HK1029061B - Direct hair dye compositions and methods containing novel anthraquinone mixtures - Google Patents

Description

Direct hair dye compositions and methods containing novel anthraquinone mixtures

Technical Field

The present invention relates generally to compositions and methods for preparing direct-acting, semi-permanent hair dyes that produce true color without adversely affecting the structure and condition of the hair after use. More particularly, the present invention relates to hair coloring compositions and methods comprising novel anthraquinone ("AQ") dyes in addition to other additives and components typically used in semi-permanent hair dye compositions.

Background

For the semi-permanent dyeing of keratin fibers, such as human hair, direct dyes are essential elements in hair dyes. In contrast to oxidative dyes which are conventionally developed with the aid of oxidizing agents, such as hydrogen peroxide, dyes which act directly dye the hair themselves at room temperature, without oxidizing agents. Unlike oxidative dyes, semi-permanent or direct dyes advantageously do not cause the appearance of a boundary phenomenon between the distal and half-length of the hair and the growing root of the hair.

Direct dye compositions for semi-permanent dyeing of hair should be optimally suited for covering gray colors, as well as for giving a new color to hair of any color. The dyed hair should not be susceptible to fading from light or rubbing, such as by scrubbing. Semi-permanent dyes should be benign in terms of toxicity. If another substance, such as a permanent hair waving agent or the like, is used on the hair, they should not easily change in color.

Commercially available colorant disperse blue 3(DB3) is a widely used semi-permanent hair colorant. It is actually three blue anthraquinones: mixtures of disperse blues 3, 14 and 23 (i.e. DB3, DB14 and DB 23). Mixtures of DB3, DB14 and DB23 were produced during the production of commercially available colorants DB3, DB3 being synthesized by reacting quinizarine (i.e. 1, 4-dihydroxyanthraquinone) or leucoquinizarine with a mixture of 2-aminoethyl alcohol and methylamine (Ventkataraman, k., 1952, synthetic dye chemistry, volume II, Academic press inc., new york, page 809; abrahrt, e.n., 1968, dyes and their intermediates, new york, Pergamon press, new york, page 176), as represented by the following reaction formula:

as understood by those skilled in the art, the technical name of a particular DB3 anthraquinone is 1- [ (2-hydroxyethyl) amino ] -4- (methylamino) -9, 10-anthracenedione (International cosmetic ingredient dictionary, monograph, sixth edition, eds., J.A. Wenniger and G.N. McEwen, Jr., cosmetics, toiletries and perfumes Association (CTFA), Washington, 1995, pages 350-351). DB23 is chemically known as 1, 4-bis [ (2-hydroxyethyl) amino ] -9, 10-anthracenedione, DB14 is chemically known as 1, 4-bis (methylamino) -9, 10-anthracenedione.

Mixtures of various anthraquinones containing the commercially available colorant DB3 have been shown to be effective as hair dyes because the presence of multiple anthraquinones in the mixture results in a synergistic effect (Ventkataraman, k., 1952, Ibid.). However, since the commercially available colorant DB3 is a mixture of characteristics, there are several disadvantages in hair dye compositions as a direct result. One disadvantage is the potential batch-to-batch variation in the ratio of DB 3: DB 14: DB23 contained in products containing commercially available colorant DB3, which may affect hair coloring characteristics. Another disadvantage is that the ratio of anthraquinone components varies from manufacturer to manufacturer (bite, m.j).&McConnell, r.l., textile chemist and colorist, 28 (3): 14, 1996), which results in a different composition (see table 1) and different staining characteristics. Yet another disadvantage is that different manufacturers can add different color toners, such as disperse violet 1(DV1), i.e., 1, 4-diaminoanthraquinone (table 1); these toners will also change the dyeing effect. The use of mixtures containing DB3 also makes quantitative analysis rather difficult, since at least three sets of quantitative analysis are conventionally necessary to resolve the components by chromatographic separation.

TABLE 1Composition of a commercially available DB3 sample analyzed by HPLC★
				Artisil blue B (Sandoz Co.)	Intraserse brilliant blue BSupra (Crompton)&Knowles Co., Ltd
DB3	30.7％	28.6％
			DB14	9.1％	4.4％
DB23	14.2％	17.3％
			DV1	0％	11.3％

^★The remainder of the sample was other colored components and a colorless dispersant.

Accordingly, it would be an advance in the art for such a direct hair coloring product containing anthraquinone dyes that results in darker and more positive hair coloring, but avoids the above-listed disadvantages associated with the use of known anthraquinone mixtures in hair coloring agents.

The use of 1, 4-di (mono or poly) hydroxyalkylamino-9, 10-anthracenedione for coloring hair is disclosed in U.S. patent No.5,226,924, a. The synthesis and use of specific anthraquinone mixtures is not described. The anthraquinone dyes disclosed by Junino et al specifically require a 2, 3-dihydroxypropylamino group at the 4-position of the molecule.

U.S. patent No.3,368,942, w.j.kaiser et al, discloses aminoanthraquinone hair dyes which are soluble in water, but is not described in relation to the specific anthraquinone mixtures described in the present invention.

U.S. patent No.4,834,768, j.f. griollier, discloses dye compositions for direct dyeing of hair, including anthraquinone among other dyes, and requiring the use of xanthan gum.

