Patent Application
20250017838
The present invention relates to a cosmetic agent for oxidatively dyeing keratin fibers, which agent contains at least one oxidation dye precursor of developer type (a), at least one oxidation dye precursor of coupler type (b), and isatin (c).
A further subject matter is a multicomponent packaging unit (kit-of-parts) comprising two agents packaged separately in two containers, wherein the agent in the first container contains the ingredients (a), (b), and (c), and the agent in the second container contains at least one oxidizing agent from the group consisting of hydrogen peroxide and its addition products to organic or inorganic compounds.
A further subject matter is a method for oxidatively dyeing keratinous fibers, in which an agent containing (a), (b), and (c) is applied to the keratinous fibers and rinsed out again after an exposure time.
In order to provide color-changing cosmetic agents, and in particular for keratinous fibers, such as hair, a person skilled in the art is aware of various dyeing systems depending upon the coloration requirement. So-called oxidative dyeing agents are used for permanent, intense coloring having appropriate fastness properties. Such dyes typically contain oxidation dye precursors, known as developer components, and coupler components, which together form the actual dyes under the influence of oxidizing agents-for example, hydrogen peroxide. Oxidative dyeing agents are characterized by outstanding, long-lasting coloring results.
The oxidation dye precursors (developers and couplers) themselves are not colored, but, rather, the actual dyes are only formed in the course of application when the oxidation dye precursors come into contact with the oxidizing agent (hydrogen peroxide). In a chemical reaction, the developers used as oxidation dye precursors (such as p-phenylene diamine or its derivatives) are first oxidatively converted by hydrogen peroxide into a reactive intermediate, also called quinonimine or quinone diimine, which then reacts in an oxidative coupling reaction with the couplers to form the corresponding dye.
With oxidative dyeing agents, hair can be dyed both in intensive mode shades and in natural shades by choosing the suitable developer components and coupler components. A large area of application for the oxidative dyeing agents is the coloring of gray hair in a natural shade, which resembles the hair color that the user had when they were younger. A person skilled in the art knows the use of developers based upon the base body of 1,4-diaminobenzene (para-phenylene diamine) and couplers having a resorcinol structure (1,3-dihydroxybenzene) as a classic combination for generating oxidative colorings in the brown to dark-blonde range.
Said oxidation dyes have been used for decades. Although they are only intended for extracorporeal use on keratin fibers such as head hair, eyelashes, and eyebrows, contact of the dyeing agent with the scalp cannot be completely avoided during use. In order to ensure the highest possible product safety for customers, the commercially available oxidation dye precursors are continuously checked in terms of their physiological compatibility, e.g., by the Scientific Committee on Consumer Products (SCCP), an advisory body of the European Commission. It is known that some of the oxidation dye precursors, and in particular some of the oxidation bases of the para-phenylene diamines type, can have a certain potential for sensitization. The customer is therefore advised to perform a test with a small amount of the colorant on the skin before using the dyeing agent on the hair in order to exclude allergic reactions during or after the dyeing process. In addition to skin sensitization, other physiological effects are also monitored.
Resorcinol, 4-chlororesorcinol, and 2-methylresorcinol are common oxidation dye precursors with a 1,3-dihydroxybenzene base body. In its last opinion from March 2021, SCCP came to the conclusion that the use of resorcinol in oxidative hair dyes at a resorcinol concentration of up to 1.25 wt % in the ready-to-use mixture was considered safe. The SCCP stated that resorcinol has a thyroid-inhibiting effect. Although a definite exposure level required for such effect cannot be derived from the available studies in humans, most of these studies indicate a relatively much higher exposure than is the case in cosmetics.
In order to take into account the concerns of some consumers with regard to product safety, the object of the present invention was to provide an agent for oxidatively dyeing keratin fibers, and in particular human hair, with which a broad color spectrum can be covered, and in particular a natural color palette with cool natural shades and warm natural shades, and a gold color series which leads to colors having high fastness properties, without impairing product safety. In particular, dyeing in these natural shades should be possible without the use of couplers of the resorcinol type.
Many users dye their hair the same shade for decades and do not wish for a sudden, obviously visible, change to their usual hair color. For these users, it is therefore essential to allow the customary, resorcinol-containing hair dye to be replaced by a new, resorcinol-free product without a shift in shade. A central challenge of the present application was therefore to find a new, resorcinol-free hair dye which, in its color effect and its color result, corresponds as precisely as possible to the resorcinol-containing dyeing agent used to date.
Surprisingly, it could now be found that this object can be achieved excellently by an oxidative dyeing agent which contains at least one oxidation dye precursor of the developer type (a) and at least one oxidation dye precursor of the coupler type (b) and isatin (c).
A first subject matter of the present invention is therefore an agent for oxidatively dyeing keratinous fibers, and in particular human hair, containing, in a cosmetic carrier,
The work leading to this invention has shown that the oxidative coloring of hair induced by oxidizing agents, such as hydrogen peroxide, using a developer and a coupler in combination with isatin leads to very intense colorations with excellent fastness properties. It was also particularly advantageous that the color effect of a corresponding resorcinol-containing dyeing agent could be accurately reproduced with this dye combination.
Keratin fibers are in principle understood to mean all types of animal hair, e.g., wool, horsehair, angora hair, furs, feathers, and products or textiles manufactured therefrom. Preferably, however, the keratinous fibers are human hair.
The term, “agent for oxidative dyeing,” of the keratin fibers used according to the invention is understood to mean oxidative dyeing agents. Oxidative dyeing agents contain oxidation dye precursors, so-called developers, and coupler components. Developers and couplers diffuse separately into the keratin fibers and, in a chemical reaction with one another, form the actual dyes under the influence of an alkalizing agent (e.g., ammonia) and an oxidizing agent (hydrogen peroxide). Depending upon the quantity of oxidizing agent employed, the keratin fibers are simultaneously lightened to a greater or less extent during coloring, since the oxidizing agent not only initiates the dye-forming process of the developers and couplers, but also oxidatively destroys the hair's own pigments (melanins). Depending upon the used amounts of the oxidation dye precursor products and of the oxidizing agent, the oxidative coloration can therefore be predominantly a coloration (with high dye proportion) or predominantly a lightening (with high proportion of oxidizing agent). In the latter case, the oxidation dye precursors are mostly used for shading the brightening result.
The agents according to the invention contain the components essential to the invention in a cosmetic carrier, and preferably in a suitable aqueous, alcoholic, or aqueous-alcoholic carrier. For the purpose of hair coloring, such carriers are for example creams, emulsions, gels, or also surfactant-containing foaming solutions, such as for example shampoos, foam aerosols, foam formulations, or other preparations which are suitable for application to hair.
The oxidative dyeing agent described above is a ready-to-use dyeing agent which is applied in this form containing the components (a) and (b) and (c) for application to the keratin fibers.
