of the present invention, washing tests are made comparing the formulation of the present invention with a standard heavy-duty synthetic powder and a synthetic heavy-duty potassium polyphosphate built liquid detergent. The apparatus used in these tests is a Launder-Ometer, the standard laboratory washing machine of the American Association of Textile Chemists and-Colorists, manufactured by The Atlas Electric Devices Company of Chicago, Illinois. This machine consists of a water bath, having positioned herein a rotor which carries 20 glass jars or similar sample holders. The rotor is driven in the water bath at a speed of 42 rpm, the temperature of the water bath being thermostatically controlled at 120 F.
In making the test, two fabric specimens, impregnated with a standard soil, consisting of lamp black,
wheat starch, and a mixture of vegetable and mineral oils, are placed in each glass .jar with ml. of water and 0.5 g.-1 g. of the detergent to be tested, the water having a known hardness. Ten rubber balls are placed in each jar to provide mechanical agitation for the samples and the jars are closed and placed in the Launder-Ometer. The jars are rotated in the Launder- Ometer for a period of 30 minutes at a temperature of 120 F after which time the fabric specimens are rinsed, by agitation, for 30 seconds in 6 liters of distilled water at a temperature of F. The patches are then placed between two cotton towels and ironed with an electric iron until dry. The amount of light reflected from the patches is measured both before and after the washing test with a standard photometer, the gain in the amount of reflectance after washing being used as the measure of the effectiveness of the detergent. The standard soil used in these tests consists of 3 gms. of Germantown lampblack, 6 gms. of wheat starch and 9 gms. of a vegetable shortening, which materials are warmed to 100 F. and mulled into a paste. To this paste is added 12.9 grns. of a high grade, impurity free mineral oil, designated by the manufacturer as Nujol, and the mixture is stirred at a temperature of 100 F. until homogeneous. This mixture is stirred into three liters of carbon tetrachloride and allowed to stand for 2 hours, whereafter Indian Head cotton cloth is impregnated with the mixture. Following the impregnation, cloth is dried and 2" .x 2 /2" rectangular swatches are cut from the cloth, which swatches are used in the above-described test.
The results of these washing tests are shown in the following example. It is to be noted in the example that the heavy-duty powder synthetic detergent which is used is a commercial product containing about 20% of a synthetic detergent which is a combination of a sodium alkyl aryl sulfonate and a sodium alcohol sulfate about 2% of a condensed alkanol amide of a fatty acid as a foam stabilizer, about 45% of sodium tripolyphosphate as the alkaline builder, about 7% of sodium metasilicate as the corrosion inhibitor, about 18% of sodium sulfate to increase the bulk of the product, about 1% sodium carboxy methyl cellulose as the soil suspending agent and the remainder (about7%) water.
The synthetic heavy-duty liquid detergent used is, likewise, a commercial product containing about 10% of potassium alkyl aryl sulfonate as the synthetic detergent, about 7% of a condensed alkanol amide of a fatty acid as the foam stabilizer, about 20% of tetrapotassium pyrophosphate as the alkaline builder, about 7.5% sodium xylene sulfonate as the solubilizing agent, about 12% liquid potassium silicate (30% solution) as the corrosion inhibitor, about 3% potassium hydroxide, about 1% sodium carboxy methyl cellulose as the soil suspending agent, and the remainder (about 40%) water.
Example XI V Detergent Cone. Soiled Washed (Name of H20 Hardness Cloth Cloth Gain Detergent (ppm. of 02.00;) Reflec- Reflecon 100 m1. tance tanee Heavy Duty Powder 0.5 Distilled H20"-.- 38. 3 76. 5 38.2 K Built Liquid 0.5 Distilled H10---" 38. 3 71.2 32.9
0.5 Distilled H10..." 31. 6 68.0 36.4 0.5 35. 5 78.0 42. 5 0.5 32. 6 71. 9 38. 3 0. 5 33. 5 (i6. 0 32. 5 0.7 36. 5 74. 3 37. 8 0. 5 37. 5 75. 3 37.8 0.5 35.6 67.8 32. 2 0.5 34. 4 67. 8 33. 4 0.5 39. 7 74. 7 35.0 0. 5 40. 4 68. 8 28. 4 0. 5 36. 5 58. 7 22. 2 0. 7 39. 5 70. 9 31. 4
From the above example, it can be seen that when equal quantities, by weight, of the detergent formulations are used, the' synthetic liquid heavy-duty detergents .of the present invention are at least comparable in washing effectiveness to the heavy-duty powder and the potassium built heavy-duty liquid. It must be noted however, that the formulations of the present invention contain only about 40% active ingredients as compared to the potassium built liquid which contains 50% active ingredients or the heavy-duty powder which contains almost 100% active ingredients. It can thus be seen that when quantities of the detergents are used containing equivalent amounts of active ingredients, i.e., .7 gm. of the formulation of the present invention and .5 gm. of the potassium built liquid, the washing effectiveness of the formulation of the present invention are equal to or better than that of the potassium built liquid. Likewise, for the heavy-duty powder, it would be necessary to use better than 1 gm. of the present formulation to have active ingredients equivalent to those in a half a gram of a heavy-duty powder and similar washing elfectivene'ss would result.
