US2406902A - Soap-like preparations - Google Patents

Description

Patented Sept. 3, 1946 SOAP-LIKE PREPARATIONS Albert L. Rawlins, Grosse Pointe Woods, Mich., assignor to Parke, Davis & Company, Detroit, Mich., a corporation of Michigan No Drawing. Application November 23, 1942, Serial No. 466,671

8 Claims. 1

The invention relates to new and useful germicidal soap-like preparations where the products are especially suitable because of their lathering proper-ties and practical germicidal effectiveness when actually used for cleansing the skin.

An object of the invention is to provide new and valuable lathering detergents which make use of readily available higher alkyl amine salts having detergent properties, but possessing little or none of the lathering properties of ordinary soap, by combining said salts with certain substantially non-lathering quaternary ammonium compounds which coact with said higher amine salts to produce a rich full bodied and permanent lather when worked up with water.

A further object of the invention is to provide new non-irritating germicidal soap-like preparations of increased germicidal and detergent action.

United States Patent No. 2,274,807 describes the use as detergents of water-soluble salts of primary straight-chain alkyl amines in which the alkyl group contains 10 to 18 carbon atoms. Although these compounds are detergents in a general sense, I have found that the individual compounds of the series vary considerably in effectiveness when used for particular detergent purposes. For example, most of them are highly effective for use on textiles, fabrics and wash goods generally. On the other hand, I have found that certain important members of the series when used alone are entirely unsatisfactory for special detergent purposes. More particularly, I have found that, although the salts of hexadecyl amine, and also octadecyl amine, are good detergents for some purposes, such as washing clothes, they are entirely unsuited for employment as lathering soaps for use on the skin.

In order to be satisfactory as a substitute for soap, a detergent should readily work up with water, for example, when rubbed between ones hands, to give a rich, thick-bodied lather of a more or less permanent nature. Because of the increased bulk of such a lather, as compared with the material from which it is generated, it is easy to work into the different corners and crevices of the body and the skin and thereby effectively and economically produces its detergent action, I have found that acid addition salts of hexadecyl and octadecyl amines definitely fail to meet these requirements, since they only yield a small amount of more or less thin, transparent bubbles, with practically no suds or lather, when worked up with water as is commonly done with a hand soap or toilet soap. n the other hand, these two amines are readily available commercially.

I have discovered that said salts of hexadecyl amine and octadecyl amine, when used with a germicidal water-soluble high molecular quaternary ammonium compound which has little or none of the latherlng properties mentioned above, give combinations which are not only excellent lathering preparations suitable for toilet and like uses, but which also retain the germicidal properties of the quaternary ammonium compound. Thus,

the products of this invention are surprisingly effective as germicidal soap-like preparations.

The salts of hexadecyl amine and octadecyl amine which may be used are Water-soluble, or at least slightly water-solublaand may be mineral acid addition salts such as a hydrohalic acid salt, a sulfate or a phosphate or the like, and also organic carboxylic acid addition salts where the acid is monobasic or polybasic, such as acetic,

propionic, buytric, and succinic acids, organic hydroxy acids, e. g. citric, lactic and tartaric acids, any of the isomeric valeric acids, benzoic, salicylic and like acids. A common characteristic of such acids is that they do not give water insolubl salts with hevadecyl amine or octadecylamine. Hence, the organic acid constituent is usually an acid of relatively low molecular weight.

In general, any germicidal high molecular quaternary ammonium compound may be used with the acid addition salts of hexadecyl and octadecyl amines provided the quaternary compound is appreciably water-soluble. However, I have found that the best results are obtained if the germicidal high molecular quaternary ammonium compound is at least soluble to the extent of 1 part in of water and has a surface tension of less than about 40 dynes/cm. in 1% aqueous solution at 25 C.

Although the amine salts and the quaternary compounds may be used together in widely varying proportions, it is usually preferable, for reasons of economy, to use more of the cheaper amine salts.

The following examples illustrate how the above mentioned objects of the invention may be attained.

Example 1 A quantity of hexadecyl amine is dissolved in ether, absolute alcoholic hydrochloric acid added to form the hydrochloride of the amine, the mixture cooled, filtered and washed with ether. The filtered and washed solid product is the hydrochloride of hexadecyl amine. It is only slightly soluble in water. It cannot be used with water in any proportion to form a lather. It is. for" practical purposes, totally useless as a soap for toilet purposes.