Patents disclosing anthraquinone dyes for use in hair coloring are U.S. patent No.3,168,441, m.bil et al; U.S. patent No.3,449,056, f.pum et al; U.S. patent nos. 5,486,629; 5,360,930, respectively; 5,169,403, respectively; 5,314,505, a. chan et al; U.S. patent No.5,112,359, b.murphy et al and U.S. patent No.5,520,707, m. None of these patents disclose that the novel anthraquinone dye mixtures have improved dyeing properties and improved color intensity when used with other dyes, as described herein.

DE4,031,342 discloses 1, 4-bis- (hydroxyalkyl) aminoanthraquinones, but does not disclose specific anthraquinone mixtures having the chemical structure described for the anthraquinone component of the present invention.

The use of anthraquinone dyes, such as DB23, in synthetic fibres, such as polyolefin fibres, has been described, for example in us patent nos. 2,199,183 and 3,235,322, but is clearly distinguished compositionally from anthraquinone dyes used in the colouring of keratin fibres, such as animal and human hair. 1, 4-diaminoanthraquinone disperse dyes have been disclosed in unrelated fields of technology for use on substrates of synthetic polymers such as cellulose acetate, nylon and polyesters (R.S. Sinclair et al, 1975, J.S.D.C., 91: 399-.

Blue anthraquinone DB23 has been disclosed in U.S. Pat. Nos. 4,835,314, 4,921,504, 5,030,241 and 5,037,446, but in each case was applied as the sole anthraquinone dye in the dye composition. None of these previous patents disclose DB23 as a component of a novel anthraquinone mixture, which has a stronger synergistic effect than DB3 when applied to dyed human hair with other anthraquinones, such as disperse violet 1.

The anthraquinone compounds and mixtures of the present invention are distinguished from prior art hair coloring compounds and provide surprising and advantageous hair coloring properties upon application.

Summary of the invention

The object of the present invention is to provide a direct dye composition for the semi-permanent dyeing of keratin fibres, including animal and human hair, in particular human hair. The compositions of the present invention comprise a novel anthraquinone mixture comprising three anthraquinone components. Other components conventionally used in such semi-permanent dye compositions are also included in the composition. The invention also provides a method for using the composition as a direct dye.

It is another object of the present invention to provide novel anthraquinone mixtures with smaller batch-to-batch, and manufacturer-to-manufacturer differences than the commercially available DB3 colorants. According to the invention, the novel anthraquinone dye mixture has strong, positive and lasting hair dyeing capability.

In addition, it is another object of the present invention to provide novel anthraquinone dye mixtures which, as described, show a surprising and unexpected synergistic dyeing effect compared to the commonly known DB3 when applied alone or in combination with other anthraquinones conventionally used in hair dyeing, such as disperse violet 1.

Other objects and advantages of the present invention will become apparent from the following detailed description.

Detailed description of the invention

The present invention provides novel anthraquinone dyes, more preferably novel anthraquinone mixtures, for use in direct hair dyeing, especially for semi-permanent dyeing of human hair. According to the invention, the novel anthraquinone mixtures have surprisingly been found to dye the hair more strongly than commercially available DB3 or DB 23.

According to the invention, the novel anthraquinone dye mixtures contain three blue anthraquinones having the general formula shown below:

wherein R is₁And R₂Independently of one another are straight-chain or branched monohydroxy radicals C₂-C₆Alkyl, with the proviso that in two of the anthraquinones, R₁And R₂Are identical, and therefore these anthraquinones are symmetrical, in the third anthraquinone, R₁And R₂Is different, therefore, this anthraquinone is asymmetric.

According to the invention, the novel anthraquinone mixtures are prepared by reacting quinizarine with two amines, preferably primary monohydroxyalkylamines, each having a substituent, namely a monohydroxyalkyl group (linear or branched). Alkyl is preferably C₂-C₆An alkyl group. For example, for the synthesis of the anthraquinone mixtures according to the invention, a mixture of amines, for example NH₂R₁+NH₂R₂Is applied, wherein R₁And R₂As defined above.

Examples of suitable hydroxyalkylamines for use in the synthesis of the anthraquinone mixtures of the present invention include, but are not limited to, 1-amino-2-propanol, 3-aminopropanol and 2-aminoethanol. Furthermore, all isomers of aminobutanol, aminopentanol and aminohexanol can also be used for the synthesis of the mixtures of the invention, provided that the amine is a primary amine. The synthesis of the anthraquinone mixtures of the present invention is similar to the synthetic method set forth above for the preparation of DB 3.

The present invention encompasses several different anthraquinone mixtures, as described and illustrated below. The mixture 1 according to the invention is prepared by reacting quinizarine with 2-aminoethanol and 3-aminopropanol. Mixture 1 contains three different anthraquinone components, namely: DB 23; 1- [ (2-hydroxyethyl) amino-4- [ (3-hydroxypropyl) amino ] -9, 10-anthracenedione (1); and 1, 4-bis [ 3-hydroxypropyl) amino ] -9, 10-anthracenedione (2).

