WO2012079952A2 - Brightening agent composed of molded bodies and containing acylpyridinium compounds - Google Patents

Abstract

The invention relates to a molded body which contains at least one acylpyridinium derivative of formula (I), and to agents for brightening keratin fibers that are produced by dissolving and/or dispersing such a molded body with the aid of an oxidant preparation.

Description

 "Lightening agent of moldings containing acylpyridinium compounds"

The present invention relates to agents for brightening keratinic fibers, in particular human hair, containing a special bleach activator.

The change of hair color is an important area of modern cosmetics dar. For the purpose of brightening your own hair color or for bleaching market different Blondiermittel with different Blondierleistung are available. The basics of the Blondierverfahren are known in the art and can be found in relevant monographs, eg. B. Kh. Schräder, Basics and Formulations of Cosmetics, 2nd edition, 1989, Dr. med. Alfred Hüthig Verlag, Heidelberg, or W. Limbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York, be read.

The oxidizing agents contained in Blondiermitteln are able to lighten the hair fiber by the oxidative destruction of the hair dye melanin. For a moderate bleaching effect, the use of hydrogen peroxide - preferably using ammonia or other alkalizing agents - is sufficient as the oxidizing agent alone; to achieve a greater bleaching effect, a mixture of hydrogen peroxide and peroxodisulfate salts is usually employed. However, the whitening is also accompanied by damage to the hair, since not only the natural coloring components of the hair, but also the other structural components of the hair are oxidatively damaged. Depending on the severity of the degree of damage, this ranges from rough, brittle and difficult to comb hair over a reduced resistance and tear resistance of the hair to hair breakage. With larger amounts of hydrogen peroxide and optionally the peroxodisulfates are usually accompanied by greater damage to the keratin. Although bleaching agents hitherto on the market generally show good lightening performance, they can not be considered optimal due to hair damage, long application times and the possible skin irritation due to the high concentrations of oxidizing and alkalizing agents. There is therefore still a need for lightening agents which show good lightening performance without at the same time damaging the hair fiber.

Usually bleaching agents containing hydrogen peroxide are used as a two-component system, wherein the first component consists of an aqueous hydrogen peroxide solution, for example in the form of an emulsion or dispersion, and the second component is in the form of an alkaline cream base.

For the strong lightening of very dark hair, the sole use of hydrogen peroxide or its addition products to organic or inorganic compounds is often not sufficient. In these cases, a combination of hydrogen peroxide and Peroxomonosulfaten or peroxodisulfates is usually used. The persulfates are the Blondiermitteln usually added as a third component, usually powdered or pasty. However, mixtures of hydrogen peroxide and persulfates are very strong oxidants that expose the keratin fibers to be blended to extremely harsh oxidative conditions associated with severe damage. Therefore, it appears advantageous with respect to a gentle bleaching, if the addition of persulfates can be minimized.

An enhancement of the whitening effect in the bleaching of hair with the aid of a combination of certain acylpyridinium derivatives and hydrogen peroxide is known from the document WO 2009/135700 A1.

In the course of further work with certain acylpyridinium derivatives, however, it has been found that their formulation in the form of aqueous emulsions, creams or gels can lead to problems in terms of storage stability. When stored in dissolved form, the lightening enhancing effect of the acylpyridinium derivatives, especially at too high pH values of the solution, can not be maintained for a long time.

It was therefore the object of the present invention to provide an application possibility for acylpyridinium derivatives as activators of the whitening action in bleaching agents, which ensures a high stability of these compounds even during prolonged storage.

It has now surprisingly been found that the use of certain moldings containing acylpyridinium compounds as bleach activators, bleaching agents are obtained which can be significantly improved in terms of their whitening performance and in particular with regard to their storage stability.

The molded articles contain the acylpyridinium compounds as a solid in powder or tablet form. Immediately before use, these are then dissolved with stirring in water. When using the Acylpyridiniumderivate as a solid whose solution behavior is crucial. There must be no clumping of the solid, which would greatly affect the brightening performance. In addition to the optimal rheological properties of the ready-to-use colorant, rapid dissolution of the tablet is therefore also desirable.

The shaped bodies according to the invention are distinguished by optimized properties with regard to dusting behavior, the completeness of the dissolution and the speed of the dissolving process.

A first subject of the invention is therefore a shaped body containing at least one acylpyridinium derivative of the formula (I),

(I), in which

R _{1 is} a C ₁ -C ₅ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, a carboxy-C ₂ -C ₆ alkyl group, an aryl-C 1 -C 4 -alkyl group, a heteroaryl-C 1 -C 4 -alkyl group, an aryl group or a heteroaryl group,

 R 2, R 3 and R 4 each independently represent hydrogen, a C 6 -C 6 alkyl group

Halogen atom or a C _r C ₆ acyl group, with the proviso that at least one of R 2, R 3 and R 4 is a C 1 -C 4 acyl group, and

X ^"stands for a physiologically acceptable anion.

The moldings according to the invention may have any geometric shape, such as concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal and octagonal prismatic as well as rhombohedral forms. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. The training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with a circular or oval cross-section and shaped bodies with spherical geometry are inventively preferred. Particularly preferred are shaped bodies in the form of spherical geometry.

The cylindrical configuration detects the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter greater than 1. If the base molding has corners and edges, these are preferably rounded off. As additional optical differentiation is an embodiment with rounded corners and beveled edges.

The spherical design comprises not only a spherical shape but also a hybrid of spherical and cylindrical shape, wherein each base of the cylinder is capped with a hemisphere. The hemispheres preferably have a radius of about 4 mm and the entire shaped body of this embodiment has a length of 12 to 14 mm.

An inventive shaped body with a spherical configuration can be produced by the known methods. It is possible to produce the moldings by extrusion of a premix with subsequent shaping.

In a further preferred embodiment, therefore, nearly spherical shaped bodies, in particular by extrusion and subsequent rounding for shaping, are produced.

In a further embodiment, the portioned compacts can be designed in each case as separate individual elements.

However, it is also possible to form compacts which connect a plurality of such mass units in a compact, wherein in particular by predetermined predetermined breaking points, the easy separability portioned smaller units is provided. The formation of the portioned tablets as tablets in cylindrical or cuboidal shape may be appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices for producing such compacts.

Another possible spatial form of the shaped body according to the invention has a rectangular base area, wherein the height of the shaped body is smaller than the smaller rectangle side of the base area. Rounded corners are preferred in this offer form. Another molded article that can be produced has a plate-like or tabular structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin segments, broken and portioned to the Use can come. If the shaped bodies according to the invention contain, in addition to the acylpyridinium compound, further ingredients, in a further embodiment it may be advantageous not to compress the various components exclusively to form a uniform tablet.

During tableting, in this embodiment moldings are obtained which have a plurality of layers, ie at least two layers. It is also possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. For example, if components are included in the moldings that interact negatively, it is possible to incorporate one component in the faster soluble layer and incorporate the other component into a slower soluble layer so that the components do not already during the dissolution process react with each other.

