US3496110A - Shampoo - Google Patents

Description

Sta

and James Douglas N.J., assiguors to Colgate-Palm- New York, N.Y., a corporation of ABSTRACT OF THE DISCLOSURE A preferred conditioning shampoo is disclosed which contains (1) 12 to 30% of a detergent mixture which includes (a) a mixture of C -C alkyl di-lower-alkyl amine oxides having an average of 10 to 17 carbons in the alkyl group and a ratio of C -C alkyl groups to C -C alkyl groups in the range of about 1:1 to 4:1, (b) a long chain amino of phosphoric carboxylic or sulfonic amphoteric detergent in acid or salt form and (c) a long chain quaternary ammonium cationic detergent wherein the weight ratio of C -C alkyl di-lower-alkyl amine oxide to cationic detergent is in the range of 0.6 to 24 and the weight ratio of C -C alkyl di-lower-alkyl amine oxide to amphoteric detergent is in the range of .5 to 12 and (11) water, the pH of the shampoo being in the range of 4.5 to 6.5. An aqueous acidic conditioning shampoo comprising a mixture of amine oxides and a quaternary ammonium salt is also set forth.

This invention relates to the production of conditioning shampoos.

The production of a good conditioning shampoo has been a goal of chemists in the field of hair treatment for a long time. Shampoos which thoroughly clean the hair usually leave it in a statically electrified state, in which the individual hairs repel each other, or in a state in which simple combing produces this undesired electrification; in either case the hair is very diflicult to manage. To overcome this defect, creme rinses containing antistatic agents have been employed after shampooing, but the use of these materials naturally requires additional time, effort and expense on the part of the user.

An effective conditioning shampoo must satisfy many requirements. Besides removing soil from the hair, it must yield a good foam, which is long-lasting and remains in place on the hair without running, comparable to the foam of current commercial shampoos. It must be easily rinsed from the hair, with water, and the rinsing r must not only cause the foam to disappear but also eliminate the undesirable residual soapy feel on the hair. It must leave the hair lustrous and with a pleasant feel. It must reduce or eliminate the snarling of the hair which ordinarily results when the user runs her fingers repeatedly through the hair during shampooing which snarling makes it difficult for the user to continue working the hair with her fingers. It must promote easy wet-combing of the washed and rinsed hair, allowing the strands of hair to slip easily on each other and to slip easily past the comb. It must also promote easy dry combing; thus, there should be little drag on the comb during dry combing and the strands of hair should not tend to fly apart and become disaligned during or directly after the dry combing process. It must reduce static electrification of the hair; this can be tested, for example, by dry combing a hair tress, containing several hundred hairs, using a given number of strokes (e.g. 15 strokes) at a given tempo with a comb made of hard rubber or other insulating material, then placing the back of the comb against the lower, free, end of the tress and moving the comb upward, with its back against the side of the tress; the number of strands which follow the comb and become disaligned from the main body of the tress is an indication of the static electrification of the hair. The conditioning shampoo must also be substantially non-irritating and non-damaging to the eyes.

In accordance with one aspect of this invention, a conditioning shampoo satisfying the foregoing requirements comprises an acidic aqueous mixture containing a cationic detergent, an amphoteric detergent, and a mixture of higher alkyl dialkyl amine oxides having an average of about 10 to 17 carbon atoms in the higher alkyl group and in which the weight ratio of higher alkyl groups containing 10 to 14 carbon atoms to those containing 15 to 20 carbon atoms is about 1:1 to 4:1 (preferably about l /zzl to 3:1). Those higher alkyl dialkyl amine oxides in which the higher alkyl is C to C are present in amount in the range of 0.6 to 24 times (preferably more than 1 and still more preferably about 2 to 5 times) the amount of the cationic agent, and in the range of /2 to 12 times (preferably more than 1 and still more preferably about 2 to 5 times) the amount of the amphoteric agent. The concentration of the cationic agent in the aqueous mixture, as used, is in the range of about 0.5 to 5%, preferably about 2 to 4%, and the concentration of the other components is such that the total amount of the detergents in the mixture is in the range of about 12 to 30%, preferably about 15-25%. It will be appreciated, of course, that the composition may be supplied in more highly concentrated form, for subsequent dilution with water. Preferably the total amount of the amine oxide is greater than the combined amounts of the other detergents.