Another particular mixture according to the invention, mixture 2, was prepared as shown in reaction scheme B by treating quinizarine with 2-aminoethanol and 1-amino-2-propanol, which contained three different anthraquinone components, namely: DB 23; 1- [ (2-hydroxyethyl) amino ] -4- [ (2-hydroxypropyl) amino ] -9, 10-anthracenedione (3); and 1, 4-bis [ 2-hydroxypropyl) amino ] -9, 10-anthracenedione (4).

Mixture 1 Mixture 2

In mixture 2, 1- [ (2-hydroxyethyl) amino ] -4- [ (2-hydroxypropyl) amino ] -9, 10-anthracenedione, component (3), is a novel compound produced according to the invention. The component (3) is separated from the other anthraquinone components of the mixture by reversed phase high pressure liquid chromatography. The chromatographic conditions used were a Bondclone column (150X 3.9 mm); the mobile phase is acetonitrile/water, 75: 25 (volume/volume); the flow rate was 1.5 ml/min and the column temperature was 25 ℃. The peak of the separated sample component was detected at 260/635 nm. The elution times for the individual components of mixture 2 were as follows: DB23 was 5.9 minutes; the novel compound (3) was 8.5 minutes, and the compound (4) was 12.8 minutes. As will be appreciated by those skilled in the art, the individual anthraquinone compounds can be isolated, for example, by collecting the eluate at the appropriate time for elution and removing the solvent by conventional methods well known in the art.

The liquid chromatographic conditions described for the separation of the anthraquinone compounds constituting mixture 2 can likewise be used for the separation of the three anthraquinone components constituting mixture 1. The elution times for the individual components of mixture 1 were as follows: DB23 was 5.9 minutes; compound (1) was 8.2 minutes and Compound (2) was 11.6 minutes.

As shown in reaction scheme C, mixture 3 was prepared by treating quinizarin with 1-amino-2-propanol and 3-aminopropanol, a third particular mixture of the invention, as described below. Mixture 3 contains three different anthraquinone components, namely: 1, 4-bis [ (2-hydroxypropyl) amino ] -9, 10-anthracenedione (4); 1- [ (2-hydroxypropyl) amino ] -4- [ (3-hydroxypropyl) amino ] -9, 10-anthracenedione (5); and 1, 4-bis [ 3-hydroxypropyl) amino ] -9, 10-anthracenedione (2).

Mixture 3

The relative proportions of the individual anthraquinone components in the anthraquinone mixtures of the present invention will vary and can be adjusted by the ratio of the two amines used in the synthesis of the mixture. Regardless, the mixture contains three anthraquinone components. The anthraquinone mixtures of the present invention also contain both asymmetric and symmetric anthraquinone components. For example, in mixture 1, compound (1) is asymmetric, while both DB23 and compound (2) are symmetric. In mixture 2, compound (3) is asymmetric, while both DB23 and compound (4) are symmetric. Similarly, in mixture 3, compound (5) is asymmetric, while compounds (4) and (2) are both symmetric.

The two symmetrical anthraquinone compounds may be present in the mixtures of the present invention in the same or different concentrations, preferably, each in the range of about 1% to about 80% by weight, based on the total weight of the mixture. The asymmetrical anthraquinones preferably comprise about 10% to about 70% by weight, based on the total weight of the mixture.

It is understood that, unless otherwise indicated, the concentrations of the components in the mixture and/or in the composition of the invention are in weight percent (wt/wt), based on the total weight of the mixture or composition.

For example, in one anthraquinone mixture of the present invention, the asymmetric anthraquinone (e.g., compound (1) in mixture 1 and compound (3) in mixture 2) can comprise about 10% to about 70% of the total weight of the mixture, and the mixed symmetric anthraquinone (e.g., DB23 and compound (2) in mixture 1, DB23 and compound (4) in mixture 2) can comprise about 30% to about 90% of the total weight of the mixture.

More preferred mixtures according to the present invention contain from about 25% to about 65% of the asymmetric anthraquinone and from about 3% to about 70% of each of the symmetric anthraquinone compounds. Most preferred mixtures contain from about 30% to about 60% of the asymmetric anthraquinone and from about 5% to about 50% of each of the symmetric anthraquinone compounds.

The anthraquinone components which make up the individual mixtures of the present invention have very similar polarities and therefore do not have the above-mentioned disadvantages of varying from batch to batch, and from manufacturer to manufacturer, in dyeing, associated with the application of the commercially available colorant DB 3. For example, standard thin layer chromatography conditions applied to separate the three components of commercially available DB3 (e.g., 9: 1 chloroform: methanol on silica support) did not separate the components of inventive mixture 1 at all, and separated the components of inventive mixture 2 very rarely. These results demonstrate that the components in each anthraquinone mixture of the present invention have similar polarities, whereas the different components of commercially available DB3 have fundamentally different polarities. The similar polarity of the components of the novel anthraquinone mixtures of the present invention leads to the result (as exemplified by mixtures 1, 2 and 3) that variations in the ratios of these components are not expected to have a substantial effect on the dyeing. In contrast, this improved property of the inventive mixture was not achieved with the commercially available DB 3.

According to an embodiment of the invention, the direct dye mixture, as described, is formulated into a composition for semi-permanent coloring of keratin fibers, including human or other hair. The compositions contain a tinctorially effective amount of the anthraquinone mixtures of the present invention in a cosmetically acceptable vehicle, as further described below.

