US3630654A - Aqueous alcoholic acid dye-carboxylated polymer compositions for dyeing and grooming hair - Google Patents

Aqueous alcoholic acid dye-carboxylated polymer compositions for dyeing and grooming hair Download PDF

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US3630654A
US3630654A US3630654DA US3630654A US 3630654 A US3630654 A US 3630654A US 3630654D A US3630654D A US 3630654DA US 3630654 A US3630654 A US 3630654A
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hair
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Norman Allen Rosenthal
Donald Joseph Delano
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Bristol-Myers Co
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/02Cosmetics or similar toilet preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/062Oil-in-water emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/02Cosmetics or similar toilet preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/731Cellulose; Quaternized cellulose derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8164Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88Polyamides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065Preparations for temporary colouring the hair, e.g. direct dyes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S424/00Drug, bio-affecting and body treating compositions
    • Y10S424/02Resin hair settings

Abstract

An oil-in-water emulsion capable of dyeing and grooming hair containing an acid dye, a slightly water-soluble alcohol and a water-soluble carboxy containing polymer.

Description

United States Patent Norman Allen Rosenthal Sterling Forest, Tuxedo, N.Y.;

Donald Joseph Delano, Whippany, NJ. [21] Appl. No. 729,373

[22] Filed May 15, 1968 [45] Patented Dec. 28, 1971 [73] Assignee Bristol-Myers Company New York, N.Y.

[72] Inventors [54] AQI IEOUS ALCOHOLIC ACID DYE- CARBOXYLATED POLYMER COMPOSITIONS FOR DYEING AND GROOMING HAIR 511 mu A6llr 7/12 [50] Field otSearch 8/l0.1, 10, 93, 42 B; 424/70 [56] Relerences Cited UNITED STATES PATENTS 3,261,754 7/1966 Peters et al. 8/10.1 3,344,031 9/1967 Bartoszewiczm, 8/10.1 3,352,755 11/1967 Lerner et a1. 8/10.1

Primary Examiner-Jerome D. Goldberg Assistant ExaminerVera C. Clarke Attorneys-William F. Moss, 111, David J Mugford and Irving l-loltzman AQUEOUS ALCOHOLIC ACID DYE-CARBOXYLATED POLYMER COMPOSITIONS FOR DYEING AND GROOMING HAIR This invention relates to an oil-in-water emulsion composition capable of dyeing polyamide and protein fibers. More particularly, it concerns compositions which are capable of imparting color to protein fibers, such as human hair at ambient temperatures.

The solvent assist dyeing of human hair is known in the prior art. This is exemplified by the Peters et al. US. Pat. No. 3,261,754 which describes a composition of matter that may be used in dyeing hair, comprising an aqueous liquid containing a dye and having incorporated therein certain organic compounds such as benzyl alcohol, amyl alcohol, and amyl acetate. The patents generally state that said organic compounds may constitute up to about 20 percent by volume of the composition. With regard to benzyl alcohol, however, they suggest the use of from 3 to about percent by volume based on the total volume of the composition. The optimum dyeing is said to be obtained by 4 percent by volume of benzyl alcohol.

Peters et al. also suggest that in connection with benzyl alcohol, a pH' of from 5 to about 9 is preferred. In addition, they suggest the use of certain emulsifying agents, such as sodium lauryl sulfate, and the use of certain thickeners, such as sodium alginate.

Although the concepts described in the Peters et al. patents are useful in hair dyeing from a practical point of view, their invention leaves something to be desired. Thus, for example, with regard to the quantity of dye employed, they indicate the necessity of using from 0.5 to 4 percent by weight of dye in their compositions. This is unelconomical, and, moreover, results in the so-called crocking" or rub-off.

The British Pat. to Gillette No., 959,132, is concerned with dyeing of human hair with a dye composition containing an acid dye, together with sufficient free base to provide a pH of 8.5 to 12.5 in aqueous solution. The patentee also suggest the use of certain organic solvents in their composition, among which are included certain alcohols such as benzyl alcohol. In addition, they recommend the use of certain thickeners in their composition. Thus, for example, example 9 of the British Pat. suggests the use of 2 percent by weight of Carbopol 934. Since the compositions of the British patent are highly alkaline, and since it is well known that Carbopol 934 gets at the higher pl-ls, the compositions of example 9 of the British Pat. is, obviously, a gelled composition.

