US3149042A

US3149042A - Hair preparations

Info

Publication number: US3149042A
Application number: US38459A
Authority: US
Inventors: Habicht Lojo; Kluge Arno
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 1959-07-09
Filing date: 1960-06-24
Publication date: 1964-09-15
Anticipated expiration: 1981-09-15
Also published as: CH443567A; SE301023B; BE592793A; NL253568A; GB908888A; NL140725B; DE1134477B

Description

3,149,042 HAIR PREPARATIONS Lojo Habicht, Hamburg, and Arno Kluge, Bad Soden,

Taunus, Germany, assignors to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware No Drawing. Filed June 24, 1960, Ser. No. 38,459 Claims priority, application Germany, July 9, 1959, P 23,120 14 Claims. (Cl. 167-87) 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 an aqueous 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 Bari 0.05 570% of a water sglub le dgcjn g agent selected from the group consisting of water-soluble salts of sulfur oxygen acids having from 2 to 3 sulfur atoms, salts of phosphorous acid, and reducing sugars, and 0.05 to of a diamide having the formula wherein X is selected from the group consisting of oxygen and sulfur, and R R R and R are selected from the group consisting of hydrogen, alkyl, alkylol and acyl and mixtures thereof, and n is from 1 to 2, in an aqueous medium.

Suitable diamide compounds having the above formula include u r ea, thiourea, biuret, thiobiuret, dithiobiuret and their water-soluble monoand polyalkyl, -alkylol and -acyl derivatives. In general the alkyl, alkylol and acyl groups may be of saturated or unsaturated nature and may be straight chain or branched having not more than 4 carbon atoms, although in the case of biuret derivatives it is preferred that the chain length of the alkyl, alkylol and acyl groups be limited to not more than 2 carbon atoms. Examples of suitable compounds include, e.g.,

1,3-dimethyl-urea, 1-methyl-3-acetyl-urea, tetramethyl-urea, 1,1-diethyl-urea, l-ethyl-3-propionyl-urea, 1,1-dipropyl-urea, l-propyl-B-butyryl-urea, 1-methyl-1-isobutyl-urea, l-(tert.butyl)-urea,

l ,S-hydroxymethyl-urea, l-hydroxypropyl-urea, l-formyl-urea, 1,3-diacetyl-urea, 1,3-dimethyl-thiourea, 1,1,3-triethyl thifi1'r'ea, l-propyl-thiourea, l-ethyl-3-propyl-thiourea, 1-methyl-3-isobutyl-thiourea, l-acetyl-thiourea, l-methyl-biuret, 3-methyl-biuret, l-ethyl-biuret, 1,5-dimethyl-biuret,

1,3,5 -trimethyl-biuret, l-hydroxymethyl-biuret, 1,5-dihydroxymethyl-biuret, l-acetyl-biuret,

O U U Q1.)

i'tL LEXLR tut...

1-formyl-5-acetyl-biuret, 1,S-dimethyl-l-acetyl-biuret, 1,3,5-trimethyl-l-acetyl-biuret, 3-ethyl-l-acetyl-biuret, l-mcthyl-thiobiuret, l-ethyl-thiobiuret,

l -acetyl-thiobiuret, 1-hydroxymethyl-thiobiuret, l-methyl-dithiobiuret.

The reducing agents of the present invention are watersoluble and skin-compatible, i.e. may be applied to the skin in the proportions of the present compositions on a daily schedule without any untoward effect. Preferred for use as reducing agents are the reducing sugars, i.e. sugars which are characterized by containing a fre carbonyl group, the ability to reduce Fehlings solution, and the inability to reduce iodine solutions. Such sugars include, e.g., monosaccharides such as glucose, fructose, a mixture of both such as invert sugar, and galactose, as well as reducing disaccharides such as maltose and lactose. These sugars are especially stable against air oxygen as well as against other components of the hair preparation, particularly perfumes, and may therefore be used at relatively high concentrations, i.e., up to 20%. Moreover, it has been found that use of these sugars is highly beneficial in that they lower substantially both the cloud point and the clear point of the present aqueous compositions.

