US3149338A - Hair preparations containing a diamide and process of use thereof - Google Patents

Description

- Patented Sept. 15, 1964 3,149,338 HAIR iREPARATEflNS QGNTAHQTNG A DEAD/HER AND PRG-CESS 43F USE TE EREQF Loin Habicht, Aumuhle, near Hamburg, and Arno Kluge,

Bad Sorlen, Taunus, Germany, assignors to Qolgate- Palmolive Company, New York, N.Y., a corporation of Delaware No Drawing. Filed lune 17, 1960, Ser. No. 36,754 (Ilaims priority, application Germany, duly 7, 1959, P 23,1tl2 11 Claims. (Cl. l6787) The present invention relates to a cosmetic composition suitable for daily use in the care of the hair. More particularly it relates to hair cleansing and grooming compositions such as hair lotions, tonics, shampoos and the like which may be used in the daily toilet.

in accordance with the present invention a cosmetic composition suitable for daily use in the care of the hair and scalp comprises a substantially non-volatile organic toilet agent for the daily care of the hair and a diamide compound having the formula wherein X is selected from the group consisting of oxygen sulfur, R R R and R are selected from the group consisting of hydrogen alkyl, alkylol and acyl, and R is selected from the group consisting of hydrogen and alkyl, said R R R R and R containing up to two carbon atoms each, and from 40 to 99.45% of a volatile aqueous solvent medium, said composition having a pH of from 4 to and being free of reducing agents. Suitable such compounds include biuret, thiobiuret, dithiobiuret, and their waterand alcohol-soluble monoand polyalkyl, -alkylol and -acyl derivatives wherein the alkyl, alkylol and acyl groups have in general not more than 2 carbon atoms, e.g. l-rnethyl-biuret, S-methylbiuret, l-ethyl-biuret, 1,5-dimethyl-biuret, 1,3,5-trimethylbiuret, l-hydroxymethyl-biuret, 1,5-dihydroxymethyl-biuret, I-acetyl-biuret, 1-forrnyl5-acetyl-biuret, 1,5-dimethyl-l-acetyl-biuret, 1,3,5-trimethyl-l-acetyl-biuret, 3-ethyll-acetyl-biuret, l-methyl-thiobiuret, l-ethyl-thiobiuret, 1 acetyl-thiobiuret, 1 hydroxymethyl-thiobiuret, and l-methyl-dithiobiuret.

The cosmetic compositions of the present invention may be prepared in a wide variety of physical forms. They may be liquids, pastes or solids and may consist of one or more phases. They may, for example, constitute a single aqueous or aqueous-alcoholic phase, or may comprise an aqueous and a separate oily phase as in two layer systems or emulsions of the water-in-oil or oil-inwater types.

The instant compositions and their constituents are skin-compatible, being suitable for periodic use at short, i.e. daily or at the most weekly, intervals, as distinguished from decorative or treating compositions such as hair dye ing or waving compositions which can be used only at much greater intervals. Thus it is contemplated that the present cosmetic compositions may be prepared in the form of daily hair grooming products such as hair 10- tions, hair dressings, hair tonics and the like, or they may be prepared in the form of hair cleansing products such as shampoos, the non-volatile organic toilet agent for daily care of the hair being present in each instance in an amount from 0.5 to 98% by Weight of the composition.

In the case of hair grooming compositions, the nonvolatile organic toilet agent for the daily care of the hair stituent containing 8 to 26 carbon atoms.

is an agent which facilitates grooming of the hair and helps to keep the hair in place. Such hair groonnng agents include, e.g., castor oil, mineral o1l, lower alkoxypolyoxy lower alkylene glycols such as butoxypolyoxypropylene glycol, higher molecular weight copolymers of random mixtures of ethylene oxide and propylene oxide, esters of fatty acids such as isopropylmyristate or the coconut oil fatty acid ester of polyethylene glycol having an average molecular Weight of about 400, polyhydric alcohols such as glycerol and propylene glycol, gums such as gum tragacanth, lacquers such as shellac, and the like. It is preferred to employ those substantially non-volatile organic hair grooming agents which have a molecular weight greater than about and preferably greater than about 200 and which contain an alcoholic hydroxyl group such as the aforementioned glycols, polyhydric alcohols, polymerized alkylene oxides, and castor oil. The foregoing organic hair grooming materials desirably are employed in the instant hair grooming preparations in an amount from 0.5 to 50% and higher depending on the nature of the respective compound and its compatibility in the desired system.