As with regard to the disclosure of the US. Pat. to Peters et al., the invention of the British patent to Gillette, likewise leaves much to be desired from a commercial point of view. This is particularly reflected in the relative lack of efficicicy in dyeing which is characteristic of compositions like that of the Gillette patent that is made manifest by the relative lack of intensity in the dyeings obtained by these compositions.

It has now been found that very intense dyeings can be achieved with acid dyes at very low dye concentrations by dyeing them form an aqueous emulsion system containing an alcoholic hydroxy group containing organic solvent which is slightly soluble in water, together with a water-soluble polymer containing free carboxy groups. It is also essential that the composition have a pH in the range offrom about 3 to 4 to assure among other things that the water-soluble polymer is maintained in a water-soluble or in an ungelled form in the composition. This composition also serves to simultaneously groom, as well as color the hair.

It is accordingly an object of the present invention to provide a solvent assist dyeing composition which gives very intense dyeings at relatively low concentrations of dye.

It is a further object of the present invention to provide a method for dyeing hair designed to accomplish these results.

It is also an object of the present invention to provide a composition which simultaneously colors and grooms hair.

Other and more detailed objects of this invention will be apparent from the following description and claims.

The compositions of the present invention are oil-in-water emulsions which are capable of dyeing hair at ambient temperatures. They contain acid dyes in the range of from about 0.05 to 0.3 percent by weight and have a pH which is in the range of from about 3 to 4. The oil phase of the emulsion compositions is the internal phase and comprises essentially a slightly water-soluble alcoholic hydroxy groupcontaining organic solvent, which has distributed therein an acid dye. The continuous phase of this emulsion composition is the aqueous phase which has distributed thereinthe water-soluble polymer containing carboxy groups. The environment of the composition is such as tomaintain the water-soluble carboxy containing polymer in its free acidwater-soluble form.

The compositions of the present invention have several advantages. The high degree of efiiciency with-which the dyes are utilized in this invention permits their use in very low concentrations. This eliminates the problem of "rub-off or crocking," which is characteristic of the prior art compositions. In addition, the combined use of the organic solvent, together with the carboxylated polymer serves to leave the hair in a lustrous groomed state. Moreover, because of the relatively low concentration of dye, these compositions may be applied with the hands of the user, in the manner in which hair grooms are generally applied, without the danger of coloring the skin of the hands.

The dyes which are useful-for the purposes of the present invention are the so-called acid dyes which are readily and effectively bound to protein substrates and which are known to be medically safe. Any of a variety of these acid dyes may be used singly or in a combination. in accordance with. the present invention. These fall into a number of well-known categories of dyes such as the azo dyes (e.g., monoazo, diazo, etc.); azopremetallized dyes, pyrazoline, xanthene, anthraquinone, indigoid, nitro, azine, or triphenylmethane dyes, etc. By way of illustration there is given in the following table a number of specific dyes, identified by their Color Index designation, as well as their general chemical nature which are useful herein.

TABLE 1 Name Chemical Category C.l. Acid Brown No. 44 (page 1346) Azo-Premetallized Neutral Dyes C.l. Food Yellow No. 4 (C1 [9140) Pyrazaline C.l. Solvent Orange No. 2 (CI 12100) Monouzo C.l. Acid Orange No. 24 (CI 20170) Diazo C.l. Acid Yellow No. 73 (CI 45350) Xanthene C.l. Acid Green No. 25 (C161570) Anthraquinone C.l. Food Blue No. 1 (Cl 73015) Indigoid C.l. Food Blue No. 2 (Cl 42090) Triphenylmethane C.l. Acid Black No. 1 (Cl 20470) Diazo C.l. Acid Red No. 26 (CI 16150) Monoazo C.l. Acid Red No. 33 (Cl 17200) Monoazo C.l. Basic Violet No. 10(Cl 45170) Xanthene C.l. Solvent Red No. 58(C168210) Xanlhene C.l. Acid Brown No. 44 ("page 1346) Azo-Premetallized C.l. Acid Blue No. 166 (page 1302) Azo-Premetallized C 1. Acid Black No.64 (page 1400) Azo-Premeiallized Color Index. Volume 1, Second Edition,