The layer structure of the moldings can be carried out both in a stack, wherein a solution process of the inner layers at the edges of the molded body already takes place when the outer layers are not yet completely dissolved. In the stack-like arrangement, the stacking axis can be arranged as desired to the tablet axis. For example, in the case of a cylindrical tablet, the stacking axis may be parallel or perpendicular to the height of the cylinder.

However, according to a further embodiment, it may also be preferred if complete envelopment of the inner layer is achieved by the respectively further outermost layer, which leads to a prevention of premature dissolution of constituents of the inner layer. Preference is given to moldings in which the layers are coated with the various active ingredients.

Similar effects can also be achieved by coating ("coating") individual components of the composition to be pressed or of the entire molding. For this purpose, the bodies to be coated can be sprayed, for example, with aqueous solutions or emulsions, or obtained by the process of melt coating a coating. The person skilled in the art will be familiar with suitable coating materials and will select them according to the technical requirements.

Furthermore, the shaped bodies according to the invention can consist of a shaped body which is produced by known tabletting processes and has a depression, preferably in this embodiment the basic shaped body is produced first and the further compressed part is applied in a further working step . in these Base molding introduced or introduced. The resulting product is hereinafter referred to by the generic term "tray molding" or "depression tablet".

The basic shaped body according to the invention can in principle assume all realizable spatial forms. Particularly preferred are the spatial forms already mentioned above. The shape of the trough can be chosen freely, wherein according to the invention moldings are preferred in which at least one trough is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal , five-, seven- and octagonal-prismatic as well as rhombohedral form. Completely irregular shapes such as arrow or animal shapes, trees, clouds etc. can also be realized. As with the basic moldings, wells with rounded corners and edges or with rounded corners and chamfered edges are preferred.

The size of the trough compared to the entire molded body depends on the desired use of the shaped body. Depending on whether in the second compressed part a smaller or larger amount of active substance should be included, the size of the trough may vary. Regardless of the intended use, moldings are preferred in which the weight ratio of base molding to mold filling is in the range from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, more preferably from 3: 1 to 50: 1 and especially from 4 : 1 to 30: 1.

With regard to the surface portions which make up the basic shaped body or the hollow filling on the overall surface of the shaped body, shaped bodies are preferred in which the surface of the pressed-in cavity filling is 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface of the filled base molding.

The trough filling and the base molding are preferably colored optically distinguishable. In addition to optical differentiation, well tablets have performance advantages on the one hand by different solubilities of the different areas on the other hand, but also by the separate storage of the active ingredients in the various molding body areas.

Shaped bodies in which the pressed-in cavity filling dissolves more slowly than the basic shaped body can be preferred according to the invention. By incorporating certain constituents, on the one hand, the solubility of the well filling can be selectively varied; on the other hand, the release of certain ingredients from the well filling can lead to advantages in the brightening process. It may be preferred according to the invention to separately encapsulate individual active ingredients before their incorporation into the shaped body; For example, it is conceivable to use particularly reactive components or else the fragrances in encapsulated form.

The production of the shaped body according to the invention is carried out first by the dry mixing of the ingredients, which may be pre-granulated in whole or in part, and subsequent Informbringen, in particular pressing into tablets, wherein known methods can be used.

For small production quantities, eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. For larger throughputs you usually choose rotary tablet presses.

However, the method for producing the shaped bodies is not limited to compressing only a particulate premix into a shaped body. Rather, the method can also be extended to the effect that in a manner known per se multilayer moldings are produced by preparing two or more premixes which are pressed together. Here, the first-filled premix is slightly pre-pressed to get a smooth and parallel to the mold bottom extending top end, and end-pressed after filling the second premix to the finished molded body. In the case of three-layered or multi-layered moldings, a further pre-compression takes place after each premix addition, before the shaped article is finally compressed after the addition of the last premix.

As an essential ingredient, the shaped articles according to the invention contain at least one acylpyridinium derivative according to formula (I). Examples of those mentioned as substituents of the compounds of the formula (I) are mentioned below by way of non-limiting example. Examples of C 6 -C 6 -alkyl radicals are the groups -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH ( CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , - CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ . Examples of a C ₂ -C ₆ -alkenyl group are a prop-2-enyl group (allyl group), a 2-methyl-prop-2-enyl group, a but-3-enyl group, a but-2-enyl group, a pentoxy group. 4-enyl group or a pent-3-enyl group, wherein the prop-2-enyl group is preferred. Examples of a C ₂ -C ₆ -hydroxyalkyl group are -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH (OH) CH ₃ and -CH ₂ CH ₂ CH ₂ CH ₂ OH, where the Group -CH ₂ CH ₂ OH is preferred. Examples of C 6 -C 12 alkoxy-C 1 -C 6 -alkyl groups are the groups -CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₃ , - CH ₂ CH ₂ CH ₂ OCH ₂ CH ₃ , -CH ₂ CH ₂ OCH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ OCH (CH ₃ ) ₂ . Examples of a carboxy-C _r C ₆ -alkyl group are the carboxymethyl group, the 2-carboxyethyl group or the 3- Carboxypropyl. Examples of aryl-C Ce-alkyl groups are the benzyl group and the 2-phenylethyl group. Examples of a heteroaryl-C 1 -C 4 -alkyl group are the pyridin-2-ylmethyl group, the pyridin-3-ylmethyl group, the pyridin-4-ylmethyl group, the pyrimidin-2-ylmethyl group, the pyrrol-1-ylmethyl group, the pyrrole-1 ylethyl group, the pyrazol-1-ylmethyl group or the pyrazol-1-yl-ethyl group. Examples of an aryl group are the phenyl group, the 1-naphthyl group or the 2-naphthyl group. Examples of a heteroaryl group are the pyridin-2-yl group, the pyridin-3-yl group, the pyridin-4-yl group, the pyrimidin-2-yl group, the pyrrol-1-yl group, the pyrrol-2-yl group, the pyrazole group. 1-yl group, the pyrazol-3-yl group or the pyrazol-4-yl group. Examples of a C 1 -C ₆ acyl group are acetyl (1-oxo-ethyl), 1-oxo-propyl, 1-oxo-butyl, 1-oxo-pentyl, 1-oxo-2,2-dimethylpropyl and 1-oxo hexyl.

In one embodiment of the present invention, preference is given to those compounds of the formula (I) in which the radical R 1 has the general structure (I) for a C ₁ -C ₄ -alkyl group, for a C ₂ -C ₆ -alkenyl group or for a C ₂ -C ₆ -hydroxyalkyl group. It is preferred according to the invention if the radical R 1 is a C 1 -C 4 -alkyl group, preferably methyl, ethyl, n-propyl or isopropyl and particularly preferably methyl.

