US 2954347 A
Description (OCR text may contain errors)
Patented Sept. 27, 1960 DETERGENT COMPOSITION Wayne L. St. John and William J. Griebstein, Cincinnati, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Oct. 27, 1955, Ser. No. 543,256
14 Claims. (Cl. 252-109) tatable cylinder or drum With ridges, sometimes referred to as ribs, projecting internally from and lengthwise of the cylindrical wall. In use, the detergent solution and soiled clothes are introduced into the drum, then agitation is effected by rotating the drum, the ribs assisting in tumbling the clothes with the washing solution. It has been found that detergent compositions which suds profusely, such as the heavy-duty detergent compositions containing anionic synthetic detergents, do not give their best cleansing performance when employed in such machines because the suds tend to cushion the movement of the clothes being washed and diminish agitation to the point Where inefficient cleansing results. Thus, there has arisen a demand for detergent compositionswhich possess superior heavy-duty cleansing power with depressed suds producing power.
An eifort by others to solve the problem thus recognized has resulted in the development of detergent compositions from nonionic synthetic detergents such as the high molecular weight ether and ester derivatives of ethylene and propylene oxide condensation products. Such synthetic compounds possess cleansing activity with relatively low sudsing performance, but they are not equal in washing efliciency to heavy-duty anionic synthetic detergent compositions in the cleansing of heavily soiled cotton fabrics.
Other efforts have been made to cope with the sudsing problem by employing a suds depressant in combination with the detergent composition. However, anionic sulfate and sulfonate detergents (such as the water-soluble salts of the sulfuric acid esters of higher aliphatic alcohols and water-soluble salts of alkylated benzene suldetergent compositions which will meet the qualifications above stated.
A further object is to provide a heavy-duty anionic synthetic detergent composition which has adequate heavy-duty cleansing power with depressed sudsing tions, for example, those described in Byerly U'.S.P.
2,486,921 and Strain U.S.P. 2,486,922 and including synthetic anionic sulfate or sulfonate detergents with from 1 to 5 parts of alkali metal tripolyphosphate, are not materially modified with respect to cleansing efficiency by the addition of certain fatty acid mixtures, or soaps thereof, or mixtures of fatty acids and soaps, as more fully hereinafter defined. However, the sudsing power of such detergent compositions is materially decreased so that the detergent composition can be employed in automatic drum-type washers which require low sudsing characteristics. for etficient washing performance.
In general, the suds depressant which is suitable for use in accordance with the present invention is constituted of a mixture of at least 3 different high molecular weight compounds having acyl radicals of different carbon atom content and selected from the group consisting of saturated fatty acids having from about 16 to about 31 carbon atoms and alkali metal soaps thereof, said mixture containing more than 50% of said compounds having at least 16 carbon atoms and at least 5% of said compounds having at least 20 carbon atoms. According to our experience, such mixture of compounds is strikingly more efficient in depressing the sudsing characteristics than is any single compound, and we have found that complexity of the mixture is an important aspect, at least 3 different compounds and preferably 4 or more being desirable in the mixture.
For various reasons, including economy and ease of handling, we prefer to use mixtures of fatty acids in preparing the compositions of our inventions, and emphasis is placed herein on the use of saturated fatty acids having 16 or more carbon atoms in the acyl radical. However, since complexity of the mixture is an important element in its efficacy as a suds depressant (without materially affecting cleansing efficiency adversely), the presence of other fatty acids, such as saturated C (myristic) acid and unsaturated (oleic and linoleic) fatty acid, is not harmfuland can even be beneficial, provided the mixture otherwise is constituted of at least 50% of saturated fatty acids having 16 or more carbon atoms and at least 5% of saturated fatty acids having at least 20 carbon atoms. 1
Variations in fatty acid compositions meeting the above specifications can fall within the following range of percentages:
. Percent My-ristic acid 025 Palmitic acid 05O Stearic acid 050 Arachidic acid 0-40 Behenic acid 0-40 Lignoceric acid 0-25 Cero'tic acid 0-25 Melissic acid 0-15 Oleic acid 0-30 Linoleic acid 0- 10 A fatty acid composition which finds particular value in the practice of the present invention is a commercial product known as Hyfac 431. Bulletins issued by the manufacturer report that this product'is a mixture of fatty acids derived from hydrogenated fish oil andis constituted of about 8% myristic acid, 29% Palmitic acid, 18% stearic acid, 26% arachidic'acid, 17% behenic acid and 2% oleic acid.