C.l. Acid Black No. 58 age 397) AzwPremelallized C.l. Acid Orange No. 86 (page 1088) Azo-Premetallized C.l. Acid Violet No. 75 age 1226) Azu-Premetallized C.l. Acid Yellow No. 114 (page 1050) Azo-Premetallized C.l. Acid Black No. 131 (page 5-122) Azo-Premetallized C.l. Acid Orange No. 12(C.l. 15970) Monnazo C.l. Acid Red No. (CI 22245) Dialo C.l. Acid Yellow No. 29 (Cl 18900) Munoazo C.l. Acid Blue No. 59 (Cl 50315) Aline C.l. Acid Blue No. 127 (CI 61 I35) Anthraquinone C.l. Acid Brown No. 13(Cl 10410) Nilro C.l. Acid Black No. 48 (Cl 65005) Anthraquinone Color Index. Second Edition Supplement, 1963 As noted above, a feature of" the present invention is the fact that the acid dyes are used at relatively low concentrations. Typically, they may constitute from about 0.05 to about 0.3 percent by weight of the total composition. In the preferred form of the invention, they will comprise about 0.15 percent by weight of the composition.

Another essential feature of the present invention is that the organic solvent employed must have only a limited water solubility. This may vary somewhat, but in general, the water solubility of the solvent will fall in the range of from about 0.5 to 5.0 percent.

Another necessary characteristic of the solvent is that it contains at least one free alcoholic hydroxy group. It has been found, for example, that the esterification of the alcoholic groups renders these alcohols inoperative for applicants purposes. Accordingly, esters, such as the benzyl benzoate, methyl salicylate or amyl acetate, are not operative in the present invention. Similarly, it has been found that solvents which contain no alcoholic hydroxy groups at all are not functional in the instant invention. Solvents, such as the hydrocarbon solvents cannot be employed for the present purposes.

The alcoholic solvents which are appropriate for use in this invention are further characterized by the fact that they are capable of forming hydrogen bonded structures with free carboxy groups, such as are present on polymeric free carboxy containing materials. In this category are found the organic alcohols which possess a limited water solubility as described above.

These alcohols may be more particularly described by way of the following general formula:

in which R and R are hydrogen or alkyl and R is selected from the group consisting of aryl (e.g., phenyl; hydroxyalkylphenyl); aralkyl (e.g., phenylalkyl; hydroxyalkylphenylalkyl); o-alkyl; -alkylene-o-alkyl and alkyl-o-aryl (e.g., alkyl-ophenyl) in which the alkyl group has one to seven carbon atoms, and the alkylene group has from two to nine carbon atoms and the aryl and aralkyl moieties have from six to 14 carbon atoms.

Of special utility are the alcohols that can be considered as hydroxyalkyl benzenes. They can be described by the formula:

(CHDHOH kjP-KCHMOHL,

inwhichnis l or2andpis0or 1.

By way of illustrating specific alcohols that are useful for the present purpose, there may be mentioned linear aliphatic alcohols, e.g., octanol-l and n-hexyl alcohol; branched c..ain aliphatic alcohols, e.g., t-pentyl alcohol, isoamyl alcohol, octanol-2; unbranched chain aralkyl alcohols, e.g., benzyl alcohol, B-phenyl-ethanol; and phenylpropanol, i.e., CH CH CH OH; branched chain arylalkyl alcohols, e.g., phenyl methyl carbinol, and phenyl dimethyl carbinol; xylene glycols, e.g., l,2-bishydroxymethyl benzene; ether alcohols, e.g., anisyl alcohol.

The quantity of alcoholic solvent used in accordance with the present invention is also an important feature. In general, it will constitute between 5 to 40 percent by weight of the total composition. However, by far, the best results are obtained when the alcoholic solvent and particularly benzyl alcohol, constitutes to percent by weight of the composition. The quantity of this solvent that is employed herein exceeds in a large degree its solubility in water. it is such that in the absence of the carboxylated polymer, described in more detail below, two phases would normally be present. The acid dyes are far more soluble in the alcoholic organic solvent than in water. Consequently, in the finished emulsion of the present invention, the dye is contained in the so-called oil phase which comprises the alcoholic organic solvent.

As noted above, it is a feature of the present invention to incorporate a carboxylated polymer in this composition. This carboxylated polymer is characterized by the fact that it is soluble in water and that is has an abundance of free COOH groups. It is further characterized by the fact that it is stable in an acid medium (e.g., pH of about 3 to 4), that is, does not gel or does not precipitate out of solution. it is also a charac' teristic of the carboxylated polymer employed herein that it has the capability of suspending the alcoholic solvent component of this composition (which is of limited water solubility) in its acidic aqueous medium. Any carboxylated polymer which meets the above criteria can be employed in the practice of this invention.