In the case of hair cleansing compositions or shampoos, the non-volatile organic toilet agent for the daily care of the hair is a cleansing agent such as a water-soluble organic detergent. Preferably this detergent is an anionic sulfate or sulfonate, i.e. a sulfated or sulfonated compound having a hydrophobic substituent containing 8 to 26 carbon atoms, desirably from 12 to 18 carbon atoms, per molecule.

Detergents of this preferred type which may be suitably employed include the sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, e.g., coconut oil monoglyceride monosulfate and fallow diglyceride monosulfate; the long chain'pure or mixed'allryl sulfates such as lauryl sulfate, cetyl sulfate, and higher fatty alcohol sulfates derived from coconut oil; the hydroxy sulfonated higher fatty acid esters such as, e.g., higher fatty acid esters of 2,3-dihydroxypropane sulfonic acid; the lugher fatty acid esters of low molecular weight alkyiolsulfonic acids, e.g., oleic acid ester of isethionic acid; the sulfated higher fatty acid alkylolamides such as, e.g., CthSIiOIZLrldC sulfates; the higher fatty acid amides of amino alkyl sulfonic acids, e.g., the lauric amide of taurine, and the like.

Other anionic synthetic detergents which may be employed in shampoos are the sulfonic acid salts of alkylated aromatic hydrocarbon compounds having an alkyl sub The aromatic portion of the molecule may be monoor polynuclear, e.g., benzene, toluene, Xylene, naphthalene, phenanthrene, anthracene, etc., and may contain other substituents such as hydroxyl groups or short chain alkyl groups such as, e.g., in phenol, cresol, phenol ethers, toluene, Xylene, etc. The long chain alkyl substituent of the alkylated aromatic molecule preferably is saturated and may be straight chain or branched. Representative long chain alkyl groups include the dodecyl, hexyl, octyl, nonyl, and decyl groups as well as mixed alkyls derived from fatty materials, cracked parafiins or polymers of lower mono olefins, etc. In general, the alkylated aromatic detergents employed will be a mixture of compounds having alkyl substituents of varying chain length since the chain length is dependent upon the sharpness of the fractionation of the aliphatic hydrocarbon used for the alkylation. The average chain length of the alkyl substituents shouldbe in general from 9 to 15 carbon atoms and preferably between 12 and 14 carbon atoms.

These various anionic detergents are employed in shampoos prepared in accordance with the present invention in the form of their water-soluble salts. Thus, detergents may be used in the form of their alkali salts, e.g.,

as sodium, potassium or lithium salts, or as ammonium salts, as well as in the form of salts of nitrogen containing bases, e.g., as salts of low molecular alkylolamines such as mono-, diand triethanolamine, and as mixtures of various of these salts.

Other anionic detergents which may also be employed include water-soluble alkyl phosphates, sulfated ethylene oxide condensates of hydrophobic materials such as higher fatty acids, fatty alcohols, alkyl aromatic hydrocarbons and the like, sulfonated oils, soaps such as sodium, potassium and triethanolamine soaps of higher fatty acids containing from 12 to 18 carbon atoms as well as mixtures of soaps being especially useful such as sodium laurate, sodium palmitate, sodium oleate and the potassium and/or triethanolamine soaps of coconut oil, palm oil, and tallow fatty acids.

lauroyl pyridinium bromide, cetyl trimethyl ammonium chloride or cetyl pyridinium chloride may also be used alone or'in combination with other compatible detergents. Suitable salts of cationic detergents are the chloride, bromide, acetate and sulfate. V

Suitable detergents are furthermore the amphoteric detergents such as salts of the N-alkyl compounds of betaamino propionic acid wherein the alkyl group is derived from a fatty acid fatty acids.

Shampoos in accordance with the present invention may be prepared in any convenient physical form and may consist of one or more phases. Thus such a shampoo such as the mixture of coconut oil 'may be a solid product such as a bar or a powder, or a clear, homogeneous single phase liquid such as an aqueous or aqueous-alcoholic composition, or it may contain two or more liquid or mixed liquid and solid phases, as in ably comprise 'at least and prferably from to 40% "of the instant shampoos when they are prepared in a liquid or paste formQand from 15 to 98% when the shampoo is prepared in the form of a solid'composition;