In fact, the novel anthraquinone mixtures of the present invention are most often used in combination with one or more other conventionally known dye compounds for use in direct hair dye compositions. A large number of such direct colorants are known, including nitro dyes, azo dyes or other anthraquinone dyes and the like. The doping of the dyes of the present invention with other dyes provides the desired color or shade. The amount of each dye used depends on the lightness or depth of the desired shade, as well as the desired shade. Advantageously, the anthraquinone mixtures according to the present invention provide a very positive colour and sufficient affinity to adhere to hair. Non-limiting examples of a number of dye components suitable for use in formulating hair coloring compositions in combination with the anthraquinone mixtures of the present invention include the following:

yellow/orange: acid orange 3, disperse black 9, HC orange 1, HC orange 2, HC orange 3, HC yellow 2, HC yellow 4, HC yellow 5, HC yellow 6, HC yellow 7, HC yellow 9, HC yellow 10, HC yellow 11, HC yellow 12, HC yellow 13, HC yellow 14, HC yellow 15, 4-nitro-o-phenylenediamine, 2-nitro-5-glyceryl methylaniline, 4-nitrophenylaminoethylurea, hydroxyethyl-2-nitro-p-toluidine, 3-methylamino-4-nitrophenoxyethanol, 2-amino-6-chloro-4-nitrophenol, 2-chloro-6-ethylamino-4-nitrophenol, basic yellow 57, solvent orange 45, 4-nitro-m-phenylenediamine, natural orange 6, 2-hydroxyethylamino-5-nitrobenzylether, 2-amino-3-nitrophenol, 6-nitro-o-toluidine, N-ethyl-3-nitro-p-aminobenzoic acid, N-hydroxyethyl-2, 6-dinitro-p-aminobenzyl ether, 6-nitro-2, 5-pyridinediamine and 4-chloro-5-methyl-2-nitrophenol.

Preferred yellow/orange dyes are: acid orange 3, disperse black 9, HC orange 1, HC yellow 2, HC yellow 4, HC yellow 5, HC yellow 6, HC yellow 7, HC yellow 9, HC yellow 10, HC yellow 12, HC yellow 14, HC yellow 15, 4-nitro-o-phenylenediamine, 2-nitro-5-glyceryl methylaniline, 4-nitrophenylaminoethylurea, hydroxyethyl-2-nitro-p-toluidine, 3-methylamino-4-nitrophenoxyethanol, 2-amino-6-chloro-4-nitrophenol, 2-chloro-6-ethylamino-4-nitrophenol, basic yellow 57.Red-orange/Red: HC Red 1, HC Red 3, HC Red 7, HC Red 10, HC Red 11, HC Red 13, HC Red 14, 2-Nitro-phenylenediamine, 3-Nitro-p-hydroxyethylAminophenol, 4-hydroxypropylamino-3-nitrophenol, 4-amino-3-nitrophenol, picric acid, N- (2-hydroxyethyl) picric acid, basic Red 76, disperse Red 17, N-methyl-3-nitro-p-phenylenediamine, 2-chloro-5-nitro-N-hydroxyethyl-p-phenylenediamine, 4-amino-2-nitrodiphenylamine-2 ' -carboxylic acid and 4-amino-4 ' -dimethylamino-2-nitrodiphenylamine-2 ' -carboxylic acid.

Preferred for the red-orange/red dye are: HC red 1, HC red 3, HC red 7, HC red 10, HC red 11, 2-nitro-p-phenylenediamine, 3-nitro-p-hydroxyethylaminophenol, 4-hydroxypropylamino-3-nitrophenol, 4-amino-3-nitrophenol, picric acid, and basic red 76.Purple color: disperse Violet 1, disperse Violet 4, HC blue 2, HC blue 6, HC blue 9, HC blue 10, HC blue 11, HC blue 12, HC Violet 1, HC Violet 2, N' -bis (2-hydroxyethyl) -2-nitro-p-phenylenediamine, 2-nitro-4- [ bis (2-hydroxyethyl) amino group]Diphenylamine and basic violet 14.

Preferred for the violet dye are: disperse violet 1, HC blue 2, HC blue 12, HC violet 2 and basic violet 14.

Blue color: disperse blue 1, disperse blue 3, basic blue 7, basic blue 9, basic blue 17, basic blue 26 and basic blue 99.

Preferred for the blue dye are: disperse blue 1, disperse blue 3, basic blue 9, basic blue 7, basic blue 26 and basic blue 99.

Brown/black: alkaline brown 16, alkaline brown 17 and acid black 1.

Preferred dyes for brown/black are: alkaline brown 16 and alkaline brown 17.

In accordance with the present invention, the anthraquinone mixtures and their compositions may optionally contain one or more dispersants, such as lignin sulfates. When used, the dispersant may be present in the mixture or composition in an amount of about 30% to about 70% by weight.

The compositions of the present invention may also be formulated to contain other cosmetic ingredients conventionally used, including but not limited to: solvents, surfactants, thickeners, antioxidants, preservatives, perfumes, humectants and other components typically employed in hair dye compositions, as described further below. Particularly useful are those substances or agents that can make the product more aesthetically appealing, such as perfumes, protein hydrolysates, vitamins and plant extracts. Examples include chamomile oil, eucalyptus oil, aloe vera, ginseng, and provitamin B.