The importance of the free carboxy groups of the polymer used herein is demonstrated by the fact that the corresponding ester or amide polymeric compounds are not operative for the purposes of the present invention. It is further illustrated by the fact that even among the carboxy-containing polymers, better results are obtained with the polymers that have a higher density of carboxylic acid groups than those with a lower density of carboxylic acid groups. Thus, for example, the polymer resulting from the water hydrolysis of maleic anhydride methylvinyl ether copolymers (e.g., Gantrez AN 119,139 or 169) is a polycarboxylic acid copolymer possessing two COOH groups per maleic anhydride residue, and one carboxyl group per repeat polymer segment. The addition of dye and phenyl-ethanol to said polymer solution followed by emulsification with a Waring blender results in a mixture that gives excellent dyeing on wool which was superior to that obtained with a carboxy containing polymer having fewer carboxy groups, e.g., Carbopol 934.

A number of well-known water-soluble carboxylated polymers which are known in the prior art are useful in the present invention. These include the synthetic polymers, as well as polymers prepared from natural materials, e.g., cellulose. Water-soluble carboxylated (a) vinylic polymers, (b) polymeric amino acids, e.g., polyglutamic acid and (c) cellulosic derivatives, e.g., carboxymethylcellulose that have the characteristic described above for the carboxylated polymer may be used.

As illustrative of the water-soluble carboxylated vinylic polymers, there may mentioned the polyacrylic acid and the cross-linked polyacrylic acids. Typical among these are the products sold on the market by B. F. Goodrich Chemical Company under the trademarks Carbopol-934, Carbopol- 940" and Carbopol-941" which are described in US. Pat. Nos. 2,798,053; 2,912,358 and 3,027,303. Particularly useful is Carbopol-941 which is characterized by the fact that a 0.4 percent solution of this polyacrylic acid polymer at pH 3.5 has a viscosity between about 400 to 600 cps. and 10,000 at pH 7.0.

Also illustrative of the water-soluble carboxylated vinylic polymers that may be used in accordance with the present invention, mention may be made of ethylene-maleic anhydride copolymers. They are marketed under the trademark EMA by Monsanto and available in a variety of molecular weights in linear and cross-linked form. Table ll below gives a list of the EMA polymers of this type that are useful for the present purposes.

On reaction with water the EMA resins give clear solution as the result of hydrolyses of the anhydride. These resulting polymers possess vincinal carboxylic acid groups and accordingly, are acidic in nature of pH; e.g., 2.5 for a 1 percent solution.

In their hydrolyzed form, the uncross-linked resins may be expressed by the general formula:

TABLE lll Polymer Concentration Viscosity (cps.)

Gantrez AN-l l9 5% solution l5 cps. (low viscosity) Gantrez AN-l39 5% solution cps. (med. viscosity) Gantrez ANl69 5% solution 200 cps. (high viscosity) In their hydrolyzed form, these resins may be expressed by the general formula:

wherein n is from 1,600 to 16,000.

As noted above, another class of water-soluble polymers that are useful for the purposes of this invention are the watersoluble carboxylated cellulose derivatives. Chief among these is carboxylated cellulose derivatives. Chief among these is carboxymethylcellulose having the above specified characteristics. Similarly, other carboxyalkyl cellulose derivatives, e.g., carboxyethyl cellulose, carboxypropyl cellulose having the desired characteristics may also be employed.

Similarly, polymeric amino acid having free -COOH groups are also suitable for use in accordance with the present invention also providing they have the characteristics outlined above, i.e., (a) soluble in water, (b) stable at the acid pl-ls. (c) are capable of suspending the alcohol of limited water-solubility in the aqueous composition. By way of specific illustration, polyglutamic may be mentioned. The polyglutamic acid polymer is made by the method of Brian G. Overell and Vladimir Petrov, Journal of Chemical Society, 232 1955) by polymerization of b-benzyl derivative of the N-carboxy-anhydride of glutamic acid. Here the range of n values are n=35 to n=200, wherein n is the number of monomeric units.

The amount of carboxylated polymer that may be used in compositions of the present invention may vary somewhat. In general, however, they will constitute about 0.1 to 2.0 percent by weight of the total composition.

