US 2052026 A
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Description (OCR text may contain errors)
Patented Aug. '25,, 1936 PATENT OFFICE EMULSION Benjamin It. Harris, Chicago, ill.
No Drawing. Application March 5, 1984, Serial N0. 714,113
My invention relates in general to water-oil emulsions and process of producing the same, and is a continuation in part of my prior copending application Serial No. 431,964, filed February 27, 1930.
In the art of making water in oil emulsions and oil in water emulsions; it is customary to bring the ingredients into intimate contact with each other by shaking, agitating, beating, homogenizing, grinding, working in a colloid mill or using some other means for the purpose-of subdividing the disperse phase in intimate contact with the continuous phase, and. enerally speaking, in the presence of a suitable emulsifying agent.
Some of the better known emulsions of this kind are, for example, mayonnaise, which is an emulsion of oil in water with egg yolk as the emulsifying agent; oleomargarine, which is essentially an emulsion of oils and fats and water with finely subdivided clotted casein as the emulsifying agent; vanishing cream, which is stearic acid emulsified with potassium or sodium soap in water; cold creams which essentially are emulsions of-.oleaginous materials with soap and water; certain types of furniture polishes, which likewise are emulsions of various kinds of oils,
among them mineral oil and turpentine and water or aqueous liquid .such as vinegar with a suitable emulsifying agent, bread dough and cake batters, etc.
These and similar emulsions are generally made with vegetable, animal or mineral oils and fats, which are, for all practical purposes, immiscible with water and aqueous liquids.
The stabilities of these emulsions vary, but on aging, sooner or later, all of them reach a point where an appreciable separation of one or the other phase or both phases commences to become noticeable. The ease with which this deterioration sets in, is dependent upon a number of factorsthe relative proportion of emulsifying agent; character of the emulsifying agent; the thoroughness of initial emulsiflcation; storage conditions, etc.
One of the principal objects of my invention is to stabilize emulsions of this general character.
I have found that emulsions of the general character described above as well as other emulsions comprising oleaginous and fatty materials and water or aqueous liquids may. be appreciably improved by the introduction of a proportion of certain types of materials, which I designate as hydrophillic lipins and which are described in greater detail hereinafter. In certain cases, if desired, the oleaginous substance may be entirely replaced by hydrophillic lipins.
One of the principal differences between my hydrophillic lipins and the oleaginous substances used heretofore in water and oil emulsions is that my substances have a more or less marked affinity for water and aqueous liquids, whereas the oleaginous substances used heretofore, such as corn 011, cotton seed oil, various marine oils, linseed oil, tung oil, oleo oil, beef stearine, turpentine, liquid paraflin, etc., are distinctly immiscible with water, are not readily wetted by water to any appreciable extent and do not show the aflinity for water, which characterizes, in part, my hydrophillic lipins.
Generally speaking, the hydrophillic properties of my lipins manifest themselves by capacity, in varying degrees, to imbibe water, to be wetted by water and to foam or froth with water. It is common knowledge to those skilled in the art that the fats and oils used heretofore are, generally speaking, notably deficient in this capacity.
In general, my hydrophillic lipins are characterized by the presence of a group of moderately 30 high molecular weight, say, from about six carbons up, and of predominantly oleaginous or A hydrocarbon characteristics, which imparts the strictly oleaginous character to a portion of the hydrophillic lipin molecule and another group, or association of groups, of relatively smaller molecular weight with at least one unesterifled hydroxyl group attached to carbon and with distinctly hydrophillic characteristics; that is, a group which imparts to the molecule as a whole a certain degree of aflinity for water and aqueous media not possessed by the oleaginous materials such as linseed oil, lard, petrolatum, soybean oil, etc., heretofore used in oil and water emulsions.
Some of my hydrophillic lipins which are of particular value are the following: 1, 6-dilauryl diglycerol, mono mellisyl ester of diethylene glycol, monoleyl diglycerol, mono-abietic acid ester of triglycerol, mono stearyl glycerol, mono cetyl 50 ether of glycerol, mono oleyl glycerol, and diethylene glycol mono-stearate.
I 0 on Calla-0-CHrH-CH:0-CHz(' H})+ONH While the above listed examples represent single, pure substances, in practice I often find it more convenientto use mixtures of ethers of the above types prepared from mixtures of alcohols such as may be prepared by the reduction of themixed fatty acids of coconut oil, palm kernel oil, beef tallow, cottonseed oil, corn oil, and the like, or by the reduction of the oils and fats directly.
An example of the way in which my invention may be carried out in the manufacture of vanishing cream is as follows:
Gms. Rosewater 1400 Glycerine 300 Stearic acid 120 Potassium hydroxide 12 Mono-cetyl ether of glycerol 60 The ingredients, exclusive of the lipins, are warmed (to saponify), and agitated together in the usual order and manner by means of a suitnection with the above product 'will give the finished product a good texture, greater resistance to syneresis and excellent spreading value on the skin.
Hydrophillic lipins can also be used in the preparation of cold creams. Where lanolin is used, the lanolin may be entirely or partially substituted with hydrophillic lipins. In formula where beeswax is used, this product may also be substituted in part or in whole with lipin.
In cosmetic cold cream formulae, which contain a proportion of white Vaseline or oils or fats, a part of the fatty ingredient may be substituted with the hydrophillic lipin to give desirable results. Thus, for example, in the following formula:
Stearic a i 1000 grams Lar 200 grams Ammonia water (Sp. g. 0.880) cc. Distilled water 7700 cc. Scent of the constitutional structure of my hydrophillic lipins is that the fatty character of the otherwise oleaginous molecule is partly offset and attenuated bythe presence of hydrophillic hydroxyl groups attached to carbon. The extent of this effect, however, is generally not so great as to render the lipin freely miscible with certain aqueous media as is the case for example with the ordinary sulphonated oils of commerce.
