US3658985A - Oil and fluorescent dye containing luster imparting liquid shampoo - Google Patents

Abstract

A LIQUID SHAMPOO FOR IMPROVING THE COMBING PROPERTIES AND LUSTER OF HAIR WASHED THEREWITH COMPRISING AN AQUEOUS DETERGENT COMPOSITION SUITABLE FOR SHAMPOOING HAIR WHICH CONTAINS OIL FROM THE GROUP CONSISTING OF MINERAL OIL, VEGETABLE OIL, ANIMAL OIL AND SYNTHETIC OIL AND A HAIR SUBSTANTIVE FLUORESCENT DYE IN PROPER PROPORTIONS.

Description

United States Patent Office 3,658,985 Patented Apr. 25, 1972 ABSTRACT OF THE DISCLOSURE A liquid shampoo for improving the combing properties and luster of hair washed therewith comprising an aqueous detergent composition suitable for shampooing hair which contains oil from the group consisting of mineral oil, vegetable oil, animal oil and synthetic oil and a hair substantive fluorescent dye in proper proportions.

DESCRIPTION The present invention relates to a liquid shampoo for improving the combing properties and luster of all colors of hair which comprises an aqueous detergent composition suitable for use in shampooing hair which contains, in addition to the ingredients for cleaning and, if desired, for conditioning the hair, oil from the group consisting of mineral, vegetable, animal oils, and synthetic oils, and hair substantive fluorescent dye in proper proportions.

Detergent compositions for use in shampooing hair are of two general types. One of these types includes shampoos which are formulated primarily for cleaning the hair and underlying skin and which will be referred to herein as cleaning type shampoos. These compositions do not include ingredients which are intended to be, or which are capable in any substantial measure of being, deposited on the hair during the shampooing operation. Another type includes so called hair conditioning shampoos which do contain such ingredients. Te present invention is equally applicable to shampoo compositions of both of these types.

There have been suggestions in the prior art to use mineral oil in shampoos. One such suggestion proposed the use of mineral oil up to about 3% but, in effect, condemned this proposal on the ground that it is diflicult to wash out. Another proposal recommended the use of at least 5% liquid oily material in an aqueous detergent composition to form a two phase system, viz, an oil phase to float on the top of an aqueous phase as a sharply defined, clear, separate layer and an essential ingredient in this composition was an emulsion breaker in sufficient proportion to insure the rapid and sharp separation of the two phases after they had been emulsified by shaking.

It has also been proposed to add coumarin type fluorescent dyes to shampoo compositions for the purpose of imparting luster to hair. This proposal has not been put into practice in shampoos because the added brilliance and luster which the presence of the dye in the shampoo composition was intended to achieve was not observable in the absence of mineral or like oil by the user or others except in the case of very light colored hair.

It has now been discovered that improved combing properties and an observable and highly desirable shine or luster and other properties mentioned hereinafter can be imparted to hair of all colors by shampoo compositions which contain proper proportions of both oil from the group consisting of mineral, vegetable, animal and synthetic oils and a hair substantive fluorescent dye, which is practically colorless and emits, in ultra-violet light, radiation in the blue end of the visible spectrum so that substrates on which it is present appear Whiter or brighter than without it but not of substantially different hue. Examplesof suitable dyes of this type are pyrazoline derivativesrepresented by the formula:

in which A and B are different and represent oxygen and nitrogen, and R represents individually hydrogen, alkyl groups having 1-6 carbon atoms, chlorine or fluorine.

The preferred oxazole dye is the one in which each R is hydrogen and it is referred to herein under the name Dye A.

These dyes are effective at less than 1%, even from small proportions as low as 0.01% and no practical increased benefit is obtained in general by having more than about 0.1 to 0.2% of such a dye present in the shampoo.

The mineral oil used in compositions made in accordance with the invention may be any mineral oil that dissolves in the detergent compositions in suflicient proportions to function as described herein and may be a light to heavy hydrocarbon oil but is preferably a light mineral oil, such as a water-clear, completely saturated, mineral oil having a Saybolt viscosity of about 50-80 desirably 55-65 cps. at F., a specific gravity compared with water when the oil and water are at 25 C., of 0.831 to 0.871, a flash point of 280 F. minimum and a fire point of 305 F. minimum, as obtained by the Cleveland open cup method. The mineral oil may be replaced in whole or part by olive oil or other comparable vegetable and animal oils such as linseed oil, castor oil, cottonseed oil, safllower oil, almond oil, peanut oil, coconut oil, lanolin derivatives such as lanolin esters, lanolin alcohols and ethylene oxide adducts thereof. Synthetic oils, i.e., esters of higher fatty acids having about 10-20 carbon atoms such as isopropyl myristate, palmitate and stearate may also be used.

