US2581677A - Phosphate detergent composition in - Google Patents

Phosphate detergent composition in Download PDF

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US2581677A
US2581677A US2581677DA US2581677A US 2581677 A US2581677 A US 2581677A US 2581677D A US2581677D A US 2581677DA US 2581677 A US2581677 A US 2581677A
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alkali metal
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detergent
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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
    • 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
    • C11D1/24Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds containing ester or ether groups directly attached to the nucleus
    • 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
    • C11D1/04Carboxylic acids or salts thereof
    • 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
    • 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
    • C11D1/123Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143Sulfonic acid esters
    • 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
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • 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
    • C11D1/28Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/65Mixtures of anionic with cationic 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
    • C11D3/046Salts
    • 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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Description

Patented Jan. 8, 1952 PHOSPHATE DETERGENT COMPOSITION IN HOMOGENEOUS LIQUID FORM Samuel Machlis, New Rochelle, N. Y., and Edwin B. Michaels, Stamford, Conn., assignors to The Stamford Chemical Company, Stamford, Conn.,
a partnership No Drawing. Application November 18, 1948, Serial No. 60,837
2 Claims.
The invention relates to a composition of matter having detergent properties. More particularly, it pertains to a composition in liquid form and includes correlated improvements and discoveries whereby preparation and utilization thereof are enhanced.
It has previously been proposed to prepare detergent compositions containing synthetic compounds which have synergistic characteristics. Further, alkali metal phosphates have been found to improve the detergent value of synthetic mixtures. However, all of such previously prepared combinations have consisted of mixtures of dry powders inasmuch as it has not been possible to form homogeneous compositions of synthetic detergents having a significant concentration in solution of an alkali metal phosphate. It is the principal object of the invention to provide a detergent composition which does not possess the foregoing disadvantages.
An object of the invention is the provision of a detergent composition containing an alkali metal phosphate and a plurality of synthetic or- .ganic detergents in a homogeneous liquid state which is readily soluble in water.
Another object of the invention is to provide a liquid detergent composition containing synthetic organic detergents having synergistic properties but which are not among themselves miscible to form homogeneous compositions.
A further object of the invention is the provision of a composition of matter having detergent properties which may be readily, effectively and economically prepared.
A more particular object of the invention is to provide a detergent composition in liquid 'form and'containing complex polyphosphates which are substantially stabilized so that they do not specifically a pyrophosphate, a plurality of synthetic organic detergents having synergistic properties, an" alkali metal aryl sulfonate, and
water. The alkali metal phosphate may be present in an amount from about 5% to about 30% and utilization may be made of sodium hexametaphosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate and trisodium phosphate. We have found that where a complex polyphosphate is included in the composition, its value as measured by calcium ion sequestration, does not dissipate on storage, although, it is present in an aqueous solution.
The synthetic organic detergents may include. an amide-of a sulfonated higher fatty acid, as
those present in cocoanut oil, viz: lauric, myristic, palmitic, stearic and oleic; a sulfated higher aliphatic monohydric alcohol, which may be lauryl. myristyl or stearyl, and an alkyl aryl sulfonate having the general formula R-R'SO3M in which R represents an alkyl group containing from 12-15 carbon atoms, R represents an aromatic residue as a benzene, napthalene and anthracene residue and M represents sodium and potassium. The alkali metal aryl sulionate may be a sodium or potassium xylene sulfonate, toluenesulfonate, cumene sulfonate and tretrahydronaphthalene sulfonate. It will be realized that the synthetic organic detergents and the other constituents as the higher fatty acid amides may be employed alone and in compatible admixtures.
It has been our finding that solutions containing more than 5% of an alkali metal phosphate are of value as detergent compositions in the event that such compositions also contain significant amounts of certain synthetic organic detergents having synergistic properties. tion may speciallybe made of an amide of sulfonated cocoanut oil fatty acids. However, when this amide is added to an alkali metal phosphate solution of more than 5% concentration there is an immediate separation into two layers which renders the composition useless as a detergent. In the event that certain sodium aryl sulfonates are added, such 'as sodium xylene sulfonate, the solution containing the phosphate and amide no longer separates into two layers or phases but in contradistinction thereto forms a clear homogeneous solution having distinctive detergent qualities.