As indicated above, the shampoo is acidic, its pH being in the range of about 4 /2 to 6 /2. It is found that the performance (e.g. static, dry combing and foam properties) is significantly better when the shampoo is acidic than when it is neutral. A pH of about 5-6 is preferred. Any suitable acid may be used for adjusting the pH, e.g. hydrochloric, citric acetic, sulfuric, alkylsulfuric (e.g. monoethyl sulfate), phosphoric, malic, etc.

The higher alkyl dialkyl amine oxide mixture preferably contains higher alkyl dimethylamine oxides, the higher alkyl groups being typically decyl, lauryl, myristyl, cetyl, stearyl, eicosyl or other higher alkyl groups of about 1020 carbon atoms, derived for example from tallow, hydrogenated tallow, coconut oil, etc. In place of one or both of the methyl groups there may be used ethyl, hy- (ll(1)Xy ethyl, hydroxypropyl or similar lower alkyl radica s.

The amphoteric detergent is preferably a substituted aminocarboxylic acid having a substituent with a pendent long chain hydrophobic group, e.g. an alkyl of about 10-20 carbon atoms. Preferably the long chain substituent is connected to the amino nitrogen by a C-N bond and the amino and carboxyl groups are joined, through NC and CC bonds, respectively, by a divalent radical (e.g. an alkylene radical of 24 carbon atoms, preferably 2 carbon atoms). Most preferably the amino group is monosubstituted by the long chain radical; however it is within the broader scope of the invention to use detergents in which the amino group is disubstituted, the second substituent being, for example, methyl or other lower alkyl or --RCOOH where R is a divalent radical such as an alkylene radical of 2-4 carbon atoms. Betaines in which there are three substituents on the amino nitrogen, may also be used. In the most preferred form of the invention, the long chain alkyl group is directly attached to the amino nitrogen; however, the attachment may be through intermediate structure such as through an imidazoline ring of which the nitrogen of the amino acid is a part.

Examples of specific amphoteric detergents are N- higher alkyl-beta-aminopropionic acid; N-higher alkylbeta-iminodipropionic acid, and N-higher alkyl, N,N- dimethyl glycine (a betaine); the higher alkyl group may be, for example, that derived from coco fatty alcohol, lauryl alcohol, myristyl alcohol (or a lauryl myristyl mixture), hydrogenated tallow alcohol, cetyl, stearyl, or blends of such alcohols.

Other amphoteric detergents are the fatty imidazolines such as those made by reacting a long chain fatty acid (e.g. of to carbon atoms) with diethylene triamine and a monohalocarboxylic acid having 2 to 6 carbon atoms, e.g. l-coco-S-hydroxyethyl-5-carboxymethylimidazoline; betaines containing a sulfonic group instead of the carboxylic group; betaines in which the long chain substituent is joined to the carboxylic group without an intervening nitrogen atom, e.g. inner salts of 2-trimethylamino fatty acids such as Z-trimethylaminolauric acid, and compounds of any of the previously mentioned types but in which the nitgrogen atom is replaced by phosphorus (e.g. carboxymethyl dimethyl dodecyl phosphonium inner salt).

The amphoteric detergents are often supplied in the sodium or other salt forms, which may likewise be used in the practice of this invention. It is preferred to use those amphoteric detergents which dissolve and foam readily in acidified water.

The cationic detergents are quaternary ammonium salts having long chain hydrophobic radicals (e.g. alkyl radicals of 10-20 carbon atoms), such as 1-methyl-1- higher alkylamidoethyl-2-higher alkylimidazolinium salts in which the alkyl groups have, for example, 10-20 carbon atoms, ethoxylated long chain fatty quarternary ammonium compounds, higher alkyl benzyldimethylammonium salts, higher alkyl-pyridinium salts, higher alkyl isoquinolinium salts, di( higher alkyl) dimethylammonium salts, etc. The anion of the water-soluble quaternary ammonium compound is most usually a chloride or methosulfate (OOS OCH ion, but other ions may be used as is well known in the art, e.g. bromide, phosphate, dialkyl phosphate or acetate ions.