The detergent system in which the oil and fluorescent dye or optical brightener are used in combination may be any suitable shampoo composition including compositions of the cleaning type and conditioning type.

CLEANING TYPE SHAMPOOS A preferred detergent system for the cleaning type shampoos is one based on fatty alcohol sulfates such as triethanolammonium lauryl sulfate. Other anionic detergents of the organic sulfuric acid reaction type, i.e., the sulfated and sulfonated detergents (including suitable mixtures thereof) may also be used, such as the alkyl sulfates, including alkyl ether sulfates, having about 8 to 22, preferably 12 to 18 carbon atoms per molecule, e.g., cetyl sulfate and lauryl polyethenoxy (l-S EtO groups) sulfate; the aliphatic acyl-containing compounds wherein the acyl radical has about 8 to about 22 carbon atoms, and more particularly the aliphatic carboxylic ester type containing at least about 10 and preferably about 12 to about 16 carbon atoms to the molecule, such as water soluble salts of the sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, e.-g., coconut oil monoglyceride monosulfate, tallow diglyceride monosulfate, the hydroxy sulfonated higher fatty acid esters, e.g., higher fatty acid esters of 2,3-dihydroxy propane sulfonic acid and of isethionic acid; higher fatty acid amides of low molecular weight amino acids, e.g., oleic acid amides of amino alkyl sulfonic acids and lauric acid amide of taurine, and the like; and alkyl and alkylaryl sulfonate detergents, although these are not preferred generally because of their great drying power. The alkyl sulfonates include olefin sulfonates and paraifin sulfonates. The aromatic sulfonate detergents may be mononuclear or polynuclear in structure, the aromatic nucleus being derived from benzene, toluene, xylene, phenol, cresols, naphthalene and the like. The alkyl substituent on the aromatic nucleus may vary widely provided the desired detergent power of the active ingredient is preserved. While the number of sulfonic acid groups present on the nucleus may vary it is usual to have one such group present in order to preserve as much as possible a balance between the hydro philic and hydrophobic portions of the molecule. Specific examples of suitable alkyl aromatic sulfonate detergents are higher alkyl aromatic sulfonates in which the higher alkyl substituent on the aromatic nucleus may be branched or straight-chain in structure comprising such groups as decyl, dodecyl, keryl, pentadecyl, hexadecyl, mixed long chain alkyls derived from long chain fatty materials, cracked paraffin wax olefins, polymers of lower monoolefins, and the like. Preferred examples of this class are the higher alkyl mononuclear aryl sulfonates wherein the alkyl groups have about 8 to 22, and preferably about 12 to 18 carbon atoms. Other anionic detergents which may be present, usually with a sulfate or sulfonate detergent of the kinds specified above, include water soluble salts of fatty acids and substituted fatty acids such as coconut and tallow soaps, salts of fatty acid amides of lower aliphatic amino acids such as glycine, sarcosine, and the like.

These various anionic detergents are to be used in the form of their water soluble salts such as the amine, alkali metal and alkaline earth metal salts. While the sodium and potassium salts and the like may be suitably employed, it is preferred to use the ammonium, lithium, amine including alkylolamine salts in view of their generally greater solubility in aqueous solution. More particularly it is preferred to use the ammonium, mono ethanolarnine, diethanolamine, triethanolamine salts and mixtures thereof because of the excellent results attained with their use, particularly with the higher alkyl sulfates, the higher fatty acid monoglyceride sulfates (and mixtures thereof) as the active ingredients.

The proportion of the anionic sulfate or sulfonate detergent in the liquid shampoo composition is generally at least about usually between 10-35% and preferably from 25%.

