Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS2833722 A
Publication typeGrant
Publication dateMay 6, 1958
Filing dateMar 1, 1955
Priority dateMar 1, 1955
Publication numberUS 2833722 A, US 2833722A, US-A-2833722, US2833722 A, US2833722A
InventorsGeorge O Funderburk, Robert C Johnson, Russell H Smith
Original AssigneeDu Pont
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Detergent compositions
US 2833722 A
Images(1)
Previous page
Next page
Description  (OCR text may contain errors)

May 6, 1958 a. o. FUNDERBURK ETAL 2,

DETERGENT COMPOSITIONS Filed March 1. 1955 (a) g rage-$0 M (b) c H -NHCH CH COONo mm. of Foam INVENTORS GEORGE O. FUNDERBURK ROBERT C. JOHNSON RUSSELL H. SMITH BY QMQeL ATTORNEY DETERGENT COMPOSITIONS Application March 1, 1955,'Serial No. 491,346

6 Claims. (Cl. 252-152) This invention relates to detergent compositions of inatter. It is an object of this invention to provide improved detergents, characterized by their ability to produce and maintain copious foam in the presence of greasy soil and by improved ability to emulsify such soil and hold it in suspension. Additional important objects andeffects of this invention will appear as the description proceeds.

Detergent compositions such as soapand synthetic detergents have for many years been admixed withvarious other chemical materials, which enhance the detergent power of the former. Common examples of such materials are sodium sulfate, sodium carbonate, and various polyphosphates and silicates. These materials are generally referred to in the art as builders, and their principal efiect is to improve the cleansing power of the detergent in so far as the power to remove solid solid particles from textile fiber is concerned. Thus, the test commonly applied to detergents containing such adjuvants is generally a measurement of the degree of whiteness imparted to (or light reflected by) a white piece of fabric which has been darkened by a standard soil prior to testing and which has then been washed for a standard length of time by a standard bath containing the detergent being tested.

Ourinvention differs from the aforegoing field in'that we are interested primarily in improving the capacity of a detergent to remove greasy soil from various articles, not necessarily textiles. Typical examples of the field in which we are interested are the washing of dishes by hand or in a dishwashing machine and the shampooing of human hair.

The power of a detergent to emulsify greasy soil is generally related to its power to produce and maintain foam in the presence of greasy soil. The two practically go hand-in-hand, and the one may be taken as a convenient yard stick for the other. Thus, in household use, the housewife is accustomed to adding'more detergentwhen foam disappears from the dishwater or washing .ma-

chine. To the detergent manufacturer, this persistence of foam in the presence of grease constitutes mileage per unit of active component.

Our invention is also not to be confused with the problem of preparing a composition of matter adapted to produce copious foam for its own value, as for instance in fire extinguishers. .Such foams are frequentlymade from non-detergent materials and have no detergent power whatever in the usual sense. Also, in their field of application grease is not ordinarily present; and the problem, generally, is how to produce a maximum volume of foam from a given weight of the composition or in a given time limit, or how to produce a foam of certain-qualities for instance as to bubble size, stability in time, etc.

We are not concerned with such problems. Our problem is to endow the composition with the power to emulsify a maximum quantity of grease, and in so far as foaming is an index to this power, our problem is to produce a detergent which will continue to-produce foam 2,833,722 Patented May 6, 1958 until a great many greasy dishes have passed through the washing bath containing the detergent.

Our present invention is based on the observation that the foaming powers in the presence of grease of salts of mono-n-dodecyl sulfuric acid such as the sodium, potassium, ammonium, diethanolammonium and triethanolammonium salts, are increased considerably, in some cases practically doubled, if these salts are admixed with a minor quantity (say 10 to 30% by weight of the combination) of an auxiliary agent as defined below.

The auxiliary agent above referred to may be defined as an N-alkyl-beta-amino propionate of the general formula wherein R is a normal alkyl radical of 10 to 12 C -atoms, while X is a water-solubilizing cation and may be exemplified by sodium, potassium, ammonium, diethanolammonium and triethanolammonium.

theless fall short when the soil to be removed is characterized by copious proportions of grease or oil.