Oxidative dyeing agents contain oxidation dye precursors, so-called developers, and coupler components, for the formation of the coloring. Developers and couplers diffuse separately into the keratin fibers and form the actual dyes in a chemical reaction with one another under the influence of ammonia as alkalizing agent and an oxidizing agent. Depending upon the quantity of oxidizing agent employed, the keratin fibers are simultaneously lightened to a greater or less extent during coloring, since the oxidizing agent not only initiates the dye-forming process of the developers and couplers, but also oxidatively destroys the hair's own pigments (melanins). Depending upon the amounts of oxidation dye precursor products and the oxidizing agent used, the oxidative coloration can therefore be predominantly a coloration (with high dye proportion) or predominantly a lightening (with high proportion of oxidizing agent). In the latter case, the oxidation dye precursors are mostly used for shading the brightening result.
As a first essential component, the oxidative dyeing agents according to the invention contain at least one oxidation dye precursor of the developer type, also referred to as developer for short.
Particularly suitable oxidation dye precursors of the developer type are selected from the group consisting of p-toluylene diamine, 2-methoxymethyl-p-phenylene diamine, 2-(2-hydroxyethyl)-p-phenylene diamine, N,N-bis-(2-hydroxyethyl)-p-phenylene diamine, p-phenylene diamine, and physiologically tolerated salts thereof.
In a particularly preferred embodiment, an agent according to the invention is therefore characterized in that it contains at least one oxidation dye precursor of developer type (a) selected from the group consisting of p-toluylene diamine, 2-methoxymethyl-p-phenylene diamine, 2-(2-hydroxyethyl)-p-phenylene diamine, N,N-bis-(2-hydroxyethyl)-p-phenylene diamine, p-phenylene diamine, and the physiologically tolerated salts thereof. p-toluylene diamine is alternatively also referred to as 2,5-toluylene diamine, p-toluylene diamine (abbreviation: PTD), 2,5-diaminotoluene, 2-methyl-p-phenylene diamine, or 2,5-diaminomethylbenzene. PTD has the CAS number 95-70-5. 2-methoxymethyl-p-phenylene diamine is also alternatively referred to as 2-methoxymethyl-1,4-benzene-diamine and, in the form of its free base, bears the CAS number 337906-36-2. 2-(2-hydroxyethyl)-p-phenylene diamine is alternatively referred to as 2-(2,5-diaminophenyl) ethanol and, in the form of its free base, bears the CAS number 93841-24-8. N, N-bis-(2-hydroxyethyl)-p-phenylene diamine in the form of its free base has the CAS number 7575-35-1.
With an oxidative dyeing agent, which contains a developer (a) of the aforementioned group with the basic structure of the 1,4-diaminobenzene, hair can be dyed with very high intensity in natural shades, and in particular in dark brown, medium brown, and dark blonde shades. It was also particularly surprising that the hair could be colored in a shade which was particularly strongly similar to the shade obtained with a dyeing agent containing the classic combination of PDT and resorcinol.
The agents which contain at least one oxidation dye precursor of the developer type (a), which is selected from the group of p-toluylene diamine, 2-methoxymethyl-p-phenylene diamine, and the physiologically tolerated salts thereof, have proven to be very particularly suitable for achieving the object according to the invention.
In a particularly preferred embodiment, an agent according to the invention is therefore characterized in that it contains at least one oxidation dye precursor of developer type (a) selected from the group consisting of p-toluylene diamine, 2-methoxymethyl-p-phenylene diamine, and the physiologically tolerated salts thereof.
However, the agent according to the invention can also contain other developers (a) to form shades with a reddish natural tone. For example, developers from the group of 4-amino-3-methylphenol, p-aminophenol, 4,5-diamino-1-(2-hydroxyethyl)-pyrazole, and their physiologically tolerated salts are particularly suitable for this purpose. These developers can be used either as a component of the group on its own or also together with one or more developers having a basic structure of p-phenylene diamine.
In a particularly preferred embodiment, an agent according to the invention is therefore characterized in that it contains at least one oxidation dye precursor of developer type (a), which is selected from the group consisting of 4-amino-3-methylphenol, p-aminophenol, 4,5-diamino-1-(2-hydroxyethyl) pyrazole, and the physiologically tolerated salts thereof.
The developers of the above-mentioned groups can be used in the form of their free base or else in the form of their physiologically tolerated salts in the agent according to the invention. A physiologically tolerated salt is understood to mean a salt of the developer that is well tolerated by the user under physiological conditions, i.e., during use of the agent. Physiologically tolerated salts are in particular the chlorides, bromides, sulfates, and hemisulfates of developers (a).
In a further particularly preferred embodiment, an agent according to the invention is therefore characterized in that it contains at least one oxidation dye precursor of developer type (a) which is selected from the group of p-toluylene diamine, p-toluylene diamine sulfate, p-toluylene diamine chloride, p-toluylene diamine bromide, 2-methoxymethyl-p-phenylene diamine, 2-methoxymethyl-p-phenylene diamine sulfate, 2-methoxymethyl-p-phenylene diamine chloride and 2-methoxymethyl-p-phenylene diamine bromide, 4,5-diamino-1-(2-hydroxyethyl)-pyrazole chloride, 4,5-diamino-1-(2-hydroxyethyl)-pyrazole bromide, and 4,5-diamino-1-(2-hydroxyethyl) pyrazole sulfate.
The developers(s) are preferably used in specific quantity ranges in the agent according to the invention. The agent preferably contains, relative to the total weight of the agent, one or more oxidation dye precursors of developer type (a) in a total amount of 0.001 to 10.0 wt %, preferably 0.01 to 6.0 wt %, more preferably 0.1 to 5.0 wt %, and very particularly preferably 0.15 to 4.7 wt %.
In particularly preferred embodiment, an agent according to the invention is thus characterized in that the agent contains, relative to the total weight of the agent, one or more oxidation dye precursors of developer type (a) in a total amount of 0.001 to 10.0 wt %, preferably 0.01 to 6.0 wt %, more preferably 0.1 to 5.0 wt %, and very particularly preferably 0.15 to 4.7 wt %.
Depending upon the desired color effect, it can furthermore be preferred if the agent additionally contains one or more further oxidation dye precursors of the developer type selected from the group of bis-(2-hydroxy-5-aminophenyl)-methane, 1,3-bis-(2,5-diaminophenoxy)-propan-2-ol, N,N′-bis-(4-aminophenyl)-1,4-diazacycloheptane, 1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane, 4-amino-2-aminomethylphenol, 4-amino-2-(1,2-dihydroxyethyl) phenol, 4-amino-2-(diethylaminomethyl)phenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, and the physiologically tolerated salts thereof.
The developer or the additional developers can, relative to the total weight of the agent, be contained in the agent in a total amount of 0.001 to 10.0 wt %, preferably 0.01 to 6.0 wt %, more preferably 0.1 to 5.0 wt %, and very particularly preferably 0.15 to 4.7 wt %.
The base hue of the natural nuance can be produced by the combination of the developer (a) with isatin (c). In addition to the oxidation dye precursors (a) and isatin (c), the oxidative dyeing agent contains at least one oxidation dye precursor of the coupler type (b) in order to intensify the color result, the precise shading, and/or the fine adjustment of the desired hue.