Further, we have found that the composition may include also more than 1% of a sulfated higher aliphatic monohydric a1cohol,.as sodium laurylsulfate, since the sulfated alcohol becomesreadilysoluble although such a concentration thereof will 'not'form a-homogeneous solution Men- lowing eiiamples are presented.
- 3 in water. Consequentl the composition contains an alkali metal phosphate in combination with a plurality of synthetic organic detergents having synergistic properties, and we have found that the detergent qualities of such a composition exhibit values markedly. in excess of the additive values of the individual constituents.
This was demonstrated by a detergency study of the following compositions;
- Per cent 'a. Tetrapotassium pyrophosphaters a- 15 Water. 85 b. Sodium lauryl sulfate a f2 Alkyl aryl sulfonate mnsn'uefine- 2. Sulfonated cocoanut oil fatty acid amide" 5 Water v 91 c. Tetrapotassium pyrophosphat'e i.1'3 Sulfonated cocoanut oil fatty acid amide 5 Alkyl aryl sulfonate 2 Sodium lauryl sulfate; 2 Sodium xylene sulfonate -w 4.5 Water 7 7 73.5
The detergency study was made on soiled glass wicking according to the method described in Soap and Sanitarybliemicals, September 1948, using a concentration or 0.2% with the following "results: Per "cen t fletrgeney ;a -2 b-r 7 c-AB When *a and b are combined the detergency is almost double the additive value, hence a 'syner- 'gisti'c effect.
As an illustrative embodiment of a manner in which the invention may be practiced, the'fol- Example 1 V 7 Per cent Tetrapota's'sium pyro'phosphate l3 Sulfonated coco'anu-t oil fatty acid amiden Alkyl aryl sulfonate '2' Sodium lauryl sulfate 2 Sodium xylene sulfo'nate 4.5 Water 73.5
Example 2 Per cent Tetrapotassium pyrophosphatm- ;.si e 26 Sulionated cocoanut oil fatty acid amidee Alkyl aryl sulfonate ie;; i 4 Sodium lauryisulfateeeme l-;- 4 Sodium xylene sulfonateenunheim; -ea- 10 Water e 45 Example 3 V Per cent Tetrapotassium pyrophosphatee i 1'3 Polymerized ethylene oxide condensation product ,5. Allryl aryl sulionate Sodium lauryl sulfates 2 Sodium xylene sulfonate ..a. $5 Water i I 73.5
Sulfonated cocoanut oil fatty acid amide 3-25 l .The compositions herein described have distinctlve detergent properties, and the phosphate which is a significant part of the composition, together with the synthetic organic detergents yields a composition of which the use is economically feasible. Moreover, the utilization of these liquid "detergent compositions fl rOViIdes values which have not been attained previously in the employment of detergents. Further, since synthetic organic detergents are usually prepared in 10 the liquid state, in fact, many of them being liquids normally, the cost of drying these compounds to a free-flowing powder is obviated by the present invention, and thereby a raw material of lower cost isprovided.
Additionally, the ultimate use of a detergent is in a dilute aqueous solution. Solid detergents require time and effort to disperse or dissolve them to form a solution, and especially so since some are poorly soluble whereas others due to their aflinity for water form lumps and gelled masses which are difiicult to handle.
Furthermore, powdered detergents vary greatly in density and in bulk which leads to inaccuracies in use unless special care is taken with respect to the amounts being employed. Also, neither weighing facilities nor time therefor are readily available either in the household or in the plant where the detergent is being used. This consequently leads to waste which is entirely and readily overcomewhen a homogeneous liquid composition as provided .by the present in.-
vention is employed, due to the fact that the liquid can, be measured accurately by volume.
Another advantage of the composition in ho mogeneous liquid form is that it may easily be utilized in automatic dispensing apparatus.
Since certain changes may be made in the above composition of matter and different embodiments of the invention could be made without departing from its scope, it is intended that all matter contained in the above description shall be interpreted as illustrative a'nd not in a 1imiting sense.
It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween. q
Having described our invention, what We claim as new and desire to secure by Letters Patent is: 41.. A composition in the form of a homogeneous liquid having detergent propertiesand consisting essentially of an aqueous medium con}- .55 taining an alkali metal phosphate inan amount from about 13 to about 26%, a sulfonated higher fatty acid amide inan amount from about 5 to about 10% an alkyl-ar-yl sulfonate having the general formula R- R -sOaM in which R represents an alkyl group containing from 12-15 carbon atoms, R represents an aromatic residue of the group consisting of a benzene, naphthalene and anthracene residue and M. represents a metal of the group consisting of sodium and potassium ,in an amount from about 2 to about 4%, a sulfated higher aliphatic monohydric alcohol in an amount from about 2 to about 4 and an alkali metal aryl sulfonate in an amount from about 4.5 to about 10%, said composition re-- 0 taining its homogeneity upon standing.
2. A compositionin the form of a homogeneous liqu d having deter n properties and consistin essentially of an aqueous medium containing tetrapotassium pyrophosphate in an amount from 1.3 toabout26%, a sulfonated higher fatty acid 5 amide from about 5 to about 10%, an alkyl aryl sulfonate having the general formula 6 REFERENCES CITED The following references are of record in the file of this patent:
Number Number 15 547,688
UNITED STATES PATENTS Name Date Orelup Nov. 20, 1934 Friesenhahn Apr. 30, 1935 Katzman Dec. 26, 1939 Lind Mar. 12, 1946 Cornell et a1 Mar. 7, 1950 FOREIGN PATENTS Country Date Great Britain Sept. 7, 1943