The dye compositions according to the invention can be formulated to have a basic, acidic or neutral pH in the range of about 5 to 12, preferably about 6 to 11. The appropriate pH may be adjusted with a suitable pH adjusting agent which does not cause toxicity under the conditions of its use.

When the compositions of the present invention are to be basic, the alkalizing agent can be applied over a wide range of concentrations, depending on the dye and the particular alkalizing agent used and the desired pH. Illustratively, the weight percent of the alkalizer can vary from 0% to about 10%, preferably from about 0.05% to about 5%, and most preferably from about 0.10% to about 3%. Any of a wide variety of alkalizing agents can be used to adjust the pH of the present dye compositions, provided that the alkalizing agent does not chemically react with the dye used, does not precipitate the dye, and is not harmful and toxic to the scalp. Amine hydroxides or aqueous ammonia solutions are acceptable alkalizing agents because they are not toxic over a wide range of concentrations and are economical. However, other non-limiting examples of alkalizing agents that can be used in place of or in combination with ammonia or any other compatible derivative of ammonia include: alkylamines, such as monoethylamine, diethylamine, dipropylamine or triethylamine; alkyldiamines such as 1, 3-diaminopropane; mono-, di-and triolamines, such as monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol and 2-amino-2-methyl-1, 3-propanediol; polyalkylpolyamines such as diethylenetriamine; or heterocyclic amines such as morpholine, piperidine, 2-methylpiperidine and piperazine. Combinations or mixtures of the above agents are also suitable for use.

Acidulants that may be employed include inorganic or organic acids and acid salts such as sulfuric, formic, oleic, lactic, acetic, tartaric, phosphoric, hydrochloric, and citric acids are non-limiting examples. Other pH adjusting agents that may be used include ammonium sulfate, sodium dihydrogen phosphate, or potassium hydrogen sulfite. Illustratively, the acidulant is present in an amount from about 0% to about 5%, preferably from about 0.05% to about 1%. In addition, the compositions of the present invention may contain buffering agents to maintain the pH within a particular and/or desired range. In general, the alkalizing agent, acidifying agent and buffering agent used in the compositions of the present invention are referred to as pH adjusting agents.

As will be appreciated by those skilled in the art, the semi-permanent dye compositions of the present invention may also contain various conventional adjuvants or additives, such as perfumes, chelating agents, film forming products and hair treatment agents, dispersants, surfactants, hair conditioners, emulsifiers, chelating agents, preservatives, opacifiers, humectants, biocides and antioxidants, as well as any other adjuvants conventionally used in cosmetic compositions, as further described herein. Typically, these additives, when applied, will be present in amounts ranging from about 0.01% to about 60%, more preferably from about 0.5% to about 55%.

Typical chelating agents that can be used in the compositions of the present invention include salts of ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, phosphates, pyrophosphates, and zeolites.

Surfactants that can be formulated into the direct dye compositions of the present invention include anionic, cationic, nonionic or amphoteric surfactants or mixtures thereof. Examples of suitable types of surfactants include, but are not limited to: higher alkyl benzene sulfonates; alkyl naphthalene sulfonate; sulfonated esters of alcohols and polybasic acids; taurate; fatty alcohol sulfates; sulfates of branched or secondary alcohols; alkyl dimethyl benzyl ammonium chloride; salts of fatty acids or fatty acid mixtures; alkanolamides of N-alkoxylated fatty acids and the like.

Examples of specific surfactants that can be used in the present invention are: sodium lauryl sulfate; polyoxyethylene laurate; tetradecyl sulfate; glyceryl stearate; triethanolamine oleate; sodium salt of hexadecyl methyl taurate; cetylpyridinium chloride; dodecyl sulfonate; tetradecyl sulfonate; lauric acid diethanolamide; polyoxyethylene stearate; ethoxylated oleyldiethanolamide; polyethylene glycol amides of hydrogenated tallow; octadecyl dimethyl benzyl ammonium chloride; sodium dodecylbenzenesulfonate; triethanolamine salts of p-dodecylbenzenesulfonic acid; sodium nonyl naphthalene sulfate; dioctyl sodium sulfosuccinate; sodium N-methyl-N-oleyl taurate; oleate of sodium iso-sulfate; sodium lauryl sulfate and the like. The amount of surfactant can vary over a wide range, for example from about 0.05% to about 15%, preferably from about 0.10% to about 5%.

Suitable thickeners that may optionally be incorporated in the compositions of the present invention include one or more of those commonly used for coloring hair. More particularly, illustrative, non-limiting examples are: such as sodium alginate or gum arabic, guar gum, xanthan gum or cellulose derivatives, for example methylcellulose, such as Methocel 60HG, or the sodium salt of carboxymethylcellulose or hydroxyethylcellulose, such as Cellosize QP-40. Also suitable for use are acrylic polymers, such as sodium polyacrylate. In addition, inorganic thickeners such as bentonite may be used. The thickeners may be used alone or in admixture and can vary in amount over a wide range, for example from about 0.1% to about 20%. Conventionally, the amount of thickener in the compositions of the present invention will vary from about 0.5% to 5%. The viscosity of the composition may vary from about 1 centipoise to about 100,000 centipoise. For a typical lotion composition, the viscosity of the composition is between about 100 centipoise and about 10,000 centipoise.