Very well-suited couplers can be selected for example from the group consisting of 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol, 5-(2-hydroxyethyl)amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylene diamine, 2-(2,4-diaminophenoxy) ethanol, 1,3-bis(2,4-diaminophenoxy)propane, 1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene, 1,3-bis(2,4-diaminophenyl)propane, 2,6-bis(2′-hydroxyethyl)-1-methylbenzene, 1-amino-3-bis(2-hydroxyethyl)aminobenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline, or mixtures of said compounds, or the physiologically tolerated salts thereof.
In a particularly preferred embodiment, an agent according to the invention is thus characterized in that it contains at least one oxidation dye precursor of the coupler type (b) which is selected from the group of 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol, 5-(2-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylene diamine, 2 (2,4-diaminophenoxy)ethanol, 1,3-bis (2,4-diaminophenoxy)propane, 1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene, 1,3-bis(2,4-diaminophenyl)propane, 2,6-bis(2′-hydroxyethyl)-1-methylbenzene, 1-amino-3-bis(2-hydroxyethyl)aminobenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline, and the physiologically tolerated salts thereof.
Particularly natural shades with great similarity to the corresponding resorcinol-containing dyes could be obtained if the dyeing agent additionally contained one or more couplers (b) which were selected from the group consisting of 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-amino-3-hydroxypyridine, 1-methoxy-2-amino-4-(2-hydroxyethyl-amino)benzene, 6-hydroxyindole, or mixtures of these compounds, or the physiologically tolerated salts thereof. For this reason, the use of couplers (b) from this group is explicitly very particularly preferred.
In an explicitly very particularly preferred embodiment, an agent according to the invention is therefore characterized in that it contains at least one oxidation dye precursor of coupler type (b) which is selected from the group consisting of 3-amino-phenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-amino-3-hydroxypyridine, 1-methoxy-2-amino-4-(2-hydroxyethylamino) benzene, 6-hydroxyindole, and the physiologically tolerated salts thereof.
The couplers from the above-described group (b) are preferably used in specific quantity ranges in the agent according to the invention. Particularly positive results were obtained when the agent contained, relative to the total weight of the agent, one or more oxidation dye precursors of the coupler type (b) in a total amount of 0.001 to 10 wt %, preferably 0.01 to 5 wt %, more preferably 0.1 to 3.5 wt %, and very particularly preferably 0.15 to 2.5 wt %.
In a further preferred embodiment, an agent according to the invention is characterized in that the agent contains, relative to the total weight of the agent, one or more oxidation dye precursor of coupler type (b) in a total amount of 0.001 to 10 wt %, preferably 0.01 to 5 wt %, more preferably 0.1 to 3.5 wt %, and very particularly preferably 0.15 to 2.5 wt %.
As already described above, with the agents of the present application, intense colorations in the natural tone range should be developed which reproduce the shades that are produced with resorcinol-containing dyeing agents as well as possible, without being dependent upon the use of resorcinol-type couplers.
Resorcinol-type couplers or couplers from the group of resorcinols are understood to mean 1,3-dihydroxybenzene and its derivatives. Derivatives of 1,3-dihydroxybenzene are all compounds which have a 1,3-dihydroxybenzene basic structure and carry further substituents, but both hydroxyl groups of the 1,3-dihydroxybenzene must still be present.
The couplers from the group of resorcinols used as standard in market products are resorcinol, 2-methylresorcinol, and 4-chlororesorcinol. Couplers from the group of resorcinols are therefore understood in particular to be resorcinol, 2-methylresorcinol, and 4-chlororesorcinol. In the agents of the present application, these couplers are to be dispensed with, and therefore it is preferred if the total amount of oxidation dye precursors of the coupler type contained in the agent from the group of resorcinols, and in particular from the group consisting of resorcinol, 2-methylresorcinol, and 4-chlororesorcinol, is below 0.1 wt %, preferably below 0.05 wt %, particularly preferably below 0.01 wt %, and very particularly preferably 0 wt %.
In a further very particularly preferred embodiment, an agent according to the invention is therefore characterized in that, relative to the total weight of the agent, the total amount of the oxidation dye precursors of the coupler type contained in the agent from the group of resorcinols, and in particular from the group consisting of resorcinol, 2-methylresorcinol, and 4-chlororesorcinol, is below 0.1 wt %, preferably below 0.05 wt %, particularly preferably below 0.01 wt %, and very particularly preferably 0 wt %.
As a third component essential to the invention, the oxidative dyeing agent is isatin (c). Isatin is the compound of formula (ISA), which can alternatively also be referred to as 2,3-indoline-dione or as 2,3-dioxoindoline
Isatin has the CAS number 91-56-5.
With regard to an optimal achievement of the object according to the invention, isatin (c) is preferably contained in specific quantity ranges in the agent according to the invention. Particularly good results were obtained when the agent contained, relative to the total weight of the agent, 0.001 to 10 wt %, preferably 0.01 to 5 wt %, more preferably 0.1 to 3.5 wt %, and very particularly preferably 0.15 to 2.5 wt % isatin (c).
In a particularly preferred embodiment, an agent according to the invention is thus characterized in that it contains, relative to the total weight of the agent, 0.001 to 10 wt %, preferably 0.01 to 5 wt %, more preferably 0.1 to 3.5 wt %, and particularly preferably 0.15 to 2.5 wt % isatin (c).
Isatin is commercially available from various suppliers, such as Acros, Sigma Aldrich, Thermo Scientific, etc.
The shade resulting from the coloring on the hair depends both upon the amounts of the developer(s) (a) and the coupler(s) (b) used and upon the amount of the isatin (c) contained in the agent. As is known from typical practice in coloring, the higher the amounts of developers (a), couplers (b), and isatin (c) used, the higher the intensity of the coloration. However, the naturalness of the resulting coloring can be controlled by the quantitative ratio in which the developers of group (a) and isatin (c) are used with respect to one another in the oxidative dyeing agent.
The colorations produced on the hair then had a particularly high similarity to the colorations obtained with resorcinol-type couplers if the agent contained the developers (a) and isatin (c) in a weight ratio which has a value of 2:1 to 1:2, preferably 1.9:1 to 1:1, more preferably 1.9:1 to 1.1:1, even more preferably 1.8:1 to 1.1:1, and very particularly preferably 1.7:1 to 1.2:1. This effect was observed in particular in the darker natural shades, such as dark brown and medium blonde.
In a particularly preferred embodiment, an agent according to the invention is thus characterized in that the weight ratio of all the developers of the group (a) contained in the agent to the isatin (c) contained in the agent, i.e., the weight ratio (a)/(c), has a value of 2:1 to 1:2, preferably 1.9:1 to 1:1, more preferably 1.9:1 to 1.1:1, even more preferably 1.8:1 to 1.1:1, and very particularly preferably 1.7:1 to 1.2:1.
In the preferred weight ratio (a)/(c) of 1.9:1 to 1:1, for example, the developer(s) (a) is/are used in the agent either in the same amount as isatin (c) or in an up to 1.9-fold weight excess. Very particularly preferably, compared to isatin (c), the developers (a) are used in a 1.2-fold to 1.7-fold weight excess.