. In U. S. Patent 2,619,467, compositions of matter are described and claimed wherein alkylamino-propionate agents of the same general type as above but having longer alkyl chains are admixed witha small quantity of other surface-active agents which have a more predominantly hydrophilic character, forthe purpose of improving the detergent properties of said propionates... Now, although the patent embraces broadly in its list of hydrophilic auxiliary agents soluble salts of sulfates ofla'large variety of hydroxy conipounds,.including the fatty alcohols of intermediate molecular weight}? its s'pecific exas a matter of fact salts of monododecyl sulfuric acid amples fail to include compositions of this, type.

We have investigated this subject, and havefound that decrease the foaming powers of decyland dodecyl beta alanine salts (alanine being here used as a short name The impairment. of the tration of the dodecyl sulfate increases until, when the proportion of the two agents is about 50:50 by weight, the. foam breaks down altogether. In. spite of the above detrimental effect of the specified admixture, we have found, nevertheless and toour'great surprise, that when water-soluble salts of decyl ordodecyl beta alanine are added to water-soluble monododecyl sulfates,-but in such quantities that the alanine compound is. present only in minor proportions. (10 to 30%, of the weight of the mixtures), the compositionagain acquires high foaming qualities, and the grease suspending powers t of. the dodecyl sulfate component become greatly in- 18, page 99; 19,41).

- creased.

The entire subject is made clearer by the accompanying drawing, wherein the sole figure constitutes a graph showing the behavior of mixtures of sodium dodecyl sulsition by weight of the sulfate and propionate components.

it will be noted that whereas the pure alanine compound produces about 220 of foam in the above test, the height of the foam drops/rapidly as quantities of sodium dodecyl sulfate are admixed therewith, until at about 50%, the foam has reached a minimum of such low value as to put the admixture practically in the classification of non-foamers. However; as the propertifon of sodium dodecyl sulfate is increasedstill further, the foaming qualities of the mixture begin to rise and reach a maximum at about the 80:20 point by weight. The optimum; for practical purposes lies somewhere in the regionof 1 to 30% of the alanine compound and 90 to 70% of the alkylsulfate salt.

Such a behavior of the mixture is very surprising as a. matter of knowledge and constitutes a most valuable contribution to the practical field, inasmuch as it enablesus to provide for practical use a relatively inexpensive but highly effective cleansing agent for greasy articles and for hair shampoos.

The compositions of matter prepared according to this invention may be dr mixtures, aqueous pastes or aque ous solutions of the two components. In all cases, any of the conventional detergent builders and fillers may also be present. These are chosen by the formulator'; depending on the color, odor, consistency and performance he desires. The mode of compounding may follow-'ordi nary practice such as milling together the dry substances) or pastes, or simply mixing together the solutions.

The requisite dodecyl sulfate component may be 100% material or a commercial grade of this agent. A com--- mon commercial form of this agent is obtained by snl fation of an alcohol mixture resulting from the catalytichydrogenation or sodium-alcohol reduction of coconut oil. This hydrogenation or reduction gives mixed higher, normal, straight-chain alcohols, which usually are fractionated to give a mixture having the desired properties. One of the common commercial grades of this mixture has the following approximate composition by weight: 10, 12, 61%; 14, 11% and C18 For the alanine component, likewise, commercially available grades thereof may be employed.

For the purpose of testing our novel compositions We have adopted the following procedure as a standard:

One liter of 0.1% solution, in water of 300 p. p. m. hardness, of the composition to be tested is placed in a relatively wide and shallow, circular enameled pan. Then 55 g. of a standard greasy soil are added, and the mixture is agitated moderately for 5 minutes at 24 to 26 C. If a voluminous foam is produced, the detergent mixture meets the strict requirements of this invention for operability; i. e., it has the capacity to emulsify a heavy load of greasy soil in hard water and simultaneously foam copiously.

The concentration index above (0.1%) refers to total per cent of active ingredient. That is, if either component is diluted with builders, fillers or water, the weight thereof employed for the test is proportionately increased.

The standard greasy soil above referred to may be made up at will, but in our tests it was made up essentially as in U. S. P. 2,702,278 issued to Cupery and Funderburk, except that the last two ingredients there mentioned (salicylanilide and ammonium hydroxide) were omitted.