Although applicants do not want to be bound by any theory of operation of their invention, it is their view supported by the evidence that the high-dyeing efficiency obtained in accordance with the present invention is a result of a unique interaction between the hydroxylated organic solvent and the carboxylated polymer, the effect of which is to enhance the dye penetration of the fiber. The specific nature of the polymer solvent interaction is believed to be one involving the hydrogen bonding between the carboxy groups of the polymer and the hydroxy group of the organic alcoholic solvent. The alcohol containing the dissolved dye is complexed with the carboxylic acid polymer which is dissolved in the aqueous phase. in this fashion the dye is maintained in emulsion form homogeneously distributed throughout the aqueous phase.

When the emulsion compositions of the present composition are applied to hair, the alcoholic solvent droplets containing the dye have an affinity for the hair and become arranged along the longitudinal axis of the fiber. The individual droplets then coalesce into larger drops which eventually form a continuous coating along the hair fiber. Although on an overall basis, the dye is employed in relatively low concentrations, at the point of application to the hair fiber, the dye is present in relatively high concentrations within the individual solvent droplet This serves to give relatively high-intensity dyeings.

It is a feature of the present invention that the compositions disclosed herein will serve to simultaneously groom and color the hair. These compositions are adapted to be applied on a regular daily basis without the necessity of removing them from the hair a short time after application. They are designed to gradually impart to the hair the desired color over a period of time which may be 1 or 2 weeks. They particularly are suitable for covering the gray hair in men through the daily application of the material as a hair groom. This lends itself to a continuous process which would take care of new growth of gray hair that develops.

With regard to this aspect of the invention, the compositions may also contain other agents commonly found in hair grooming compositions which are compatible with the system and purpose of these compositions. Thus, other compatible grooming agents, gloss imparting agents, antidandruff agents, bactericidal agents, etc., which do not interfere with the primary coloring function of the compositions may be employed.

The compositions of this invention can be made using the usual emulsion formation techniques well known to those skilled in the art. Thus, for example the dyes are first dissolved in the alcoholic solvent. The alcoholic dye solution is then added to the aqueous solution containing the water-soluble carboxylated polymer and, where desired, a surfactant. This mixture is subjected to a high-shear mixing operation to form the oil-in-water emulsion.

To test the effectiveness of the compositions of this invention, in the examples below, 1 gm. samples of mixed hair percent gray hair and 20 percent dark brown) was treated three times with 0.5 gm. of the particular composition being tested. The material is combed through the hair at ambient temperature and the hair sample is allowed to dry. This was re peated three times with 0.5 gm. of product to simulate 1 to 2 weeks of normal daily application to living hair. The effect of this treatment is reported in the particular example below relating to the product in question.

The following examples are further illustrative of this invention. It is to be understood, however, that the invention is not limited thereto.

EXAMPLE 1 A composition was prepared having the following percent by weight of ingredients:

C.l. Acid Black 131 Carbopnl 941 Benzyl Alcohol Deionized Water qs.

An intense gray, fast to washing, was obtained on hair sample treated as described above after three applications.

EXAMPLE 2 A composition was prepared having the following percent by weight of ingredients:

C.l. Acid Brown 44 C.l. Acid Black l3l Cl. Acid Yellow l2? See Color Index I963 Supplement,

page -6 00.03% Benzyl Alcohol 10.00% Deionized Water qs. l00.00% Gantrez AN 0.40%

Gantrez AN-ring alkylated PVP (GAF Co.).

A medium drab brown, fast to washing, was obtained on a hair sample treated as described above after three applications.

EXAMPLE 3 A composition was prepared as in example 1 excepting that carboxymethylcellulose is used in place of Carbopol 941. Similar results are obtained.

EXAMPLE 4 A composition was prepared having the following percent by weight of ingredients:

C.l. Acid Black 48 (C.|. 65005) 00.08% C]. Acid Brown 44 00.077: Benzyl Alcohol l0.00% EM A-8l 0.40% Deionized Water qs. l00.00%

EMA-8| (Monsanto) -cthylene-maleic anhydride copolymer.

A warm, brown, fast to washing, was obtained on a hair sample treated as described above after three applications.

EXAMPLE 5 A composition was prepared having the following percent by weight of ingredients:

(.l. Acid Black 48 (Cl 65005) 00.25% Benzyl Alcohol 50.007: Carbopol 94] 0.40% Sodium lauryl sulfate ether 00.20; Deionized Water qs. l00.00%

An intense brown/black, fast to washing, was obtained on a hair sample treated as described above after three applications.

