US2733213A

US2733213A - Jtdtclu wiiilc

Info

Publication number: US2733213A
Authority: US
Publication date: 1956-01-31
Anticipated expiration: 1973-01-31

Description

United States Patent G SYNTHETIC DETERGENT COMPOSITIONS Peter T. Vitale and Muriel Eileen Liftin, Brooklyn, N. Y., assignors to Colgate-Palmolive Company, Jersey City, N. L, a corporation of Delaware No Drawing. Application October 29, 1949, Serial No. 124,511

11 Claims. (Cl. 252-137) The present invention relates to new synthetic detergent compositions, and, more particularly, to compositions of the type of sulfated and sulfonated aliphatic acyl-containing detergents having improved properties, and to a process for preparing the same.

Various additives have been incorporated in a wide range of concentrations to modify the properties of synthetic detergent compositions in a desired manner. These additives individually may affect one or more of the following properties or mechanisms involved in the action of the detergent composition including foaming, foam stability, dispersion, suspension, interfacial tension, modification of micellar structure, etc. In view of the varied nature of many synthetic detergents, additives in general exhibit a certain degree of specificity of action. Accordingly, there has been a considerable amount of experimentation to discover substances which aid the efiiciency of known detergent compositions.

It has now been discovered that the simultaneous presence of the higher aliphatic acid amide type compounds and tri-polyphosphates in synthetic detergent compositions of the aliphatic acyl-containing sulfate and sulfonate type wherein the acyl radical has about 8-22 carbon atoms give improved surface-active properties. It is significant moreover that the improvements in either the detersive power or foaming properties may be of a synergistic order.

The synthetic detergent compositions comprised by the invention contain as the active ingredient the surface active synthetic sulfated or sulfonated aliphatic acyl-containing compounds wherein the acyl radical has about 8-22 carbonatoms. Within the scope of such definition are the 7 higher fatty acid ethanolamide sulfates; the sulphuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, e. g. coconut oil monoglyceride monosulfate, tallow diglyceride monosulfate; the hydroxy sulfonated higher fatty acid esters, e. g. higher fatty acid esters of 2,3 dihydroxy propane sulfonic acid; the higher fatty acid esters of low molecular weight alkylol sulfonic acids, e. g. oleic acid ester of isethionic acid; and the like. More particularly, it is preferred to use the sulfated and sulfonated aliphatic carboxylic esters containing at least about 10 carbon atoms, especially those having about twelve to about twenty-six carbon atoms to the molecule,

which may be derived from fatty oils, mono and di glycerides, partial fatty acid esters and ethers of polyglycols, etc.

These detergents are commonly used in the form of their water soluble salts. Of these, the alkali metal (e. g. sodium, potassium) and ammonium salts are preferred though other salts such as the amine, alkylolamine, alkaline earth metal (e. g. calcium, magnesium) salts may be used if desired. Their concentration in the detergent compositions of the present invention is generally at least about 10, and preferably at least about 20% by Weight of total solids. Compositions with very high concentrations of these active ingredients of the order of up to about 90% are prepared for specialized uses generally. With 2,733,213 Patented Jan. 31, 1956 built compositions, however, it is preferred to use an active ingredient content of about 20 to about 50%.

The amides to be used in conjunction with the polyphosphates are preferably the surface-active higher amide having the formula:

wherein RCO is an aliphatic acyl radical, preferably of a higher fatty acid, having from about 10 to 20, and preferably about 12 to 16 carbon atoms, and X and Y may each be selected from the group consisting of hydrogen, and alkyl and alkylol radicals of 1 to about 5 carbon atoms each, and preferably about 2 carbon atoms. With the non-alkylol containing amides, it is preferred that the acyl radical be about l0-14 carbon atoms. With the monoalkylolamides, it is generally preferred that the acyl radical be about 10 to 16 carbons, whereas with the dialkylolarnides, acyl radicals of slightly longer chain length of about 12 to 20 carbon atoms are preferred generally. Specific examples of amides which comes Within the scope .of the invention are: palmitylethanolamide, myristylethanolamide, laurylethanolamide, oleylethanolamide, myristamide, lauramide, stearamide, lauric diethanolamide, and amide type mixtures prepared from mixtures of higher fatty acids derived from various fats, oils, and waxes of animal, vegetable or marine origin.