For the formation of the colors in the oxidative dyeing process, the oxidative dyeing agent according to the invention preferably contains at least one oxidizing agent (d), in which it is particularly preferably hydrogen peroxide and/or the hydrogen peroxide addition products to organic or inorganic compounds.
In a preferred embodiment, hydrogen peroxide itself is used as an aqueous solution in the oxidative dyeing agent. The concentration of a hydrogen peroxide solution is determined by the legal requirements, on one hand, and by the desired effect, on the other; preferably, 6 to 12 wt % solutions in water are used. Oxidatives that are preferred according to the invention are characterized in that they contain 0.5 to 20 wt %, preferably 1 to 12.5 wt %, especially preferably 2.5 to 10 wt %, and, in particular, 3 to 8 wt % hydrogen peroxide, relative in each case to the total weight of the oxidative dyeing agent.
In a further particularly preferred embodiment, an agent according to the invention is thus characterized in that it contains:
(d) at least one oxidizing agent from the group consisting of hydrogen peroxide and its addition products to organic or inorganic compounds.
In a particularly preferred embodiment, an agent according to the present invention is characterized in that it contains, relative to the total weight of the agent, 0.5 to 20 wt %, preferably 1 to 12.5 wt %, more preferably 2.5 to 10 wt %, and particularly preferably 3 to 8 wt % hydrogen peroxide (d).
Furthermore, the agents according to the invention can optionally contain at least one direct dye. These are dyes which are drawn directly onto the hair and which do not require an oxidative process in order to form the color. Direct dyes are typically nitrophenylene diamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols.
The direct dyes are each used preferably in an amount of from 0.001 to 20 wt %, and in particular from 0.05 to 5 wt %, in each case in relation to the total preparation for use. The total quantity of direct dyes is preferably at most 3 wt %.
Direct dyes can be divided into anionic, cationic, and non-ionic direct dyes, which are selected and used by a person skilled in the art according to the requirements of the support base.
Preferred anionic direct dyes are the compounds known under the international names or trade names, Bromphenolblau, Tetrabromphenolblau, Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57:1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1, and Acid Black 52.
Preferred cationic direct dyes are Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347/Dystar), HC Blue No. 16, Basic Blue 99, Basic Brown 16, Basic Brown 17, Yellow 87, Basic Orange 31, and Basic Red 51.
In particular, non-ionic nitro dyes and quinone dyes and neutral azo dyes are suitable as non-ionic direct dyes. Preferred non-ionic direct dyes are the compounds known under the international names or trade names, HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis-(2-hydroxyethyl)amino-2-nitrobenzene, 3-nitro-4-(2-hydroxyethyl)aminophenol, 2-(2-hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-amino-4-(2-hydroxyethyl)amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene, 2-[(4-amino-2-nitrophenyl)amino]benzoic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and salts thereof, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid, and 2-chloro-6-ethylamino-4-nitrophenol.
Coloring processes on keratin fibers typically take place in an alkaline environment. To protect the keratin fibers as well as the skin as much as possible, however, it is not desirable to adjust to too high a pH value. It is therefore preferred if the pH of the ready-to-use agent is between 6 and 11, and in particular between 7 and 10.5. The pH values in the sense of the present invention are pH values which have been measured at a temperature of 22° C.
The alkalinizing agents that can be used to adjust the preferred pH according to the invention can be selected from the group formed by ammonia, alkanolamines, basic amino acids, and inorganic alkalinizing agents such as alkali (alkaline earth) metal hydroxides, alkali (alkaline earth) metal metasilicates, alkali (alkaline earth) metal phosphates, and alkali (alkaline earth) metal hydrogen phosphates. Preferred inorganic alkalinizing agents are magnesium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, and sodium metasilicate. Organic alkalizing agents that can be used according to the present invention are preferably selected from monoethanolamine, 2-amino-2-methylpropanol, and triethanolamine. The basic amino acids that can be used as an alkalizing agent according to the present invention are preferably selected from the group consisting of arginine, lysine, ornithine, and histidine, and especially preferably arginine.
Preferably, an emulsifier or a surfactant is also added to the oxidative dyeing agents, wherein surface-active substances are referred to as surfactants or emulsifiers depending upon the field of application and are selected from anionic, cationic, zwitterionic, amphoteric, and non-ionic surfactants and emulsifiers.
In a further very particularly preferred embodiment, an agent according to the invention is therefore characterized in that it contains at least one surfactant selected from the group consisting of anionic, amphoteric, zwitterionic, and non-ionic surfactants.
Suitable anionic surfactants in agents according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group, such as for example a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol ether or polyglycol ether groups, ester, ether and amide groups, and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium, and ammonium, and mono-, di-, and trialkanol ammonium salts having 2 to 4 carbon atoms in the alkanol group,
in which R preferably represents an aliphatic, optionally unsaturated hydrocarbon functional group having 8 to 30 carbon atoms, R′ represents hydrogen, a functional group (CH2CH2O)yR, and x and y independently of one another represent a number from 1 to 10,
Preferred anionic surfactants are alkyl sulfates, alkyl ether sulfates, and ethercarboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.
Surface-active compounds that carry, in the molecule, at least one quaternary ammonium group and at least one carboxylate, sulfonate, or sulfate groups are referred to as zwitterionic surfactants. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethyl ammonium glycinates, e.g., cocoalkyl dimethyl ammonium glycinate, N-acyl-aminopropyl-N,N-dimethyl ammonium glycinates, e.g., cocoacyl aminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group, and cocoacyl aminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name, Cocamidopropyl Betaine.
Amphoteric surfactants are understood to be surface-active compounds which, in addition to a C8-C24 alkyl or acyl group, also contain at least one free amino group and at least one —COOH—or —SO3H group in the molecule and are capable of forming inner salts. Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids, and alkylaminoacetic acids having in each case about 8 to 24 carbon atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-coco-alkylaminopropionate, coco-acylaminoethylaminopropionate, and C12-C18 acyl sarcosine.
It has also proven to be advantageous if the coloring and lightening agents according to the invention contain further, non-ionogenic surface-active substances. Non-ionic surfactants contain, as a hydrophilic group, e.g., a polyol group, a polyalkylene glycol ether group, or a combination of a polyol group and polyglycol ether group. Such compounds include, for example
Particularly suitable non-ionic surfactants are C8-C22 alkyl monoglycosides and oligoglycosides and their ethoxylated analogs. In particular, non-ethoxylated compounds have proven to be particularly suitable.
Particularly preferred are those alkyl polyglycosides of the formula RO-(Z)x where R
These compounds are characterized in that any mono- or oligosaccharides can be used as sugar building block Z. Usually, sugars with 5 or 6 carbon atoms as well as the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose, and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose, and sucrose; glucose is particularly preferred.
The alkylpolyglycosides which can be used according to the invention contain on average 1.1 to 5 sugar units. Alkylpolyglycosides having x values of 1.1 to 2.0 are preferred. Very particular preference is given to alkylglycosides in which x is 1.1 to 1.8.
The alkoxylated homologs of said alkylpolyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and/or propylene oxide units per alkylglycoside unit.