Shampoo compositions containing the anionic sulfate and sulfonate type detergents are generally so elfective in removing soil and oily materials that the hair is left somewhat unmanageable unless other ingredients are present which modify this action. Among the modifying ingredients that may be present in the shampoo compositions are non-ionic surface active agents such as higher fatty alcohols, including ether alcohols, and fatty acid amides, particularly fatty acid alkylolamides. Thes ingredients act to improve both the quantity and the quality of the foam produced during shampooing. The fatty alcohols and the fatty acyl group in the amides may have from 8 to carbon atoms per molecule. Preferably the alcohols used have from 12 to 16 carbon atoms per molcule while the fatty acids used in making the amides are preferably derived from coconut oil in which the major proportion of the fatty acids have 12 and 14 carbon atoms per molecule. For the alkylolamides used, each alkylol group usually has up to about 3 carbon atoms. It is preferred to use the monoethanol amides of lauric and myristic acids but diethanolamides and isopropanolamides of fatty acids having about 10 to 14 carbon atoms in the acyl radical are satisfactory. Examples are capric, lauric, myristic and coconut 4 monoethanolamides, diethanolamides and isopropanolamides and mixtures thereof. There may be employed also the alklol amides which are substituted by additional alkylol groups, suitable examples being the above amides condensed with one or two moles of ethylene oxide.

When used, the non-ionics may be present in the shampoo compositions up to about 10%, preferably up to about 4% of the alcohol and up to about 8% of the fatty acid alkylolamides.

In some cases it is desirable to thicken the shampoo composition somewhat which can readily be accomplished by the addition of cellulose ethers such as hydroxypropyl methyl cellulose and an electrolyte such as sodium chloride. The proportion of cellulose ether used may vary from 0 to about 2%. The electrolyte or salt content may vary from 0 to about 2%.

It is preferred to adjust the pH of detergent compositions based on anionic sulfate and sulfate detergents so that the composition is relatively close to neutral, e.g., a pH of 5-9 preferably about 6.5-8.5. For this purpose acidic materials such as citric acid and basic materials such as triethanolamine may be added to obtain the proper pH. Citric acid also serves as a sequestering and bufiering agent and is frequently added for this purpose even if not needed for pH adjustment. Generally speaking minor proportions up to a maximum of about 2% of each of these ingredients is sufiiicent to obtain the desired pH adjustment.

It is desired in many cases to color the shampoo composition a desirable shade such as yellow, green, amber, blue, etc. For this purpose any suitable dyes may be incorporated in the solution. For example, D&C yellow No. l, in a 1% solution, may be added to a shampoo composi tion of the above type at a level of about 0.050% to produce a desirable yellow color. A very attractive green color can be obtained by using about 0.2% FD&C yellow No. 5 (1% solution) and a 0.1% FD&C blue No. 1 (1% solution). An amber color is obtained by using about 0.075% D&C orange No. 4 (1% solution) with 0.025% red No. 2 (0.1% solution). An attractive blue color can be obtained by using 0.25% FD&C blue No. l (1% solution) and 0.050% D&C red No. 19 (0.1% solution).

Where dyes are added to the composition it is preferred to include a color preservative e.g., a compound which absorbs ultra violet light, e.g., a mixture of 2,2'-dihydroxy-4,4'-dimethoxy benzophenone and other tetra-substituted benzophenones, referred to hereafter as Preservative X, and 2,4-dihydroxy benzophenone, referred to hereafter as Preservative Y, and mixtures thereof. These materials are very effective in small proportions and in general about 0.025% adequately protects the composition from color change on exposure of the composition to light during storage and use. They may be used, however, within broader ranges of about 0.01 to 0.1%. Preservative X is preferred for all the above colors except blue for which Preservative Y is preferred.

It is also preferred to include a material which inhibits bacterial growth in the detergent compositions, e.g., formaldehyde USP which is effective when about 0.1% is present. Other preservatives may also be used.

In general it is preferred to include a perfume of a suitable type and odor in the composition for its cosmetic appeal to the user. Perfume may be present within the range of 0-2%.

The liquid vehicle in which the foregoing ingredients are carried, primarily in solution, is water which may be replaced in part by a lower aliphatic monohydric alcohol, e.g., ethyl, propyl, and isopropyl alcohols. In some formulations lower aliphatic polyhydric alcohols such as propylene glycol and glycerine may be used. Alcohol may be present within the range of about 010%. In making up the compositions it is preferred to use deionized water so as to avoid discoloration and other adverse effects of the water hardness.