The diamide compounds of the present invention constitute a minor proportion, on the order of 0.05 to 10% of the instant hair preparations, the most suitable amount depending on the characteristics desired; Thus, in a clear, homogeneous, single phase,.aqueous type of hair preparation preferably an amount on the order of 0.25 to 'the case of cream-shampoos, lotion-shampoos, pasteshampoos, and the like. The foregoing detergents desir- 1.0% of the composition in employed. In a single phase 1 For example, an'aqueous cosmetic composition may comprise from 0.05 to 10% of diamide, from 0.5 to 50% of the non-volatile organic toilet agent, and as the balance,

e. g.14099.45%, a volatile aqueous solvent medium such as water or mixtures of water and a lower monohydric alcohol such as ethanol or isopropyl alcohol. In the reparation of a clear, homogeneous single phase aqueous shampoo, preferably 0.5 to 2% of one of the instant diamide compounds, 5 to 20% water soluble detergent, and 7894.5% water and other components are used, Whereas in a shampoo containing aqueous alcohol wherein said diamide compounds and detergents are each more soluble, more than 2% of the diamide may be used in combination with 5 to 40% of the detergent, the balance being aqueous alcohol and other components. In solid, powder or cream shampoos amounts of 0.05 up to 10% of diamide are possible in combination with 15 to 98% of the detergent and'a balance of water and/ or other components.

The instant hair preparations may also contain as adjuvant materials various substances such as vitamins, hormones, cholesterol, lanolin, bactericides, plant extracts, buffers, and the like in compatible proportions, although the preparations should be free of substantial quantities of water insoluble sohd substanceswhich may be deposited on and clog the pores of the scalp. Desirably the present compositions have a pH of 4 to 10 as they appear to be most effective in this range.

The hair preparations of the invention exhibit unusua ly excellent hair grooming properties. They render the hair soft and manageable, impart a high gloss and luster, and are particularly effective in controlling or preventing the formation of dry flaky scales of sloughed-oif skin.

The efiiciency of aqueous compositions prepared in accordance with the present invention is favorably infiuenced by the presence of a water soluble material which reduces the surfaceand/or interfacialatension of water (e.g. alcohol in alcoholic hair tonics, soaps or synthetic detergents in shampoos, emulsifiers in hair dressings). The presence of these surface active materials is believed to reduce the interfacial tension between the aqueous phase containing the instant water soluble diamides and the hair v and scalp so that soil and oily secretions are more easily temperature or elevated temperature in the amount of water, alcohol or aqueous alcohol required for the respective hair preparation. Thereafter, the toilet agent for the daily care of the hair may be added in the usual way, i.e.

in the case of hair tonics, liquid shampoos or hair rinses the hair grooming agent may be added to the liquid containing the diamide of the invention, and in the case of hair creams of the oil-in-water or water-in-oil type, the

liquid containing the diamide may be heated to 50-70 C. and emulsified with the molten fats, mineral oils orlike hair grooming agents, the emulsion, if necessary, being homogenized thereafter.

Cream shampoos formulated in accordance with the present invention may be prepared by mixing an aqueous detergent paste with an appropriate diamide compound and any other desired components with stirring at an elevated temperature (4060 C.)..

Powder shampoos may be made by homogeneously mixing the desired components in a mixer.

. Specific hair preparations according to the invention are illustrated by the following examples. All parts indicated 'areby weight unless otherwise specified.

EXAMPLE 1 v V Hair Lotion To 56 parts of ethyl alcohol 96% and 6 pmts of glycerine 98%- ina suitable mixer 2 parts of biuret are added with stirring. After complete dissolutionof the biuret,

0.19 partof perfume and 0.01 part of dyestuif are introduced as coloring for the lotion, and after short stirring 35.8 parts of deionized waterare added. For clarification 0.1 part of magnesium carbonateis stirred into the solution and filtered oif again.

Water 45 .6

The hair lotions of Examples 2 and 3 are prepared in a Way analogous to Example 1.

EXAMPLE 4 Hair Cream [Oil-imwzxter emulsion] 14 parts of diglycol laurate, 34 parts of mineral oil and 0.2 part of a preservative (e.g. methyl-p-hydroxy benzoic acid ester) are heated to 80 C. This mix is slowly and thoroughly stirred into a solution of 1 part of thiobiuret in 50.5 parts of water. After cooling to 35 C., 0.3 part of perfume is added. Finally the cream is homogenized on a roller mill.