EXAMPLE 6 A composition was prepared as in example 4 above, excepting that in place of EMA-81, there is employed polyglutamic acid. Similar results are obtained.

EXAMPLE 7 A composition was prepared having the following percent by weight of ingredients:

(.l. Acid Black I3] 003% lrgacet Black Rl. (Cl Acid Black l32), See Color Index I963 Supplement. page 5-l 23 0.02% Z-Phenylethanol 5.0% Sodium Lauryl Sulfate ether 0.l7r Carhopol 941 0.4'7r Deionized Water 94.0%

A silver gray shade was imparted to the hair.

EXAMPLE 8 A composition was prepared having the following in- Water 48.000-

A medium brown shade was imparted to the hair. Although the invention has been described with reference to specific forms thereof, it will be understood that many changes and modifications may be made without departing from the spirit of this invention.

What is claimed is:

1. An oil-in-water emulsion composition capable of dyeing hair comprising a slightly water-soluble alcoholic organic solvent having at least one free hydroxy group and a water solubility of from about 0.5 to 5 percent, from 0.05 to 0.3 percent by weight of an acid dye and a water-soluble acid stable polymer containing an abundance of free carboxy groups and capable of complexing said solvent and acid dye contained therein, said composition having a pH in the range of about 3 to 4, the internal oil phase ofsaid emulsion comprising said organic solvent having distributed therein said acid dye; the aqueous external phase containing said water soluble polymer; said organic solvent being present in sufficient quantity so as to serve as a solvent for said acid dye; said water soluble polymer being present in sufficient quantity to complex said solvent and acid dye dissolved in said solvent whereby said dye is maintained in emulsion form homogenously distributed throughout the aqueous phase.

2. The composition according to claim 1 wherein said water-soluble polymer selected is capable of functioning as a hair-grooming agent.

3. The composition according to claim 2 wherein said alcoholic solvent is of formula:

1'11 l r()t)ll it:

wherein R and R are hydrogen or alkyl; R is selected from the group consisting ofaryl, aralkyl, -O-alkyl; akylene-O-alkyl, alkyl-O-aryl in which the alkyl groups contain one to seven carbon atoms, the alkylene group has from two to nine carbon atoms and the aryl and aralkyl moieties have from six to 14 carbon atoms.

4. The composition according to claim 3 wherein said alcohol is of formula:

climnon inwhichnis 1 or2andpis0or l.

5. The composition according to claim 2 wherein said water-soluble polymer is a carboxylated vinylic polymer.

6. The composition according to claim 5 wherein said carboxylated vinylic polymer is a polyacrylic acid polymer.

7. The composition according to claim 5 wherein said carboxylated vinylic polymer is a hydrolyzed copolymer of ethylene and maleic anhydride.

8. The composition according to claim 5 wherein said carboxylated vinylic polymer is a hydrolyzed copolymer of methyl vinyl ether and maleic anhydride.

9. The composition according to claim 2 wherein the alcohol is benzyl alcohol.

10. The composition according to claim 9 wherein said benzyl alcohol constitutes between about 10-20 percent by weight ofsaid composition.

11. The composition according to claim 10 wherein said benzyl alcohol constitutes 10 percent by weight of said composition.

12. The composition according to claim 11 wherein the water-soluble polymer is a carboxy containing poly-acrylic acid.

13. The composition according to claim 2 wherein the alcohol is B-phenylethanol.

3 ,6 3 O ,65 4 9 all 14. The composition according to claim 2 wherein the al- 16. The composition according to claim 1 wherein said solcoho] is v-phenyl propanol. vent is present in the range of from about 5 percent to 40 per- 15. The method for simultaneously grooming and coloring cent y weight and said P y is P in the range of from hair which comprises applying thereto the composition of about mzpercem by weight ofthe composmonclaim 2.