Addition products of alkylene oxide to saturated linear fatty alcohols and fatty acids containing from 2 to 30 mol ethylene oxide per mol of fatty alcohol or fatty acid, have proved to be suitable as further preferred non-ionic surfactants. Preparations with excellent properties are likewise obtained if they contain fatty acid esters of ethoxylated glycerol as the non-ionic surfactants.
Particularly preferred non-ionogenic surface-active substances are, because of the simple processability, substances which are commercially available in pure form as solids or liquids. In this connection, the definition of purity does not refer to chemically pure compounds. Instead-particularly if they are products on a natural basis-mixtures of different homologs can be used, e.g., with various alkyl chain lengths, as obtained in products based upon natural fats and oils. Mixtures of different degrees of alkoxylation are usually also present in alkoxylated products. In this connection, the term, purity, instead refers to the fact that the selected substances shall preferably be free of solvents, set-up agents, and other accompanying substances.
Products with a “normal” homolog distribution as well as those with a narrow homolog distribution may be used as surfactants which are addition products of ethylene and/or propylene oxide to fatty alcohols, or derivatives of said addition products. “Normal” homolog distribution is to be understood in this case as mixtures of homologs which are obtained when reacting fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides, or alkali metal alkoxides as catalysts. In contrast, a narrow homolog distribution is obtained when hydrotalcites, alkaline-earth metal salts of ether carboxylic acids, alkaline-earth metal oxides, hydroxides, or alkoxides, for example, are used as catalysts. The use of products with a narrow homolog distribution range may be preferred.
The anionic, non-ionic, zwitterionic, or amphoteric surfactants are used in amounts of 0.1 to 45 wt %, preferably 1 to 30 wt %, and very particularly preferably 1 to 15 wt %, relative to the total amount of the ready-to-use agent.
Also preferred according to the invention are cationic surfactants of the quaternary ammonium compound, esterquats, and amidoamine type. Preferred quaternary ammonium compounds are ammonium halides, and in particular chlorides and bromides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides, and trialkyl methyl ammonium chlorides, e.g., cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, and tricetyl methyl ammonium chloride, and the imidazolium compounds known under the INCI names, Quaternium-27 and Quaternium-83. The long alkyl chains of the aforementioned surfactants preferably have 10 to 18 carbon atoms. The quaternized protein hydrolysates represent other cationic surfactants that can be used according to the invention.
The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid fractions with dialkylaminoamines and are characterized by their good biodegradability alongside a good conditioning effect. One compound from this substance group which is particularly suitable according to the invention is the stearamidopropyl dimethylamine available commercially under the name, Tegoamid® S 18.
Also highly biodegradable are quaternary ester compounds-so-called “esterquats.” Esterquats are known substances that contain both at least one ester function and at least one quaternary ammonium group as structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines, and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold for example under the trademarks, Stepantex®, Dehyquart®, and Armocare®. The products, Armocare® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethyl ammonium chloride, and Dehyquart® F-75, Dehyquart® C-4046, Dehyquart® L80, and Dehyquart® AU-35 are examples of such esterquats.
The cationic surfactants are contained in the agents used according to the invention preferably in amounts of 0.05 to 10 wt %, relative to the total agent. Particular preference is given to amounts of 0.1 to 5 wt %.
In one preferred embodiment, preference may be given to non-ionic, zwitterionic, and/or amphoteric surfactants and mixtures thereof.
In a further preferred embodiment, the effect of the active ingredient according to the invention can be enhanced by emulsifiers. Such emulsifiers are, for example
The agents according to the invention contain the emulsifiers preferably in amounts of 0.1 to 25 wt %, and in particular 0.5 to 15 wt %, relative to the total amount of the ready-to-use agent. According to the invention, particular preference may be given to non-ionogenic emulsifiers and surfactants having an HLB value of 10-15. Among these emulsifier types, very particular preference may be given to those emulsifiers which contain no ethylene oxide and/or propylene oxide in the molecule.
Further work has shown that the oxidative formation of intense colorations from the components (a), (b), and (c) functions in particular in the cosmetic carrier formulations the fat component content of which is not excessively high. A strong color application was then observed in particular if, relative to the total weight of the agent, the total amount of the fatty components contained in the agent was below 25 wt %, preferably below 20 wt %, more preferably below 15 wt %, and very particularly preferably below 13 wt %.
In a further preferred embodiment, an agent according to the invention is characterized in that, relative to the total weight of the agent, the total amount of the fatty components contained in the agent is below 25 wt %, preferably below 20 wt %, further preferably below 15 wt %, and very particularly preferably below 13 wt %.
“Fatty components” in the sense of the invention are understood to be organic compounds with a solubility in water of less than 1 wt %, and preferably less than 0.1 wt % at room temperature (22° C.) and atmospheric pressure (760 mmHg).
Under the definition of fat components fall explicitly only uncharged (i.e., non-ionic) compounds. Fat constituents have at least one saturated or unsaturated alkyl group having at least 8 C atoms. The molecular weight of the fat component is at most 5,000 g/mol, preferably at most 2,500 g/mol, and particularly preferably at most 1,000 g/mol. The fat components are either polyoxyalkylated or polyglycerylated compounds.
Fatty components in this connection are understood to be components from the group consisting of C12-C30 fatty alcohols, C12-C30 fatty acid triglycerides, and/or hydrocarbons. In the sense of the present invention, only non-ionic substances are explicitly considered fatty components. Charged compounds, such as fatty acids and salts thereof, are not understood to be fatty components.
C12-C30 fatty alcohols can be saturated, mono-or polyunsaturated, linear, or branched fatty alcohols having 12 to 30 C atoms.
Examples of preferred linear, saturated C12-C30 fatty alcohols are dodecan-1-ol (dodecyl alcohol, lauryl alcohol), tetradecan-1-ol (tetradecyl alcohol, myristyl alcohol), hexadecan-1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol), octadecan-1-ol (octadecyl alcohol, stearyl alcohol), arachyl alcohol (eicosan-1-ol), heneicosyl alcohol (heneicosan-1-ol), and/or behenyl alcohol (docosan-1-ol).
Linear unsaturated fatty alcohols are, for example, (9Z)-octadec-9-en-1-ol (oleyl alcohol), (9E)-octadec-9-en-1-ol (elaidyl alcohol), (9Z,12Z)-octadeca-9,12-dien-1-ol (linoleyl alcohol), (9Z,12Z,15Z)-octadeca-9,12,15-trien-1-ol (linolenoyl alcohol), gadoleyl alcohol ((9Z)-eicos-9-en-1-ol), arachidone alcohol ((5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraen-1-ol), erucyl alcohol ((13Z)-docos-13-en-1-ol), and/or brassidyl alcohol ((13E)-docosen-1-ol).
By a C12-C30 fatty acid triglyceride in the sense of the present invention are understood the triesters of trivalent alcohol glycerol with three equivalents of fatty acid. Both structurally similar and different fatty acids may be involved in the ester formation within a triglyceride molecule.
According to the invention, fatty acids are to be understood as saturated or unsaturated, unbranched or branched, unsubstituted or substituted C12-C30 carboxylic acids. Unsaturated fatty acids may be mono-unsaturated or poly-unsaturated. With an unsaturated fatty acid, the C-C double bond(s) thereof may have the cis or trans configuration.