Generally, any related fatty acid mixture having about 515% myristic acid, about 25-35% palmitic acid, about 15-25% stearic acid, about 2030% arachidic acid, and about 1020% behenic acid is of outstanding utility in the practice of this invention.
As above indicated, the mixture of alkali metal soaps of the fatty acids can be employed as well as the fatty acids (and mixtures of fatty acids and soaps) to depress the sudsing action without materially afiecting cleansing performance to" an undesirable degree. Actually, the normal alkalinity desirable in such heavy-duty detergent compositions is sutficient to convert fatty acid to soap, and in washing solutions of the present detergent compositions the fatty acids can exist substantially wholly as the alkali metal soaps.
The products of our invention can be prepared by incorporating the fatty acid or soap mixture in the crutching apparatus prior to formation of the product in its. final form, :such as flake, granule, powder, etc. In accordance with another procedure, the detergent composition (without suds depressant) in its final form can be sprayed with therappropriate mixture of fatty acids to yield a product with the characteristics herein described. The performance of the final product is not materially modified by its method of preparation, and whether fatty acid, soap or mixture of soaps and fatty acid is homogeneously dispersed throughout each particle of detergent composition, 'or whether the fatty acid has been sprayed on the particles is immaterial insofar as the cleansing and suds- 4 1 More broadly expressed, the ratio of fatty acid mixture to active anionic synthetic detergent can vary from 0.1 :1 to 1:1.
The following examples are given to illustrate the manner in which the invention may be practiced. All parts shown are by weight.
Example I .To 97 parts of a granular mixture of about 18 parts sodium alkyl benzene sulfonate (the alkyl radical averaging about 12 carbon atoms and being derived from polypropylene), about 48 parts of sodium tripoly-' phosphate, about 6 parts of silicate solids, and about 28 parts of miscellaneous ingredients of which the major portion was water and sodium sulfate, were added 3 parts of a commercial mixture of fatty acids derived from hydrogenated fish oil and bearing the brand name of Hyfac 431. This fatty acid mixture had the following approximate constitution.
. Percent Myristic acid 8 Palmitic acid 29 Stearic acid l8 Arachidic acid I 26 Behenic acid 17 ing properties of washing solutions of the final products are concerned.
We have indicated above that the detergent composi tions which may have sudsing power depressed by practice of the present invention include those of Byerly U.S. 2,486,921 and those of Strain 2,486,922. The active ingredients of such compositions embody an anionic synthetic sulfate or sulfon-ate detergent salt and alkali metal tripolyphosphate, the ratio of the tripolyphosphate to the synthetic detergent in the heat-dried products of Strain ranging from 1:1 to 5:1. The anionic synthetic to which reference is made is hereinafter generally referred to as a Water-soluble alkali metal salt of an organic sulfuric reaction product having in its molecular structure an alkyl radical having from about 8 to about 18 carbon atoms and a radical selected from the group consisting of sulfonic acid'and sulfuric acid ester radicals. Important examples of the synthetics which form an active part of the compositions of the present invention are the alkyl sulfates, especially those derived by sulfation of higher alcohols produced by reduction of glycerides of tallow or coconut oil; alkyl benzene sulfonates, especially those of the types described in US. Patents 2,220,099 and 2,477,383; alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols from tallow and coconut oil;
coconut oil fatty acid monoglyceride sulfates and sulfonates; Water soluble salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e. g. tallow or coconut oil alcohols) and about three moles of ethylene oxide; and others known in the art, a number being specifically set forth in the Byerly and Strain patents. Detergent compositions prepared from such Water soluble synthetic detergent salts and containing from about 10% to about 40% of active anionic synthetic with alkali metal tripolyphosphate or other higher polyphosphate within the range of ratios above mentioned, are particularlyuseful in the preparation of the present compositions. In many such compositions, miscellaneous ingredients including moisture, coloring agents, brightening agents, perfume, carboxymethylcellulose, sodium sulfate, silicate, sodium carbonate and other alkaline salts, and other materials well known as constituents in detergent compositions can be present. The sudsing power of all of these detergent compositions is materially depressed by combination with the mixture of compounds herein disclosed without substantially affecting the cleansing efficiency adversely.