Also suitable for use as inorganic skin-compatible reducing agents are the water-soluble salts of dithionous ago, thiosulfuric acid, trithionic acid, and phosphorous acid, e.g. sodium dithiom te, sodium thiosulfate, sodium trithionate, and the sodium salt of phosphorous acid.

The instant water-soluble reducing agents are employed in the present hair preparations in an amount from about 0.05 up to 5%, and sometimes up to 20%. In the case of the reducing sugars, the preferred proportion is in the range of 1 to 5%, whereas the inorganic reducing salts desirably are used in an amount within the range of 0.5 to 2% of the final product.

Normally, the diamide is present in an amount from about 0.05 to 10% and preferably from 0.5 to 5% of the hair preparation, and typically the ratio of reducing agent to diamide will be 1:5 to 5:1 and preferably 1:2 to 2:1.

The present aqueous compositions may be prepared in various forms including inter alia, aqueous and aqueousalcoholic solutions, emulsions, pastes, crearnsflotions and the like. They may consist of one or more phases, at least one of which however is aqueous. For instance the hair preparation may consist of 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-in-water type.

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 composition such as hair dyeing 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 from decorative or treating compositions such as hair dressings, hair tonics and the like, in which case the nonvolatile toile t agent for the daily care of the hair is a hair grooming agent, 9 r they may be prepared in the farm of ham cleansing products such as shampoos, in which case the non-volatile toilet agent for the daily care of the hair is a detergent mate i a l. In both hair grooming and hair cleansing compositions however, the nonvolatile toilet agent for the daily care of the hair is normally present in an amount from 0.5 to 65% by weight of the composition.

In the case of hair grooming compositions, examples of agents which facilitate grooming of the hair and help to keep the hair in place include, e.g., castor oil, mineral oil, lower alkoxypolyoxy lower alkylene glycols such as butoxypolyoxy propylene 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 grooming agents which have a molecular weight above about 75 and preferably above 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 about 0.5 to 65% and preferably about 2 to 50% by weight of the composition.

In the case of hair cleansing compositions or shampoos, the non-volatile organic toilet agent for the care of the hair is a cleansing agent such as a water soluble organic detergent. Desirably 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, preferably 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 tallow diglyceride monosulfate; the long chain pure or mixed alkyl 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 higher fatty acid esters of low molecular weight alkylol sulfonic acids, e.g., oleic acid ester of isethionic acid; the sulfated higher fatty acid alkylolamides such as, e.g., ethanolamide sulfates; the higher fatty acid amides of amine 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 substituent containing 8 to 26 carbon atoms. 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 substituent should be 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 the detergents may be used in the form of their alkali salts, e.g., sodium, potassium or lithium salts, as well as in the form of salts of nitrogen containing bases, e.g., ammonium or lower alkylolamine salts such as mono-, diand triethanolamine salts, and mixtures of various 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.

Further suitable organic detergents include nonionic detergents such as the lower alkylene oxide condensation products of hydrophobic compounds, e.g., the ethylene oxide condensation products with higher fatty acids, higher fatty alcohols or alkylated aromatic hydrocarbons, polypropylene glycols having a molecular weight greater than 900, amide and amine condensates such as fatty acid alkylol amides, e.g., N-bis(2-hydroxyethyl)-lauramide, and finally the condensation products of fatty acid chlorides with hydrolyzed natural proteins often referred to as lysalbinic acid derivatives.

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

Shampoos in accordance with the present invention may be prepared in various forms and may consist of one or more phases. The shampoos suitably may be prepared as a clear, homogeneous, single phase liquid such as an aqueous or aqueous-alcoholic composition, or they may contain two or more liquid or mixed liquid and solid phases, as in the case of cream shampoos, lotion shampoos, paste shampoos, and the like. The foregoing detergents desirably comprise at least about 5% and preferably from about 15 to 40% of the instant shampoos, and may be substantially higher in the case of solidscontaining products, e.g. pastes.