It has been found that the acylpyridinium derivatives according to formula (I) according to the invention have particularly advantageous properties when they carry the acyl group either in the 2- or 4-position on the pyridine ring. Preferred compounds of the formula (I) are furthermore those compounds in which either the radical R 2 or the radical R 4 is a C -C acyl group, preferably an acetyl group. It is further preferred if one of the radicals R 2 or R 4 is an acetyl group, while the other of these radicals and the radical R 3 are each hydrogen. A further embodiment of the present invention is therefore characterized in that the shaped body contains as acylpyridinium derivative according to formula (I) at least one 2-acetylpyridinium derivative and / or 4-acetylpyridinium derivative. Suitable acetylpyridinium derivatives are in particular the physiologically tolerable salts which contain as cation an acetylpyridinium derivative selected from 4-acetyl-1-methylpyridinium, 4-acetyl-1-allylpyridinium, 4-acetyl-1- (2-hydroxyethyl) pyridinium, 2-acetyl 1-methylpyridinium, 2-acetyl-1-allylpyridinium and 2-acetyl-1- (2-hydroxyethyl) pyridinium.

It is preferred if the anion X ^" according to formula (I) is selected from halide, in particular chloride, bromide and iodide, benzenesulfonate, p-toluenesulfonate, C 2 -C 4 -alkylsulfonate, trifluoromethanesulfonate, acetate, trifluoroacetate, perchlorate,% sulfate, hydrogensulfate Tetrafluoroborate, hexafluorophosphate or tetrachlorozincate. It is advantageous if the physiological compatible anion X ^"is a halide ion (in particular chloride or bromide), hydrogen sulfate, p-toluenesulfonate, benzenesulfonate or acetate.

In particular, such shaped bodies are preferred according to the invention, which are characterized in that the acylpyridinium derivative according to formula (I) is selected from at least one compound of the group formed from 4-acetyl-1-methylpyridinium p-toluenesulfonate, 4-acetyl-1 -methylpyridinium-benzenesulfonate, 4-acetyl-1-methylpyridinium hydrogensulfate, 4-acetyl-1-methylpyridinium acetate, 4-acetyl-1-allylpyridinium p-toluenesulfonate, 4-acetyl-1-allylpyridinium-benzenesulfonate, 4-acetyl -1-allylpyridinium hydrogensulfate, 4-acetyl-1-allylpyridinium acetate, 2-acetyl-1-methylpyridinium p-toluenesulfonate, 2-acetyl-1-methylpyridinium benzenesulfonate, 2-acetyl-1-methylpyridinium hydrogensulfate, 2-acetyl-1-methylpyridinium acetate , 2-acetyl-1-allylpyridinium p-toluenesulfonate, 2-acetyl-1-allylpyridinium-benzenesulfonate, 2-acetyl-1-allylpyridinium hydrogensulfate and 2-acetyl-1-allylpyridinium acetate. Particularly preferred agents according to the invention are characterized in that they contain, as the acylpyridinium derivative of the formula (I), a compound selected from 4-acetyl-1-methylpyridinium p-toluenesulfonate and / or 2-acetyl-1-methylpyridinium p-toluenesulfonate, especially 4-acetyl-1-methylpyridinium p-toluenesulfonate.

An embodiment of the present invention is characterized in that the acylpyridinium derivatives of the formula (I) in a weight fraction of 2 to 100 wt .-%, in particular from 5 to 95 wt .-%, and in particular 10 to 80 wt. -%, in each case based on the total weight of the molding, are included.

In addition to the acylpyridinium derivative of the formula (I) according to the invention, it may be advantageous if the shaped article of the first subject of the invention contains further ingredients.

In particular, the addition of an ammonium compound in the molding can lead to improved Aufhellergebnissen.

An embodiment of the first subject of the invention is therefore a shaped body, which is characterized in that the shaped body additionally contains at least one ammonium compound selected from ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium carbamate.

An embodiment of the present invention is characterized in that in the molding according to the invention, the ammonium compound (s) in a weight fraction of 2 to 50 Wt .-%, in particular from 5 to 35 wt .-%, and in particular 8 to 30 wt .-%, in each case based on the total weight of the molding, are included.

Furthermore, improved brightening results can be obtained if the moldings additionally contain at least one optionally hydrated Si0 ₂ compound.

To further increase the lightening power, at least one optionally hydrated SiO ₂ compound may additionally be added to the molding according to the invention. Although even small amounts of the optionally hydrated Si0 ₂ compounds increase the lightening power, it may be preferred according to the invention, the optionally hydrated Si0 ₂ compounds in a proportion of 0.5 wt .-% to 75 wt .-%, particularly preferably from 3 Wt .-% to 50 wt .-% and most preferably from 5 wt .-% to 35 wt .-%, in each case based on the total weight of the inventive molding to use. The proportions indicate in each case the content of the Si0 ₂ - compounds (without their water content) in the moldings again.

With regard to the optionally hydrated Si0 ₂ compounds, the present invention is in principle not limited. Preference is given to silicic acids, their oligomers and polymers, and salts thereof. Preferred salts are the alkali metal salts, in particular the potassium and sodium salts, and alkaline earth metal salts, in particular magnesium salts. The magnesium salts and sodium salts of silicas, especially magnesium silicate and sodium silicate, are most preferred.

The optionally hydrated Si0 ₂ compounds can be present in various forms. According to the invention, the Si0 ₂ compounds are preferably used in the form of silica gels (silica gel), in the form of silicates or particularly preferably as water glass. These Si0 ₂ compounds may be partially present in aqueous solution.

Particularly preferred according to the invention are water glasses which are formed from a silicate of the formula (SiO ₂ ) _n (Na ₂ O) _m (K ₂ O) _p , where n is a positive rational number and m and p are each independently a positive one rational number or 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 2: 1 and 4: 1. Preferred is sodium silicate.

Also preferred according to the invention are metasilicates which are formed from a silicate of the formula (SiO ₂ ) _n (Na ₂ O) _m (K ₂ O) _p , where n is a positive rational number and m and p are each independently a positive one rational number or for 0, with the stipulations that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is at most 1: 1. Particularly preferred is sodium metasilicate ([Na ₂ Si0 ₃ ] _x ).

A further embodiment of the first subject of the invention is therefore a shaped body which is additionally characterized in that it additionally contains at least one optionally hydrated SiO ₂ compound, preferably selected from silica, magnesium silicate, sodium silicate and / or sodium metasilicate.

Furthermore, the shaped body according to the invention may contain at least one dissolution accelerator. The term dissolution accelerator includes gas-evolving components, preformed and trapped gases, disintegrants and mixtures thereof.