The following examples illustrate this aspect of the invention further.

Example 1 A shampoo was prepared from the following constituents:

150 grams of a 30% solution in water of a higher alkyldimethylamine oxide mixture containing 60-65% lauryl dimethylamine oxide, -30% myristyl dimethylamine oxide and 10-15% cetyl dimethylamine oxide; 75 grams of a 20% solution in water and isopropanol (in 1:1 ratio) of a higher alkyl dimethylamine oxide containing 95% cetyl dimethylamine oxide, 3% lauryl dimethylamine oxide and 2% myristyl dimethylamine oxide; grams of a solution in water of a blend of N-higher alkyl fl-aminopropionic acid and the corresponding N-higher alkyl fl-iminodipropionate (the ratio of the former, monocarboxylic acid, to the latter, dicarboxylic acid, being 10:1) in which the higher alkyl radicals are lauryl and myristyl in ratio of 2.321 (known as Deriphat 170-C); 20 grams of a mixture of 75% l-methyl l-long chain alkylamidoethyl-2-long chain alkylimidazolinium methosulfate (Culversoft S-75") in which the long chain alkyl radicals are 1.5% saturated C14, 24% saturated C16, 4.5% ethylenically unsaturated C16, 25% saturated C18 and 45% ethylenically unsaturated C18, 15% isopropanol, 3% glycerine and 2% water; and 225 grams of deionized water.

The pH of the mixture was adjusted to 5.5 by addition of a small amount of 12 N hydrochloric acid.

Example 2 Example 1 was repeated except that in place of the 75 grams of the 20% solution of the blend of higher alkyl dimethylamine oxide (95% cetyl) there was used 300 grams of a 5% solution in water of that same blend of amine oxides, and in place of the Culversoft S- there was used 17 grams of Culversoft W5. (a product containing 86-88% of an ethoxylated fatty quaternary ammonium chloride, 10-12% isopropanol, less than 1% free amine [calculated as trimethylamine, molecular weight 59], less than 2.5% amine hydrochloride [calculated as trimethylamine hydrochloride, molecular weight 95.5] The amount of separately added deionized water was reduced to 3 grams and the ingredients, before acidification, were heated together at 72 C. with moderate mixing in an open vessel and then cooled to room temperature. 6 grams of water were then added, to replace the 6 grams lost during the heating. The pH was then adjusted to 5 .5 by the addition of a small amount of 85% phosphoric acid (instead of the hydrochloric acid).

In a use test of the shampoo by a representative group of women, the shampoo was found to leave the hair soft, less dry, easy to comb, and feeling as if it had been creme rinsed, and was reported by the women to be significantly superior to current commercial shampoos.

The shampoos of this invention, while safe to the eyes, have the desirable property of causing slight stinging when present in high, concentration in the eyes; this warns the user to rinse out the shampoo from her eyes promptly so that there is little or no undesired removal of natural fats and oils from the tissue.

Another aspect of this invention relates to conditioning shampoo compositions in which the amphoteric detergent may be omitted entirely or used in reduced amount. In this case there is included in the shampoo compositions a significant amount of higher alkyl dialkylamine oxide having at least 18 carbon atoms in the higher alkyl group, i.e. at least 5%, and preferably at least about 10%, of the total amount of the higher alkyl dialkyl amine oxides should be such a C (01' higher) higher alkyl amine oxide. In such compositions the ratio of the total amount of amine oxides to the amount of the cationic agent should be at least 08:1 and less than 30:1 (preferably more than 1:1 and still more preferably about 2:1 to 5:1); the average molecular weight of the amine oxides is at least about 230 (preferably above 240), the average molecular weight of the higher alkyl groups is preferably at least and more preferably at least and the weight ratio, in the amine oxides, of higher alkyl groups containing 10 to 12 carbon atoms to those containing 13 to 20 carbon atoms is in the range of about 3:12 to 13:2 (preferably about 2:1 to 1:2). The compositions made without the amphoteric detergent do not, however, have all the excellent qualities of the previously described compositions. They are not quite as good with respect to foam volume, foam texture, foam density, feel and slip.

The following example illustrates this aspect of the invention further.