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 hair preparation preferably 0.25 to 1.0% may be employed. In a single phase composition containing aqueous alcohol the diamide compounds are more soluble and therefore preferably 0.25 to 2.0% may be employed. In cream type or solid-containing preparations wherein the partly limited solubility of the diamide compounds is not a concentration-lmiting factor, amounts of diamide on the order of up to about 10% may be used.

For example, an aqueous cosmetic composition may comprise from 0.05 to 10% of diamide, from 0.05 to 20% of water soluble reducing agent, from 0.5 to 65% of the non-volatile organic toilet agent, and, as the balance, e.g. 5 to 99.4%, 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 preparation of a clear, homogeneous single phase aqueous shampoo, typically 0.25 to 2% of the instant diamide compounds, 0.25 to 5% of water soluble reducing agent, 5 to 20% water soluble detergent, and 73 to 94.5% water and various adjuvants are used, whereas in a shampoo containing aqueous alcohol wherein the diamide compounds and detergents are each more soluble, more than 2% of the diamide may be used, e.g. up to 5%, in combination with 5 to 40% of the detergent, the balance being aqueous alcohol and other components.

The present hair preparation 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 solid substances which may be deposited on and clog the pores of the scalp. Desirably the instant compositions have a pH of 4 to as they appear most effective in this range. In this connection it is preferred that the reducing agent and diamide in compositions characterized by a pH above 8 (typically such as, for example, soap shampoos) be, respectively, a reducing sugar and biuret or thiobiuret or their alkylor alkylolderivatives in view of the better stability thereof at an elevated pH as compared to urea.

The hair preparations of the invention exhibit unusually 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-otf skin.

The efiiciency of aqueous compositions prepared in accordance with the present invention is favorably influenced by the presence of a water soluble material which reduces the surfaceand/or interfacial-tension 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 and scalp so that soil and oily secretions are more easily displaced and eliminated, thus aiding in the grooming and care of the hair.

Specific hair preparations according to this invention are illustrated by the following examples. All quantities indicated are by weight unless otherwise specified.

EXAMPLE 1 Hair Tonic Parts Isopropyl alcohol 50.0 Propylene glycol 2.5 Sodium thiosulfate cryst. 0.4 Urea 0.6 Perfume, coloring 0.2 Water 46.

EXAMPLE 2 Hair Tonic Isopropyl alcohol 55.0 Glycerine 4.0 Hexachlorophene 0.2 1,3-dimethyl-urea 2.0 Sodium dithionite 1.0 Perfume, preservative 0.2 Water 37.6

EXAMPLE 3 Hair Tonic Ethyl alcohol 96% 80.0 Isopropyl myristate 10.0 1,3 ,5 -trimethyl-biuret 1.5 Disodium phosphite 1.0 Perfume, coloring 0.4 Water 7.1

EXAMPLE4 Hair Cream (OiI-in-u-ater emulsion) Part1:

Mineral oil 40.0 White petrolatum 5.0 Stearic acid 3.0 Cetyl alcohol 1.5 Preservative 0.2 Part II:

Triethanolamine 1.3 Sodium trithionate 0.4 Biuret 0.6 Water 47.7 Part III: Perfume 0.3

Part I is heated to 65 C. and slowly added with thorough stirring to part II previously heated to 60 C.

The cream is cooled with stirring to 40 C. at which temperature part III is added.

EXAMPLE 5 Hair Cream (Water-in-oil emulsion) Part I: Parts White petrolatum 7.5 Mineral oil 37.5 Lanolin anhydrous 3.0 Sorbitan sesquioleate 3.0 Beeswax 2.0

Preservative 0.2

Part II:

Borax 0.5

Thiobiuret 0.5 Disodium phosphite 1.0 Water 44.5 Part III: Perfume 0.3

Components of part I are combined by melting together at 75 C. Then part II previously heated to 75 C. is added with stirring at this temperature. The cream is stirred for 10 minutes at 70-75 C. and then cooled slowly with stirring to 45 C. At this temperature part III is added. After cooling with stirring to 30 C. the cream is homogenized.