In one embodiment of the present invention, gas-developing components are used as the dissolution accelerator. Upon contact with water, these components react with each other to form gases in-situ, which create a pressure in the tablet that disintegrates the tablet into smaller particles. An example of such a system are specific combinations of suitable acids with bases. Preference is given to mono-, di- or trihydric acids having a pKa value of 1.0 to 6.9. Preferred acids are citric, malic, maleic, malonic, itaconic, tartaric, oxalic, glutaric, glutamic, lactic, fumaric, glycolic and mixtures thereof. Particularly preferred is citric acid. Further alternative suitable acids are the homopolymers or copolymers of acrylic acid, maleic acid, methacrylic acid or itaconic acid having a molecular weight of 2,000 to 200,000. Especially preferred are homopolymers of acrylic acid and copolymers of acrylic acid and maleic acid. Preferred bases are according to the invention carbonates, bicarbonates and mixtures thereof, bicarbonates are very particularly preferred. These gas-evolving components are preferably present in the moldings according to the invention in a proportion of at least 10% by weight, in particular of at least 20% by weight.

In a particularly preferred embodiment of the present invention disintegration auxiliaries, so-called shaped body disintegrants, are incorporated into the moldings as dissolution accelerators in order to shorten the disintegration times. These substances, which are also referred to as "disintegrants" due to their effect, increase their volume (swelling) when water enters. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives. As preferred disintegrating agents, cellulose-based disintegrating agents are used in the context of the present invention, so that preferred Moldings such a cellulose-based disintegrant in proportions of 0.5 to 70 wt .-%, preferably 3 to 30 wt .-%, based on the total molded article. Cellulosic disintegrating agents which can be used besides cellulose also include cellulose derivatives, in particular methylcellulose, ethylcellulose, hydroxyethylcellulose (HEC) and carboxymethylcellulose (CMC). The cellulose derivatives mentioned are preferably not used as the sole cellulosic disintegrating agent but are used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. As a cellulose-based disintegrating agent or as a component of this component, microcrystalline cellulose is used.

In a preferred embodiment of the shaped bodies according to the invention, they contain a mixture of starch and at least one saccharide in order to accelerate the dissolution, in particular in addition to at least one cellulosic disintegrant. Disaccharides are preferably used saccharides of this embodiment. Said mixture is preferably present in a weight ratio of starch and the saccharides used from 10: 1 to 1: 10, more preferably from 1: 1 to 1: 10, most preferably from 1: 4 to 1: 8 in the molding.

The disaccharides used are preferably selected from lactose, maltose, sucrose, trehalose, turanose, gentiobiose, melibiose and cellobiose. Particular preference is given to using lactose, maltose and sucrose and very particularly preferably lactose in the moldings according to the invention.

The starch-saccharide mixture is contained in the molding preferably in a proportion of 5 to 70% by weight, preferably 20 to 40% by weight, based on the total weight of the molding.

According to the invention, it may be desirable to integrate substantive dyes in the moldings. As a result, undesirable reddish or yellowish color impressions, which are occasionally caused by different rates of decomposition of the melanin pigments in the hair, can be compensated for by a slight coloration, in particular in cool shades.

Nitrofarbstoffe have proven to be particularly suitable. According to the invention, nitro dyes are to be understood as meaning the coloring components which have at least one aromatic ring system which carries at least one nitro group. Particularly preferred nitro dyes are HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 12, HC Violet 1 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, 1- (2-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, picramic acid and their Salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. In addition to the nitro dyes, the azo dyes, anthraquinones or naphthoquinones are also preferred substantive dyes according to the invention. Preferred substantive dyes of this type are, for example, Disperse Orange 3 Disperse Blue 3, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9 and Acid Black 52 and also 2-hydroxy-1,4-naphthoquinone. Furthermore, it may be preferred according to the invention if the substantive dye carries a cationic group. Particularly preferred are (i) cationic triphenylmethane dyes, especially Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, (ii) aromatic systems substituted with a quaternary nitrogen group, in particular Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and (iii) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, especially those in EP-A2-998 908, which are incorporated herein by reference , in the claims 6 to 1 1 disclosed dyes.

Preferred anionic substantive dyes are those under the international designations or trade names 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, Acid Black 52, bromophenol blue and tetrabromophenol blue known compounds. Dye combinations preferred according to the invention are those which contain at least the combination of tetrabromophenol blue and Acid Red 92; Tetrabromophenol blue and Acid Red 98; Tetrabromophenol blue and Acid Red 94; Tetrabromophenol Blue and Acid Red 87 or Tetrabromphenol Blue and Acid Red 51.

Furthermore, the moldings according to the invention may also contain naturally occurring dyes such as those found in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu and alkano root.

The moldings according to the invention preferably contain the substantive dyes in a proportion of 0.01 to 20% by weight.

In a particularly preferred embodiment, the shaped bodies contain at least one pearlescent pigment. Frequently used pearlescent pigments are natural pearlescent pigments, such as, for example, fish-silver (guanine / hypoxanthine mixed crystals from fish scales) or mother-of-pearl (from groundwood) Mussel shells), monocrystalline pearlescent pigments such as bismuth oxychloride, and pearlescent pigments based on mica or mica / metal oxide. The latter pearlescent pigments are provided with a metal oxide coating. By the use of the pearlescent pigments, gloss and optionally additionally color effects are achieved in the moldings according to the invention.

However, the coloring by the pearlescent pigments used in the moldings does not influence the whitening result of the dyeing of the keratin fibers. Mica-based and mica / metal oxide-based pearlescent pigments are preferred according to the invention. Mica belongs to the layer silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. To produce the pearlescent pigments in conjunction with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide. Suitable metal oxides include Ti0 ₂ , Cr ₂ 0 ₃ and Fe ₂ 0 ₃ . By appropriate coating, interference pigments and color luster pigments are obtained as pearlescent pigments according to the invention. In addition to a glittering optical effect, these pearlescent pigment types also have color effects. Furthermore, the pearlescent pigments which can be used according to the invention can furthermore contain a color pigment which does not derive from a metal oxide.

Oxidizing agents may furthermore be present in the shaped body according to the invention. Although the choice of the oxidizing agent is in principle subject to no restrictions, it may be preferred according to the invention to use addition products of hydrogen peroxide, in particular of urea, melamine or sodium borate, as the oxidizing agent. The use of percarbamide is particularly preferred. Furthermore, it is possible to carry out the oxidation with the aid of enzymes, the enzymes being used both for the production of oxidizing per-compounds and for increasing the conversion of a small amount of existing oxidizing agents. Oxidases such as tyrosinase and laccase but also glucose oxidase, uricase or pyruvate oxidase are preferred. Furthermore, the procedure is called, the effect of small amounts (eg., 1% and less, based on the total agent) to enhance hydrogen peroxide by peroxidases.

The lightening can be further assisted and increased by adding certain metal ions to the molding. Such metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the lightening can be accelerated. However, it has also proven to be practicable to use the metal ions in the form of their complexes or also attached to zeolites to increase the brightening power. In a preferred embodiment, the shaped body according to the invention is free of oxidizing agents. In this case, it is necessary to mix the shaped body with an oxidation preparation before use. In this case, it is particularly preferred if the shaped body is dissolved or dispersed in an aqueous oxidizing agent preparation immediately before use. Preferably, the aqueous oxidizing agent preparation is an aqueous solution of hydrogen peroxide.

