US2334709A - Emulsion - Google Patents

Description

aiente Nov. 23, 1943 means ESKON Morris Katzman, Frank J. Calm, and Albert K. Epstein, Chicago, Ill., assignors to The Emulsol Corporation, Chicago, 11., a corporation of Illinois No Drawing. Application December 19, 1940.

' Serial No. 370,810

Claims.

This invention relates to the preparation of emulsions or dispersions containing aqueous and ole'aginous materials and compositions therefor, and is particularly concerned with the preparation of cosmetic preparations in the form of emulsions of oleaginous and aqueous materials, which emulsions have an acid reaction or a pH below 7.

Emulsions or dispersions of the character referred to have heretofore been prepared in which emulsifying or dispersing agents, or combinations thereof, of numerous types, have been utilized. While the stability of these emulsions or dispersions is enhanced by the addition of said emulsifying or dispersing agents or combinations there- 01, still, in many instances, the improvements have not been sufiicientiy marked so as to provide a completely satisfactory solution to the problems confronting those versed in the art Among the numerous emulsifying or dispersing agents whose use has been suggested for enhancing the stability of oleaginous-aqueous emulsions are the higher molecular weight aliphatic alcohol sulphates and sulphonates, the sulphonated oils such as Turkey-red oil, the sulphates and phosphates of the higher fatty acid monoglycerides, monoglycerldes and diglycerides of higher molecular weight aliphatic, particularly, fatty acids, and the like. It has also been proposed to utilize mixtures of higher fatty acid monoglycerides or the like with salts of sulphonic acid derivatives or sulphuric acid esters of higher molecular weight aliphatic alcohols, as, for example, combinations of monolaurin with lauryl sodium sulphate and the like. It has been proposed also to employ combinations of monoglycerides or other partially esterified polyhydric alcohols together with fatty acid amino products resulting from reacting higher molecular weight fatty acid acyl halides with protein decomposition products. Furthermore, the suggestion has been made to utilize, as emulsifying agents for aqueous-oleaginous emulsions, mixtures of agents one of which contains a colloidal cation and the other a colloidal anion. In none of these cases have the agents which have been proposed to be used been found fully satisfactory.

In accordance with the present invention, emulsions or dispersions of excellent character and stability, particularly cosmetic emulsions having an acid reaction, are produced by utilizing a combination of certain agents, hereinafter defined and described in detail. These agents comprise an intimate mixture of (1) cation-active substances and (2) non-ionic substances, the

non-ionic substances substantially predominating in amount over the cation-active substance at least in mostcases.

The cation-active substances may be of aliphatic, earboxylic, or heterocyclic character and, as will be understood, comprise substances in which the surface activity is due to a group or radical present in the cationic portion of the molecule. Among the cation-active'compounds which may be employed in accordance with the present invention are the bases or their salts, such as may be derived from pentavalent nitrogen, and further the sulphonium, phosphonium and arsonium, etc. bases and their salts. The quaternary ammonium compounds are examples of satisfactory compounds, the pyridonium or pyridinium compounds being specific examples thereof. In the bases or their salts, the innocuous anions may be hydroxide, chloride, sulphate,

bromide, iodide, acetate, etc. The groups inducing cation activity comprise long chain groupings such as aliphatic hydrocarbon chains having at least six and preferably from twelve to eighteen carbon atoms. The long chain groupings may be composed of two or more benzene nuclei or.

other cyclic radicals, either combined directly or, for example, through carbon or nitrogen or tertiary amines.

other linkages, with or without aliphatic chains substituted for the hydrogen in rings.

Examples of cation-active substances which may be used in accordance with our invention include octyl pyridinium iodide, dodecyl pyridinium bromide, hexadecyl pyridinium iodide, octadecyl pyridinium bromide, dodecyl pyridinium iodide, dodecyl pyridinium chloride, dodecyl-triethyl ammonium iodide, octyl-triethyl ammonium .iodide, decyl-triethyl ammonium iodide, dodecylacids, particularly, fatty acids. examples of such esters are, for example, higher 'mono-olein, monq palmitin;

This group of substances is disclosed in the copending application of Albert K. Epstein and Morris Katzman, Serial No. 370,354 filed December 16, 1940.

The non-ionic substances are, in general, allphatic polyhydroxy substances or polyhydric al- ,boxylic, aliphatic (including cohols incompletely esterifled with higher molecular weight aliphatic (including cycloaliphatic) Representative molecular weight fatty acid monoglycerides such as monocaprylin, monolaurin,

higher molecular weight fatty acid mono-esters oi polyglycerols, glycols and polyglycols such as the stearic acid mono-ester of diglycerol, the oleic acid monoester of ethylene glycol, the-oleic mono-ester oi diethylene glycol, and the like.