80 g. of the hexadecyl amine hydrochloride are mixed thoroughly with g. of para-tertiaryoctyl phenoxyethoxyethyl dlmethyl benzyl ammonium chloride. This quaternary ammonium compound, when used alone with water in any proportion, cannot be worked up into a lather and is not satisfactory for use as a lathering soap preparation. However, the mixture of the quaternary compound with the hydrochloride of hexadecyl amine, prepared as described, is an excellent product for use in the same manner as a toilet soap or a germicidal soap. It has the advantage of readily being worked up with water into a rich full bodied lather which does not deteriorate but is quite permanent.

The soap-like mixture of this example can be molded or pressed into cakes and other forms if desired. It can also be mixed with varying quantities of water and other compatible liquids to form paste-like products or liquids such as liquid soap preparations.

Instead of using the hydrochloride of hexadecyl amine, the acetate or other organic acid salt of the amine can be used. The mixture of the two substances can also be incorporated with inert fillers of solid or semi-solid nature.

Example II A mixture consisting of about 75% by weight of octadecyl amine hydrochloride and about by weight of hexadecyl amine hydrochloride is used. Such a mixture is obtained by saponiflcation of ordinary animal fats to get a mixture of fatty acids, converting the latter to a mixture of amides, dehydrating the amides to their nitriles, hydrogenating the latter and converting the resulting mixture of hexadecyl amine and octadecyl amine to the mixture of hydrochlorides mentioned.

200 grams of the mixture of hydrochlorides thus prepared are mixed thoroughly with 50 grams of paratertiaryoctyl phenoxyethoxyethyl dimethyl benzyl ammonium chloride to give a product which is even superior to the product of example I in lathering and soap-like properties. When used on the hands like a soap, no irritation results and the skin is left clean, disinfected and velvety smooth.

Example III Thisexample is carried out like Example I but using octadecyl amine salt instead of hexadecyl amine hydrochloride. A product having about the same action and usefulness for germicidal soap purposes as the product of Example I is obtained.

Example IV Bromoethylate oi N-dodee'yi benzotri- The quaternary ammonium compounds can be used alone or in mixtures with one another, and mixtures of these with mixtures of one or more salts of hexadecyl amin and octadecyl amine may be used. The following example is an illustration of such a variation of the invention.

Example '1' 25 A mixture 01' quaternary ammonium compounds is used which is derived from a mixture of higher alkyl amines obtained from coconut oils. Such a mixture of amines can be obtained by saponifying coconut oil, separating the mixture of fatty acids thus produced, converting the mixture of acids to their amides, dehydrating the amides to their nitriles and hydrogenating the latter 'to a mixture of higher alkyl amines. This mixture of higher alkyl amines can then be converted by known methods into a mixtureof water-soluble quaternary ammonium compounds of the general formula I /CHI R-N-CH:

where R represents the mixture of higher alkyl radicals derived from the coconut oil, and X is the anion of an acid.

1 lb. of a mixture or hexadecyl amine hydrochloride (75%) and octadecyl amine hydrochloride (25%) is mixed well with 5% ounces oi the mixed dimethyl benzyl high molecular alkyl ammonium chlorides or the above formula derived from coconut oils. This combination in its various physical forms is an excellent lathering soaplike preparation.

What I claim as my invention is:

1. A lathering soap-like preparation comprising a germicidal mixture, free from skin-irritating properties, consisting 01' a substantially nonlathering germicidal water-soluble high molecular weight quaternary ammonium compound and a substance of the class consisting of a watersoluble acid addition salt of hexadecyl amine, a

water-soluble acid addition salt of octadecyl amine and mixtures of said acid addition salts, 05 said germicidal mixture being free from skinirritating compounds and salts of amines of higher molecular weight than octadecyl amine and lower molecular weight than hexadecyl amine, and the weight of said substance in said germicidal mixture ranging from about three times to about four times the weight of said quaternary ammonium compound.