Another object of the present invention is therefore a means for whitening keratinischen fibers, which is characterized in that the means immediately prior to application by dissolving and / or dispersing a shaped body of the first subject of the invention, in an oxidizing agent preparation M1, in a cosmetic carrier Hydrogen peroxide is produced.

Under keratinic fibers or keratin fibers are furs, wool, feathers and especially human hair to understand. Although the compositions according to the invention are primarily suitable for whitening keratin fibers, in principle there is nothing to prevent their use in other fields as well.

The agents according to the invention contain the active ingredients in a cosmetic carrier. The cosmetic carrier is preferably aqueous, alcoholic or aqueous-alcoholic. For the purpose of hair bleaching such carriers are for example creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. For the purposes of the invention, an aqueous carrier contains at least 40% by weight, in particular at least 50% by weight, of water. For the purposes of the present invention, aqueous-alcoholic carriers are to be understood as meaning water-containing compositions containing from 3 to 70% by weight of a C 1 -C 4 alcohol, in particular ethanol or isopropanol. The compositions of the invention may additionally contain other organic solvents such as methoxybutanol, ethyl diglycol, 1, 2-propylene glycol, n-propanol, n-butanol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether, and diethylene glycol mono-n-butyl ether. Preference is given to all water-soluble organic solvents.

As an essential constituent, the agent according to the invention contains at least hydrogen peroxide as the oxidizing agent. Preferably, hydrogen peroxide itself is used as the aqueous solution. However, hydrogen peroxide can also be used in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds, such as sodium percarbamide, polyvinylpyrrolidinone n H ₂ O ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide. Hydrogen peroxide is preferably 0.1 to 25 wt .-%, particularly preferably 1 to 20 wt .-% and particularly preferably 4.5 to 9 wt .-%, each calculated to 100% hydrogen peroxide and based on the ready-to-use agent on the total weight of the ready-to-use agent.

For an effective lightening result, it is necessary that regardless of the mixing ratio between the shaped body and the oxidizing agent preparation, a sufficient amount of acylpyridinium derivatives according to formula (I) is present in the ready-to-use agent.

A preferred embodiment of the second subject of the present invention is therefore characterized in that the acylpyndinium derivatives of the formula (I) in a proportion by weight of 0.1 to 15 wt .-%, in particular from 0.2 to 10 wt .-% , And in particular 0.5 to 5 wt .-%, each based on the total weight of the composition are included.

Bleaching processes on keratin fibers usually take place in an alkaline medium. However, in order to protect the keratin fibers as well as the skin as much as possible, it is not desirable to set too high a pH. For the purposes of the present invention, the pH values are pH values which were measured at a temperature of 22 ° C.

It may be useful for stability reasons to store certain ingredients at a neutral or slightly acidic pH and only at the time of application to suspend an alkaline environment.

For the adjustment of the pH, common acidifying and alkalizing agents are known to the person skilled in the art. The alkalizing agents which can be used for adjusting the pH are typically selected from ammonia, inorganic salts, in particular the alkali metals and alkaline earth metals, organic alkalizing agents, in particular alkanolamines, amines and basic amino acids. Acidifying agents which are preferred according to the invention are indulgent acids, such as lactic acid, citric acid, acetic acid, malic acid or tartaric acid, dilute mineral acids and their acid-reacting salts in water and organic phosphoric or sulphonic acids.

However, to improve lightening performance, the ready-to-use bleaching agents preferably have an alkaline pH. Therefore, it is preferred to adjust an agent of the second subject of the invention to an alkaline pH between 6 and 12, especially between 9 and 11, immediately prior to application to the keratinic fibers. A further embodiment of the second subject of the invention is therefore an agent which is characterized in that it additionally contains at least one alkalizing agent.

The alkalizing agents which can be used according to the invention are preferably selected from the group formed from ammonia, inorganic alkalizing agents, in particular the alkali and alkaline earth metals, organic alkalizing agents, in particular alkanolamines, amines and basic amino acids.

Inorganic alkalizing agents usable in the present invention are preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

The alkanolamines which can be used as alkalizing agents according to the invention are preferably selected from primary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Preferred alkanolamines are selected from the group consisting of 2-aminoethane-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropane -2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1 -Amino-2-methylpropan-2-ol, 3-aminopropane-1, 2-diol, 2-amino-2-methylpropane-1,3-diol. Alkanolamines which are particularly preferred according to the invention are selected from the group consisting of 2-aminoethane-1-ol, 2-amino-2-methylpropan-1-ol and 2-amino-2-methylpropane-1,3-diol. The basic amino acids are preferably selected from the group consisting of arginine, lysine, ornithine and histidine, most preferably arginine.

However, particularly preferably as alkalizing agent, the agent contains ammonia. An embodiment of the present invention is therefore characterized in that the agent contains as alkalizing agent ammonia and / or monoethanolamine.

In order to avoid instabilities due to undesirable reactions between the individual ingredients during storage of the agents, it is expedient to bring the ingredients into contact with each other only immediately before use. For this it is expedient to prepare the ingredients separately from each other. On the other hand, it may be useful for stability reasons to store certain ingredients at a neutral or slightly acidic pH and only at the time of application to suspend an alkaline environment. These ingredients include hydrogen peroxide. The ready-to-use, inventive agent is preferably prepared before use by mixing a shaped article of the first subject invention F1 and an oxidation preparation M1, containing in a cosmetic carrier hydrogen peroxide.

If the shaped article of the first subject of the invention does not contain an alkalizing agent for adjusting an alkaline pH in the resulting ready-to-use agent, it may be advantageous according to the invention to additionally add an alkalization preparation M2 containing an alkalizing agent in a cosmetically acceptable carrier to the agent before use ,

It may therefore be preferred if the oxidation preparation M1 comprising hydrogen peroxide has a weakly acidic pH. A further embodiment of the present invention is therefore characterized in that the oxidation preparation M1 has a pH of from pH 2 to pH 6, preferably from pH 2.5 to pH 4.5.

Ready-to-use agents according to the invention are preferably aqueous preparations. The compositions according to the invention can furthermore contain all active substances, additives and auxiliaries known for such preparations. It may be preferred to incorporate certain active ingredients, additives and auxiliaries either in the shaped body and / or in the oxidation preparation M1 and optionally in the alkalization preparation M2.

It has proved to be advantageous if the ready-to-use agents contain at least one stabilizer or complexing agent. Particularly preferred stabilizers are phenacetin, alkali benzoates (sodium benzoate) and salicylic acid.