The following composition represents a preferred formulation for a shampoo formulated in accordance with the present invention utilizing a higher fatty alcohol sulfate as the detergent:

'Example I Percent Triethanolammonium lauryl sulfate 21.0

Natural fatty alcohol (C -C 0.9 Coconut monoethanolamide 5.0 Mineral oil-extra light 2.0 Dye A 0.1 Color (Ext. D&C yellow #1, 1% solution) 0.05 Preservative X 0.025 Hydroxypropyl methyl cellulose 0.95 Citric acid (anhydrous) 0.25 Triethanolamine 0.7 Sodium chloride 0.8 Formaldehyde USP 0.1 Perfume 0.5 Ethyl alcohol (SD 40) 7.0 Deionized water, q.s.

Total 100.000

The pH of this composition is about 7.0 and its viscosity is 45:5 seconds, as tested on a number 5 Raymond flow meter at 77 F.

Another satisfactory formula based on triethanolamine lauryl sulfate as the detergent is formulated in accordance with Example II.

This composition has a pH of about 7.5 and about the same viscosity as Example I.

The presence of the mineral oil and the fluorescent dye in compositions of the type described has a number of very desirable effects, including improved combing and better appearance. The latter can be demonstrated by a so-called half head test. In making this test skilled operators wash the hair on one side of the head of a female subject with a composition containing the mineral oil and fluorescent dye and the hair on the other half of the head with an identical composition except that there is no mineral oil and fluorescent dye present. Precautions are taken to prevent contamination of the hair on the other side of the head while the hair on one side is being shampooed. After shampooing the hair is set and dried, the rollers removed, the hair parted in the middle and combed down each side. Each subject is observed by ten female evaluators in sunlight, indirect sunlight, fluorescent light and ultra violet light. The evaluators are asked to indicate the preferred side of the head, or if no preference is found so to state. In making one test, for example, using four female subjects having, respectively, blonde, red, brown and black hair, each subject is given flwelve one teaspoonful applications of the two shampoos to each respective side of the head using city water to moisten and to rinse the hair. The results of the test are given in Table I in which the shampoo containing the mineral oil and fluorescent dye is designated active and the same composition without them placebo.

TABLE I Votes for Active Placebo preference There is a high level of confidence that the diiference in the appearance of the hair observed by the evaluators is real. When the data are subjected to a statistical sign test, as described in Dixon and Massey, Introduction to Statistical Analysis, Chapter 17 and Table A-10a in the Appendix the level of confidence on the total results is 99%.

When the product is tested in an identified product test by any number of users who apply the test shampoo of the present invention identified as Bright Side in accordance with their ordinary shampooing practice, in comparison with their own preferred commercial shampoo, it is found that the composition containing mineral oil and optical brightener is preferred to the commercial shampoo, because of a number of attributes possessed by or attributed to the Bright Side formula, including the following:

Ratio of Attributes: preference Gives luster or shine to the hair 2:1 Highlights the natural color of the hair 2:1 Better lathering 3:2 Leaves the hair color naturally bright 3:2

In addition hair washed with the products containing mineral oil and optical brightener gives much improved Wet and dry snag removal, comb slip and less raspiness on combing.

Conditioning type shampoos Shampoos of the present invention can also be prepared utilizing a hair conditioning type shampoo as the base in which the oil and optical brightener are incorporated. Some people who use shampoos of the cleaning type find that their hair is left in a statically electrified state in which the individual hairs repel each other or in a state in which simple combing produces such electrification. In either case the hair is diflicult to manage and cream rinses have been available commercially for use in such cases following the shampoo to improve the wet combing of the hair and reduce static. The objective or hair conditioning shampoos is to make the use of a separate cream rinse unnecessary, but experience has shown that hair washed with such shampoos, thoroughly rinsed and then combed wet produces an undesirable foam on the comb. The present invention substantially overcomes this difiiculty and gives improved wet combing and luster due to the combined effects of the presence of mineral oil and an optical dye.

Examples III, IV and V set forth satisfactory compositions of hair conditioning shampoos.

Example Percent III IV V Myristyl dimethyl amine oxide 12. 0 12.0 6.0 Tallow amldopropyl dimethyl hydroxyethyl ammonium chloride 3. 0 3.0 0. 5 N-lauryl-myristyl betaalanine 3. 0 3. 0 8. 0 Laurie-myristic diethanolamide 3. 0 4. 0 1. 6 Soluble protein 1. 5 1. 5 Citric acid (anhydrous) 0. 25 0. 2 0. 25 Mineral oil, extra light 0. 5 2. 0 Olive oil 1. 5 Dye A- 0.1 0.1 0.1 Caustic soda (to adjust to pH 9) q.s. q.s q.s. Deionized water (with and without additives such as dyes, perfumes. stabilizers, preventatives) q.s. q.s. q.s.