Antioxidants which may also be incorporated into the present dye compositions include various compounds which are well known and commonly used in the art for this purpose. Suitable antioxidants are: inorganic sulfites such as sodium sulfite, thioglycolic acid and other mercaptans; butylated Hydroxytoluene (BHT); sodium dithionite; ascorbic acid and its derivatives in various forms, such as sodium ascorbate, erythorbic acid, ascorbyl palmitate, ascorbyl laurate and the like. The amount of antioxidant may vary widely when applied. But in general the amount of antioxidant will be on the order of from about 0.001% to about 1%.

Modulators that can be incorporated into the compositions of the present invention include, but are not limited to: an encapsulated silicone; siloxanes, such as amino-functional and carboxy-siloxanes; a volatile siloxane; conjugates of plant extracts and polypeptides; dimethyl dialkyl amine chloride (DMDAAC/acrylic acid type polymer) and dialkyl quaternary ammonium compound, wherein alkyl is C_12-16. Other well-known conditioning agents such as lanolin, glycerin, oleyl alcohol, cetyl alcohol, mineral oil and petrolatum can also be added.

As described, the novel anthraquinone mixtures are formulated into the compositions of the present invention in a tinctorially effective amount, i.e. in a concentration sufficient to color the hair. These amounts can vary over a wide range, but generally they are from about 0.001% to greater than about 5%, for example 10%. Preferably, the dye will comprise from about 0.05% to about 5%, more preferably from about 0.1% to about 3% of the composition.

For their use, the compositions according to the invention may contain water as a suitable carrier, which is usually an important component of the composition. The amount of water can vary over a wide range and will depend to a large extent on the amount of other additives used in the composition. Thus, the water content can be as small as about 10%, but is preferably from about 70% to about 99% of the hair dye composition.

According to the invention, the dye composition is preferably aqueous. The term aqueous composition as used herein has its ordinary general meaning and includes any aqueous composition useful for the present purpose. This includes true solutions of the dye in an aqueous medium, either alone or in combination with other substances or additives that may also be dissolved or dispersed in an aqueous medium. The aqueous dye compositions of the present invention also include any dye mixture comprising an aqueous medium, either alone or in combination with other components. The dye may be colloidally dispersed in the medium or may also be intimately mixed therein.

In addition, the aqueous medium may contain water, or water with additional or auxiliary cosmetically acceptable organic solvents. The latter may be used as a common solvent to enhance the solubility of the dye or some other organic substance. Other auxiliary solvents suitable for this purpose include, but are not limited to: ethanol, carbitol, benzyl alcohol, phenethyl alcohol, isopropanol; or glycols or glycol ethers such as propylene glycol, ethylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, glycerol and the like. The concentration of these organic solvents in the compositions of the invention is generally, for example, from about 0.5% to 20%, preferably from about 2% to 10% of the composition.

The compositions according to the invention can be provided in the form of various conventional preparations for treating keratin fibres and for coloring hair. Typically, the novel anthraquinone dye mixtures of the present invention, or combinations thereof, are incorporated into a liquid hair coloring vehicle of the type suitable for applying a direct coloring substance to hair. A large number of such excipients are well known and understood by those skilled in the art. These excipients can vary from simple aqueous solutions and/or suspensions of dyes to very complex aqueous compositions or thickened or colloidal liquids such as creams, foams, mousses, lotions, pastes, gels and the like. Generally, the anthraquinone mixtures of the present invention are formulated in a cosmetically acceptable vehicle, as described, containing another dye or a mixture of other dyes, nonionic, anionic or cationic surfactants, solvents, thickeners, antioxidants, preservatives, fragrances and the like. In these aqueous compositions, the carrier or excipient may be water or a mixture of water and other solvents such as ethanol or polyethylene glycol. The dyes of the present invention may also be formulated as an aerosol or aerosol system such as an aerosol emulsion system in which the dye or dye mixture is contained in the aqueous phase of the system (e.g., as described in U.S. patent No.4,021,486, Halasz et al).

It is possible to use an emulsifier when the final form of the hair dye will be an emulsion. Many emulsifiers are also surfactants themselves. Illustrative of the general class of emulsifiers include anionic, cationic, nonionic, amphoteric, fatty acid esters, and sorbitan fatty acid esters. Examples include, but are not limited to: mono-, di-and trialkyl ether phosphates, long chain fatty acids with hydrophilic compounds such as glycerol, polyglycerol, or sorbitol, and long chain alkyl primary and secondary amines, quaternary ammonium and quaternary pyridinium compounds.

The aqueous dye compositions of the present invention are prepared by conventional methods used in hair dyeing technology. They can therefore be prepared by dissolving or suspending the dye in water in the desired concentration. Organic solvents miscible in water, e.g. C₁-C₄Aliphatic alcohols, such as ethanol or glycol ethers, can be used to facilitate the obtaining of the dye solution. In one embodiment, the dye may be first dissolved in a solvent, and this solution then diluted with water. Dispersion of the various components can also be facilitated by heating the composition before or after dilution with water, the heating temperature varying between about 40 ℃ and 110 ℃. As a general guide, the concentration of the co-solvent or diluent is from about 5% to about 95%, depending on storage, handling and application considerations.