Also preferred according to the invention is the use of so-called complexing agents. Complex images are substances that can complex metal ions. Preferred complexing agents are so-called chelate complexing agents, ie substances which form cyclic compounds with metal ions, a single ligand occupying more than one coordination site on a central atom, ie being at least "bidentate". Customary and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and hydroxyethanediphosphonic acids or their alkali metal salts. Also, complex-forming polymers, ie polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and react with suitable metal atoms generally with the formation of chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can come from only one macromolecule or belong to different polymer chains. Preferred complexing agents 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 its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its Hexane atriumsalz and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta- or Octosatriumsalz.

According to the invention, the agent can be applied to the hair together with a catalyst, which additionally activates the oxidation of the dye precursors. Such catalysts are z. For example, certain enzymes, iodides, quinones or metal ions. Suitable enzymes for this purpose are, for. As peroxidases, which can significantly increase the effect of small amounts of hydrogen peroxide. Use of certain metal ions or complexes may also be preferred. Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ .

The ready-to-use agents may additionally contain surface-active substances selected from anionic as well as nonionic, zwitterionic, amphoteric and cationic surfactants.

Anionic surfactants are characterized by a water-solubilizing anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group of about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of such anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, linear and branched fatty acids having 8 to 30 C atoms. Atoms (soaps); Ethercarbonsäuren, in particular the formula RO (CH ₂ CH ₂ 0) _x CH ₂ COOH, in which R is a linear alkyl group having 8 to 30 carbon atoms and x = 0 or 1 to 16; sarcosides; acyltaurides; isethionates; Sulfosuccinic acid mono and dialkyl esters and sulfosuccinic acid monoalkyl polyoxyethyl esters; linear alkanesulfonates; linear α (alpha) olefin sulfonates; Sulfonates of unsaturated fatty acids; α-sulfofatty acid methyl ester of fatty acids; Alkyl sulfates and alkyl ether sulfates, in particular of the formula RO (CH ₂ CH ₂ O) _x SO ₃ H, in which R is a linear alkyl group having 8 to 30 carbon atoms and x is 0 or a number from 1 to 12; Mixtures of surface active hydroxysulfonates; sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers; Esters of tartaric acid and citric acid with alcohols; Alkyl and / or alkenyl ether phosphates of the formula RO (C ₂ H ₄ O) _x P (= O) (OH) (OR '), where R is an aliphatic, optionally unsaturated hydrocarbon radical having 8 to 30 carbon atoms, R' is hydrogen, a radical (CH ₂ CH ₂ O) _y R and x and y independently represent a number from 1 to 10; sulfated fatty acid alkylene glycol esters of the formula RC (0) 0 (alkO) _n SO ₃ H, in which R is a linear or branched, aliphatic, saturated and / or unsaturated alkyl radical having 6 to 22 C atoms, alk is CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ and n is a number from 0.5 to 5; and monoglyceride sulfates and monoglyceride ether sulfates.

Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate, sulfonate or sulfate group in the molecule. Examples of such zwitterionic surfactants are the betaines such as the N-alkyl-N, N-dimethylammonium glycinates, N-acyl-aminopropyl-N, N-dimethylammoniumglycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Amphoteric surfactants are understood as meaning those surface-active compounds which, apart from a C ₈ -C ₂₄ -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts , Typical 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 each having about 8 to 24 C Atoms in the alkyl group. Exemplary amphoteric surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine.

Nonionic surfactants and emulsifiers contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Examples of such compounds are addition products of from 1 to 50 mol of ethylene oxide and / or from 0 to 5 mol of propylene oxide onto linear and branched fatty alcohols containing from 8 to 30 carbon atoms, to fatty acids containing from 8 to 30 carbon atoms and to alkylphenols having from 8 to 15 carbon atoms. Atoms in the alkyl group; with a methyl or C ₂ -C ₆ alkyl radical end-capped addition products of 1 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and at Alkylphenols having 8 to 15 C atoms in the alkyl group; Polyglycerol esters and alkoxylated polyglycerol esters; polyol; higher alkoxylated, propoxylated and in particular ethoxylated, mono-, di- and triglycerides with a degree of alkoxylation greater than 5, such as glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide; Amine oxides; hydroxy mixed; Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates and sorbitan monolaurate + 20 moles of ethylene oxide (EO); Sugar fatty acid esters and addition products of ethylene oxide to sugar fatty acid ester; Addition products of ethylene oxide with fatty acid alkanolamides and fatty amines; Fatty acid-N-alkyl; Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15 carbon atoms in the alkyl chain and 5 to 30 ethylene oxide and / or propylene oxide units; Alkylpolyglycosides corresponding to the general formula RO- (Z) _x , where R is alkyl, Z is sugar and x is the number of sugar units.

The nonionic emulsifiers in the context of the invention furthermore include the polymerization products of ethylene oxide and propylene oxide onto saturated or unsaturated fatty alcohols; Fatty acid esters of polyhydric alcohols with saturated or unsaturated fatty acids; Alkyl esters of saturated or unsaturated fatty acids or alkylphenols and their alkoxylates; in particular ethylene glycol ethers of fatty alcohols; mixed ethylene and propylene glycol ethers with fatty alcohols; Fatty acid esters of sorbitan and polyethylene glycol; Esters of non-hydroxylated C ₆ -C ₃₀ -alkyl monocarboxylic acids with polyethylene glycol; and addition products of alkylphenols to ethylene and / or propylene oxide.

Cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines are preferred according to the invention in ready-to-use agents. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, and the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolyzates. Alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines, such as stearamidopropyl-dimethylamine. Likewise 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) dimethylammonium chloride, as well as Dehyquart F-75, Dehyquart C-4046, Dehyquart L80 and Dehyquart AU-35 are examples of such esterquats. The cationic surfactants are contained in the compositions according to the invention preferably in amounts of 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

In a preferred embodiment, anionic, nonionic, zwitterionic and / or amphoteric surfactants and mixtures thereof may be preferred. The compositions of the invention may contain other active ingredients, auxiliaries and additives. Other active substances, auxiliaries and additives which can be used according to the invention are, for example, anionic polymers (such as carbomers, copolymers and crosspolymers of acrylic acid, methacrylic acid, maleic acid, itaconic acid and optionally further nonionic monomers); cationic polymers (such as Polyquaternium-4, Polyquaternium-10, Polyquaternium-24, Polyquaternium-67, Polyquaternium-72, Polyquaternium-75, Polyquaternium-29, Polyquaternium-6, Polyquaternium-7, Polyquaternium-22); nonionic polymers (such as vinylpyrrolidinone-vinyl acrylate copolymers, polyvinylpyrrolidinone and vinylpyrrolidinone / vinyl acetate copolymers and polysiloxanes); zwitterionic and amphoteric polymers (such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.

Butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers); Thickening agents (such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g., methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as Amylose, amylopectin and dextrins, clays such as bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol); Structural amides (such as sugar, maleic acid and lactic acid) and bodying agents (such as sugar esters, polyol esters or polyol alkyl ethers); Protein hydrolysates (in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids); Perfume oils; Care oils; cyclodextrins; Defoamers such as silicones; Dyes and pigments for staining the agent; Anti-dandruff agents (such as Piroctone Olamine, Zinc Omadine and Climbazole); Sunscreens (especially derivatized benzophenones, cinnamic acid derivatives and triazines); Active ingredients (such as allantoin, pyrrolidonecarboxylic acids, cholesterol and their salts); other fats and waxes (such as fatty alcohols, beeswax, montan wax and paraffins); Swelling and penetration substances (such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates); Opacifiers (such as latex, styrene / PVP and styrene / acrylamide copolymers); Pearlescing agents (such as ethylene glycol mono- and distearate and PEG-3-distearate); Propellants (such as propane-butane mixtures, N ₂ 0, dimethyl ether, C0 ₂ and air) and antioxidants.

The choice of these other substances will be made by those skilled in the art according to the desired properties of the agents. With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schräder, bases and formulations of cosmetics, 2nd edition, Hüthig book Verlag, Heidelberg, 1989, referenced.

For the strong lightening of very dark hair, the sole use of hydrogen peroxide or its addition products to organic or inorganic compounds is often unsatisfactory. In these cases, a combination of hydrogen peroxide and persulfates or peroxodisulfates is generally used in commercially available bleaching agents. It has been found that the addition of the acylpyridinium derivatives of the general formula (I) according to the invention alone already leads to a significant improvement in the whitening performance, so that the addition of persulfates can generally be dispensed with.

However, in a further embodiment, if the consumer wishes to have a very strong bleaching, it may be preferred if in addition to hydrogen peroxide, the acylpyridinium compound of the formula (I) additionally contains at least one inorganic persulfate salt or peroxodisulfate salt in the lightening agent keratinic fibers is included.

Preferred peroxodisulfate salts are ammonium peroxodisulfate, potassium peroxodisulfate and sodium peroxodisulfate. The peroxodisulfate salts may be contained in an amount of from 0.1 to 25% by weight, in particular in an amount of from 0.5 to 15% by weight, based on the total weight of the ready-to-use agent. These peroxodisulfates are also preferably added to the composition only immediately prior to use in order to avoid storage instabilities.

The compositions according to the invention are preferably used for lightening and bleaching human hair. Here, as desired by the user, the entire hair can be bleached or only certain parts of hair, such as highlights, which are optionally separated from the remaining hair, for example by means of films treated.

Since the ready-to-use agents are prepared by dissolving and / or dispersing the shaped article according to the invention according to the first subject of the invention in an oxidizing agent preparation M1 and optionally adding an alkalization preparation M2 immediately before use, it is advantageous to offer the preparations to the user in a set. Therefore, a preferred dosage form of the agent is a separately packaged packaging unit, wherein the shaped body according to the first subject of the invention and the oxidation preparation M1 and optionally the alkalization preparation M2 are each packaged separately from each other.

A third aspect of the present invention is therefore a multi-component packaging unit (kit-of-parts), which comprises at least two containers which are manufactured separately from each other,

wherein a first container C1 at least one agent M1, containing in a cosmetically acceptable carrier as the oxidizing agent at least hydrogen peroxide and a second container C2 contains at least one molded article according to the first subject of the invention.

For the purposes of the present invention, container is understood to mean an envelope which is present in the form of an optionally reclosable bottle, a tube, a can, a sachet, a sachet or similar wrappings. The wrapping material according to the invention are no limits. However, these are preferably casings made of glass or plastic.

Furthermore, it may be particularly advantageous according to the invention if said kit-of-parts contains at least one further hair treatment agent in a separate container, in particular a conditioner preparation or a bleaching powder with peroxodisulfates. In addition, the packaging unit application aids, such as combs, brushes or brushes, personal protective clothing, especially disposable gloves, and optionally include instructions for use.

If the addition of an alkalization preparation M2 to the ready-to-use agent is required, it is advantageous to also add this agent M2 separately packaged to the multicomponent packaging unit.

A preferred embodiment of the third subject of the invention is therefore a multi-component packaging unit which additionally comprises a further container C3 and is characterized in that the container C3 contains at least one agent M2 containing in a cosmetically acceptable carrier at least one alkalizing agent.

With regard to further embodiments of this subject matter, mutatis mutandis, what has been said about the preceding subjects of the invention applies.

The individual components of the multi-packaging unit are mixed together immediately prior to application and the resulting lightening agent is then applied by the user to keratinic fibers.

The ready-for-use agent for lightening human hair is preferably used. In this case, the means for whitening either on the entire main hair, but also on individual parts of hair, such as highlights, are applied. Another object of the present invention is therefore a method for whitening human hair, which is characterized in that

 (i) preparing a ready-to-use agent by mixing the agent M1 and a shaped body and optionally a means M2 of a multi-component packaging unit according to the preceding subject of the invention,

 (ii) immediately after application of this ready-to-use agent is applied to the brightened hair parts,

 (iii) leave for a period of time on the hair

 (iv) and then the agent is rinsed from the hair.

The exposure time is 5 to 60 minutes, preferably 30 to 45 minutes, before the agent is finally rinsed out. The application temperatures can range between 15 and 40 ° C. After the exposure time, the remaining agent is removed by rinsing off the hair. The washing with a shampoo is eliminated if a strong surfactant-containing carrier was used.

In the context of this article of the invention mutatis mutandis the above statements apply analogously.

Another object of the present invention is the cosmetic use of an agent of the second subject of the invention for whitening keratin-containing fibers, in particular human hair.

It has been found that by using the moldings according to the invention, the bleaching agents obtained can be significantly improved with regard to their whitening performance and in particular with regard to their storage stability and the moldings by optimized properties in terms of Staubverh, the completeness of the resolution and the speed of the dissolution process distinguished.