Claims (1)

1. A COMPOSITION IN THE FORM OF A HOMOGENEOUS LIQUID HAVING DETERGENT PROPERTIES AND CONSISTING ESSENTIALLY OF AN AQUEOUS MEDIUM CONTAINING AN ALKALI METAL PHOSPHATE IN AN AMOUNT FROM ABOUT 13 TO ABOUT 26%, A SULFONATED HIGHER FATTY ACID AMIDE IN AN AMOUNT FROM ABOUT 5 TO ABOUT 10%, AN ALKYL ARYL SULFONATE HAVING THE GENERAL FORMULA R-R1-SO3M IN WHICH R REPRESENTS AN ALKYL GROUP CONTAINING FROM 12-15 CARBON ATOMS, R1 REPRESENTS AN AROMATIC RESIDUE OF THE GROUP CONSISTING OF A BENZENE, NAPHTHALENE AND ANTHRACENE RESIDUE AND M REPRESENTS A METAL OF THE GROUP CONSISTING OF SODIUM AND POTASSIUM IN AN AMOUNT FROM 2 TO ABOUT 4%, A SULFATED HIGHER ALIPHATIC MONOHYDRIC ALCOHOL IN AN AMOUNT FROM ABOUT 2 TO ABOUT 4% AND AN ALKALI METAL ARYL SULFONATE IN AN AMOUNT FROM ABOUT 4.5 TO ABOUT 10%, SAID COMPOSITION RETAINING ITS HOMOGENEITY UPON STANDING.
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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1038695B (en) * 1955-10-05 1958-09-11 Unilever Nv Detergents and cleaning agents
US2859182A (en) * 1956-11-02 1958-11-04 Lever Brothers Ltd Heavy duty liquid detergent composition
US2860107A (en) * 1957-07-25 1958-11-11 Lever Brothers Ltd Controlled sudsing heavy duty liquid detergent
US2864770A (en) * 1956-10-03 1958-12-16 Procter & Gamble Liquid detergent composition
US2877185A (en) * 1956-06-29 1959-03-10 Procter & Gamble Clear liquid detergent composition
US2877186A (en) * 1956-06-29 1959-03-10 Procter & Gamble Liquid detergent composition
US2915463A (en) * 1958-06-06 1959-12-01 Ella E Williams Method of treating water
US2920045A (en) * 1955-09-06 1960-01-05 Colgate Palmolive Co Heavy duty liquid detergent compositions
US2936288A (en) * 1960-05-10 Composition
US2994665A (en) * 1959-04-15 1961-08-01 Lever Brothers Ltd Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents
US3001945A (en) * 1959-04-29 1961-09-26 Procter & Gamble Liquid detergent composition
US3021284A (en) * 1958-10-30 1962-02-13 Atlantic Refining Co Liquid detergent compositions
US3023168A (en) * 1958-11-25 1962-02-27 Atlantic Refining Co Heavy duty liquid detergent
US3052635A (en) * 1960-12-14 1962-09-04 Colgate Palmolive Co Liquid laundering compositions
US3066104A (en) * 1958-02-10 1962-11-27 Diamond Alkali Co Heavy duty liquid synthetic detergent composition
US3085982A (en) * 1959-04-22 1963-04-16 Procter & Gamble Liquid detergent composition
US3101324A (en) * 1960-12-12 1963-08-20 Colgate Palmolive Co Liquid detergent composition
US3111218A (en) * 1958-05-26 1963-11-19 United States Steel Corp Method of drawing wire and a lubricant therefor
US3150098A (en) * 1959-06-01 1964-09-22 Lever Brothers Ltd Liquid detergent
US3192166A (en) * 1960-11-14 1965-06-29 Procter & Gamble Liquid detergent composition
US4018720A (en) * 1975-07-14 1977-04-19 The Procter & Gamble Company Laundry detergent compositions in emulsion/suspension
DE3712206A1 (en) * 1987-04-10 1988-10-20 Benckiser Knapsack Gmbh ALKALINE DISPERGATOR