2. A lathering soap-like preparation comprising agermicidal mixture, tree from skin-irritating properties, consisting of a substantially non lathering germicidal high molecular weight quaternary ammonium compound water-soluble at least to the extent of one part in onehundred of water and having a surface tension of less than about forty dynes per square centimeter in 1% aqueous solution at 25 C. and a substance of the class consisting of a water-soluble acid addition salt of hexadecyl amine, a water-soluble acid addition salt of octadecyl amine and mixtures of said acid addition salts, said germicidal mixture being free from skin-irritating compounds and salts of amines of higher molecular weight than octadecyl amine and lower molecular weight than hexadecyl amine, and the weight of said substance in said germicidal mixture ranging from about three times to about four times the weight oi said quaternary ammonium compound.

3. A lathering soap-like preparation comprising a germicidal mixture, free from skin-irritating properties, consisting of a substantially nonlathering germicidal water-soluble paratertiary octyl phenoxyethoxyethyl dimethyl benzyl quaternary ammonium salt and a substance of the class consisting of a water-soluble acid addition salt of hexadecyl amine, a water-soluble acid addition salt of octadecyl amine and mixtures of said acid addition salts, said germicidal mixture being free from skin-irritating compounds and salts of amines of higher molecular weight than octadecyl amine and lower molecular weight than hexadecyl amine, and the weight of said substance in said germicidal mixture ranging from about three times to about four times the weight of said quaternary ammonium salt. i 4. A lathering soap-like preparation comprising a germicidal mixture, free from skin-irritating properties, consisting of a substantially nonlathering germicidal water-soluble para-tertiary octyl phenoxyethoxyethyl dimethyl benzyl quaternary ammonium salt and a substance'of the class consisting of a water-soluble mineral acid addition salt of hexadecyl amine, a water-soluble mineral acid addition salt of octadecyl amine and mixtures of said acid addition salts, said germicidal mixture being free from skin-irritating compounds and salts of amines of higher molecular weight than octadecyl amine and lower molecular weight than hexadecyl amine, and the weight of said substance in said germicidal mixture ranging from about three times to about four times the weight of said quaternary ammonium salt.

5. A lathering soap-like preparation comprising a germicidal mixture, free from skin-irritating properties, consisting of a substantially non lathering germicidal water-soluble para-tertiary octyl phenoxyethyoxyethyl dimethyl benzyl quaternary ammonium salt and a substance of the class consisting of a water-soluble hydrohalic acid addition salt of hexadecyl amine, a watersoluble hydrohalic acid addition salt of octadecyl amine and mixtures of said acid addition salts, said germicidal mixture being free from skin-irritating compounds and salts of amines of higher molecular weight than octadecyl amine and lower molecular weight than hexadecyl amine, and the weight of said substance in said germicidal mixture ranging from about three times to about four times the weight of said quaternary ammonium salt.

6. A lathering soap-like preparation comprising a germicidal mixture, free from skin-irritating properties, consisting of a substantiall non-lathering germicidal water-soluble para-tertiary octyl phenoxyethyoxyethyl dimethyl benzyl quaternary ammonium salt and a substance of the class consisting of a water-soluble hydrochloric acid addition salt of hexadecyl amine, a water-soluble hydrochloric acid addition salt of octadecyl amine and mixtures of said acid addition salts, said germicidal mixture being free from skin-irritating compounds and salts of amines of higher molecular weight than octadecyl amine and lower molecular weight than hexadecyl amine, and the weight of said substance in said germicidal mixture ranging from about three times to about four times the weight of said quaternary ammonium salt.

7. A lathring soap-like preparation comprising a germicidal mixture, free from ,skin irritating properties, consisting of a substantially nonlathering germicidal water-soluble para-tertiary octyl phenoxyethoxyethyl dimethyl benzyl quaternary ammonium salt and a water-soluble mixture of acid addition salts of hexadecyl amine and octadecyl amine in the proportions of approximately one mole of hexadecyl amine salt to 3 moles of octadecyl amine salt, and the total weightof said acid addition salts in the mixture being about four times the total weight of said quaternary ammonium salt.

8. A combination of hexadecyl amine hydrochloride and octadecyl amine hydrochloride, in the proportion of approximately 1 mole of the former to 3 moles of the latter, with an amount of para-tertiary octyl phenoxyethoxyethyl dimethyl benzyl ammonium chloride equal to about one fourth the total weight of said hydrochlorides.

ALBERT L. RAWLINS.