The polyphosphate additives in the detergent compositions referred to herein are preferably the water soluble inorganic tri-polyphosphates of the formula:

M representing an alkali metal (e. g. sodium, potassium) or ammonium group. Y

These additives may be incorporated either together or separately with the active ingredient at any point during the manufacturing process at which subsequent operations will not adversely modify the properties of the detergent composition. In general, this addition may be accomplished by wet-mixing the solid polyphosphates and the amides wtih the active ingredient, or by dry-mixing these materials which are solid under normal conditions in comminuted form. The best results are not achieved by me chanically intermixing the comminuted solid components. A variety of procedures, which have proven to be convenient, economical, and productive of the best results are:

(l) The addition of the solid polyphosphates and molten amides to a hot aqueous slurry of the active ingredient of about 40 to 50% concentration with vigorous stirring to form a smooth, uniform and homogeneous paste.

(2) The amides may be dissolved in a suitable solvent, e. g. ethanol, and added to a slurry of the active ingredient, before, during, or after addition of the polyphosphates.

(3) A cream emulsion of the polyphosphates and amides in water with a minor proportion of the active ingredient may be prepared and incorporated into the slurry of the active ingredient in the manner set forth above.

Thereafter, these compositions may be made up in the form of solutions, pastes, or as dry or partially hydrated solid products, preferably in a finely divided condition.

The amount of the mixed additives is sufficient to produce a beneficial action on the detersive or foaming prop erties of the detergent compositions referred to herein. The amount of amides is minor in proportion to the weight of total solids, and generally varies within rather definite proportions of the order of about 1 to about 10% and preferably from about 1 to about 5%. The tri-polyphosphates, however, may be used in any desired proportion. To some extent, the degree of improvement appears to be proportional to its content in the composition. In general, the greater the percentage of tri-polyphosphate, the better the result where the active ingredient has been maintained constant. For best results, the proportion of phosphate should be at least 20% by weight, and preferably within the range of about 20 to about 50%. An amount of active ingredient of about 20 to about 50% with about l-% amides, and about 50% polyphosphates produces sufficient deterging properties in an aqueous solution for even heavily soiled laundry; and such composition is economical to prepare and convenient for use in the home or commercially.

It may be noted that the total washing efiiciency of a detergent composition is the result of both the amount of soil removed and the amount redeposited. It has been ascertained that the mixed additives in the relationship set forth may perform the dual function of both increasing the soil removal power and of inhibiting the soil redeposition power generally of the detergent compositions referred to herein. In addition, the mixed additives may effect a synergistic increase in detergency, particularly in soft water, such that these aliphatic acyl-containing detergent compositions may possess a high level of detersive efficiency in an aqueous solution.

These results are ,evident from a consideration of the following data and examples which are merely illustrative of the present invention and it will be understood that the invention is not limited thereto.

The effect of these mixed additives may be determined by standard soil removal and soil redeposition tests. Briefly, these tests involve the addition of a large number of standard soiled cotton swatches and unsoiled cotton swatches to a detergent solution at 120 F. The system is agitated in a standard manner and the swatches are then rinsed, dried and examined under a Hunter reflectorneter. The increase in reflectance of the soiled swatches is an indication of the soil removal value and the decrease in reflectance of the unsoiled cloths is the redeposition value. The values in the tablets are expressed in Hunter units X 10 A higher value in the soil removal column is an indication of better washing power, and lowor values in the soil redeposition column are more desirable.

