DE10230414A1 - Shaped body with pearlescent pigment - Google Patents

Abstract

The present invention relates to moldings which, in addition to a cosmetically acceptable carrier, contain at least one cosmetic active ingredient and at least one pearlescent pigment and at least one dissolution accelerator, and a process for treating keratin fibers with these moldings and a kit for use in this process.

Description

The present invention relates to moldings which, in addition to being cosmetically acceptable Carrier at least one cosmetic active ingredient, and at least one pearlescent pigment and contain at least one dissolution accelerator, and a method for Treatment of keratin fibers with these moldings.

The human body today is used in many different ways with cosmetic preparations treated. This includes cleaning the skin and hair Detergents such as B. shower baths, soaps or shampoos, care and Regeneration of the hair with rinses and treatments, as well as bleaching, dyeing and Deforming the hair with dyes, tints, waving agents and Styling preparations.

All of these cosmetic preparations are contained in a cosmetic carrier corresponding active ingredients that have the desired effect of the cosmetic treatment justify. These active ingredients need to work well even after several weeks of storage still have an effective effect, sufficient storage stability in this Have carriers. For this reason, multi-component products are often included single components that are stable in storage are marketed only immediately before use to be mixed into a non-storage-stable but effective cosmetic preparation. Packaging as a solid, e.g. B. in the form of moldings, another Offer the possibility of formulating a storage-stable preparation.

A molded article in itself should, especially when combined with cosmetic products Used, have an attractive and special appearance. Out For this reason, the use of substances that have a special optical effect z. B. effect a pearly shine, desirable. The for this purpose usable pearlescent pigments give a shaped body the desired optical effect, however, it was found that moldings with pearlescent pigments slowed down dissolution rate. Shaped body with pearlescent pigments continue to tend to form small clumps upon dissolution, which in turn affect the rheology of the application mixture. Consequently, both the dissolving behavior of the pearlescent pigment-containing moldings, especially in viscous ones Media such as B. creams, as well as the rheology of the application mixture is a problem represents.

It was therefore an object to provide moldings which are both in terms of Solution behavior of the molded body and the rheology of the resulting Satisfy application mix and at the same time an optimal effect of cosmetic Enable active ingredients.

It has now surprisingly been found that by using the inventive Shaped body achieved an acceptable dissolution time and the rheology of the Application solution is improved. Furthermore, the storage stability meets the posed Conditions. Furthermore, the effectiveness of the cosmetic was surprisingly Active ingredients increased.

• A) mindestens ein Perlglanzpigment und
• B) mindestens einen Auflösungsbeschleuniger.

A first subject of the present invention is therefore molded articles containing, in addition to a cosmetically acceptable carrier, at least one cosmetic active ingredient, and

• A) at least one pearlescent pigment and
• B) at least one dissolution accelerator.

According to the invention, keratin fibers include furs, wool, feathers and in particular understand human hair. Although the moldings according to the invention in the first Line is suitable for dyeing keratin fibers, there is in principle one Use contrary to anything.

Pearlescent pigments are pigments that have a pearlescent sheen. Pearlescent pigments consist of thin leaflets that have a high refractive index have and partly reflect the light and partly transparent to the light are. The mother-of-pearl-like sheen is created by interference of the pigment Generates light (interference pigment). Pearlescent pigments are usually thin leaves of the above material, or contain the above. Material as thin multilayer films or as components arranged in parallel in a suitable carrier material.

The pearlescent pigments used according to the invention are either natural Pearlescent pigments such as B. fish silver (guanine / hypoxanthine mixed crystals Fish scales) or mother-of-pearl (from ground mussel shells), monocrystalline flaky pearlescent pigments such. B. bismuth oxychloride and pearlescent pigments based on mica and mica metal oxide. The latter pearlescent pigments are mica with a metal oxide coating.

By using the pearlescent pigments in the moldings according to the invention Shine and possibly additional color effects achieved. A cosmetic application a preparation containing pearlescent pigment does not change the color of the treated one material containing keratin. When using the shaped body, for example in hair dyes, influences color and shine through in the moldings pearlescent pigments did not use the color result of the coloring. Leave the pigments wash off hair after use.