Esters based upon glycerol with a fatty acid can be specified as fatty acid triglycerides, wherein the fatty acid is selected from the group consisting of dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), tetracosanoic acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), petroselinic acid [(Z)-6-octadecenoic acid], palmitoleic acid [(9Z)-hexadec-9-enoic acid], oleic acid [(9Z)-octadec-9-enoic acid], elaidic acid [(9E)-octadec-9-enoic acid], erucic acid [(13Z)-docos-13-enoic acid], linoleic acid [(9Z,12Z)-octadeca-9,12-dienoic acid], linolenic acid [(9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid], eleostearic acid [(9Z,11E,13E)-octadeca-9,11,3-trienoic acid], arachidonic acid [(5Z,8Z,11Z,14Z) -eicosa-5,8,11,14-tetraenoic acid], and/or nervonic acid [(15Z)-tetracos-15-enoic acid].
The fatty acid triglycerides may also be of natural origin. The fatty acid triglycerides or mixtures thereof, e.g., corresponding natural fatty acid triglycerides, occurring in soybean oil, peanut oil, olive oil, sunflower oil, macadamia nut oil, moringa oil, apricot kernel oil, marula oil, and/or optionally hydrogenated castor oil.
Hydrocarbons are compounds composed exclusively of carbon and hydrogen atoms and having 8 to 80 C atoms. Especially preferred in this context are aliphatic hydrocarbons, such as mineral oils, liquid paraffin oils (e.g., paraffinum liquidum or paraffinum perliquidum), isoparaffin oils, semisolid paraffin oils, paraffin waxes, solid paraffin (paraffinum solidum), Vaseline, and polydecene.
In this respect, liquid paraffin oils (paraffinum liquidum and paraffinum perliquidum) have proven to be particularly suitable. The hydrocarbon is very particularly preferably paraffinum liquidum, also referred to as white oil. Paraffinum liquidum is a mixture of purified, saturated, aliphatic hydrocarbons, consisting mainly of hydrocarbon chains having a C-chain distribution of from 25 to 35 C atoms.
Furthermore, it has proved advantageous if the according to the invention contain at least one stabilizer or complexer. Conventional complexing agents and stabilizers that are preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylene diamine tetra acetic acid (EDTA), N-hydroxyethyl ethylene diamine triacetic acid, diethylene triamine penta acetic acid (DTPA), ethylene diamine disuccinic acid (EDDS), hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserindiacetic acid, N,N-di-(2-hydroxyethyl)glycine, N-(1,2-dicarboxy-2-hydroxyethyl) glycine, N-(1,2-dicarboxy-2-hydroxyethyl)aspartic acid or nitrilotriacetic acid (NTA), ethylene diamine diglutaric acid (EDGA), 2-hydroxypropylene diamine disuccinic acid (HPDS), glycinamide-N,N′-disuccinic acid (GADS), ethylene diamine-N-N′-diglutaric acid (EDDG), 2-hydroxypropylene diamine-N-N′-disuccinic acid (HPDDS), diaminoalkyldi-(sulfosuccinic acid) (DDS), ethylenedicysteic acid (EDC), ethylene diamine-N-N′-bis-(ortho-hydroxyphenyl)acetic acid (EDDHA), N-2-hydroxyethylamine-N,N-diacetic acid, glyceryliminodiacetic acid, iminodiacetic acid-N-2-hydroxypropylsulfonic acid, aspartic acid-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonic acid, B-alanine-N,N′-diacetic acid, aspartic acid-N,N′-diacetic acid, aspartic acid-N-monoacetic acid, dipicolinic acid, and salts and/or derivatives thereof, geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), the higher homologs thereof with up to 8 carbon atoms, and also derivatives thereof containing hydroxy or amino groups and 1-aminoethane-1,1-diphosphonic acid, the higher homologs thereof with up to 8 carbon atoms, and also derivatives containing hydroxy or amino groups, aminophosphonic acids such as ethylene diamine tetra(methylene phosphonic acid) (EDTMP), diethylene triamine penta(methylene phosphonic acid) (DTPMP), and higher homologs thereof, or nitrilotris(methylene phosphonic acid), phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, cyclodextrins, and alkali stannates (sodium stannate), alkalipyrophosphates (tetrasodiumpyrophosphate, disodiumpyrophosphate), alkaliphosphates (sodium phosphate), and phosphoric acid and salts thereof.
In the alkali pH values required according to the invention of the treatment solutions, these complexers are present at least partially as anions. It does not matter whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, preference is given to alkali, ammonium, or alkyl ammonium salts, and in particular sodium salts.
Complexers preferred according to the invention are nitrogen-containing polycarboxylic acids, in particular EDTA, and phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or the di- or tetrasodium salt thereof, and/or ethylene diamine tetramethylene phosphonate (EDTMP) or the hexasodium salt thereof, and/or diethylene triamine pentamethylene phosphonate (DTPMP) or the hepta-or octasodium salt thereof.
The dyes according to the invention can preferably contain further auxiliary substances and additives. For instance, it has proven to be preferred according to the invention if the agents contain at least one thickening agent. There are no basic restrictions with regard to these thickeners. Both organic and purely inorganic thickeners may be used.
According to a first preferred embodiment, the thickening agent is an anionic, synthetic polymer. Preferred anionic groups are the carboxylate group and the sulfonate group.
The examples of anionic monomers which the polymeric anionic thickener may consist of are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, and 2-acrylamido-2-methylpropanesulfonic acid. Here, the acidic groups may be present wholly or partly as sodium-, potassium-, ammonium-, mono-, or triethanol ammonium salt. Preferred monomers are maleic acid anhydride, and in particular, 2-acrylamido-2-methylpropane sulfonic acid and acrylic acid.
Preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Here, allyl ethers of pentaerythritol, sucrose, and propylene may be preferred crosslinking agents. Such compounds are commercially available, for example, under the trade name, Carbopol®. Also preferred is the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid, which is commercially available, for example, under the name, Rheothik® 11-80.
Within this first embodiment, it may further be preferred to use copolymers of at least one anionic monomer and at least one non-ionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred non-ionic monomers are acrylamide, methacrylamide, acrylic acid esters, methacrylic acid esters, itaconic acid monoesters and diesters, vinyl pyrrolidinone, vinyl ethers, and vinyl esters.
The anionic acrylic acid and/or methacrylic acid polymers or copolymers are contained in the agents according to the invention preferably in an amount of 0.1 to 10 wt %, and particularly preferably 1 to 5 wt %, in each case relative to the weight of the agent.
Preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C1-C6 alkyl esters, such as are marketed under the INCI name, Acrylate Copolymers. One preferred commercial product is Aculyn® 33 from Rohm & Haas, for example. However, copolymers of acrylic acid, methacrylic acid, or their C1-C6 alkyl esters and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol are further preferred. Suitable ethylenically unsaturated acids are in particular acrylic acid, methacrylic acid, and itaconic acid, and suitable alkoxylated fatty alcohols are in particular Steareth-20 or Ceteth-20. Such copolymers are marketed by Rohm & Haas under the trade name, Aculyn® 22, and by National Starch under the trade names, Structure® 2001 and Structure® 3001.