Total 100.00 100.00 100.00

Referring to Examples [[1, IV and V it will be seen that these conditioning shampoos contain a combination of detergents consisting of a higher alkyl amine oxide surfactant, an amphoteric surfactant, and a cationic surfactant. The pH of these shampoos may be adjusted within the range of about to 9.6, preferably about 8.9 to 9.2. These shampoos in the preferred pH range are quite compatible with materials used on hair, particularly resin-type hair sprays, and they are entirely suitable for use on hair that has been damaged by bleaches, hair waving and straightening compositions, exposure to sun and sea water, etc. At lower pH values within the 5-7 range, which approximate the natural pH of the skin, some of the compounds which change from salt to acid form as pH is reduced may be present in the shampoo in more or less acidified form, i.e., M as defined hereinafter may include hydrogen as well as the named cations.

Suitable higher alkyl amine oxides are those having the formula:

CH2 H\2 h.

Typical higher alkyl groups which may be present include decyl, lauryl, myristyl, cetyl, stearyl, eicosyl or other higher alkyl groups of about -20 carbon atoms, derived for example from tallow, hydrogenated tallow, coconut oil, etc. The amine oxides in which the average number of carbon atoms in the higher alkyl groups is above about have given compositions whose foams (produced during shampooing of the hair) have a creamier appearance, with a smaller bubble size. Most preferably both R, and R are methyl groups, but other radicals, e.g., ethyl, hydroxyethyl or hydroxypropyl, may be used in place of one or both methyl groups.

The water-soluble, ampholytic or amphoteric detergents which can be used in the compositions of this invention generally contain a hyprophobic alkyl group of about 10 to carbon atoms, at least one anionic watersolubilizing group, e.g., carboxy, sulfo, sulfate, or phosphono, and at least one cationic group, e.g., non-quaternary nitrogen, quaternary ammonium, or quaternary phosphonium group, in their molecular structure. The alkyl group may be straight chain or branched and the specific cationic atom may be part of a heterocyclic ring.

Examples of suitable ampholytic detergents include the alkyl beta-aminopropionates, R N(H)C H COOM; the alkyl beta-aminodipropionates, R N(C H COOM) and the long chain imidazole derivatives sold under the trade name Miranol having the following formula:

l .l 2 R on R1 c. 2

+ ReCOOM wherein R is an alkyl group of about 10 to 20 carbon atoms, R is an alkylene or hydroxyalkylene group containing 1 to 4 carbon atoms and M is a water-soluble cation, e.g., alkali metal, ammonium or alkylolammonium. The higher alkyl group of the aminopropionates and iminodipropionates may be, for example, derived from coco fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, or blends of such alcohols; whereas the higher alkyl group of the imidazole derivatives is derived from coconut oil or tallow, Preferred detergents are sodium N-lauryl beta-aminopropionate, disodium N-lauryl beta-iminodipropionate, and the sodium salt of 2-lauryl-cycloimidium-1 hydroxyl, l-hydroxy-ethanoic acid, l-ethanoic acid.

Other suitable amphoteric, imidazole detergents have the following structure:

wherein R is a higher acyclic group of 7 to 17 carbon atoms and M is a water-soluble cation, e.g., sodium, potassium, ammonium, and mono-, dior tri-alkylolammonium. The acyclic groups may be derived from coconut oil fatty acids (a mixture of fatty acids containing 8 to 18 carbon atoms), lauric fatty acid, and oleic fatty acid, and alkyl groups of 7 to 17 carbons are preferred acyclic groups. Such detergents can be prepared by dehydrating the reaction product of a higher fatty acid and a hydroxyalkyl alkylene polyamine, e.g., beta-hydroxyethyl ethylene diamine, and neutralizing the resultant material as described in US. Pat. 2,267,965.

Other suitable amphoteric detergents are the sultaine and betaine types having the following general structure:

wherein R is an alkyl group containing about 8 to 18 carbon atoms, R and R are lower alkyl groups containing 1 to 3 carbon atoms, R is an alkylene or hydroxyalkylene group containing about 1 to 4 carbon atoms, and X is an anion selected from the group consisting of sO -(sultaiue) and COO (betaine). Preferred compounds are I-(myristyl dimethylammonio) acetate and 1-(myristyl dimethylammonio)-2-hydroxypropane-3-sulfonate.