EXAMPLE 6 Liquid Shampoo 52.2 parts of N-lauryl-B-amino-propionic acid triethanolamine salt 40% and 2 parts of coconut oil fatty acid isopropanolamide are dissolved in 40.3 parts of water with stirring at 35 C. Then 2.5 parts of lactose, 2.0 parts of biuret, 0.15 part of preservative, 0.05 part of coloring and 0.5 part of perfume are added while stirring.

EXAMPLE 7 Liquid Shampoo Water 42.8

Liquid shampoos of Examples 7 and 8 are prepared in the same was as described in Example 6.

EXAMPLE 9 Cream Shampoo 35 parts of sodium coconut oil monoglyceride monosulfate technically pure and 5 parts of lauroyl isopropanolamide ethoxylate (having an average of 2 moles of ethylene oxide) are added with stirring to a solution prepared from 56 parts of water, 2.5 parts of l-propylthiourea, 1 part of disodium phosphite and 0.2 part of preservative and being previously heated to 60-65 C. After cooling to about 40 C., 0.3 part of perfume is added.

EXAMPLE 10 Hair F ixative 1 part of fine-powdered gum tragacanth is dispersed in 6 parts of ethyl alcohol 96%. To this dispersion 2 parts of castor oil, 0.15 part of preservative and 0.35 part of perfume are added. Then an aqueous solution consisting of 86.5 parts of water, 1 part of acetyl-biuret and 2 parts of maltose being previously heated to 30 C. is slowly added with stirring. The product obtained is allowed to stand for 24 hours and is then filtered after some stirring.

EXAMPLE 11 Clear Single Phase Liquid Shampoo Parts Ammonium coconut oil monoglyceride monosulfate 15.45 Ammonium sulfate 1.90 Methyl cellulose 0.80 Dextrose 2.00 Urea 5.00 Disodium dihydrogen pyrophosphate 0.10 Tetrasodium pyrophosphate 0.10 Perfume 0.50 Ethanol 9.36 Water 64.79

This shampoo formulation exhibits a cloud point and a clear point each of which are at least F. lower than a similar formulation in which the dextrose is replaced with water.

What is claimed is:

1. An aqueous cosmetic composition suitable for daily use in the care of the hair and scalp which comprises a substantially non-volatile organic toilet agent for the care of the hair, 0.05 to of a water soluble reducing agent selected from the group consisting of water soluble salts of sulfur oxygen acids having from 2 to 3 sulfur atoms, salts of phosphorous acid, and reducing sugars, and 0.05 to 10% of a diamide having the formula R1NCN l.

wherein X is selected from the group consisting of oxygen and sulfur, R R R and R are independently selected from the group consisting of alkyl, alkylol and acyl containing not more than 4 carbon atoms, hydrogen, and n is from 1 to 2, in an aqueous medium.

2. An aqueous cosmetic composition as set forth in claim 1 having a pH from 4 to 10.

3. An aqueous cosmetic composition as set forth in claim 1 wherein said reducing agent is a reducing sugar and said diamide is urea.

4. An aqueous shampoo which comprises from 5 to of a water soluble organic detergent, from 1 to 5% of a water soluble reducing sugar, and 0.5 to 5% of a diamide having a formula XRa wherein X is selected from the group consisting of oxygen and sulfur, and R R R and R are independently selected from the group consisting of alkyl, alkylol and acyl containing not more than 4 carbon atoms, hydrogen,

and n is from 1 to 2, and as a balance an aqueous medium.