Claims (15)

  1. 2. The composition according to claim 1 wherein said water-soluble polymer selected is capable of functioning as a hair-grooming agent.
  2. 3. The composition according to claim 2 wherein said alcoholic solvent is of formula: wherein R1 and R2 are hydrogen or alkyl; R3 is selected from the group consisting of aryl, aralkyl, -O-alkyl; alkylene-O-alkyl, alkyl-O-aryl in which the alkyl groups contain one to seven carbon atoms, the alkylene group has from two to nine carbon atoms and the aryl and aralkyl moieties have from six to 14 carbon atoms.
  3. 4. The composition according to claim 3 wherein said alcohol is of formula: in which n is 1 or 2 and p is 0 or 1.
  4. 5. The composition according to claim 2 wherein said water-soluble polymer is a carboxylated vinylic polymer.
  5. 6. The composition according to claim 5 wherein said carboxylated vinylic polymer is a polyacrylic acid polymer.
  6. 7. The composition according to claim 5 wherein said carboxylated vinylic polymer is a hydrolyzed copolymer of ethylene and maleic anhydride.
  7. 8. The composition according to claim 5 wherein said carboxylated vinylic polymer is a hydrolyzed copolymer of methyl vinyl ether and maleic anhydride.
  8. 9. The composition according to claim 2 wherein the alcohol is benzyl alcohol.
  9. 10. The composition according to claim 9 wherein said benzyl alcohol constitutes between about 10-20 percent by weight of said composition.
  10. 11. The composition according to claim 10 wherein said benzyl alcohol constitutes 10 percent by weight of said composition.
  11. 12. The composition according to claim 11 wherein the water-soluble polymer is a carboxy containing poly-acrylic acid.
  12. 13. The composition according to claim 2 wherein the alcohol is Beta -phenylethanol.
  13. 14. The composition according to claim 2 wherein the alcohol is Nu -phenyl propanol.
  14. 15. The method for simultaneously grooming and coloring hair which comprises applying thereto the composition of claim 2.
  15. 16. The composition according to claim 1 wherein said solvent is present in the range of from about 5 percent to 40 percent by weight and said polymer is present in the range of from about 0.1 to 2 percent by weight of the composition.
US3630654A 1968-05-15 1968-05-15 Aqueous alcoholic acid dye-carboxylated polymer compositions for dyeing and grooming hair Expired - Lifetime US3630654A (en)

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3973901A (en) * 1973-12-06 1976-08-10 National Starch And Chemical Corporation Hair coloring composition containing a water-soluble cationic polymer and a process for use thereof
US4036241A (en) * 1975-10-01 1977-07-19 Avon Products, Inc. Film-forming carboxy-containing resin and a polyvalent metal salt in a hair spray and a method of using the same
US4210161A (en) * 1978-07-03 1980-07-01 Helene Curtis Industries, Inc. Creme rinses with hair holding properties
US4272516A (en) * 1976-11-08 1981-06-09 Societa Italo-Britannica-L. Manetti-H. Roberts Co. Process for improving transcutaneous and transfollicular absorption of cosmetic compositions
EP0420713A1 (en) * 1989-09-25 1991-04-03 Shagbark Research, Inc. Composition and method for coloring and moisturizing the skin
US5254333A (en) * 1990-07-10 1993-10-19 Kao Corporation Hair treatment composition and hair dye composition
US5281240A (en) * 1992-09-21 1994-01-25 Dow Corning Corporation Method of coloring hair with water soluble acid dyes
FR2713926A1 (en) * 1993-12-22 1995-06-23 Oreal Process for the direct dyeing of human keratin fibers using sulphonic dyes and water vapor.
US5601620A (en) * 1991-02-15 1997-02-11 Shiseido Company Ltd. Acidic hair dye compositions which comprise acid dyes, benzyl alchol, and polysiloxanes
WO1997018795A1 (en) * 1995-11-23 1997-05-29 L'oreal Use of a composition containing a film-forming polymer dispersion and a non-melanic pigment for temporarily dyeing human or animal hair
EP0806198A2 (en) * 1996-05-09 1997-11-12 Wella Aktiengesellschaft Dyeing composition
US5942216A (en) * 1994-12-06 1999-08-24 Helene Curtis, Inc. Water-in-oil-in-water compositions
US6096099A (en) * 1998-05-26 2000-08-01 Kao Corporation Hair dye composition comprising acid dyes
JP2007222670A (en) * 2007-05-29 2007-09-06 Jms Co Ltd Turbo type blood pump
EP2065030A1 (en) * 2006-09-01 2009-06-03 Kao Corporation One-package hair dye composition
FR2942593A1 (en) * 2009-02-27 2010-09-03 Oreal Composition, useful for dyeing human keratin fibers, comprises in a medium one or more cationic or nonionic synthetic dyes and 3-phenyl-1-propanol
WO2010097559A3 (en) * 2009-02-27 2013-12-19 L'oreal Composition containing a dye and 3-phenyl-1-propanol and dyeing of keratin fibres