, Water of 300 p. p. m. hardness was employed to make the conditions of the test more drastic, inasmuch as grease-emulsification and foaming are more difficult to attain in hard water.

Without limiting our invention, the following examples will illustrate our preferred mode of procedure. Parts mentioned are by weight. All alkyl radicals named are normal.

Example 1 267 parts of a commercial aqueous paste .of sodium "monoalkyl sulfate (of a composition as above indicated, 'the C component predominating, and the total active ingredient of the mixture being 30% by weight) are :mixed with 66.7 parts of a commercial aqueous paste of .N-decyl-beta-amino-sodium propionate (30% active ingredient). The active ingredient of the resulting mixture .is thus likewise equal to 30% by Weight, and contains parts of the sodium monoalkyl sulfate and 20 parts of 'the mentioned propionate.

The product is an essentially odorless, stiff, White paste. At 0.1% active ingredient concentration in water, it gives voluminous foam when subjected to the above standard test. In contrast, neither the sulfate salt nor the propionate alone, produces any foam whatsoever under the same conditions. Only greasy curds are formed.

If the above product is drum-dried, a dry white solid results which has the same good grease-emulsifying and foaming properties as the paste, when tested at the same active ingredient concentration.

Example 2 A liquid detergent composition of 40% total A. 1. (active ingredient) is prepared by mixing 80 parts of the tri ethanolamine salt of mono-dodecyl sulfate (as a 40% A. I. aqueous solution), 20 parts of the triethanolamine salt of N-decyl-beta-amino propionic acid and 30 parts of water. The product is a slightly viscous, amber liquid. It emulsifies a heavy load of greasy soil and foams copiously at the same time, whereas its components give only greasy curds when used singly under the same conditions.

In a similar manner, the following additional compositions were prepared, tested and found to give excellent performance for the purposes of this invention. In this table, the two components (a) and (b) were mixed in each example in the proportions indicated.

(a) represents a dodecyl sulfate salt of the formula C; H OSO M, wherein M is a cation as indicated.

(b) represents a beta-alkyl alanine salt of the formula RNHCH CH -COOX, wherein R is decyl or dodecyl, as indicated, while X is a cation as named in the respective column.

Wei h Example M: R X ILtti o l H Sodium Decyl Sodium 9:1 d0 (1 7:3 do 8:2 Potassium. D yl 8:2 Ammonium- 8 2 Diethanol- 9:1

ammonium. d0- 7:3 Triethauol- 9 l ammonium.

7:3 Dodecyl Potassium 8:2 0........ d0 Amm0niurn 8:2 Diethanolam- Decyl do.- 8:2

monium. Triethanold0 1o 8:2

ammonium. o (lo Diethanolam- 8:2

monium. Sodium do. v d0 8:2 Diethanolam- Dodecyl... do 8:2

momum. 19 d0 Decyl "do 8;2 20 do do Triethanol- 8:2

. ammonium. 21 Sodium .do; ..d0 8:2

In all the examples above, essentially the same results are obtained when the named decyl or dodecyl alanine salts are replaced respectively by the corresponding dodecyl or decyl homologs. Also, in all the examples above, greasy curds and no foam are obtained when either ingredient (a) or (b) is used alone to the same total A. I. concentration (0.1%), in the above standard tests.

Example 22 30 parts of the 80:20 detergent composition prepared in Example 5 above and 65 parts of tetrasodium pyrophosphate were mixed together intimately to produce a dry detergent product. When made up at 0.1% A. I. concentration (based on 80:20 mixture) in hard water of 300 p. p. m. and then tested in the manner previously described, this detergent solution foamed voluminously in the presence of the heavy load of greasy soil.

Control solutions containing respectively sodium dodecyl sulfate alone and beta-decylamino-sodium propionate alone, but each containing the same proportion of tetrasodium pyrophosphate as the aforegoing dry detergent product, produced no foam when treated under the same condition at 0.1% A. 1. concentration.

Example 23 30 parts of the 80:20 detergent composition prepared in Example 5 above were mixed intimately with 15 parts of sodium sesquisilicate' (Na HSiO 5I-l O) and 50 parts of sodium sulfate to produce a dry detergent product. When tested as above at 0.1% A. I. in hard water containing a heavy load of greasy soil, this product produced voluminous foam, while control solutions containing the same builders but only one or the other of the named principal ingredients (in the same total weight), pro-.'