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1981792A (en) * 1934-11-20 Sulphated condensation products of
US1999631A (en) * 1929-12-14 1935-04-30 Unichem Chemikalien Handels A Detergent composition
US2184770A (en) * 1938-07-15 1939-12-26 Emulsol Corp Sulphonic derivatives
GB547688A (en) * 1941-04-18 1942-09-07 Unilever Ltd Improvements in washing agents and in the manufacture thereof
US2396278A (en) * 1933-11-15 1946-03-12 Procter & Gamble Detergent composition
US2500024A (en) * 1950-03-07 Aqueous detergent

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1981792A (en) * 1934-11-20 Sulphated condensation products of
US2500024A (en) * 1950-03-07 Aqueous detergent
US1999631A (en) * 1929-12-14 1935-04-30 Unichem Chemikalien Handels A Detergent composition
US2396278A (en) * 1933-11-15 1946-03-12 Procter & Gamble Detergent composition
US2184770A (en) * 1938-07-15 1939-12-26 Emulsol Corp Sulphonic derivatives
GB547688A (en) * 1941-04-18 1942-09-07 Unilever Ltd Improvements in washing agents and in the manufacture thereof

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2936288A (en) * 1960-05-10 Composition
US2920045A (en) * 1955-09-06 1960-01-05 Colgate Palmolive Co Heavy duty liquid detergent compositions
DE1038695B (en) * 1955-10-05 1958-09-11 Unilever Nv Detergents and cleaning agents
US2877185A (en) * 1956-06-29 1959-03-10 Procter & Gamble Clear liquid detergent composition
US2877186A (en) * 1956-06-29 1959-03-10 Procter & Gamble Liquid detergent composition
US2864770A (en) * 1956-10-03 1958-12-16 Procter & Gamble Liquid detergent composition
US2859182A (en) * 1956-11-02 1958-11-04 Lever Brothers Ltd Heavy duty liquid detergent composition
US2860107A (en) * 1957-07-25 1958-11-11 Lever Brothers Ltd Controlled sudsing heavy duty liquid detergent
US3066104A (en) * 1958-02-10 1962-11-27 Diamond Alkali Co Heavy duty liquid synthetic detergent composition
US3111218A (en) * 1958-05-26 1963-11-19 United States Steel Corp Method of drawing wire and a lubricant therefor
US2915463A (en) * 1958-06-06 1959-12-01 Ella E Williams Method of treating water
US3021284A (en) * 1958-10-30 1962-02-13 Atlantic Refining Co Liquid detergent compositions
US3023168A (en) * 1958-11-25 1962-02-27 Atlantic Refining Co Heavy duty liquid detergent
US2994665A (en) * 1959-04-15 1961-08-01 Lever Brothers Ltd Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents
US3085982A (en) * 1959-04-22 1963-04-16 Procter & Gamble Liquid detergent composition
US3001945A (en) * 1959-04-29 1961-09-26 Procter & Gamble Liquid detergent composition
US3150098A (en) * 1959-06-01 1964-09-22 Lever Brothers Ltd Liquid detergent
US3192166A (en) * 1960-11-14 1965-06-29 Procter & Gamble Liquid detergent composition
US3101324A (en) * 1960-12-12 1963-08-20 Colgate Palmolive Co Liquid detergent composition
US3052635A (en) * 1960-12-14 1962-09-04 Colgate Palmolive Co Liquid laundering compositions
US4018720A (en) * 1975-07-14 1977-04-19 The Procter & Gamble Company Laundry detergent compositions in emulsion/suspension
DE3712206A1 (en) * 1987-04-10 1988-10-20 Benckiser Knapsack Gmbh ALKALINE DISPERGATOR

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