Further preferred anionic copolymers are acrylic acid-acrylamide-copolymers as well as, particularly, polyacrylamide copolymers with monomers containing sulfonic acid groups. A particularly preferred anionic copolymer consists of 70 to 55 mol % acrylamide and 30 to 45 mol % 2-acrylamido-2-methylpropane sulfonic acid, wherein the sulfonic acid group is wholly or partially present as sodium-, potassium-, ammonium-, mono-, or triethanol ammonium salt. This copolymer can also be crosslinked, wherein preferably polyolefinically unsaturated compounds such as tetraallyloxythane, allylsucrose, allylpentaerythritol, and methylene-bisacrylamide are used as crosslinking agents. Such a polymer is contained in the commercial products, Sepigel® 305 and Simulgel® 600, from the company SEPPIC. The use of these compounds, which contain a hydrocarbon mixture (C13-C14 isoparaffin or isohexadecane) and a non-ionic emulsifier (laureth-7 or polysorbate-80) in addition to the polymer components, has proved to be particularly advantageous in the context of the teaching of the invention.
Also, polymers of maleic acid anhydride and methyl vinyl ether, and in particular those with crosslinks, are preferred thickeners. The maleic acid methyl-vinyl ether-copolymer crosslinked with 1,9-decadiene is available under the name, Stabileze® QM.
According to another embodiment, the thickener is a cationic synthetic polymer. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded to a polymer backbone built-up of acrylic acid, methacrylic acid, or derivatives thereof via a C1-C4 hydrocarbon group have been found to be particularly suitable.
Homopolymers of general formula (HP-1),
in which R1 =—H or —CH3, R2, R3, and R4 independently of one another are selected from C1-C4 alkyl, alkenyl, or hydroxyalkyl groups, m=1, 2, 3, or 4, n is a natural number, and X-is a physiologically tolerated organic or inorganic anion, as well as copolymers consisting substantially of the monomer units shown in formula (HP-1) and non-ionogenic monomer units, are particularly preferred cationic polymeric gel formers. In the context of these polymers, those are preferred according to the invention for which at least one of the following conditions applies:
As a physiologically tolerated counter ion X-, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions, as well as organic ions such as lactate-, citrate-, tartrate-, and acetate ions are considered. Halide ions are preferred, and in particular chloride.
A particularly suitable homopolymer is the poly (methacryl oxyethyl trimethyl ammonium chloride) (crosslinked, if desired) having the INCI name, Polyquaternium-37. The crosslinking can be carried out, if desired, with the help of olefinically unsaturated compounds, e.g., divinyl benzene, tetraallyloxyethane, methylene bisacrylamide, diallyl ether, polyallyl polyglyceryl ether, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose, or glucose. Methylene bisacrylamide is a preferred crosslinking agent.
The homopolymer is preferably used in the form of a non-aqueous polymer dispersion, which should have a polymer content of not less than 30 wt %. Such polymer dispersions are commercially available under the names, Salcare® SC 95 (approx. 50% polymer content, further component: mineral oil (INCI name: mineral oil) and tridecyl-polyoxypropylene-polyoxyethylene ether (INCI name: PPG-1-trideceth-6), and Salcare® SC 96 (approx. 50% polymer content, further components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: propylene glycol dicaprylate/dicaprate), and tridecyl-polyoxypropylene-polyoxyethylene ether (INCI name: PPG-1-trideceth-6).
Copolymers comprising monomer units according to formula (HP-1) contain as non-ionogenic monomer units preferably acrylamide, methacrylamide, acrylic acid C1-C4 alkyl ester, and methacrylic acid C1-C4 alkyl ester. Among these non-ionic monomers, acrylamide is particularly preferred. These copolymers can also be cross-linked like the homopolymers described above. A preferred copolymer according to the invention is a crosslinked acrylamide methacroyl oxyethyl trimethyl ammonium chloride copolymer. Such copolymers, in which the monomers are present in a weight ratio of about 20:80, are commercially available as approx. 50% non-aqueous polymer dispersion under the name, Salcare® SC 92.
In another preferred embodiment, naturally occurring thickeners are used. Preferred thickeners of this embodiment are, for example, non-ionic guar gums. According to the invention, both modified and unmodified guar gums can be used. Unmodified guar gums are marketed, for example, under the trade name, Jaguar® C, from Rhone Poulenc. Modified guar gums which are preferred according to the invention contain C1-C6 hydroxyalkyl groups. The groups are preferably hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl. Such modified guar gums are well known in the art and can be prepared, for example, by reacting the guar gums with alkylene oxides. The degree of hydroxyalkylation, which corresponds to the number of used alkylene oxide molecules in proportion to the number of the free hydroxyl groups of guar gum, is preferably between 0.4 to 1.2. Such modified guar gums are commercially available under the trade names, Jaguar® HP8, Jaguar® HP60, Jaguar® HP120, Jaguar® DC 293, and Jaguar® HP105 from Rhone Poulenc.
Further suitable natural thickening agents are also already known from the prior art.
According to this embodiment, biosaccharide gums of microbial origin, such as scleroglucan gums or xanthan gums, gums from plant exudates, such as gum arabic, ghatti gum, karaya gum, tragacanth gum, carrageenan gum, agar-agar, locust bean gum, pectins, alginates, starch fractions and derivatives, such as amylose, amylopectin, and dextrins, cellulose derivatives such as methyl cellulose, carboxyalkyl celluloses, and hydroxyalkyl celluloses, are preferred.
Preferred hydroxyalkyl celluloses are, in particular, the hydroxyethyl celluloses, which are marketed under the names, Cellosize® by Amerchol and Natrosol® by Hercules. Suitable carboxyalkyl celluloses are particularly the carboxymethyl celluloses as marketed under the names, Blanose® by Aqualon, Aquasorb® and Ambergum® by Hercules, and Cellgon® by Montello.
Preference is also given to starch and derivatives thereof. Starch is a storage material of plants, which occurs mainly in tubers and roots, in grain seeds, and in fruits, and can be obtained from a variety of plants in high yield. The polysaccharide, which is insoluble in cold water and forms a colloidal solution in boiling water, for example, can be obtained from potatoes, manioc, sweet potatoes, maranta, corn, grains, rice, legumes such as peas and beans, bananas, or the marrow of certain types of palm (for example, the sago palm). According to the invention, natural, plant-derived starches and/or chemically or physically modified starches can be used. Modification can be achieved, for example, by introducing different functional groups on one or more of the hydroxyl groups of the starch. These are usually esters, ethers, or amides of starch having optionally substituted C1-C40 functional groups. Particularly advantageous is an etherified corn starch with a 2-hydroxypropyl group, as it is marketed, for example, by the company National Starch under the trade name, Amaze®.
However, non-ionic, fully-synthetic polymers, such as for example polyvinyl alcohol or polyvinyl pyrrolidone, can also be used as thickening agents according to the invention. Preferred non-ionic, fully-synthetic polymers are marketed for example by the company BASF under the trade name, Luviskol®. Such non-ionic polymers also allow, in addition to their excellent thickening properties, a significant improvement in the sensory feeling of the resulting preparations.