The amount of suds depressant compound used in effecting depression of sudsing power will vary depending on the particular characteristics desired in the final composition, but usually the presence of about 3% to about 6% of the mixture of compounds, calculated as fatty acid and based on the total product, is preferred.
Oleic acid 2 The resulting product was dissolved .in water at about 0.4% product concentration and employed to wash soiled cotton fabrics in a horizontal rotatable drum type washer under normal laundering conditions. The sudsing characteristics of the detergent solution were depressed but excellentheavy-duty cleansing efliciency was observed.
Under comparable conditions, a corresponding solution of detergent composition having no fatty acid mixture added, sudsed so profusely that the agitating or tumbling action during washing was adversely effected with resulting unsatisfactory cleansing efliciency.
Example Il.The same general results of Example I were observed when 97 parts of the same alkyl benzene sulfonate detergent composition were mixed with 3 parts of the following fatty acid mixture.
Percent Palmitic acid 28 Stearic acid 24 Arachidic acid 24 Behenic acid 24 Similar results can be obtained by employing a mixture of substantially equal parts of the same four fatty acids.
Example IlI.--To 93 /2 parts of a granular detergent mixture of about 17 parts sodium alkyl benzene sulfonate of the same type used in Example I, about 43 parts of sodium tripolyphosphate, about 21 parts of sodium car'- bonate, and about 19 parts of miscellaneous ingredients including sodium sulfate, moisture, etc., were added 6 /2 parts of the following fatty acid mixture Percent Myristic acid 7 1.6 Palmitic acid 46.9 Stearic acid 41 Arachidic acid 5.2 Behenic acid 3.4 Oleic acid 1.8
nous suds which had the effect of interfering -with-the agitation required for adequate cleansing.
Example I V.-To 93 /2 parts of the same alkyl benzene sulfonate detergent composition employed in Example 111 were added 6 /2 parts of the following fatty acid mix- In general the same results were noted as in Example III, the composition of this example showing heavy-duty cleansing performance with depressed sudsing when employed in a rotatable drum type washer.
Example V.--An aqueous slurry containing about 16 parts of sodium alkyl benzene sulfonate of the type used in Example I, 3 parts of the fatty acid mixture employed in Example I, 45.6 parts of sodium tripolyphosphate and 10 parts of silicate solids were spray dried to form a product which had low sudsing power, but which exhibited adequate heavy-duty cleansing performance when used to wash soiled cotton fabrics in a rotatable drum type of washer.
While the foregoing examples employ alkyl benzene sulfonate type of synthetic detergents having from 9 to 15 carbon atoms, averaging about 12 carbon atoms, in the alkyl radical, other sulfate or sulfonate synthetic detergents well known in the art can be substituted therefor in these examples. Furthermore, alkali metal soaps of fatty acids employed in the depressant compositions of the foregoing examples can be substituted for the acids, or for any of them, as hereinbefore indicated.
The sudsing depressant of the present invention also finds use in detergent compositions other than laundering agents. In the case of automatic dish washing detergent compositions, for example, a small amount of anionic or nonionic synthetic detergent or wetting agent has been found to have an advantageous effect in reducing spotting and film formation. However, even small amounts of such compounds introduce sudsing problems under the conditions of violent agitation prevailing during operation of the dishwasher and the depressants herein defined have found utility in effectively depressing suds formation occasioned by the presence of either anioni'cs or nonionics.