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3261754A (en) * 1956-04-21 1966-07-19 Rapidol Ltd Solvent dyeing of human hair
US3344031A (en) * 1962-12-21 1967-09-26 Lever Brothers Ltd N, n-disubstituted isopicramic acid salts for dyeing human hair
US3352755A (en) * 1961-08-04 1967-11-14 Gillette Co Acid dye composition for human hair

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3261754A (en) * 1956-04-21 1966-07-19 Rapidol Ltd Solvent dyeing of human hair
US3352755A (en) * 1961-08-04 1967-11-14 Gillette Co Acid dye composition for human hair
US3344031A (en) * 1962-12-21 1967-09-26 Lever Brothers Ltd N, n-disubstituted isopicramic acid salts for dyeing human hair

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3973901A (en) * 1973-12-06 1976-08-10 National Starch And Chemical Corporation Hair coloring composition containing a water-soluble cationic polymer and a process for use thereof
US4036241A (en) * 1975-10-01 1977-07-19 Avon Products, Inc. Film-forming carboxy-containing resin and a polyvalent metal salt in a hair spray and a method of using the same
US4272516A (en) * 1976-11-08 1981-06-09 Societa Italo-Britannica-L. Manetti-H. Roberts Co. Process for improving transcutaneous and transfollicular absorption of cosmetic compositions
US4210161A (en) * 1978-07-03 1980-07-01 Helene Curtis Industries, Inc. Creme rinses with hair holding properties
EP0420713A1 (en) * 1989-09-25 1991-04-03 Shagbark Research, Inc. Composition and method for coloring and moisturizing the skin
US5254333A (en) * 1990-07-10 1993-10-19 Kao Corporation Hair treatment composition and hair dye composition
US5601620A (en) * 1991-02-15 1997-02-11 Shiseido Company Ltd. Acidic hair dye compositions which comprise acid dyes, benzyl alchol, and polysiloxanes
US5281240A (en) * 1992-09-21 1994-01-25 Dow Corning Corporation Method of coloring hair with water soluble acid dyes
FR2713926A1 (en) * 1993-12-22 1995-06-23 Oreal Process for the direct dyeing of human keratin fibers using sulphonic dyes and water vapor.
EP0659398A1 (en) * 1993-12-22 1995-06-28 L'oreal Process of direct hair dyeing using sulphonic groups containing dyes and steam
US5595197A (en) * 1993-12-22 1997-01-21 L'oreal Process for directly coloring keratinous fibres using sulphonic dyes and water vapor
US5942216A (en) * 1994-12-06 1999-08-24 Helene Curtis, Inc. Water-in-oil-in-water compositions
WO1997018795A1 (en) * 1995-11-23 1997-05-29 L'oreal Use of a composition containing a film-forming polymer dispersion and a non-melanic pigment for temporarily dyeing human or animal hair
US6106577A (en) * 1995-11-23 2000-08-22 L'oreal Use of a composition containing a film-forming polymer dispersion and non-melanic pigment for temporarily dyeing human or animal hair
FR2741530A1 (en) * 1995-11-23 1997-05-30 Oreal Use for the temporary dyeing of hair or animal hair with a composition based on a dispersion of polymeric film and a non-melanin pigment
EP0806198A2 (en) * 1996-05-09 1997-11-12 Wella Aktiengesellschaft Dyeing composition
EP0806198A3 (en) * 1996-05-09 2001-07-25 Wella Aktiengesellschaft Dyeing composition
US6096099A (en) * 1998-05-26 2000-08-01 Kao Corporation Hair dye composition comprising acid dyes
EP2065030A1 (en) * 2006-09-01 2009-06-03 Kao Corporation One-package hair dye composition
EP2065030A4 (en) * 2006-09-01 2013-03-06 Kao Corp One-package hair dye composition
JP2007222670A (en) * 2007-05-29 2007-09-06 Jms Co Ltd Turbo type blood pump
JP4548450B2 (en) * 2007-05-29 2010-09-22 株式会社ジェイ・エム・エス Turbo blood pump
FR2942593A1 (en) * 2009-02-27 2010-09-03 Oreal Composition, useful for dyeing human keratin fibers, comprises in a medium one or more cationic or nonionic synthetic dyes and 3-phenyl-1-propanol
WO2010097559A3 (en) * 2009-02-27 2013-12-19 L'oreal Composition containing a dye and 3-phenyl-1-propanol and dyeing of keratin fibres

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