Pearlescent pigments based on mica and on mica / metal oxide are preferred according to the invention. Mica is one of the layered 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 TiO ₂ , Cr ₂ O ₃ and Fe ₂ O ₃ . Corresponding coatings and interference luster pigments are obtained as pearlescent pigments according to the invention by means of a corresponding coating. In addition to a glittering optical effect, these types of pearlescent pigment also have color effects. Furthermore, the pearlescent pigments which can be used according to the invention can furthermore contain a color pigment which is not derived from a metal oxide.

The grain size of the preferably used pearlescent pigments is preferably between 1.0 and 100 µm, particularly preferably between 10.0 and 60.0 µm.

Particularly preferred pearlescent pigments are pigments which are marketed by Merck under the trade names Colorona®, the pigments Colorona® redhrown (47-57% by weight Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ), 43-50% by weight. -% Fe ₂ O ₃ (INCI: Iron Oxides CI 77491), <3% by weight TiO ₂ (INCI: Titanium Dioxide CI 77891), Colorona® Blackstar Blue (39-47% by weight Muscovit Mica (KH ₂ ( AlSiO ₄ ) ₃ ), 53-61% by weight Fe ₃ O ₄ (INCI: Iron Oxides CI 77499)), Colorona® Siena Fine (35-45% by weight Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ) , 55-65% by weight Fe ₂ O ₃ (INCI: Iron Oxides CI 77491)), Colorona® Aboriginal Amber (50-62% by weight Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ), 36-44% by weight % Fe ₃ O ₄ (INCI: Iron Oxides CI 77499), 2-6% by weight TiO ₂ (INCI: Titanium Dioxide CI 77891)), Colorona® Patagonian Purple (42-54% by weight Muscovit Mica ( KH ₂ (AlSiO ₄ ) ₃ ), 26-32% by weight Fe ₂ O ₃ (INCI: Iron Oxides CI 77491), 18-22% by weight TiO ₂ (INCI: Titanium Dioxide CI 77891), 2-4 % By weight Prussian Blue (INCI: Ferric Ferrocyanide C I 77510)), Colorona® Chameleon (40-50% by weight Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ), 50-60% by weight Fe ₂ O ₃ (INCI: Iron Oxides CI 77491)) and Silk ® Mica (> 98% by weight Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ )).

With regard to the pearlescent pigments which can be used in the moldings according to the invention will continue to expressly refer to the Inorganic Pigments, Chemical technology review No. 166, 1980, pages 161-173 (ISBN 0-8155-0811-5) and Industrial inorganic Pigments, 2nd edition; Weinheim, VCH, 1998, pages 211-231.

The molded body according to the invention also contains at least one Dissolution accelerator. The term resolution accelerator includes Gas-generating components, pre-formed and enclosed gases, explosives and their mixtures.

In one embodiment of the present invention, gas-evolving components are used as the dissolution accelerator. Upon contact with water, these components react with one another to form gases in-situ, which generate a pressure in the tablet which causes the tablet to disintegrate into smaller particles. An example of such a system are special combinations of suitable acids with bases. Mono-, di- or trivalent acids with a pK _a value of 1.0 to 6.9 are preferred. Preferred acids are citric acid, malic acid, maleic acid, malonic acid, itaconic acid, tartaric acid, oxalic acid, glutaric acid, glutamic acid, lactic acid, fumaric acid, glycolic acid and mixtures thereof. Citric acid is particularly preferred. It can be very particularly preferred to use citric acid in particle form, the particles having a diameter below 1000 μm, in particular less than 700 μm, very particularly preferably less than 400 μm. Further alternative suitable acids are the homopolymers or copolymers of acrylic acid, maleic acid, methacrylic acid or itaconic acid with a molecular weight of 2,000 to 200,000. Homopolymers of acrylic acid and copolymers of acrylic acid and maleic acid are particularly preferred. Preferred bases according to the invention are alkali metal silicates, carbonates, hydrogen carbonates and mixtures thereof. Metasilicates, bicarbonates and carbonates are particularly preferred, bicarbonates are very particularly preferred. Particular preference is given to particulate hydrogen carbonates with a particle diameter of less than 1000 μm, in particular less than 700 μm, very particularly preferably less than 400 μm. Sodium or potassium salts of the above bases are particularly preferred. These gas-generating components are preferably present in the colored shaped bodies according to the invention in an amount of at least 10% by weight, in particular at least 20% by weight.

In a further embodiment of the present invention, the gas is pre-formed or enclosed, so that when the dissolution of the shaped body begins, the gas evolution begins and the further dissolution accelerates. Examples of suitable gases are air, carbon dioxide, N ₂ O, oxygen and / or other non-toxic, non-combustible gases.