While there have been described various embodiments of the invention, the methods and products described are not intended to be understood as limiting the scope of the invention as it is realized that changes therewithin are possible and it is further intended that each element recited in any of the following claims is to be understood as referring to all equivalent elements for accomplishing substantially the same results in substantially the same or equivalent manner, it being intended to cover the invention broadly in whatever form its principle may be utilized.
What is claimed is:
1. A stable heavy-duty liquidsynthetic detergent composition comprising 11% to 20% of a synthetic detergent, at least 11% of which is an amine alkyl aryl sulfonate having the general formula:
where x is a number from 1 to 5, R is selected from alkyl groups having 1 to 18 carbon atoms, at least one of which has at least 8 carbon atoms, R is benzene, and R" is selected from the group consisting of hydrogen, alkyl groups and alkanol groups, said alkyl and alkanol groups containing from 1 to 8 carbon atoms, and up to of which is an alkali metal salt of a sulfuric acid ester of a higher alcohol, 15% to 20% of sodium tripolyphosphate as the alkaline builder, l% to 2% of SiO-,, as an alkali metal silicate as the corrosion inhibitor, 4% to 6% of an alkali metal aryl sulfonate, the aryl group of which is selected from the group consisting of xylene and toluene, as the solubilizing agent, and in addition to said alkali metal silicate, from 0.25 to 0.5% lithium as a lithium hydroxide, up to about 1% of potassium carboxy methyl cellulose as the soil suspending agent, the remainder of said composition being water, all of said percentages being percent by weight of the total constituents of the composition.
2. The stable heavy-duty liquid synthetic detergent composition as defined in claim 1 wherein the alkyl aryl amine sulfonate is tetrapropylene benzene triethanolamine sulfonate, the alkali metal salt of the sulfuric acid ester of a higher alcohol is sodium lauryl sulfate, the alkali metal silicate is sodium metasilicate, the alkali metal aryl sulfonate is potassium xylene sulfonate, and the lithium hydroxide is lithium hydroxide monohydrate.
3. A stable heavy duty liquid synthetic detergent formulation having the following composition in percent by weight:
Percent Tetrapropylenebenzene triethanolamine sulfonate 15.9 Potassium xylene sulfonate 4.0 Sodium tripolyphosphate 15.2 Lithium hydroxide monohydrate 2.6 Potassium liquid silicate having an SiO zK o ratio Percent of 2.2:1 as a 28.4% solution 7.3 Potassium carboxy methyl cellulose 0.8 Water Remainder 4. A stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:
5. A stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:
Percent Tetrapropylene benzene triethanolamine sulfonate" 15 .9 Sodium tripolyphosphate 15-2 Potassium xylene sulfonate 4.0 Lithium hydroxide monohydrate 1.7 Sodium metasilicate 4.6 Potassium carboxy methyl cellulose 0.8 Water Remainder 6. A stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:
Percent Keryl benzene triethanolamine sulfonate 10.9 Potassium lauryl sulfate 5.0 Potassium xylene sulfonate 4.0
Sodium tripolyphosphate 15 .2
Sodium metasilicate 4.6 Lithium hydroxide monohydrate 1.7 Potassium carboxy methyl cellulose 08 Water Remainder 7. A stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:
- Percent Tetrapropylenebenzene triethanolamine sulfonate 15.9 Sodium tripolyphosphate 15.2 Potassium xylene sulfonate 4,0
Sodium liquid silicate having an SiO :Na O ratio of 3.3:1 as a 38.0% solution 5.1 Lithium hydroxide monohydrate 1.7 KOH 0.6 Potassium carboxy methyl cellulose 0.8 Water Remainder 8. A stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:
Percent Tetrapropylene'benzene triethanolamine sulfonate 15 .9 Sodium tripolyphosphate 52 Potassium xylene sulfonate 4.0
Sodium liquid silicate having an SiO :Na O ratio of 3.3:1 as a 38.0% solution 5.1 Lithium hydroxide monohydrate 1.5 KOH 0.9 Potassium carboxy methyl cellulose 0.8 Water Remainder 9. A stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:
Percent Tetrapropylenebenzene triethanolamine sulfonate 13.6 Sodium tripolyphosphate 17.5
Potassium toluene sulfonate 4.0
Percent 'Sodiumliquid silicate having an 'SiO :Na O ratio of 10. A stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:
Percent Tetrapropylenebenzene triethanolamine sulfonate 11.1 Sodium tripolyphosphate 20.0 Potassium toluene sulfonate 4.0
Sodium liquid silicate having an SiO :Na O ratio of 11. A stable heavy-duty liquid synthetic detergent formulation having the following composition in percent by weight:
Percent Tetrapropylenebenzene triethanolamine sulfonate 15.9 Sodium tripolyphosphate 15.2 Potassium xylene sulfonate 4.0 Lithium hydroxide monohydrate 2.2 Potassium carboxy methyl cellulose 0.8
Sodium liquid silicate having an SiO :Na O ratio of 3.321 as a 38.0% solution 5.1 Water Remainder References Cited in the file of this patent UNITED STATES PATENTS 2,534,781 MacMahon Dec. 19, 1950 2,562,154 Vitalis July 24, 1951 2,581,677 Machlis Jan. 8, 1952 2,607,740 Vitale Aug. 19, 1952 2,859,182 Carroll Nov. 4, 1958 FOREIGN PATENTS 650,222 Great Britain Feb. 21, 1951 783,585 Great Britain Sept. 25, 1957