With the exception of the internally neutralized betaine and sultaine amphoteric detergents, as stated above, the foregoing amphoteric detergents are usually supplied in the sodium, potassium, alkylolammonium or other salt form. It is preferred to use those amphoteric detergents which dissolve and foam readily in water at the pH of 8.89.6 and the most preferred amphoteric detergents are the higher alkyl beta-aminopropionate salts and the higher alkyl beta iminodipropionate salts.

Cationic detergents which may be used are the quaternary ammonium compounds having at least one long chain hydrophobic radical, e.g., alkyl radicals of 10-24 carbon atoms, in their molecular structure. The higher alkyl group may be directly attached to the quaternary nitrogen or indirectly attached thereto through an imidazole group or an amidopropyl group. Suitable quaternary ammonium salts are selected from the group consisting of higher alkyl quaternary ammonium salts having the following formulas:

wherein R is a higher alkyl or alkenyl group containing an average of 10 to 24 carbon atoms, R is an alkyl or hydroxyalkyl group of 1 to 3 carbon atoms, R is an alkyl or hydroxyalkyl group of 1 to 3 carbon atoms or a benzyl group, and X is an anion selected from the group consisting of chloride, methosulfate, bromide, phosphate, dialkyl phosphate, and acetate. Preferred cationic compounds are Z-stearyl, l-methyl or l-hydroxyethyl, 1 stearylamido-ethyl imidazolinium methosulfate and tallowyl amidopropyl dimethyl hydroxyethyl ammonium chloride (tallowyl describes the mixture of C to C fatty acids obtained from tallow).

The quaternary ammonium compound is preferably one which is stable in aqueous solution or dispersion at pH 9 at room temperature and more preferably stable for at least a month at pH 9 at 120 F. The preferred quaternary amonium compounds are free of ester linkages unstable under the foregoing conditions. (Preferably the other detergent components, and the entire composition, should meet this same stability requirement.) The watersoluble quaternary ammonium compound is most usually supplied as a chloride or methosulfate Best results have been thus far obtained with compositions whose proportions are in the following ranges (the ranges being in percent by weight of the shampoo composition): water-soluble quaternary ammonium detergent surfactant about 0.1l%, preferably about 1-6%; water soluble amphoteric detergent surfactant about 220%, preferably about 312% (calculated as the acidic form of the amphoteric material); water-soluble amine oxide detergent surfactant about 118%, preferably about 4-15 Generally the total amount of the detergents in the mixture is in the range of about l230%, preferably about 15-25%. It will be appreciated, of course, that the compositions may be supplied in more highly concentrated form, for subsequent dilution with water.

The pH of the composition may be adjusted to the level previously mentioned by the use of an alkaline material. A water-soluble amine, e.g. a substantially non-volatile amine such as an alkanolamine, preferably triethanolamine, may be used for this purpose, as may inorganic bases such as sodium hydroxide or potassium hydroxide. Typically the pH of the composition remains substantially constant on considerable dilution with water; in one typical case the pH (measured electrically) was 9.05 at 20% concentration, 9.01 at 10%, 9.00 at 5%, 8.98 at 2% and 8.97 at 1% concentration.

Compositions of a wide range of viscosities may be produced from the combination of the foregoing ingredients. It is often desirable to add viscosity-adjusting ingredients. As viscosity-increasing materials there may be used long chain fatty amides, e.g. a monoethanolamide, diethanolamide or dimethylamide of a fatty acid of about to 16 carbon atoms such as lauric-myristic monoethanolamide or diethanolamide. As viscosity decreasing ingredients which also serve to lower the cloud point of the composition there may be used water-soluble solvents, such as polyhydric alcohols, e.g. propylene glycol or ethoxylated polypropylene glycol or lower alkyl ethers of such glycols. The proportion of such ingredients is generally less than 5% of the total composition, e.g. about /24%.