It is also common practice to add solvents or swelling agents to increase the penetration of hair dyes. Substances useful for swelling hair include acetic acid, formic acid, formamide, urea, ethylamine and certain alkali metal halides (e.g., potassium iodide, sodium bromide, lithium bromide, and lithium chloride). It is possible to use N-alkylpyrrolidones and epoxypyrrolidones to increase the penetration of the dye into the hair. Imidazoles, such as disclosed in U.S. patent No.5,030,629, may be used in the composition to enhance the penetration of hair dyes.

The invention also provides a process for dyeing keratin fibres, in particular human hair, in which a composition according to the invention is applied to the hair for direct dyeing. For the direct dyeing method, the composition of the invention is applied to the hair by applying the conventional techniques in this field. For example, when the composition of the present invention is applied to living hair on a person's head, it can be applied to the hair with a brush, sponge, or other contact means, such as pouring the composition directly onto the hair until saturated and/or combing the hair by hand. The reaction time or contact time of the dye composition with the hair is not critical and can vary over a wide range, such as from about 1 minute to about 2 hours, as used in hair coloring techniques. Preferably, a time period of from about 5 minutes to about 60 minutes is applied; most preferably, a period of from about 10 minutes to about 40 minutes is applied.

The hair dyeing temperature can vary within wide, conventional ranges within the skill in the art. Thus, the hair dyeing temperature can vary from about 20 ℃ to about 45 ℃. At the end of the period, the composition is rinsed from the hair with water. If desired, a shampoo or a weak acid solution may also be applied.

According to the present invention, the novel direct hair coloring compositions may be applied to natural or dyed hair, permanent wave hair or highly or lightly whitish hair.

Other advantages and features of the present invention will become apparent from the following description of the embodiments which are presented by way of example.

Examples

The following examples are intended to illustrate and explain various aspects of the practice of the invention without any limitation thereto.

Example 1

To evaluate the hair coloring properties of the mixtures according to the invention on human hair, gray-doped hair samples and hairWhite hair was dyed with the mixture 1 of the present invention, which contained about 10% to 70% of 1- [ (2-hydroxyethyl) amino-4- [ (3-hydroxypropyl) amino group]-9, 10-anthracenedione and about 30% to 90% of DB23 with 1, 4-bis [ 3-hydroxypropyl) amino]-a mixture of 9, 10-anthracenediones. These samples were also stained with 1% DB3a (Artisil Blue B) and 1% DB3B (Intraserse Brilliant Blue B Supra). Artisil Blue B (Sandoz corporation) and IntrasereseBrilliant Blue B Supra (Crompton)&Knowles company) are two examples of commercially available DB3 dye formulations commonly used in hair dye formulations (see table 1). The total amount of colorant used was the same for blend 1 of the present invention as for DB3a and DB3 b. Table 2 shows the results of comparing the hair coloring performance of inventive mixture 1 with that of commercial disperse blue DB3a and 3b products.

TABLE 2 Hunter values of the hair samples dyed with mixture 1 according to the invention and with disperse blue
										Hair with doped gray color			Whitish hair
Undyed inventive mixture 1DB3a+DB3b++	L33.3925.5829.0627.02	a-0.08-0.490.47-0.65	b5.261.651.261.23	L62.3730.5232.7733.81	a2.27-3.421.76-3.29	b19.22-14.15-10.31-11.72	ΔE46.6741.8142.47	Δb-33.37-29.53-30.94

⁺Artisil Blue B (Sandoz Co.)

⁺⁺Intrasperse Brilliant Blue B Supra(Crompton&Knowles Co., Ltd

For these analyses, the hair was dyed with a 1% concentration dye in a commercial semi-permanent hair dye base for 30 minutes at room temperature. The samples were then rinsed with water and air blown dry. In order to remove the differences which may be caused by the effect of the hair dye base, the same hair dye base was used in all tests.

The L values of the samples stained with mixture 1 indicate that these samples were stained to the deepest extent (that is, the smaller the L value, the darker the color). The results of this analysis are more convincing when testing white hair, as the substrate better demonstrates the effect of the large anthraquinone molecule. The values of b (and Δ b) and L (and Δ E) shown in table 2 demonstrate that white hair dyed with blend 1 is bluer and darker than hair dyed with any of the commercially available DB3 products used for the tests, i.e., the more negative the value of b, the more blue it is dyed.

Example 2

The hair dyeing properties of the novel anthraquinone mixtures of the present invention were evaluated in combination with other anthraquinone dyes typically used for hair dyeing. As an illustrative example, the mixture 1 of the invention is used in combination with disperse violet 1(DV 1). The whitish hair was treated with 1% strength mixture 1 or DB3a and 1% Intraperse Red Violet RHEW (disperse Violet 1, Crompton) in a commercial semi-permanent formulation at room temperature&Knowles company) for 30 minutes. The hair was then rinsed with water and air dried. The results are shown in Table 3.