In a third, particularly preferred embodiment of the present invention are disintegration aids, so-called Molded body disintegrant, incorporated into the molded body to reduce the disintegration times shorten. Molded explosives or decay accelerators are used according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical Technologie "(6th edition, 1987, pp. 182-184) understood auxiliary substances that are necessary for the rapid Disintegration of shaped bodies in water or gastric juice and for the release of the pharmaceuticals provide in an absorbable form.

These substances, which are also known as "explosives" due to their effectiveness, increase their volume when swallowing water (swelling). overflowing 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.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred moldings such a disintegrant based on cellulose in amounts of 0.5 to 70% by weight, preferably 3 to 30% by weight, based on the entire molded body contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used as the only cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid cannot be in finely divided form used, but before mixing into the premixes to be pressed into a transferred coarser form, for example granulated or compacted. The particle sizes such disintegration agents are usually above 200 μm, preferably too at least 90% by weight between 300 and 1600 µm and in particular at least 90 % By weight between 400 and 1200 microns. The disintegration aids according to the invention are, for example, commercially available under the name Arbocel® from Rettenmaier available. A preferred disintegration aid is, for example, Arbocel® TF-30- HG.

As a disintegrant based on cellulose or as a component of this component preferably used microcrystalline cellulose. This microcrystalline cellulose will obtained by partial hydrolysis of celluloses under such conditions that only the attack amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine resulting from the hydrolysis Celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 µm have and for example to granules with an average particle size of 200 microns are compactable. Suitable microcrystalline cellulose is, for example, under the Trade names Avicel® commercially available.

According to the invention, the accelerated dissolution of the shaped bodies can also be achieved by Pregranulation of the other components of the molded body can be achieved.

In a preferred embodiment of the shaped bodies according to the invention they contain in addition to the release accelerator, a mixture of starch and at least one Saccharide. The use of disaccharides according to this embodiment is prefers. Said mixture is preferably in a weight ratio of starch and the saccharides used from 10: 1 to 1:10, particularly preferably from 1: 1 to 1:10, very particularly preferably from 1: 4 to 1: 7 in the molded body.

The disaccharides used are preferably selected from lactose, maltose, Sucrose, trehalose, turanose, gentiobiose, melibiose and cellobiose. Especially lactose, maltose and sucrose are preferred and lactose is very particularly preferred used in the moldings according to the invention.

The starch-disaccharide mixture is in the molded article in an amount of 5 to 70 % By weight, preferably from 20 to 40% by weight, based on the mass of the total Shaped body, included.

According to the invention, conditioning agents are preferred as cosmetic active ingredients Active substances, restructuring active substances, oxidation dye precursors, direct pulls Dyes and oxidizing agents are incorporated into the moldings according to the invention. The moldings according to the invention particularly preferably comprise at least one cosmetic active ingredient, selected from a conditioning active ingredient and a restructuring agent

In a preferred embodiment, the moldings according to the invention contain as cosmetic active ingredient a conditioning active ingredient selected from the group, that of cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils is formed. Regarding the cationic Surfactants on the relevant statements in the section "further components" directed.

Cationic polymers can be preferred as conditioning agents. These are in usually polymers that have a quaternary nitrogen atom, for example in the form of a Ammonium group.

• - quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat® und Polymer JR® im Handel erhältlich sind. Die Verbindungen Celquat® H 100, Celquat® L 200 und Polymer JR® 400 sind bevorzugte quaternierte Cellulose-Derivate.
• - polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Acrylsäure sowie Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat® 100 (Poly(dimethyldiallylammoniumchlorid)), Merquat® 550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) und Merquat® 280 (Dimethyldiallylammoniumchlorid-Acrylsäure-Copolymer im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• - Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat® 734 und Gafquat® 755 im Handel erhältlich.
• - Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat® angeboten werden.
• - quaternierter Polyvinylalkohol

sowie die unter den Bezeichnungen

• - Polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 und
• - Polyquatemium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as are commercially available under the names Celquat® and Polymer JR®. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR® 400 are preferred quaternized cellulose derivatives.
• - polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat® 100 (poly (dimethyldiallylammonium chloride)), Merquat® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer) are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat® 734 and Gafquat® 755.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat®.
• - quaternized polyvinyl alcohol

as well as those under the designations

• - polyquaternium 2,
• - polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Cationic polymers of the first four groups, in particular, are particularly preferred polyquaternium-2, polyquaternium-10 and polyquaternium-22 are particularly preferred. Silicone oils, in particular dialkyl, are also suitable as conditioning agents. and alkylarylsiloxanes such as dimethylpolysiloxane and Methylphenylpolysiloxane, as well as their alkoxylated and quaternized analogues. Examples of such silicones are those of Dow Corning under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401 distributed products as well as the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (Containing a hydroxylamino-modified silicone, also known as amodimethicone ), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary Polydimethylsiloxanes, Quaternium-80).