EXAMPLE 5 Hair Cream [Oil-in-water emulsion] Part I Parts Mineral oil 33.0

Beeswax 3.0 Stearic acid 0.5 Cetyl alcohol 1.3 Preservative 0.2

Part II Borax 0.25

Triethanolarnine 1.85 1,5-dihydroxymethyl-biuret 5.00 Water 54.60

Part III Perfume 0.30

Part I is heated to 6065 C. and slowly added with vigorous stirring to part 11 previously heated to 60-65 C. The cream is cooled with stirring to 35 C. at which temperature part III is added.

EXAMPLE 6 Hair Cream [Water-in-oil emulsion] Part I Parts Bees wax n 1.5 Oleic acid 1.0 Mineral oil 40.6 Preservative 0.2

Part II Milk of lime 0.14% 50.0 l-formyl-S-acetyl-biuret 1 .0

Part III Magnesium sulfate solution 10% 5.0

Part IV Perfume 0.7

6 Part I is heated to 7075 C. Then part H previously heated to 60 C. is slowly added with thorough stirring, and finally part III is introduced. The cream is stirred at 70 C. for 10 minutes and then slowly cooled with stirring to 55 C. At this temperature, part IV is added. Then the cream is cooled to 35 C. and homogenized at 30 C.

EXAMPLE 7 Liquid Shampoo Part I Parts Oleic acid 5.0 Coconut oil fatty acid 4.0 Triethanolamine 5.5 Propylene glycol 5.0 Preservative 0.2

Part II Ethylene diamine tetraacetic acid sodium salt 0.5 Biuret 1.5

Water 78.0

Part III Perfume 0.3

Part I is heated to C. while stirring. After a homogeneous mix is obtained, part II previously heated to 35 C. is added with cautious stirring and finally part III is introducedf EXAh/IPLE 8 Powder Shampoo Parts Sodium lauryl isethionate 60.0 Sodium bicarbonate 34.5 l-methyl-biuret 5 .0 Perfume 0.5

The solid components are homogeneously mixed in a mixer and the perfume is added by spraying it on the powder while moving the mass in the mixer.

EXAMPLE 9 Liquid Shampoo 97.4 parts of an aqueous alcoholic solution containing 20 parts of ammonium coconut oil monoglyceride monosulfate and 20 parts of ethyl alcohol are heated to -35 C. 2 parts of 1,3,5-trimethylbiuret, 0.2 part of preservative, 0.05 part of dyestuff and 0.35 part of perfume are stirred successively into this solution.

EXAMPLE 10' Liquid Shampoo Parts N-lauryl-beta-amino-propionic acid triethanolamine salt, 40% 50.0

Coconut oil fatty acid diethanolamide 2.0 1,5-dimethylbiuret 3.0 Perfume, preservative, coloring 0.6 Water 44.4

This composition is prepared in a similar way as described in Example 9.

EXAMPLE 11 Cream Shampoo 91.8 parts of an aqueous sodium lauryl sulfate paste containing about 45- parts of sodium lauryl sulfate are heated to 5060 C. To this mix a melt from 2 parts of polyethylene glycol-400-distearate, 1.5 parts of magnesium stearate and 1 part of oleyl alcohol and then 0.2 par-t of a preservative and 3 parts of thiobiuret. are added with stirring. After cooling to 40 C. 0.5 part of perfume is introduced.

EXAMPLE 12 Hair Rinse 7 Parts Stearyl dimethyl benzyl ammonium chloride 4.0 Polyglycol-400-distearate 3 .0

l-hydroxymethyl-biuret 2.0 Perfume, preservative 0.5

Water 90.5

From all components an aqueous solution is prepared at room temperature. After standingrfor 24 hours the solution is filtered.

Although the present invention has been described with reference to particular embodiments and examples, it

wherein X is selected from the group consisting of oxygen and sulfur, R R R and R are selected from the group consisting of hydrogen, alkyl, alkylol and acyl, and R is selected from the group consisting of hydrogen and alkyl, said R R R R and R containing up to two carbon atoms each, and from to 99.45% of a volatile aqueousj solvent medium, said composition having a pH of from 4 to 10 and being freeof reducing agents.

2. A cosmetic composition as set forth in claim 1 wherein said diamide is biuret.

3. A shampoo composition comprising from about 5 to 98% of a water soluble organic detergent, and .05 to 10% of a diamide compound having the formula wherein X is selected from the group consisting of oxygen 7 and sulfur, R R R and R are selected from the group 7 consisting of hydrogen, alkyl, alkylol and acyl, and R is selected from the group consisting of hydrogen and alkyl, said R R R R and R containing up to two carbon atoms each, and water as the balance, said composition having a pH of 4 to '10 and being free of reducing agents.