I have found that the degree of the attenuation of the oleaginous characteristics is by no means the same in difierent hydrophillic lipins, but that it varies, among other things, first: with' the number and character of the hydroxyl groups present, and second: with the mass and character of the oleaginous. group or groups. The illustrations given below will serve to make these two points clear:
0f the following three substances:
Monosteaiiyl afhylene- Monostearyl glycerol Monostearyl diglyoarol able stirring apparatus or a colloid mill. Finally, while still warm, this mixture is treated with the hydrophillic lipin in a molten condition with stirring. A suitable amount of coloring and scent material may be added. Other ingredients may A is the least hydrophillic and C the most pronouncedly hydrophillic. It will be observed that while the fatty residue is constant throughout, the number of hydrophillic groups increases going from A to C.
Secondly, in the alkaline emulsions containing said ether derivatives.
Monolauryl glycerol Monostearyl glycerol Monomelissyl glycerol E 'is relatively more hydrophillic than F and F in turn is more hydrophillic than G; the hydrophillic group is the same throughout but the oleaginous character is asserted least in E by the relatively small lauryl group.
It will thus be understood by those skilled in the art, that my invention embraces a broad class of materials of varying degreesof fatty and hydrophillic characteristics. The particular purpose for which a hydrophillic lipin is to be used will, in general; in a large measure, govern the decision as to which lipin should be employed.
It is by no means to be understood that my hydrophillic lipins are limited to the particular substances specifically. named in this specification by way of example. Many organic polyhydroxy substances such as glycerol, polyglycerols, glycols, polyglycols, such as diethyleneglycol, sugars, mannitol, sorbitol, and other polyhydroxy alcohols and various other water soluble polyhydroxy substances may be used in which one or more than one hydroxyl is converted to an ether or ester group. These ether and ester groups are preferably of high or moderately high molecular weight, say, from C6 up.
In general, the hydrophillic character of a given substance may be considerably increased by esterifying one or more of its hydroxyl groups with sulphuric acid. The product so produced may be used for the purposes of my invention and is contemplated thereby, particularly when it is produced in the form of a solid as described in my co-pending application.
Throughout this specification, I have used the prefix poly to denote more than one.
I have disclosed the detailsof my invention in considerable detail so that those skilled in the art may be able to practice the same. I wish to point out, that in the use of the hydrophillic lipins of the character set forth, with a given emulsion, a
selection should be made in accordance with the emulsion product manufactured. The most pronouncedly hydrophillic lipin is not necessarily always of most value. As an example, mono-oleyl glycerol is not the most hydrophillic of the substances herein described, but I have found it of very great value in the making of mayonnaise. Among its advantages is that it is easily made, and can be furnishedin suiliciently large quantities at a satisfactory price. .Moreover, it imwherein I claim substantially non-alkaline emulsions including hydrophillic lipins which are ether derivatives of polyhydroxy substances. The claims or the instant application are drawn broadly to emulsions and more specifically to What I claim as new and desire to protect by Letters Patent of the United States is:
1. An emulsion comprising oleaginous material, aqueous material, and a higher aliphatic ether of a polyhydric alcohol, wherein said ether has a lipophile radical with at least six carbon atoms and at least one free hydroxy group derived from the polyhydric alcohol.
2. An emulsion comprising oleaginous material, aqueous material, and a higher aliphatic ether of glycerine, wherein said ether has a lipophile radical with at least six carbon atoms and at least one free hydroxy group.
3. An emulsion comprising oleaginous material, aqueous material, and a higher aliphatic ether of a glycol; wherein said ether has a lipophile radical with at least six carbon atoms and wherein said ether has at least one hydroxy group.
4. An emulsion comprising oleaginous material, aqueous material, and mono-cetyl ether of glycerol.
5. An emulsion comprising oleaginous material, aqueous material, and mono-lauryl ether of glycerol.
6. An emulsion comprising oleaginous material, aqueous material, and a higher aliphatic ether of a polyhydric alcohol, wherein said ether has a lipophile radical with at least six carbon atoms and at least one free hydroxy group, and a substance having an alkaline reaction.
'7. An emulsion comprising oleaginous material, aqueous material, and a higher aliphatic ether of glycerine having a lipophile radical with at least six carbon atoms and at least one free hydroxy group. and a substance having an alkaline reaction.
8. An emulsion comprising oleaginous material, aqueous material, and a. higher aliphatic ether of a glycol, wherein said ether has a lipophile radical with at least six carbon atoms and at least one hydroxy group, and a substance having an alkaline reaction.
9. An emulsion comprising oleaginous material, aqueous material, mono-cetyl ether of glycerol, and a substance having an alkaline reaction.
10. An emulsion comprising oleaginous material, aqueous'material, mono-lauryl ether of glycerol. and a substance having an alkaline reaction.
11. An emulsion comprising oleaginous material, aqueous material, and an ether of an organic polyhydroxy substance with not more than eighteen carbon atoms, said ether having a lipophile radical with at least six carbon atoms, and at least one free hydroxy group attached to carbon.
12. An emulsion comprising oleaginous material, aqueous material, a substance having an alkaline reaction, and an ether of an organic polyhydroxy substance with not more than eighteen carbon atoms, said ether having a lipophile radical with at least six carbon atoms. and at least one tree hydroxy group attached to carbon.
BENJAMIN R. HARRIS.