Claims (1)

1. A STABLE HEAVY-DUTY LIQUID SYNTHETIC DETERGENT COMPOSITION COMPRISING 11% TO 20% OF A SYNTHETIC DETERGENT, AT LEAST 11% OF WHICH IS AN AMINE ALKYL ARYL SULFONATE HAVING THE GENERAL FORMULA:
US714013A 1958-02-10 1958-02-10 Heavy duty liquid synthetic detergent composition Expired - Lifetime US3066104A (en)

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DED29975A DE1081589B (en) 1958-02-10 1959-02-09 Highly active, liquid, synthetic detergents and cleaning agents
FR786169A FR1228110A (en) 1958-02-10 1959-02-09 Synthetic liquid detergents

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US3303136A (en) * 1963-02-26 1967-02-07 Lever Brothers Ltd Detergent compositions
US3673096A (en) * 1968-09-26 1972-06-27 Henkel & Cie Gmbh Protein solubilizing washing rinsing and soaking compositions
US4000082A (en) * 1975-10-02 1976-12-28 Basf Wyandotte Corporation Defoaming compositions based on lithium salts

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Publication number Priority date Publication date Assignee Title
BE615983A (en) * 1961-04-17 1962-07-31

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US2534781A (en) * 1945-05-24 1950-12-19 Olin Mathieson Stable lithium hypochlorite composition
GB650222A (en) * 1948-04-19 1951-02-21 Frederick Joseph Pollok Improvements in or relating to aqueous solutions containing soapless detergents
US2562154A (en) * 1949-11-03 1951-07-24 American Cyanamid Co Wetting and detergent composition
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
GB783585A (en) * 1954-11-18 1957-09-25 Armour & Co Improvements in or relating to liquid detergent compositions
US2859182A (en) * 1956-11-02 1958-11-04 Lever Brothers Ltd Heavy duty liquid detergent composition

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US2581677A (en) * 1952-01-08 Phosphate detergent composition in
US2534781A (en) * 1945-05-24 1950-12-19 Olin Mathieson Stable lithium hypochlorite composition
GB650222A (en) * 1948-04-19 1951-02-21 Frederick Joseph Pollok Improvements in or relating to aqueous solutions containing soapless detergents
US2562154A (en) * 1949-11-03 1951-07-24 American Cyanamid Co Wetting and detergent composition
US2607740A (en) * 1950-05-03 1952-08-19 Colgate Palmolive Peet Co Liquid anionic-dialkylolamide detergent composition
GB783585A (en) * 1954-11-18 1957-09-25 Armour & Co Improvements in or relating to liquid detergent compositions
US2859182A (en) * 1956-11-02 1958-11-04 Lever Brothers Ltd Heavy duty liquid detergent composition

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US3303136A (en) * 1963-02-26 1967-02-07 Lever Brothers Ltd Detergent compositions
US3673096A (en) * 1968-09-26 1972-06-27 Henkel & Cie Gmbh Protein solubilizing washing rinsing and soaking compositions
US4000082A (en) * 1975-10-02 1976-12-28 Basf Wyandotte Corporation Defoaming compositions based on lithium salts

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