Having thus described our invention, what we claim is i l. A laundering composition possessing pronounced heavy-duty cleansing power with depressed sudsing action comprising essentially an anionic water-soluble alkali metal salt of an organic sulfuric reaction product having in its molecular structure an alkyl radical having 8 to 18 carbon atoms and a radical selected from the group consisting of sulfonic acd and sulfuric ester radicals, the said salt having pronounced detergent power in aqueous solution, at least an equal amount by weight of alkali metal polyphosphate, and as a suds depressant a mixture of at least three compounds having acyl radicals of different carbon atom content and selected from the group consisting of saturated fatty acids having from about 16 to about 31 carbon atoms and water soluble alkali metal soaps thereof, said mixture containing more than 50% of said compounds having at least 16 carbon atoms and at least of said compounds having at least 20 carbon atoms, the amount by weight of said mixture being from .1 to 1 times the amount by weight of said sulfuric reaction product salt.
2. A laundering composition possessing pronounced heavy-duty cleansing power with depressed sudsing action comprising essentially a water soluble anionic synthetic detergent salt selected from the group consisting of anionic sulfate and sulfonate synthetic detergents, an
- carbon atoms and water soluble alkalimetal soaps thereof, said mixture containing more than 50% of said compounds having at least 16 carbon atoms and at least 5% of said compounds having at least carbon atoms.
3. The laundering composition of claim 2 in which the anionic synthetic detergent is an alkyl sulfate having from 8 to 18 carbon atoms in the alkyl radical.
4. A laundering compositon in accordance with claim 2 in which the anionic synthetic detergent is an alkyl benzene sulfonate.
5. A laundering composition in accordance with claim *2 in which the compounds of the suds depressant are fatty acids.
6. A laundering composition in accordance with claim 2 in which the synthetic detergent salt is an alkyl benzene sulfonate salt and in which compounds of the suds depressant are fatty acids falling within the following ranges Percent Myristic acid 0-25 Palrnitic acid 0-50 Stearic acid 0-50 Arachidic acid 0-40 Behenic acid 0-40 Lignoceric acid 0-25 Cerotic acid 0-25 Melissic acid 0-15 Oleic acid 0-30 Linoleic acid 0-10 7. A laundering compostion in accordance with claim -2'in which the compounds of the suds depressant are water soluble alkali metal soaps.
8. A laundering composition in accordance with claim 2 in which the compounds of the suds depressant constitute a mixture of fatty acids and water soluble alkali metal soaps.
9. A laundering composition in accordance with claim 3 in which the alkyl sulfate is produced from high molecular weight alcohols derived from a glyceride of the group consisting of tallow, coconut oil, and mixtures thereof.
10. A laundering composition in accordance with claim 4 in which the alkyl radical is derived from polypropylene having from about 9 to about 15 carbon atoms in the alkyl radical.
11. A laundering composition in accordance with claim 5 in which the constituents of the fatty acid mixture fall within the following ranges.
12. A laundering composition of claim 11 in which the fatty acid mixture is constituted of about 515% myristic acid, about 25-35% palmitic acid, about 15-25% stearic acid, about 20-30% arachidic acid and about 10-20% behenic acid.
13. A laundering composition of claim 11 in which the fatty acid mixture is about 8% myristic acid, about 2.9% palmitic acid, about 18% stearic acid, about 26% ara- 7 chidic acid, about 17% behnic acid and about 2% oleic 2,560,839 acid. 2,610,950
14. A 'lalindefing composition 'in accordance with claim 11 in which the 'fatt'yacid mixture is'c'onstituted of about V V equal parts of palmitic, s'teafic, 'arachidic and behenic 5 521 566 acld.
References Cited in the file of this patent UNITED "STATES PATENTS 2,294,075 Colgate et a1; Aug. 25, 1942 10 ,Ayo et a1 July 17, 1951 Morrisroe Sept. '16, 1952 j 1 FOREIGN PATENTS Great Britain May 254, 1940 OTHER REFERENCES 1nd. andEn'g, Chem, v01. 41, No. 2 (February 1949), pp. 423-429.