Paraffin oils, synthetic, can also be used as conditioning agents prepared oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, Orange oil, almond oil, wheat germ oil and peach seed oil.

Suitable hair conditioning compounds are also phospholipids, for example soy lecithin, egg lecithin and cephaline.

The preparations used according to the invention also preferably contain at least one oil component.

Oil components suitable according to the invention are in principle all water-insoluble oils and fatty substances and their mixtures with solid paraffins and waxes. As According to the invention, water-insoluble substances are defined whose solubility in Water at 20 ° C is less than 0.1 wt .-%.

A preferred group of oil components are vegetable oils. Examples of such Oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, Wheat germ oil, peach seed oil and the liquid parts of coconut oil.

However, other triglyceride oils such as the liquid portions of beef tallow are also suitable as well as synthetic triglyceride oils.

Another particularly preferred group according to the invention as an oil component Compounds that can be used are liquid paraffin oils and synthetic hydrocarbons as well Di-n-alkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms Atoms such as di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n- undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n- undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl-n-undecyl ether and Di-tert-butyl ether, di-iso-pentyl ether, di-3-ethyl decyl ether, tert-butyl-n-octyl ether, iso-pentyl-n- octyl ether and 2-methyl-pentyl-n-octyl ether. The available as commercial products Compounds 1,3-di- (2-ethylhexyl) cyclohexane (Cetiol® S) and di-n-octyl ether (Cetiol® OE) can be preferred.

Oil components which can likewise be used according to the invention are fatty acid and Fettalkoholester. The monoesters of the fatty acids with alcohols having 3 to 24 carbon atoms are preferred. This group of substances concerns the products of the esterification of fatty acids 6 to 24 carbon atoms such as, for example, caproic acid, caprylic acid, 2-ethylhexanoic acid, Capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, Palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, the z. B. in the pressure splitting of natural Fats and oils, in the oxidation of aldehydes from Roelen's oxosynthesis or the dimerization of unsaturated fatty acids with alcohols such as Isopropyl alcohol, capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, Lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, Stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, Linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, the z. B. in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction arise in the dimerization of unsaturated fatty alcohols. According to the invention isopropyl myristate, isononanoic acid C16-18 alkyl ester (Cetiol® SN), 2-ethylhexyl stearate (Cetiol® 868), cetyl oleate, glycerol tricaprylate, Coconut fatty alcohol caprinate / caprylate and n-butyl stearate.

Dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, Di- (2-ethylhexyl) succinate and di-isotridecylacelaate as well as diol esters such as Ethylene glycol dioleate, ethylene glycol di-isotridecanoate, propylene glycol di (2-ethylhexanoate), Propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate and Oil components which can be used according to the invention are neopentyl glycol di-caprylate, likewise complex esters such as B. the diacetyl glycerol monostearate.

Finally, fatty alcohols with 8 to 22 carbon atoms can also be used according to the invention acting oil components are used. The fatty alcohols can be saturated or be unsaturated and linear or branched. Can be used in the sense of the invention for example decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, Decadienol, oleyl alcohol, eruca alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, Cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol, Caprinal alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, and their Guerbet alcohols, this list being exemplary and not limiting should have. However, the fatty alcohols derive from preferably natural fatty acids, usually from a recovery from the esters of fatty acids by reduction can be assumed. Such can also be used according to the invention Fatty alcohol cuts, which are reduced by reducing naturally occurring triglycerides such as beef tallow, Palm oil, peanut oil, turnip oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or from their transesterification products with corresponding alcohols resulting fatty acid esters are generated, and thus represent a mixture of different fatty alcohols.

The oil components are preferred in quantities of 0.05 to 10% by weight, in particular from 0.1 to 2% by weight used in the moldings according to the invention.

In a particularly preferred embodiment, the shaped body contains at least one restructuring agent. A restructuring agent is defined in such a way that it is able to stabilize the structure of keratinous material.