Among the aliphatic polyhydroxy substances whose partial esters comprise the vnc nionic agents which are used in combination with the aforementioned cation-active substances, are, for

example, including some previously mentioned,

glycerol; glycols such as ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol and the like; polygly'cols such as diethylene glycol;

- pehtaerythritok' quercitol; dihydroxy acetone;

polyglycerols such as diglycerol, triglycerol, tetraglycerol and the like including mixtures thereof;

"carbohydrates or sugars including mono', diand monostearin,

polysaccharides such as dextrose, sucrose, xylose,

arabinose, galactose, fructose, maltose, mannose, dextrin, starch, and the like; sugar alcohols such as arabitol, mannitol, sorbitol and dulcitol; and

'polyhydroxy carboxylic acids such as tartaric acid, mucic acid, saccharic acid, gluconic acid, glucuronic acid, gulonic acid, mannonic acid, trihydroxyglutaric acid, glyceric acid, carboxylic oxidation products 01 polyglycerols, others of similar character, and hydroxyethyl and hydroxypropyl ether derivatives of the above, as, for example:

' CH1O-CHt-CH:OH

CHQ- CHr-CH|OH CHr-O-CHr-CHsOH cHEo-cm-omon HOCHr-CH20H H-O-CHr-CHaOH Hr-O-CHr-CHaOH CHr-O-CHr-CHgOH n-o-cnr-onion n-o-onkcmon ore-o-cm-cmon H-d-cm-QmQB nr-o-cm-cmon 7 stances 'to form the non-ionic agents which are used in accordance with the present invention may be selected from a large group including, among those mentioned, straight chain and branched chain, saturated and unsaturated, car- I cycloaliphatic) fatty, such as caprylic acid, caproic acid, capric acid, pimelic acid, sebacic acid, behenic acid, arachidic acid, cerotic acid, erucic acid, melissic acid, stearic acid, oleic acid, ricinoleic acid, ricinelaidlc acid, ricinostearolic acid, linoleic acid, linolenic acid, lauric acid, myristic acid, palmitic acid, mixtures of any two or more of the above mentioned acids or other acids, mixed higher fatty acids derived from animal or vegetable sources, for example, lard, coconut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soya bean oil, peanut oil, castor oil, seal oils, whale oil, shark oil and other fish oils, partially or completely hydrogenated animal and vegetable oils such as those mentioned; oxidized and/or polymerized higher fatty acids or higher fatty acids derived from oxidized and/or polymerized triglyceride oils; acyloxy carboxylic acids such as hydrox and alpha-hydroxy higher carboxylic, aliphatic and fatty acids such as i-hydroxy stearic acid, dlhydroxypalmitic acid, dihydroxystearic acid, dihydroxybehenic acid, alpha-hydroxy capric acid, alpha-hydroxy stearic acid, alpha-hydroxy palmitic acid, alpha-hydroxy lauric acid, alpha-hydroxy myristic acid, alpha-hydroxy cocount 011 mixed fatty acids, alpha-hydroxy margaric acid, alpha-hydroxy arachidic acid, and the ployed in accordance with the present invention.

It will be appreciated that the proportions thereof may be varied, that various mixtures 01' diiierent-agents or'substances of the two types may be employed and that other modifications and variations may be made without departing from the guiding principles which are disclosed herein:

Example 1 250 grams of monostearin and 50 grams of a product having the formula C|IH$QC-OCIHI7NH CHI-? NHI were mixed together at 100 degrees C. until a clear liquid was obtained and the mass was then permitted to cool.

Example 2 grams of monostearin were heated to degrees C. and were mixed with 10 grams of lauryl pyridinium iodide. At 80 degrees C., the product was a clear yellow liquid.

Example 3 45 grams of the stearic acid mono-ester of diethylene glycol and grams of a compound having the following formula were heated together at approximately 100 degrees C. until a clear solution was obtained. The mass was then allowed to 0001.

Example 4 90 grams of monostearin were heated to 125 degrees C. and mixed with grams of a compound having the following formula:

until a clear solution was obtained. The mass was then permitted to cool.

Exampl 5 80 grams of monostearin were heated to 120 degrees C. and mixed with grams of the hydrochloride of the lauric acid ester of monoethanolamine until a clear solution was obtained, whereupon the mixture was permitted to cool.

Example 6 90 grams of monostearin were heated to 125 degrees C. and mixed with 10 grams of cetyl pyridinium iodide until a clear solution was obtained. The mass was then permitted to cool.

.The oleaginous-aqueous emulsions or dispersions in which the combination of cation-active substances and non-ionic agent are incorporated may be, in general, of varying character, but especially satisfactory results have been obtained in connection with acid-reacting emulsions, particularly cosmetic emulsions oi'this type. A noteworthy example of the type of cosmetic emulsion'to which the present invention relates are cosmetic astringent creams. In general, such creams contain, in addition to oleaginous and aqueous constituents, a salt of a strong acid with a polyvalent metal, such as aluminum chloride and aluminum sulphate. Although, as stated, the invention is especially concerned with cosmetic emulsionsof the character indicated, it will be appreciated that the invention is not so limited. Emulsions or dispersions containing oleaginous materials and aqueous materials, and particularly those having an acid reaction, to which the principles of the present invention may be adapted include also medicinal and pharmaceutical emulsions, furniture polishes, automobile polishes, certain resin emulsions, and the like.