TABLE 3 Comparative disperse blue 3a after dyeing with inventive mixture 1+ DV1 ★ + DV1 dyed heads
				Hunter value of hair sample
	L	a	b
				Inventive mixture 1+ DV1	26.55	6.80	-21.18
DB3a★+DV1	32.27	6.43	-11.66

^★Artisil Blue B (Sandoz Co.)

The results of the L and b value measurements shown in Table 3 clearly show that the intensity of the dyed colour and the degree of blue are greatly improved when the blend 1+ DV1 is used in combination with DB3a + DV 1. Thus, when used in combination with DV1, mixture 1 proved to have a stronger synergistic staining effect than DB 3.

Example 3

A comparison of the relative hair coloring performance of the novel anthraquinone mixtures of the present invention, mixture 1 and mixture 2 was made. The results are shown in Table 4. The white hair was dyed with a direct dye formulation containing 1% of mixture 1 or 1% of mixture 2 for 30 minutes at room temperature. The hair was then rinsed with water and air dried.

TABLE 4 Hunter value of Hair samples dyed with mixture 1 or mixture 2 according to the invention
								Hair with doped gray color			Whitish hair
Mixture 1 mixture 2	L37.3439.69	a-3.79-1.93	b1.734.71	L40.3847.12	a-10.61-6.45	B-1.67.05

The L values for the samples stained with mixture 1 indicate that these samples are darker (i.e., the smaller the L value, the darker the color) than the samples stained with mixture 2. Similar results were observed when white hair was tested as a substrate. The difference in the substantivity of mixture 1 and mixture 2 to hair may be responsible for the difference in the coloring properties of each mixture to gray and white hair, as shown in table 4.

The contents of all patents, patent applications, published documents, books, reference manuals, and abstracts cited herein are hereby fully incorporated by reference to the extent they are described in connection with the present invention

The prior art is provided.

As various changes could be made in the above-described subject matter without departing from the scope and spirit of the invention, it is intended that all subject matter contained in the above description, shown in the accompanying drawings, or defined in the appended claims be interpreted as illustrative and not in a limiting sense. Many modifications and variations of the present invention are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

Claims (11)

1. An anthraquinone mixture containing three different anthraquinone compounds having the general formula:

wherein R is₁And R₂Independently of one another are straight-chain or branched monohydroxy radicals C₂-C₆Alkyl, with the proviso that in two of the anthraquinones, R₁And R₂Are identical, and therefore these anthraquinones are symmetrical, in the third anthraquinone, R₁And R₂Is different, and thus, the anthraquinone is asymmetric, wherein the two symmetric anthraquinone compounds are present in the mixture in combination in an amount of from 30% to 90% by weight, based on the total weight of the mixture, and wherein the asymmetric anthraquinone compound is present in the mixture in an amount of from 10% to 70% by weight, based on the total weight of the mixture.

2. The mixture according to claim 1, wherein the asymmetric anthraquinone compounds comprise from 25% to 65% by weight, based on the total weight of the mixture, and the symmetric anthraquinone compounds each comprise from 3% to 70% by weight, based on the total weight of the mixture.

3. The mixture according to claim 1, wherein said asymmetric anthraquinone compounds comprise from 30% to 60% of said mixture and said symmetric anthraquinone compounds each comprise from 5% to 50% of said mixture.

4. The mixture according to claim 1, wherein R₁And R₂Each selected from the group consisting of 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, hydroxybutyl, hydroxypentyl and hydroxyhexyl.

5. The mixture according to claim 1, wherein the anthraquinone compounds are 1, 4-bis [ (2-hydroxyethyl) amino ] -9, 10-anthracenedione, 1- [ (2-hydroxyethyl) amino-4- [ (3-hydroxypropyl) amino ] -9, 10-anthracenedione and 1, 4-bis [ (3-hydroxypropyl) amino ] -9, 10-anthracenedione.

6. The mixture according to claim 1, wherein the anthraquinone compounds are 1, 4-bis [ (2-hydroxyethyl) amino ] -9, 10-anthracenedione, 1- [ (2-hydroxyethyl) amino ] -4- [ (2-hydroxypropyl) amino ] -9, 10-anthracenedione and 1, 4-bis [ (2-hydroxypropyl) amino ] -9, 10-anthracenedione.

7. The mixture according to claim 1, wherein the anthraquinone compounds are 1, 4-bis [ (2-hydroxypropyl) amino ] -9, 10-anthracenedione, 1- [ (2-hydroxypropyl) amino ] -4- [ (3-hydroxypropyl) amino ] -9, 10-anthracenedione and 1, 4-bis [ (3-hydroxypropyl) amino ] -9, 10-anthracenedione.

8. A method of dyeing keratin hair fibers comprising contacting said hair fibers with a tinctorially effective amount of a mixture according to claim 1 in a cosmetically acceptable vehicle for a time sufficient to dye said fibers.

9. The method according to claim 8, wherein said mixture is according to claim 2.

10. A composition for the colouring of keratin fibres, comprising a colouring-effective amount of an anthraquinone mixture according to claim 1, said mixture being present in a cosmetically acceptable vehicle.

11. A composition according to claim 10, wherein said mixture is a mixture according to claim 2.