The following results are obtained using as standards 0.5% concentrations in distilled water of Formula I which comprises 40% of the sodium salts of coconut oil monoglyceride monosulfates and 60% sodium sulfate and Formula II in which sodium tri-polyphosphate has been substituted in Formula I for an equivalent quantity of sodium sulfate. Where the presence of varying amounts of amide additives is indicated, these amide additives have been added in percent of total solids in the standard compositions.

The synergistic improvement in detergency in the relationship set forth effected by the use of the mixed amide type and tri-polyphosphate additives is evident from the data. Comparison of the effects of standard Formula I and II without the amide additives discloses that the tripolyphoshate has an adverse effect on the soil removal power and a moderate beneficial effect on the amount of soil redeposition. As indicated with Formula I, the various amide compounds in general have little effect on the soil removal or soil redeposition power. In contradistinction however, the combinations of amide compounds and tri-polyphosphate as exemplified by the results listed under Formula II have the unitary effect of markedly improving the soil removal power and inhibiting the soil redeposition power to a significant degree also. The unexpected and somewhat balanced effects on detersive power achieved with the mixed additives varies to some degree of course with changes in the detergent compositions and testing conditions.

From the viewpoint of foaming generally, the novel compositions of the present invention may exhibit a high level of foam stability in washing operations. The fact that the mixed additives may produce foam and suds which are more stable, of good creaminess and consistency, do not readily break down by evaporation, and have in general a longer drainage time in comparison to the effects of the polyphosphate alone is significant as these characteristics are desirable generally for a detergent composition. The effect on the foaming properties by the mixed additives however appears to have some specificity of action. In general, the amides in conjunction with the polyphosphates appear to exert a more beneficial action on the foaming properties of the detergent compositions than the alkylolamide compounds in a similar relationship.

These effects on the foaming characteristics can be studied quantitatively for a given composition. A pour foam test designed for comparative study of the relative foam stability of liquids and an appropriate apparatus for carrying out the test is set forth in United States Patent No. 2,315,983 to Ross and Miles. The foam height in millimeters of solutions tested in accordance with the Ross and Miles patent is read at various time intervals and is an indication of foam stability.

Table II sets forth the results of comparative pour foam tests at F. in hard water at 0.25% concentrations of a standard detergent composition (A) comprising about 25% sodium salts of coconut oil fatty acid monoglyceride monosulfates and about 75% sodium sulfate, of a like composition (B) in which 50% sodium tri-polyphosphate has been substituted for an equivalent quantity of sodium sulfate and of a third composition (C) which corresponds to composition (B) but in addition contains 3% myristamide.

It may be noted from the results above that composition (C) containing the mixed amide and tri-polyphosphate additives has a high level of foam stability in hard water in contradistinction to the marked foam breakdown that occurs using composition (A) which contains neither desired additive, and the added adverse effect on the foam produced by the use of composition (B) containing the tri-polyphosphate additive solely. In addition, the foam of composition (C) in washing is creamier and of a good degree of consistency. In general, these superior results may be attained in soft water solutions also.

The superior desirable effects of the mixed additives which may be obtained on the foaming properties of these detergent compositions may also be evidenced by soil tolerance tests. These tests are essentially the pour foam tests modified by the addition of a small amount of a soil to the detergent solution before testing. This procedure represents a more severe test upon the foaming properties of the detergent solution. The results of such tests on compositions A, B (containing tri-polyphosphate), and C (containing the mixed additives) described supra are set forth below:

It is evident from the data that composition (C) containing the mixed additives yields a large volume of foam of a high level of stability in comparison to the effects achieved without the mixed additives.