Water-soluble protein may also be present in the compositions. This ingredient in the compositions described above gives improved curl retention to the shampooed hair, while substantially retaining or improving the other desirable effects previously discussed. Chemically, this ingredient is a low molecular weight polypeptide obtained by hydrolysis of protein materials such as human and animal hair, horns, hides, hoofs gelatin, collagen, and the like. During hydrolysis the proteins are gradually broken down into their constituent polypeptides and amino acids by prolonged heating with acids, e.g., sulfuric acid, or alkalis, e.g., sodium hydroxide, or treatment with enzymes, e.g., peptidases. In hydrolysis, high molecular weight polypeptides are formed first and as hydrolysis proceeds these are converted progressively to simpler and simpler polypeptides to tripeptides, dipeptides, and finally to amido acids. It is obvious that the polypeptides derived from proteins are complex mixtures and in practice the average molecular weight of the hydrolysate will vary from (amino acids) to about 20,000. All satisfactory hydrolyzed polypeptides are characterized by water solubility. In compositions which contain soluble protein it is preferred to use hydrolyzed collagen of such low molecular weight as to be completely soluble in water, non-gelling, and non-denaturing with an average molecular weight below 15,000, preferably in the range of about 500 to 10,000. The amount of protein used is preferably in the range of about Az3% most preferably about 1 to 2%.

The cosmetic properties of the shampoos of the hair conditioning type may be modified as desired by incorporating the coloring dyes, color and other preservative, perfumes, and the like as described above for shampoos of the cleaning types.

The beneficial effects of the combined presence in hair conditioning type shampoos of mineral oil and optical brightener are comparable to the qualitative data given herein for cleaning type shampoos containing them.

In both types of shampoos the proportion of oil, whether mineral, vegetable, animal, or synthetic in the composition should be sufficient to produce the desired effect, usually at least about 0.5% but not enough to produce a separate phase on standing. In other words, the oil should be taken into the aqueous system, whether by dissolution or otherwise, so as to appear to the eye to be a single phase. The upper limit may vary, depending on the nature of the oil and the ingredients and proportions of the aqueous system. Generally speaking the upper limit is less than 5%, often less than 3%, and an effective maximum is about 2%.

In the description and claims where percentages are given they are by weight of the entire composition.

Although the invention has been described and illustrated in connection with certain specific examples, these are given by way of illustration and not by way of limitation.

The present invention does not embrace the detergents or any of the ingredients per se, which may be chosen and formulated in accordance with the knowledge of the art, but rather the combination consisting essentially of (1) an aqueous detergent composition suitable for shampooing containing properly chosen ingredients in proper proportions, (2) oil (mineral, vegetable, synthetic and/or animal) and (3) fluorescent dyes in proper proportions to achieve the improved luster and combing properties.

The presence in the composition of ingredients other than those specifically mentioned herein is not precluded as long as they do not adversely affect the desirable properties of the product. Those skilled in the shampoo art will recognize that modifications, and variations in ingredients and proportions may be made in formulating the aqueous system described hereinabove in which the oil and optical brightener are carried.

Having thus described the invention, what is claimed is:

1. A liquid shampoo for improving the combing properties and luster of hair comprising an aqueous mixture of (1) a water-soluble, organic detergent in an amount of from to 35% by Weight; (2) from about 0.5% to 5% by weight of an oil selected from the group consisting of mineral oil, vegetable oil, animal oil selected from the group consisting of lanolin esters, lanolin alcohols, ethoxylated lanolin esters, ethoxylated lanolin alcohols, and esters of C -C fatty acids, the proportion of said oil being insuflicient to produce a separate phase on standing; and (3) from about .01% to 1% by weight of a hair substantive fluorescent dye selected from the group consisting of a pyrazoline derivative represented by the formula and an oxazole derivative represented by the formula C-CH=CH- R R in which A and B are different and represent oxygen and nitrogen and R represents individually hydrogen, alkyl having 1 to 6 carbon atoms, chlorine or fluorine.

2. A liquid shampoo as set forth in claim 1 in which said fluorescent dye is said oxazole derivative.

3. A liquid shampoo as set forth in claim 2 in which said oxazole fluorescent dye is represented by the formula in which each R is hydrogen.

4. A liquid shampoo as set forth in claim 1 in which said fluorescent dye is said pyrazoline derivative.

5. A liquid shampoo as set forth in claim 2 in which said detergent is a water-soluble anionic detergent selected from the group consisting of an alkyl sulfate, an aliphatic acyl sulfate, an alkyl sulfonate, an aliphatic acyl sulfonate, an alkylaryl sulfonate and an olefin sulfonate, said alkyl, aliphatic acyl, alkylaryl and olefin group containing 8 to 22 carbon atoms, and said shampoo is of the cleaning type.