The following examples are representative of types of emulsions which may be made in accordance with the principles of the present invention:

Example A Example B (1) 42 grams of a mixture of monostearin and monoethanolamine (said mixture containing 90% of monostearin and 10% of the hydrochloride of the lauric acid ester of monoethanoiatccine),

14 grams of spermaceti, 4 grams of glycerine, and

cc. of water were mixed together and brought to a boil, with stirring, until a uniform emulsion or dispersion was obtained. The emulsion was then permitted to cool to about 50 degrees C.

(2) A solution was made by heating a mixture, to about'60 degrees 0., of 20 grams or" .AlClafiHzO, 20 grams of A12(SO4)3.18H2O, and. .0 cc. of water. It was allowed to cool to about 50 degrees C;

(3) The solution produced in part 2 hereof was then added slowly and with constant stirring to the emulsion of" part 2 hereof. A medium vie cous white emulsion resulted which, on standing several hours, set to a firm cream having excellent smoothness and texture. The cream was highly satisfactory as an anti-perspirant.

Example (2' was stirred constantly during the addition and until the mass had reached room temperature. The product comprised a fine dispersion of war: which could be diluted with water. The resulting product was very satisfactory for the coating and impregnating of paper stock.

Example D 20 grams of a mixture of the stearic acid mono ester of diethyleneglycol and a compound havingthe following formula (the stearic acid mono-ester of diethyieneglycol the hydrochloride of the lauric acid ester of comprising 90% of said mixture), were melted and mixed with 30 grams of light mineral oil, the mixture being heated to degrees C. Said mixture was then added slowly and with constant stirring to a solution containing d5 cc. of water and 5 grams of glacial acetic acid, said solution also being maintained at about 80 degrees C. The mixture was constantly stirred until room temperature was reached. The product was a white, viscous emulsion at room temperature and was useful as a furniture polish.

Example E 10 grams of the product of Example -3, id grams of light mineral oil and 5 grams 0;? sper= maceti were heated together to 80 degrees C. whereupon a clear oleaginous solution was formed. The same was then added slowly and with constant stirring to a solution containing 40 cc. of water and 5 grams of tartaric acid, said solution also being at 80 degrees C. The mass was constantly stirred during the addition and the stirring was continued until the resulting emulsion reached room temperature. The prod= uct, which was a heavy, white emulsion, was very useful as a cosmetic cream.

7 Example F CH: I (mm-o-o-t-Na. c1

(2) 20 grams of the mixture of part 1 hereof, 20 grams of cottonseed oil, 8 grams oi. spermaceti, 4. grams of paraflin wax, and 9 grams of mineral oil were heated together to 80 degrees C. whereuponla clear oily solution was formed. Said solution was then added slowly and with constant stirring to a solution containing 40 cc. of water and 1 gram of tartaric acid, also maintained at a temperature of 80 degrees C. The stirring was continued until the final emulsion product reached room temperature. The emulsion was of smooth, excellent consistency and was particularly useful for cosmetic purposes.

The proportions of the cation-active substance and non-ionic agent employed in the emulsions or dispersions are subject to relatively wide, variations, the amount utilized being dependent, among other things, upon the potency of the sub stances or agents selected, the specific character of the emulsions with which they are utilized, and

the exact results desired. In general, from about 0.1% to 5.0%, based upon the weight of the oleas stearic acid, palmitic acid, and the like: lanolin or wool grease, and numerous other materials of the character indicated. 7

What we claim as new and desire to protect by Letters Patent 01' the United States'is:

1. An emulsion, having a normally acid reaction, containing oleaginous material, aqueous material, and small proportions of (1) an allphatic polyhydroxy substance incompletely esterified with a higher molecular weight fatty acid, and (2) a cation-active substance in'the form of a hydrochloride of a higher molecular weight fatty acid ester of a hydroxy-alkyl primary amine.

2. An emulsion containing an oleaginous mat of a mineral acid salt of a higher molecular aginous constituent or constituents, is effective for most purposes but the amount may be increased substantially, V

It will be understood that the term oleaginous, as used in the claims, is intended to include water-repellent or hydrophobic substances such as oils and fats of animal, vegetable and mineral origin, waxes such as paraffin, carnauba wax, beeswax, montanwax, candellila wax, and

the like; higher molecular weight fatty. acids such weight fatty acid'ester of an hydroxy non-tertiary amine, and an aliphatic polyhydroxy substance incompletely esterified with a higher molecular weight fatty acid.

5. An acid-emulsifying agent comprising a 7 mixture of a cation-active substance, in the form of a hydrochloride of higher molecular weight fatty acid esters of monoethanolamine, with monostearin, the monostearin being substantially in excess of the cation-active substance.

MORRIS KATZMAN. FRANK J. CAHN. ALBERT K. EPSTEIN.