Патент USA US2406902код для вставки
Patented Sept. 3, 1946. 2,406,902 UNITED STATES PATENT OFFICE 2,406,902 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.v 466,671 (cl; 252-152) 8 Claims. 1 2 The invention relates to new and useful germi cidal soap-like preparations where the products are especially suitable because of their lathering two amines are readily available commercially. I have discovered that said salts of hexadecyl amine and octadecyl amine, when used with a ger micidal water-soluble high molecular quaternary proper-ties and practical germicidal effectiveness when actually used for cleansing the skin. . ammonium compound which has little or none of An object of the invention is to provide new the’ latherlng properties mentioned above, give 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 sub stantially 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 prepara tions of increased germicidal and detergent ac tion. . United States Patent No. 2,274,807 describes the use as detergents of water-soluble salts of combinations which are not only excellent lather ing preparations suitable for toilet and like uses, but which also retain the germicidal properties 10 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 min eral 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 hy droxy acids, e. g. citric, lactic and tartaric acids, primary straight-chain alkyl amines in which the any of the isomeric valeric acids, benzoic, salicylic alkyl group contains 10 to 18 carbon atoms. Al and like acids. A common characteristic of such though these compounds are detergents in a gen acids is that they do not give water insoluble salts eral sense, I have found that the individual com with hevadecyl amine or octadecylamine. Hence, pounds of the series vary considerably in effec the organic acid constituent is usually an acid tiveness when used for particular detergent pur of relatively low molecular weight. poses. For example, most of them are highly ef In general, any germicidal high molecular quat fective for use on textiles, fabrics and wash goods ernary ammonium compound may be used with generally. On the other hand, I have found that 30 the acid addition salts of hexadecyl and octadecyl certain important members of the series when amines provided the quaternary compound is ap~ used alone are entirely unsatisfactory for special preciably water-soluble. However, I have found detergent purposes. More particularly, I have that the best results are obtained if the germi found that, although the salts of hexadecyl amine, cidal high molecular quaternary ammonium com and also octadecyl amine, are good detergents for 35 pound is at least soluble to the extent of 1 part some purposes, such as washing clothes, they are in 100 of water and has a surface tension of less entirely unsuited for employment as lathering than about 40 dynes/cm. in 1% aqueous solution soaps for use on the skin. ' at 25° C. In order to be satisfactory as a substitute for Although the amine salts and the quaternary soap, a detergent should readily work up with 40 compounds may be used together in widely vary ing proportions, it is usually preferable, for rea water, for example, when rubbed between one’s sons of economy, to use more of the cheaper hands, to give a rich, thick-bodied lather of a amine salts. more or less permanent ‘nature. Because of the increased bulk of such a lather, as compared with The following examples illustrate how the above the material from which it is generated, it is easy 45 mentioned objects of the invention may be at tained. ‘ to work into the different corners and crevices of the body and the skin and thereby effectively and Example 1 economically produces its detergent action, I have found that acid addition salts of hexadecyl A quantity of hexadecyl amine is dissolved in and octadecyl amines de?nitely fail to meet these 50 ether, absolute alcoholic hydrochloric acid added requirements, since they only yield a‘ small to form the hydrochloride of the amine, the mix amount of more or less thin, transparent bubbles, ture cooled, ?ltered and washed with ether. The with practically no suds or lather, when worked ?ltered and washed solid product is the hydro up with water as is commonly done with a hand chloride of hexadecyl amine. It is only slightly soap or toilet soap. 0n the other hand, these 55 soluble in water. It cannot be used with water 2,400,902 Bromoethylate oi N-dodee'yi benzotri in any proportion to form a lather. It is. for" practical purposes, totally useless as a soap for azole 65 (c) Hexadecyl amine hydrohalide ______ __ 2 toilet purposes. 