Example 3 A shampoo was produced by mixing the following constituents:

15 parts of the 30% aqueous solution of the alkyldimethylamine oxide (60-65% lauryl, 25-30% myristyl, 10% cetyl) of Example 1;

5 parts of the 20% solution of higher alkyl dimethylamine oxide (95% cetyl, 3% myristyl, 2% lauryl) described in Example 1;

3.4 parts of a 30% solution in water of mixed higher alkyldimethylamine oxides containing 10-15% of lauryl dimethylamine oxide, 55-60% of myristyl dimethylamine oxide and 25-30% of cetyl dimethylamine oxide;

5.3 parts of a 19% suspension in water of mixed higher alkyl dimethylamine oxides containing 91% stearyl dimethylamine oxide, 8% cetyl dimethylamine oxide and 1% myristyl dimethylamine oxide;

2 parts of the suspension of quaternary compound of Example 1;

19.4 parts of water.

The pH of the mixture was adjusted to 5.5 by the addition of a small amount of 12 N HCl.

Example 4 A shampoo was produced by mixing the following constituents:

15 parts of the 30% aqueous solution of the alkyldimethylamine oxide (60 65% lauryl, 25-30*% myristyl, cetyl) of Example 1;

20 parts of the 5% solution in water of higher alkyl dimethylamine oxide (95% cetyl, 3% myristyl, 2% lauryl) described in Example 2;

3.4 parts of a 30% solution in water of mixed higher alkyldimethylamine oxides containing 10-15% of lauryl dimethylamine oxide, 55-60% of myristyl dimethylamine oxide and 25-30% of cetyl dimethylamine oxide;

4 parts of a 25% suspension in water of mixed higher alkyl dimethylamine oxides containing 95% stearyl dimethylamine oxide and 5% cetyl dimethylamine oxide; 1.7 parts of the Culversoft W.S. 90; 6 parts of water, and a small quantity of citric acid sufficient to lower the pH to 5.5. Small amounts of coloring agent (FD. & C, Blue #1) and perfume were also included.

Unless otherwise indicated, all proportions set forth herein are by weight.

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 can be substituted therefor without departing from the principles and true spirit of the invention.

Having thus described the invention, what is claimed is:

1. An aqueous hair conditioning shampoo which consists essentially of an acidic aqueous mixture of (a) a mixture of higher alkyl, di(C C alkyl) amine oxide detergents having an average of about 10 to 17 carbon atoms in said higher alkyl group and in which the Weight ratio of higher alkyl groups having 10 to 14 carbon atoms to those having 15 to carbon atoms is about 1:1 to 4:1; (b) an amphoteric detergent selected from the group consisting of N-higher alkyl aminopropionic acid, N-higher alkyl iminodipropionic acid, and mixtures thereof, said higher alkyl group containing 10' to 20 carbon atoms; and (c) about 0 .5 to 5% by weight of a cationic, quaternary ammonium detergent having a long chain hydrophobic radical of 10 to 20 carbon atoms in its molecular structure, the weight of C to C alkyl di(C C alkyl) amine oxide being present in the range of 0.6 to 24 times the weight of cationic detergent and in the range of /2 to 12 times the weight of the amphoteric detergent, the total concentration of the detergents being 12% to 30 by Weight of the shampoo, said shampoo having a pH of 4.5 to 6.5 and yielding a good foam with good cleansing power and leaving the hair in an easily combable condition on rinsing with water without the need for a subsequent antistatic creme rinse.

2. A composition as set forth in claim 1 in which the lower alkyls of said amine oxide are methyl, the weight ratio of higher alkyl groups having 10 to 14 carbon atoms to those having 15 to 20 carbon atoms is about l /2:1 to 3:1, and the weight of C -C alkyl dimethyl amine oxide is about 2 to 5 times the weight of the cationic detergent and about 2 to 5 times the weight of the amphoteric detergent.

3. A composition as set forth in claim 2 in which said amine oxides are present in an amount greater than the total weight of said other detergents.

References Cited UNITED STATES PATENTS 3,296,145 l/1967 Findlan et a1. 252106 LEON D. ROSDOL, Primary Examiner W. SCHULZ, Assistant Examiner US. Cl. X.R.