B e i s e l e

1. Production of the moldings

 First, the following basic recipe was mixed in a mortar:

Based on the basic formulation, the following tablets were subsequently produced as tablets containing the bleach activator:

 Number composition weights

 Basic recipe 2.32 g

 # 1 Starlac (lactose, corn starch) 0.30 g

 4-Acetyl-1-methylpyridinium p-toluenesulfonate 1, 38 g

 Basic recipe 1, 50 g

 # 2 Starlac 0.30 g

 4-Acetyl-1-methylpyridinium p-toluenesulfonate 1, 50 g

 Basic recipe 2.00 g

 # 3 Starlac 0.30 g

 4-Acetyl-1-methylpyridinium p-toluenesulfonate 2.00 g

 Basic recipe 2.50 g

 # 4 Starlac 0.30 g

 4-Acetyl-1-methylpyridinium p-toluenesulfonate 2.50 g

 Basic recipe 2.32 g

 # 5 Starlac 0.30 g

 4-Acetyl-1-methylpyridinium p-toluenesulfonate 3.00 g

 Basic recipe 3.00 g

 # 6 Starlac 0.30 g

 4-Acetyl-1-methylpyridinium p-toluenesulfonate 4.00 g

 Basic recipe 2.70 g

 # 7 Starlac 0.30 g

 4-Acetyl-1-methylpyridinium p-toluenesulfonate 3.50 g

 Basic recipe 3.00 g

 Starlac 0.30 g

 #8th

 4-Acetyl-1-methylpyridinium p-toluenesulfonate 4.00 g

 Ammonium carbonate 0.50 g

 Basic recipe 3.00 g

 Starlac 0.30 g

 # 9

 4-Acetyl-1-methylpyridinium p-toluenesulfonate 4.00 g

Ammonium carbonate 0.80 g Basic recipe 3.00 g

 Starlac 0.30 g

 # 10

 4-Acetyl-1-methylpyridinium p-toluenesulfonate 4.00 g

 Ammonium chloride 0.60 g

 Basic recipe 3.00 g

 Starlac 0.30 g

 # 11

 4-Acetyl-1-methylpyridinium p-toluenesulfonate 4.00 g

 Ammonium chloride 1.00 g

2. Application with three-component agent

 These tablets were added shortly before use in 100 g of an aqueous hydrogen peroxide preparation (Table 3) and completely dissolved by brief shaking.

Hydrogen peroxide preparation (Table 3)

 This mixture was then mixed in a 1: 1 ratio with an alkaline cream formulation (Table 4) and applied to strands of dark brown hair. After a contact time of 30 min at 32 ° C, the remaining agent was rinsed from the hair with lukewarm water and dried the hair. There was an intense lightening.

Alkaline cream formulation (Table 4)

 Raw material share [wt .-%]

C ₁₆ / C ₁₈ fatty alcohol 12.0

 Cocoalkyl fatty alcohol 2,4

 Sodium laureth sulfate (2 EO), 28% by weight 26.5

 Acrylates / Vinyl Isodecanoate Crosspolymer 0.1

 Decyl oleate 2,4

 Etidronic acid, 60% by weight 0.2

Sodium silicate (Si0 ₂ / Na ₂ O 2: 1) 0.5

 Ascorbic acid 0.2

 Ammonium sulfate 1, 0

 Ammonia, 25% by weight ad pH 10.0

Water ad 100 3. Bleaching with two-component agent

The following ingredients are mixed in a mortar and pressed into a shaped body of about 5 or 10 g:

 These tablets were added shortly before use in 100 g of an aqueous hydrogen peroxide preparation (according to Table 3) and completely dissolved by brief shaking.

The mixture was applied to strands of dark brown hair. After a contact time of 30 min at 32 ° C, the remaining agent was rinsed from the hair with lukewarm water and dried the hair. There was an intense lightening.

Claims

Patent claims

1. shaped body comprising at least one acylpyridinium derivative of the formula (I)

(I), in which

R1 represents a C _r C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkyl group hydroxy, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ alkyl group, a carboxy C ₂ -C ₆ -alkyl group, an aryl-C ₁ -C ₆ -alkyl group, a heteroaryl-C ₁ -C ₄ -alkyl group, an aryl group or a heteroaryl group,

 R 2, R 3 and R 4 each independently represent hydrogen, a C 6 -C 6 alkyl group

 Halogen atom or a C 6 -C 12 acyl group, with the proviso that at least one of R 2, R 3 and R 4 is a C 6 -C 12 acyl group, and

 X is a physiologically acceptable anion.

2. Shaped body according to claim 1, characterized in that at least one acylpyridinium derivative of the formula (I) is present, which is selected from at least one compound of the group which is formed from 4-acetyl-1-methylpyridinium p-toluenesulfonate, 4- Acetyl-1-methylpyridinium-benzenesulfonate, 4-acetyl-1-methylpyridinium hydrogensulfate, 4-acetyl-1-methylpyridinium acetate, 4-acetyl-1-allylpyridinium p-toluenesulfonate, 4-acetyl-1-allylpyridinium-benzenesulfonate sulfonate, 4-acetyl-1-allylpyridinium hydrogensulfate, 4-acetyl-1-allylpyridinium acetate, 2-acetyl-1-methylpyridinium p-toluenesulfonate, 2-acetyl-1-methylpyridinium-benzenesulfonate, 2-acetyl-1-methylpyridinium hydrogensulfate, 2- Acetyl-1-methylpyridinium acetate, 2-acetyl-1-allylpyridinium p-toluenesulfonate, 2-acetyl-1-allylpyridinium benzenesulfonate, 2-acetyl-1-allylpyridinium hydrogensulfate and 2-acetyl-1-allylpyridinium acetate, especially 4-acetyl-1 -methylpyridinium-p-toluene sulfonate.

3. Shaped body according to one of claims 1 or 2, characterized in that the shaped body additionally contains at least one ammonium compound selected from ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium carbamate.

4. Shaped body according to one of claims 1 to 3, characterized in that the shaped body additionally contains at least one optionally hydrated Si0 ₂ compound, preferably selected from silica, magnesium silicate, sodium silicate and / or sodium metasilicate.

5. A composition for lightening keratinic fibers, characterized in that the agent is prepared immediately prior to application by dissolving and / or dispersing a shaped article according to any one of claims 1 to 4, in an oxidizing agent preparation containing hydrogen peroxide in a cosmetic carrier.

6. Composition according to claim 5, characterized in that the acylpyridinium derivatives of the formula (I) in a weight fraction of 0.1 to 10 wt .-%, in particular from 0.2 to 4 wt .-%, and in particular 0.5 to 2 wt .-%, each based on the total weight of the ready-to-use agent are included.

7. Composition according to one of claims 5 or 6, characterized in that the agent additionally contains at least one alkalizing agent.

8. multi-component packaging unit (kit-of-parts), comprising at least two separate containers, wherein a first container C1 at least one agent M1 containing in a cosmetically acceptable carrier as the oxidizing agent hydrogen peroxide, and a second container C2 at least one shaped body containing at least one acylpyridinium derivative of the formula (I) according to one of claims 1 to 4.

9. multi-component packaging unit according to claim 8, comprising in addition a further container C3, characterized in that the container C3 at least one agent M2, containing in a cosmetically acceptable carrier alkalizing.

10. Cosmetic use of a composition according to any one of claims 5 to 7 for lightening ke ratin-containing fibers, in particular human hair.

11. A process for the lightening of human hair, characterized in that

 (i) preparing a ready-to-use agent by mixing the means M1 and a shaped body and optionally a means M2 of a multi-component packaging unit according to one of claims 8 or 9,

 (ii) immediately after application of this ready-to-use agent is applied to the brightened hair parts,

 (iii) leave for a period of time on the hair

 (iv) and then the agent is rinsed from the hair.