1,3-dioctyl benzotriazolium bromide--- 0.5 80 g. of the hexadecyl amine hydrochloride are mixed thoroughly with 20 g. of para-tertiary 5 (d) Octadecyl'amine lactate _________ __ 180 octyl phenoxyethoxyethyl dlmethyl benzyl am p-Tertiary octyl phenoxyethoxyethyl monium chloride. This quaternary ammonium dimethyl benzyl ammonium chloride 45 (e) Mixture of hexadecyl amine propionate (28%) and octadecyl amine propio 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 qua ternary compound with the hydrochloride of hexadecyl amine, prepared as described, is an 10 nate (72%) ____________________ __ 100 Cetyl trimethyl ammonium bromide___ 25 (f) Mixture of hexadecyl amine hydrochlo ride and octadecyl amine hydrochlo excellent product for use in the same manner as a toilet soap or a germicidal soap. It has the 15 advantage of readily being worked up with water ride 25% ______________________ __ 75 Dodecyl dimethyl benzyl ammonium chloride ________________________ __ 25 into a rich full bodied lather which does not de The quaternary ammonium compounds can be used alone or in mixtures with one another, and The soap-like mixture of this example can be mixtures of these with mixtures of one or more molded or pressed into cakes and other forms if 20 salts of hexadecyl amine and octadecyl amine desired. It can also be mixed with varying quan may be used. The following example is an illus tities of water and other compatible liquids to tration of such a variation of the invention. form paste-like products or liquids such as liquid soap preparations. Example '1' teriorate but is quite permanent. Instead of using the hydrochloride of hexadecyl A mixture 01' quaternary ammonium com amine, the acetate or other organic acid salt of 25 pounds is used which is derived from a mixture the amine can be used. The mixture of the two of higher alkyl amines obtained from coconut substances can also be incorporated with inert oils. Such a mixture of amines can be obtained ?llers of solid or semi-solid nature. Example II 30 by saponifying coconut oil, separating the mix ture of fatty acids thus produced, converting the mixture of acids to their amides, dehydrating A mixture consisting of about 75% by weight the amides/to their nitriles and hydrogenating of octadecyl amine hydrochloride and about 25% the latterl'to a mixture of higher alkyl amines. by weight of hexadecyl amine hydrochloride is used. Such a mixture is obtained by saponi? 35 This mixture of higher alkyl amines can then be converted by known methods into a mixture‘of cation of ordinary animal fats to get a mixture water-soluble quaternary ammonium compounds of fatty acids, converting the latter to a mixture of the general formula I 5" of amides, dehydrating the amides to their ni triles, hydrogenating the latter and converting the resulting mixture of hexadecyl amine and 40 R-N-CH: octadecyl amine to the mixture of hydrochlorides / mentioned. 200 grams of the mixture of hydrochlorides where R represents the mixture of higher alkyl thus prepared are mixed thoroughly with 50 grams of paratertiaryoctyl phenoxyethoxyethyl - radicals derived from the coconut oil, and X is the anion of an acid. dimethyl benzyl ammonium chloride to give a 1 lb. of a mixture or hexadecyl amine hydro product which is even superior to the product of chloride (75%) and octadecyl amine hydrochlo example I in lathering and soap-like properties. ride (25%) is mixed well with 5% ounces oi’ the When used on the hands like a soap, no irrita tion results and the skin is left clean, disinfected 50 mixed dimethyl benzyl high molecular alkyl am and velvety smooth. monium chlorides or the above formula derived from coconut oils. This combination in its vari-‘ Example III ous physical forms is an excellent lathering soap like preparation. Thisexample is carried out like Example I but /CHI ' using octadecyl amine salt instead of hexadecyl 55 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 What I claim as my invention is: - 1. A lathering soap-like preparation compris ing a germicidal mixture, free from skin-irritat ing properties, consisting 01' a substantially non lathering germicidal water-soluble high molecu 60 lar weight quaternary ammonium compound and a substance of the class consisting of a water soluble acid addition salt of hexadecyl amine, a As described above, numerous combinations of various salts of hexadecyl and octadecyl water-soluble acid addition salt of octadecyl amines with various germicidal quaternary am amine and mixtures of said acid addition salts, monium compounds are possible in accordance 05 said germicidal mixture being free from skin with the invention. Some further examples are irritating compounds and salts of amines of here given of other quaternary ammonium com ‘higher molecular weight than octadecyl amine pounds which serve to give good lathering soaps ' and lower molecular weight than hexadecyl when used with hexadecyl and octadecyl amine ‘ amine, and the weight of said substance in said salts. 70 germicidal mixture ranging from about three Grams times to about four times the weight of said (a) Hexadecyl amine hydrochloride ____ __ 400 Para-tertiary octyl phenoxyethoxy ethyl trimethyl ammonium chloride- 100 (b) Hexadecyl amine hydrochlorlde_...