Though the aliphatic acyl-containing detergents containing the aliphatic amides and polyphosphates may be used as a relatively pure mixture of these components, it is common to employ various adjuvant materials in synthetic detergent compositions. These other builders or additives may be inorganic or organic in structure and may be mixed with the active ingredient in any suitable manner. Such adjuvant materials may include any of the substances employed by the art in admixture with these detergents generally, provided the use of any such materials does not completely neutralize or remove the effect of the mixed amide and polyphosphate additives. It has been found that these added materials may vary greatly both in structure and in concentration Without impairing the improved results attained by the compositions of the present invention. Thus, such conventional inorganic builders or additives as the silicates, other alkali metal phosphates (e. g. hexametaphosphate, tetrapyrophosphate), the sulfates, carbonates, etc., may be employed in these compositions. Organic materials such as carboxymethylcellulose salts, esters (e. g. ethylene glycol monostearate, methyl palmitate), and the like may also be used under suitable conditions.

The following examples of compositions containing the mixed amides and polyphosphates are also productive of a high level of surface activity.

Example I A detergent composition comprising 30% sodium salts of coconut oil fatty acid monoglyceride monosulfates, 50% sodium tri-polyphosphate, 3% sodium silicate, 3% carbonate, 2% palmitylethanolamide and 12% sodium sulfate is prepared and exhibits good washing properties in an aqueous solution.

Example 11 An improved detergent composition is prepared containing 25% sodium salts of coconut oil fatty acid monoglyceride monosulfates, 50% sodium tri-polyphosphates, 3% coconut oil fatty acid amides, 3% sodium silicate and the remainder essentially sodium sulfate.

Example 111 An improved detergent is prepared by incorporating 3 parts of myristamide in 97 parts of a detergent composition comprising about 40% of the condensate of coconut oil fatty acids with isethionic acid as the active ingredient.

Example IV A detergent of superior properties is prepared by incorporating 3% of myristylethanolamide with a detergent composition comprising 40% of the condensate of coconut oil fatty acids with methyl taurine.

Certain general conclusions are apparent from the many tests which have been conducted to determine the effect of the mixed additives in these acyl-containing detergent compositions. The most appropriate mixture of the addi tives, their proportion to each other, and their concentration in each detergent composition may be suitably determined by routine controls since the beneficial results vary to some degree of course with changes in formulation. In each case, the proper washing conditions and the intended use of the composition (e. g. hard or soft water, general home or commercial use, shampoos, ma-

chine washing, etc.) should be taken into consideration in order to derive the maximum beneficial results.

The term consisting essentially of as used in the definition of the ingredients present in the composition claimed is intended to exclude the presence of other materials in such amounts as to interfere substantially with the properties and characteristics possessed by the composition set forth but to permit the presence of other materials in such amounts as not substantially to affect said properties and characteristics adversely.

Although the present invention has been described With reference to particular embodiments and examples it will be apparent to those skilled in the art that variations and modifications of this invention can be made and that equivalents can be substituted therefor without departing from the principles and true spirit of the invention.

Having described the invention, what is desired to be secured by Letters Patent is:

l. A detergent composition comprising about 10 to about 50% of water-soluble higher fatty acyl monoglyceride monosulfate detergent salt having a fatty acyl group of 8 to 22 carbons, in minor proportion to said detergent and from about 1 to about 10% of a higher aliphatic amide compound having the formula:

wherein RCO is an aliphatic acyl radical of about 10 to 20 carbon atoms, and X is hydrogen and Y is selected from the group consisting of hydrogen and alkylol radi-- cals having up to about 5 carbon atoms, and the balance being primarily water-soluble inorganic builder salts with about 20% to about 50% tripolyphosphate salt selected RCONHz wherein R-CO is a higher saturated fatty acyl group of about 10 to 14 carbon atoms, and the balance being primarily water-soluble inorganic builder salts with about 20% to about 50% alkali metal tripolyphosphate, the

above amounts being by weight of total solids of said detergent composition.

3. A detergent composition comprising about 10 to about 50% of water-soluble higher fatty acyl monoglyceride monosulfate detergent salt having a fatty acyl group of 8 to 22 carbons, in minor proportion to said detergent and from about 1 to about 10% of a higher saturated fatty acyl monoalkylolamide, said fatty acyl group having about 10 to 16 carbon atoms and said alkylol group having up to about 5 carbon atoms, and the balance being primarily water-soluble inorganic builder salts with about 20% to about 50% alkali metal tripolyphosphate, the above amounts being by weight of total solids of said detergent composition.