4. A shampoo composition as set forth in claim 3 wherein said diamide is biuret.

5. A hair grooming composition suitable for daily use in the care of the hair'and scalp which comprises about 0.5 to by weight of a substantially non-volatile organic hair grooming agent containing an, alcoholic hydroxyl group and having a molecular weight greater than about '75, 0.05 to 10% of a dianiide compound having the'formula J said R R R R and R containing up to two carbon atoms each, and 40 to 99.45% of a volatile aqueous sol- .ventmedium, said comp ositionihaving a pH oft-4 to 10 and being free of reducing agents. 5

6. A hair grooming preparation as set forth in claim 5 wherein said hair grooming agent is glycerine. V

7. A process for the treatment of the hair and scalp which comprises the daily application thereto of a substantially non-volatile toilet agent for the daily care of the hair and about 0.05 to 10% by weight of a diamide CO1 pound having the formula wherein X is selected from the group consisting of oxygen and sulfur, R R R and R are selected from the group consisting of hydrogen, alkyl, alkylol and aryl, and R is selected from the group consisting of hydrogen and alkyl, said R R R R and R containing up to two carbon atoms each, the said toilet agent and diamide compound being applied to the hair and scalp at a pH of 4 .to 10.

8. A cosmetic composition suitable for daily use in the care of the hair and scalp which comprises a substantially non-volatile toilet agent for the daily care of the hair and from about 0.25 to 2.0% by weight of a diamide compound having the formula wherein X is selected from the group consisting of oxygen and sulfur, R R R and R are selected from the group consisting of hydrogen, alkyl, alkylol and acyl, and R is selected from the group consisting ofhydrogen and alkyl, said R R R R and R containing up to two carbon atoms each, said composition having a pH of 4 to 10 when disposed in an aqueous liquid and being free of reducing agents. i

9. A cosmetic composition suitable. for daily use in the care of the hair and scalp which comprises a substantially non-volatile toilet agent for the daily care of the hair and from about 0.25 to 1.0% by weight of a diamide com pound having the formula wherein X is selected from the group consisting of oxygen and sulfur, R R R and R are selected from the group consisting of hydrogen, alkyl, alkylol and acyl, and R is selected from the group consisting and hydrogen and 'alkyl, V

wherein X is selected from the group consisting of oxygen and sulfur, R R R and R are selected from the group consisting of hydrogen, alkyl, alkylol and acyl, and R is selected from the group consisting of hydrogen and alkyl, said R R ,"R R and R containing up, to two carbon atoms each, said composition having a pH of 4 to 10 when disposed in an aqueous liquid and being free of reducing agents. V

11. A' hair groom ng composition suitable for daily use in the careof the hair and scalp which comprises about;

9 10 0.5 to 50% by weight of mineral oil, 0.05 to 10% of 2. References Cited in the file of this patent dialm'de compound having the formula UNITED STATES PATENTS R1\ /R4 2,371,112 Sperry Mar. 6, 1945 2,371,113 Sperry Mar. 6, 1945 OX E 0X 5 2,813,783 Gleim Nov. 19, 1957 FOREIGN PATENTS wherein X is selected from the group consisting of oxygen 75 320 N th 1 d Jul 15 1954 and sulfur, R R R and R are selected from the group 6 er an s n y consisting of hydrogen, alkyl, alkylol and acyl, and R is 10 OTHER REFERENCES selected from the group consisting of hydrogen 311d y Kurzer: Chemical Reviews, vol. 56, pages 95 to 197, said R R R R and R containing up to two carbon February-June 1956. atoms each, and 40 to 99.45% of a volatile aqueous sol- Harry: Modern Cosmeticology, vol. 1, Fourth edition,

vent medium, said composition having a pH of 4 to 10. published by Leonard Hill Ltd., 1955, pages 432 to 434.

Claims (1)

1. AN AQUEOUS COSMETIC COMPOSITION SUITALBE FOR DAILY USE IN THE CARE OF THE HAIR AND SCALP WHICH COMPRISES ABOUT 0.5 TO 50% BY WEIGHT OF A SUBSTANTIALLY NON-VOLATILE ORGANIC TOILET AGENT FOR THE CARE OF THE HAIR, ABOUT 0.05 TO 10% OF A DIAMIDE COMPOUND HAVING THE FORMULA