As inorganic thickeners, phyllosilicates (polymeric, crystalline sodium disilicates) have proven to be particularly suitable in the sense of the present invention. In particular tone, and in particular, magnesium aluminum silicates, such as bentonite, and particularly smectites, such as montmorillonite or hectorite, which may also be optionally suitably modified, and synthetic phyllosilicates, such as the magnesium phyllosilicates marketed by the company Sud Chemie under the trade name, Optigel®, are preferred.
To further increase the performance of the oxidative dyeing agents, at least one, optionally hydrated, SiO2 compound is preferably additionally added. It may be preferred according to the invention to use the optionally hydrated SiO2 compounds in amounts of 0.05 wt % to 15 wt %, particularly preferably in amounts of 0.15 wt % to 10 wt %, and very particularly preferably in amounts of 0.2 wt % to 5 wt %, in each case relative to the agent according to the invention. The specified amounts in each case reflect here the content of the SiO2 compounds (without the water content thereof) in the agents.
With regard to the optionally hydrated SiO2 compounds, the present invention is in principle subject to no limitations. Preference is given to silicic acids, oligomers and polymers thereof, and also salts thereof. Preferred salts are the alkali metal salts, and in particular the potassium and sodium salts. The sodium salts are very particularly preferred.
The optionally hydrated SiO2 compounds may be present in different forms. According to the invention, preference is given to using the SiO2 compounds in the form of silica gels, or particularly preferably as water glass. These SiO2 compounds may sometimes be present in aqueous solution.
Very particularly preferred according to the invention are water glasses, which are formed from a silicate of formula (SiO2)n(Na2O)m(K2O)p, where n represents a positive rational number, and m and p, independently of one another, represent a positive rational number or 0, with the proviso that at least one of the parameters m or p be different from 0, and the ratio between n and the sum of m and p be between 2:1 and 4:1. Preference is given to metasilicates in which the ratio between n and the sum of m and p is 1.2 or below.
Besides the components described by the empirical formula, the water glasses may also contain further additives in small amounts, such as for example phosphates or magnesium salts.
Water glasses which are particularly preferred according to the invention are marketed, inter alia, by Henkel under the names, Ferrosil® 119, Natronwasserglas 40/42, Portilc A, Portil® AW, and Portil® W, and by Akzo under the name, Britesil® C20.
The oxidative dyeing agents are preferably packaged as flowable preparations.
The agents according to the invention may also contain further active substances, auxiliaries, and additives, such as for example
The selection of these additional substances is made by the person skilled in the art according to the desired properties of the agents.
With respect to other optional components and the employed amounts of said components, reference is made expressly to relevant manuals known to the person skilled in the art, e.g., K h. Schrader, Grundlagen und Rezepturen der Kosmetika, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.
The additional active ingredients and auxiliaries are used in the agents according to the invention preferably in quantities of, in each case, 0.0001 to 10 wt %, and in particular 0.0005 to 5 wt %, relative to the total weight of the application mixture.
The agents according to the invention are agents for oxidatively dyeing or dyeing and lightening hair. In the ready-to-use agent, the oxidation dye precursors react with the oxidizing agent to form the actual dyes. The agents according to the invention are therefore usually packaged as multi-component agents, and usually as two-component agents. The first component here contains the oxidation dye precursors (a) and (b) and isatin (c), which is mixed shortly before application with a second component containing the oxidizing agent (d). Usually, both components are mixed with one another in a ratio of 1:3 to 3:1, and preferably 1:2 to 2:1. This mixture of the component-containing color cream and optionally alkalizing agent and the component-containing oxidizing agent is referred to as the application mixture or the ready-to-use agent.
A second subject matter of the present invention is a multi-component packaging unit (kit-of-parts) for oxidatively dyeing keratinous fibers, and in particular human hair, comprising, packaged separately from one another,
Alternatively, the dyeing agent can also be referred to as color cream.
The oxidative dyeing agent according to the invention of the first subject matter of the invention or the multicomponent packaging unit, the separately packaged components of which are used for producing this ready-to-use dyeing agent, are outstandingly suitable for use in corresponding dyeing methods.
A further subject matter of the present invention is therefore a method for oxidatively dyeing keratinous fibers, and in particular human hair, in which an agent as disclosed in detail in the description of the first subject matter of the invention is applied to the keratin fibers and rinsed out again after an exposure time.
While the fibers are being exposed to the agent, it can be advantageous to support the dyeing process by applying heat. Heat can be applied by an external heat source, such as, for example, hot air from a hot-air blower, and also-particularly in the case of dyeing the hair of a living subject-by the body temperature of the subject. In the latter possibility, conventionally, the part to be dyed is covered with a cap. In particular, the temperature during the exposure time is between 10° C. and 45° C., and in particular between 20° C. and 40° C. The dyeing agents according to the invention already give intense colorations at physiologically tolerated temperatures below 45° C. Therefore, they are suitable particularly for coloring human hair.
What has been stated regarding the agents according to the present invention also applies, mutatis mutandis, to additional preferred embodiments of the multicomponent packaging unit and method according to the present invention.
The following recipes were produced. Unless otherwise noted, the quantitative data are given in weight percent in each case.
The base formulation for the color cream described in Table 1 was prepared. The mixtures of oxidation dye precursors described in Tables 3 or 4 were each incorporated into the color cream. Each of the color creams produced in this way was mixed in a quantitative ratio of 1:1 with the oxidizing agent preparation OX. Each of the application-ready dyeing agents prepared in this way was then applied to a hair strand (Kerling, natural white) and left there for a period of 30 minutes. The application mixture was then rinsed out with a shampoo and dried. The hair strands were then measured colorimetrically (measurement of the lab values).
The ready-to-use dyeing agents that have been obtained with the color creams F2, F4, and F6 colored the hair in very intense, natural shades in the range of dark brown, medium brown, and dark blonde. The shade effect of these colorations was in almost exact color alignment with the resorcinol-containing dyeing agents known from the prior art based upon the color creams F1, F3, and F5.
Shades in the natural tone range with reddish hue could also be obtained by using dyeing agents according to the invention using the color creams F8, F10, and F12. The shades in the red-blonde and copper-blonde range also aligned very well in terms of color with the resorcinol-containing dyeing agents known from the prior art based upon the color creams F7, F9, and F11.
For further colorations, the base formulation described in Table 1 was prepared for the color cream. The mixtures of oxidation dye precursors described in Table 4 were each incorporated into the color cream. Each of the color creams produced in this way was mixed in a quantitative ratio of 1:1 with the oxidizing agent preparation OX. Each of the ready-to-use dyeing agents thus produced was then applied to a hair strand (Kerling, natural white) and left there for a period of 30 minutes. The application mixture was then rinsed out with a shampoo and dried. Thereafter, the hair strands were colorimetrically measured (measurement of the lab values).
| Number | Date | Country | Kind |
|---|---|---|---|
| 102022202753.1 | Mar 2022 | DE | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/EP2023/050060 | Jan 2023 | WO |
| Child | 18890167 | US |