4. A detergent composition comprising about 10 to about 50% of water-soluble higher fatty acyl monoglyceride monosulfate detergent salt having a fatty acyl group of 8 to 22 carbons, in minor proportion to said detergent and from about 1 to about 10% of a higher aliphatic amide compound having the formula:

wherein RCO- is a higher saturated fatty acyl group of about 10 to 14 carbon atoms, and the balance being primarily water-soluble inorganic builder salts with about 20% to about 50% sodium tripolyphosphate, the above amounts being by weight of total solids of said detergent composition.

5. A detergent composition comprising about 10 to about 50% of water-soluble higher fatty acyl monoglyceride monosulfate detergent salt having a fatty acyl group of 8 to 22 carbons, in minor proportion to said detergent and from about 1 to about 10% of a higher saturated fatty acyl monoalkylolamide, said fatty acyl group having about 10 to 16 carbon atoms and said alkylol group having up to about carbon atoms, and the balance being primarily water-soluble inorganic builder salts with about 20% to about 50% sodium tripolyphosphate, the above amounts being by weight of total solids of said detergent composition.

6. A detergent composition in accordance with claim 4 wherein said amide is lauramide.

7. A detergent composition in accordance with claim 5 wherein said amide is palmitoylmonoethanolamide.

8. A detergent composition in accordance with claim 5 wherein said amide is lauroylmonoethanolamide.

9. A detergent composition comprising about to about 50% of sodium higher fatty acyl monoglyceride monosulfate detergent salt having a fatty acyl group of 8 to 22 carbons, in minor proportion to said detergent and from about 1 to about 10% of a higher aliphatic: amide compound having the formula:

wherein RCO is an aliphatic acyl radical of about 10 to 20 carbon atoms, and X is hydrogen and Y is selected from the group consisting of hydrogen and alkylol radicals having up to about 5 carbon atoms, and the balance being primarily water-soluble inorganic builder salts with about 20% to about 50% sodium tripolyphosphate salt, the above amounts being by weight of total solids of said detergent composition.

10. A detergent composition comprising about 10 to 50% of detergent selected from the group consisting of water-soluble sulfated and sulfonated aliphatic acylcontaining detergent salts wherein the acyl radical has about 8 to 22 carbon atoms, in minor proportion to said detergent and from about 1 to about 10% of a higher aliphatic amide compound having the formula:

/X 11-0 O-N wherein RCO is an aliphatic acyl radical of about 10 to 20 carbon atoms, and X is hydrogen and Y is selected from the group consisting of hydrogen and alkylol radicals having up to about, 5 carbon atoms, and the balance being primarily water-soluble inorganic builder salts with about 20% to about tripolyphosphate salt selected from the group consisting of alkali metal and ammonium tripolyphosphate, the above amounts being by Weight of total solids of said detergent composition.

11. A detergent composition comprising about 10 to 50% of a water-soluble sulfated fatty acyl-containing detergent salt wherein the acyl radical has about 8 to 22 carbon atoms, in minor proportion to said detergent and from about 1 to about 10% of a higher aliphatic amide compound having the formula:

wherein RCO is an aliphatic acyl radical of about 10 to 20 carbon atoms, and X is hydrogen and Y is selected from the group consisting of hydrogen and a1- kylol radicals having up to about 5 carbon atoms, and the balance being primarily water-soluble inorganic builder salts with about 20% to about 50% sodium tripolyphosphate salt, the above amounts being by weight of total solids of said detergent composition.

References Cited in the file of this patent UNITED STATES PATENTS 2,383,737 Richardson Aug. 28, 1945 2,383,738 Richardson Aug. 28, 1945 2,383,740 Tucker Aug. 28, 1945 2,396,278 Lind Mar. 12, 1946 2,437,253 Henderson Mar. 9, 1948