6. A liquid shampoo as set forth in claim 5 in which said sulfate or sulfonate detergent is an alkyl sulfate containing 12 to 18 carbon atoms in the molecule.

7. A liquid shampoo as set forth in claim 6 which contains about to 25% by weight of said alkyl sulfate, about 1.5% to 2% by weight of mineral oil, and about 0.1% to 0.2% by weight of Z-styryl naphth(l,2-d) oxazole.

8. A liquid shampoo as set forth in claim 7 in which said alkyl sulfate is triethano'lammonium lauryl sulfate and which contains in addition up to 8% by weight of C C fatty acid mono-, diethanolamide or isopropanolamide and up to 10% by weight of a lower aliphatic monohydric or polyhydric alcohol, said shampoo composition being a single-phase liquid.

9. A liquid shampoo as set forth in claim 2 in which about 12% to about 30% by weight of detergent is present, said detergent being a mixture of 1% to 18% by weight of a higher alkyl amine oxide having the formula Br R2 N+O wherein R is alkyl containing an average of about 12 RiN(H) C2 4COOM R N(CzH C O 0M)2 and 18 CHz R 011 Ri( l l OH RzCOOM wherein R is alkyl of 10 to 20 carbon atoms, R is alkylene or hydroxyalkylene containing 1 to 4 carbon atoms, and M is a water-soluble cation selected from the group consisting of sodium, potassium, ammonium, and alkylolammonium, a Bic-17 HzC (]}R;

N-CHgCHzOCHzOHaCOOlH wherein R, is a higher acyclic group of 7 to 17 carbon atoms and M is a water-soluble cation selected from the group consisting of sodium, potassium, ammonium, and alkylolammonium, and

R;Il I -R4-X' wherein R is alkyl containing about 8 to 18 carbon atoms, R and R are lower alkyls of 1 to 3 carbon atoms, R, is alkylene or hydroxyalkylene containing 1 to 4 carbon atoms and X is S0 or 00 about 0.5% to 10% by weight of a quaternary ammonium salt selected from the group consisting of H R CON CHeC HzCH2N R2 wherein R is higher alkyl or alkenyl containing an average of 10 to 24 carbon atoms, R is alkyl or hydroxyalkyl of 1 to 3 carbon atoms, R is alkyl or hydroxyalkyl of 1 to 3 carbon atoms or benzyl, and X is an anion selected from the group consisting of chloride, methosulfate, bromide, phosphate, dialkyl phosphate, and acetate, said shampoo being of the conditioning type.

10. A liquid shampoo as set forth in claim 9 in which the proportion of said amine oxide is 4% to 15% by weight, the proportion of said amphoteric detergent is 3% to 12% by weight, and the proportion of said quaternary salt is 1% to 6% by weight.

11. A single-phase liquid shampoo consisting essentially of by weight about 6% to 12% of myristyl dimethyl amine oxide, 0.5% to 3% of tallowyl amidopropyl dimethyl hydroxyethyl ammonium chloride, 0.5% to 5% of lauric-myristic dicthanolamidc, 3% to 8% of N-lauryl- 13 myristyl beta-alanine, from 0.5% to 2% of an oil from the class consisting of extra-light mineral and olive oil, 0.1% to 0.2% of 2-styryl naphth(1,2-d)oxazole, and water.

References Cited UNITED STATES PATENTS 2,740,793 4/1956 Kendall et a1 260-310 3,133,080 5/1964 Sarkar et a1. 260-310 3,158,610 11/1964 Buell 260-240 3,267,039 8/ 1966 Schneider 424-70 X 14 3,325,422 6/1967 Marquis 252-383 3,533,955 10/1970 Pader et a1. 4 24-70 X FOREIGN PATENTS 1,519,951 2/1968 France 42470 OTHER REFERENCES 7 Keithler, The Formulation of Cosmetics and Cosmetic Specialties, Drug & Cosmetic Industry, New York (1956),

Rees, American Perfumer and Cosmetics, vol. 81, No. 4, April 1966, PP. 37-42.

ALBERT T. MEYERS, Primary Examiner 15 V. C. CLARKE, Assistant Examiner U.S. Cl. X.R.

8-101; 252Digests 1, 2, 3, 7, 13, 111, 143, 153, 158, 161; 424-359, 362