' readily appreciated.

The compositions of this invention possess an excellent combination of properties. They are light colored, odorless, non-toxic, reasonably cheap, capable of emulsifying heavy loads of greasy soil and of foaming copiously in the presence of it. They can be used both in soft Water and in hard water.

These properties make them eminently suited for the detergent in formulations designed for several important household uses. One such use is dishwashing, where heavy grease loads of widely varying compositions must be emulsified. Simultaneous foaming is also required.

Another very important household use is the washing of hair. In addition to cleansing the hair and scalp free from natural skin oils and greasy materials, shampoos must also be capable of emulsifying large amounts of mineral oil and similar materials derived from the use of hair oils. The novel compositions of this invention are excellently adapted to achieve this result.

We claim as our invention:

1. A detergent composition adapted for emulsifying greasy soil, comprising as active ingredient a mixture of a water-soluble sulfate of the formula 11-C12H25;OSO3M and a water-soluble propionate of the formula RNH-CH CH CO-OX wherein X and M represent cations selected from the group consisting of sodium, potassium, ammonium, diethanolammonium and triethanolammonium, and R is a normal alkyl radical of the group consisting of decyl and dodecyl, the proportion of the propionate being not less than 10% and not more than 30% of the combined weight of said propionate and sulfate.

2. A detergent composition adapted for emulsifying greasy soil, comprising as active ingredient a mixture of sodium n-dodecyl sulfate and sodium beta-N-n-decylamino-propionate, the proportion of the two in the order named being :20 by weight.

3. A detergent composition adapted for emulsifying greasy soil, comprising as active ingredient a mixture of sodium n-dodecyl sulfate and sodium beta-N-n-dodecylamino-propionate, the proportion of the two in the order named being 80:20 by weight.

4. A detergent composition adapted for emulsifying greasy soil, comprising as active ingredient a mixture of diethanolammonium-n-dodecyl sulfate and diethanolammonium beta-N-n-decylamino-propionate, the proportion of the two in the order named being 80:20 by weight.

5. A detergent composition adapted for emulsifying greasy soil, comprising as active ingredient a mixture of diethanolammonium-n-dodecyl sulfate and diethanolammonium beta-N-n-dodecylaminopropionate, the proportion of the two in the order named being 80:20 by weight.

6. A detergent composition adapted for emulsifying greasy soil, comprising as active ingredient a mixture of triethanolammonium-n-dodecyl sulfate and triethanolammonium beta-N-n-decylamino-propionate, the proportion of the two in the order named being 80:20 by weight.

References Cited in the file of this patent UNITED STATES PATENTS 2,619,467 Isbell Nov. 25, 1952 v UNITED STATES PATENT OFFICE CERTIFICATE OF CORECTION Patent No. 2,833,722 May 6, 1958 George 0. Funderburk et a1,

It is herebjr certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 30, for "solid solid" read solid soil column 3', line 8, for "admixture" read mixture SEAL) Attest:

ROBERT C. WATSON Commissioner of Patents Attesting Officer UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,833,722 May 6, 1958 George 0. Funderburk et a1.

It is herebi certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 30, for "solid solid" read solid soil column 3', line 8, for "admixture" read mixture Signed and sealed this 22nd day oi July 1958,

(SEAL) Attest:

ROBERT C. WATSON Attesting Officer Commissioner of Patents

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2619467 *Apr 16, 1949Nov 25, 1952 Detergent mixtures containing
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3086943 *Jun 10, 1959Apr 23, 1963Procter & GambleShampoo containing amine oxide
US4946136 *Apr 29, 1988Aug 7, 1990Amphoterics International LimitedAlkylamino and acylamino amphoteric surfactants
US5597513 *Dec 13, 1994Jan 28, 1997Cohen; ElliotContains beta aminopropionate or salt and alkoxylated alcohol; wash liquors, tramp oils, coolants
Classifications
U.S. Classification510/365, 510/235, 516/14, 516/DIG.500, 510/490
International ClassificationC11D1/94, C11D1/10, C11D1/14
Cooperative ClassificationC11D1/10, C11D1/94, Y10S516/05, C11D1/146
European ClassificationC11D1/94