___ 250 quaternary ammonium compound. 2. A lathering soap-like preparation compris ing agermicidal mixture, tree from skin-irritat 75 ing properties, consisting of a substantially non— 2,406,902 6 lathering germicidal high molecular weight quat ernary ammonium compound water-soluble at least to the extent of one part in onehundred of lathering germicidal water-soluble para-tertiary octyl phenoxyethyoxyethyl dimethyl benzyl qua ternary ammonium salt and a substance of the class consisting of a water-soluble hydrohalic acid addition salt of hexadecyl amine, a water soluble hydrohalic acid addition salt of octadecyl class consisting of a water-soluble acid addition amine and mixtures of said acid addition salts, salt of hexadecyl amine, a water-soluble acid said germicidal mixture being free from skin-irri addition salt of octadecyl amine and mixtures of compounds and salts of amines of higher said acid addition salts, said germicidal mixture 10 tating molecular weight than octadecyl amine and lower being free from skin-irritating compounds and molecular weight than hexadecyl amine, and the salts of amines of higher molecular weight than weight of said substance in said germicidal mix octadecyl amine and lower molecular weight than ture ranging from about three times to ‘about four hexadecyl amine, and the weight of said sub times the weight of said quaternary ammonium stance in said germicidal mixture ranging from, 15 salt. about three times to about four times the weight 6. A lathering soap-like preparation compris oi’ said quaternary ammonium compound. ing a germicidal mixture, free from skin-irritating 3. A lathering soap-like preparation compris properties, consisting of a substantially non-lath ing a germicidal mixture, free from skin-irritat ering germicidal water-soluble para-tertiary octyl ing properties, consisting of a substantially non phenoxyethyoxyethyl dimethyl benzyl quaternary 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 lathering germicidal water-soluble paratertiary octyl phenoxyethoxyethyl dimethyl benzyl quat ammonium salt and a substance of the class con ernary 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 micidal mixture being free from skin-irritating of said acid addition salts, said germicidal mix compounds and salts of amines of higher molecu lar weight than octadecyl amine and lower mo ture 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 sub stance in said germicidal mixture ranging from about three times to about four times thelweight of said quaternary ammonium salt. - sisting of a water-soluble hydrochloric acid addi tion salt of hexadecyl amine, a water-soluble hy drochloric acid addition salt of octadecyl amine and mixtures of said acid addition salts, said ger lecular weight than hexadecyl amine, and the weight of said substance in said germicidal mix ture ranging from about three times to about four times the weight of said quaternary ammonium salt. i ' 7. A lathéring soap-like preparation compris ing a germicidal mixture, free from ,skin irritat ing properties, consisting of a substantially non 4. A lathering soap-like preparation compris ing a germicidal mixture, free from skin-irritat ing properties, consisting of a substantially non lathering germicidal water-soluble para-tertiary lathering germicidal water-soluble para-tertiary octyl phenoxyethoxyethyl dimethyl benzyl quater octyl phenoxyethoxyethyl dimethyl benzyl qua ternary ammonium salt and a water-soluble mix nary ammonium salt and a substance'of the class 40 ture of acid addition salts of hexadecyl amine and consisting of a water-soluble mineral acid addi octadecyl amine in the proportions of approxi tion salt of hexadecyl amine, a water-soluble min mately one mole of hexadecyl amine salt to 3 eral acid addition salt of octadecyl amine and moles of octadecyl amine salt, and the total mixtures of said acid addition salts, said germi weightof said acid addition salts in the mixture cidal mixture being free from skin-irritating being about four times the total ‘weight of said compounds and salts of amines of higher molecu quaternary ammonium salt. lar weight than octadecyl amine and lower mo 8. A combination of hexadecyl amine hydro lecular weight than hexadecyl amine, and the chloride and octadecyl amine hydrochloride, in weight of said substance in said germicidal mix ture ranging from about three times to about four times the weight of said quaternary ammonium salt. the proportion of approximately 1 mole of the for mer to 3 moles of the latter, with an amount of para-tertiary octyl phenoxyethoxyethyl dimethyl ' benzyl ammonium chloride equal to about one 5. A lathering soap-like preparation comprising . fourth the total weight of said hydrochlorides. a germicidal mixture, free from skin-irritating properties, consisting of a substantially none 55 ALBERT L. RAWLINS.