5. A shampoo composition as set forth in claim 4 wherein said diamide is urea.

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

7. A shampoo composition as set forth in claim 4 wherein said reducing sugar is dextrose.

8. A hair tonic comprising from 0.5 to 65% by weight of a substantially non-volatile organic hair grooming agent having a molecular weight greater than about 75 and containing an alcoholic hydroxyl group, 0.05 to 10% by weight of a water soluble reducing agent selected from the group consisting of water soluble salts of sulfur oxygen acids having from 2 to 3 sulfur atoms, salts of phosphorous acids, and reducing sugars, and 0.05 to 5% of a diamide having the formula at n wherein X is selected from the group consisting of oxygen and sulfur, R R R and R are independently selected from the group consisting of hydrogen, alkyl, alkylol and acyl, and n is from 1 to 2, and 5 to 99.4% of an aqueous medium.

9. A hair tonic comprising from 0.5 to by weight of mineral oil, 0.05 to 10% by weight of a water-soluble reducing agent selected from the group consisting of water soluble salts of sulfur oxygen acids having from 2 to 3 sulfur atoms, salts of phosphorous acids, and reducing sugars, and 0.05 to 5% of a diamide having wherein X is selected from the group consisting of oxygen and sulfur, R R R and R are independently selected from the group consisting of hydrogen, alkyl, alkylol and acyl, and n is from 1 to 2, and 5 to 99.4% of an aqueous medium.

10. A hair tonic comprising from 0.5 to 65% by weight of isopropyl myristate, 0.05 to 10% by weight of a water-soluble reducing agent selected from the group consisting of water soluble salts of sulfur oxygen acids having from 2 to 3 sulfur atoms, salts of phosphorous acids, and reducing sugars, and 0.05 to 5% of a diamide having the formula wherein X is selected from the group consisting of oxygen and sulfur, R R R and R are independently selected from the group consisting of hydrogen, alkyl, alkylol and acyl, and n is from 1 to 2, and 5 to 99.4% of an aqueous medium.

11. A hair tonic as set forth in claim 8 wherein said diamide is urea.

12. A hair tonic as set forth in claim 8 wherein said diamide is biuret.

13. An aqueous cosmetic composition suitable for daily use in the care of the hair and scalp which comprises a substantially non-volatile organic toilet agent for the care of the hair, 0.05 to 20% of a water soluble salt of sulfur oxygen acids having from 2 to 3 sulfur atoms, and 0.05 to 10% of a diamide having the formula wherein X is selected from the group consisting of oxygen and sulfur, R R R and R are independently selected from the group consisting of alkyl, alkylol and acyl containing not more than 4 carbon atoms, hydrogen, and n is from 1 to 2, in an aqueous medium.

14. An aqueous cosmetic composition suitable for daily use in the care of the hair and scalp which comprises a substantially non-volatile organic toilet agent for the care of the hair, 0.05 to 20% of a water soluble reducing salt of phosphorous acid, and 0.05 to 10% of a diamide having the formula wherein X is selected from the group consisting of oxygen and sulfur, R R R and R are independently selected References Cited in the file of this patent 5 698767 UNITED STATES PATENTS 10 Mehafley Nov. 20, 1956 Anderson Dec. 11, 1956 FOREIGN PATENTS Great Britain Oct. 21, 1953 OTHER REFERENCES Science News Letter, March 20, 1948, page 188.

Kunz et a1 Aug. 18, 1942 Kleinicke Feb. 22, 1944 Sagarin: Cosmetics, Science and Tech., Inter Sci. Pub., 1957, pp. 401, 404, 405.

Claims

1. AN AQUEOUS COSMETIC COMPOSITION SUITABLE FOR DAILY USE IN THE CARE OF THE HAIR AND SCALP WHICH COMPRISES A SUBSTANTIALLY NON-VOLATILE ORGANIC TOILET AGENT FOR THE CARE OF THE HAIR, 0.05 TO 20% OF A WATER SOLUBLE REDUCING AGENT SELECTED FROM THE GROUP CONSISTINGOF WATER SOLULBE SALTS OF SULFUR OXYGEN ACIDS HAVING FROM 2 TO 3 SULFUR ATOMS, SALTS OF PHOSPHOROUS ACID, AND REDUCING SUGARS, AND 0.05 TO 10% OF A DIAMIDE HAVING THE FORMULA