• - linearen und/oder verzweigten Fettsäuren, bevorzugt C₂-C₃₀-Fettsäuren, besonders bevorzugt C₄-C₁₈ Fettsäuren, am meisten bevorzugt C₆-C₁₀-Fettsäuren und/oder deren physiologisch verträglichen Salzen; Weitere Beispiele leiten sich ab von den Carbonsäuren wie Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Isobuttersäure, Valeriansäure, Isovaleriansäure, Pivalinsäure, Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Milchsäure, Glycerinsäure, Glyoxylsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebacinsäure, Propiolsäure, Crotonsäure, Isocrotonsäure, Elaidinsäure, Maleinsäure, Fumarsäure, Muconsäure, Citraconsäure, Mesaconsäure, Camphersäure, Benzoesäure, o,m,p-Phthalsäure, Naphthoesäure, Toluoylsäure, Hydratropasäure, Atropasäure, Zimtsäure, Isonicotinsäure, Nicotinsäure, Bicarbaminsäure, 4,4'-Dicyano-6,6'-binicotinsäure, 8-Carbamoyloctansäure, 1,2,4- Pentantricarbonsäure, 2-Pyrrolcarbonsäure, 1,2,4,6,7-Napthalinpentaessigsäure, Malonaldehydsäure, 4-Hydroxy-phthalamidsäure, 1-Pyrazolcarbonsäure, Gallussäure oder Propantricarbonsäure, sowie von den Dicarbonsäuren ausgewählt aus der Gruppe, die gebildet wird durch Verbindungen der allgemeinen Formel (I),
  
  
  in der Z steht für eine lineare oder verzweigte Alkyl- oder Alkenylgruppe mit 4 bis 12 Kohlenstoffatomen, n für eine Zahl von 4 bis 12 sowie eine der beiden Gruppen X und Y für eine COOH-Gruppe und die andere für Wasserstoff oder einen Methyl- oder Ethylrest, Dicarbonsäuren der allgemeinen Formel (II), die zusätzlich noch 1 bis 3 Methyl- oder Ethylsubstituenten am Cyclohexenring tragen sowie Dicarbonsäuren, die aus den Dicarbonsäuren gemäß Formel (II) formal durch Anlagerung eines Moleküls Wasser an die Doppelbindung im Cyclohexenring entstehen.
• - linearen und/oder verzweigten und gesättigten und/oder ungesättigten Alkoholen, bevorzugt C₂-C₃₀-Alkoholen, besonders bevorzugt C₄-C₂₄-Alkoholen, am meisten bevorzugt C₆-C₂₂-Alkoholen; wie beispielsweise Ethanol, Butanol, Hexanol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Stearylalkohol, Oleylalkohol, Linoleylalkohol;
• - Alkylamidoaminen, z. B. Tego Amid® S 18 (Stearylamidopropyldimethylamin);
• - Aminosäuren und ihren Derivaten, z. B. Aminosäureamide, insbesondere Di-, Tri- oder Tetra-Peptide, Aminosäureester und/oder phosphorylierte Aminosäuren und/oder deren physiologisch verträglichen Salzen; wie beispielsweise Alanin, Arginin, Cystein, Glutamin, Glycin, Histidin, Lysin, Leucin, Ornithin, Isoleucin, Serin, Tyrosin, Tryptophan, Valin und Phenylalanin;
• - Peptiden, insbesondere Oligopeptiden, wie z. B. Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, wobei Peptide mit einer Masse M < 1000 besonders bevorzugt sind;
• - Polyhydroxyverbindungen; hierbei sind insbesondere zu nennen
• - Zucker mit 5 und/oder 6 Kohlenstoffatomen, insbesondere als Mono- und/oder Oligosaccharide, beispielsweise Glucose, Fructose, Galactose, Lactose, Arabinose, Ribose, Xylose, Lyxose, Allose, Altrose, Mannose, Gulose, Idose, Talose und Sucrose und/oder deren Derivate, z. B. Etherderivate, Aminoderivate und/oder Acetylderivate wie acetylierte Glucose, z. B. Tetraacetylglucose, Pentaacetylglucose und/oder 2-Acetamido-2-desoxyglucose. Bevorzugte Zucker sind Glucose, Fructose, Galactose, Allose, Lactose, Arabinose und Sucrose; Glucose, Galactose und Lactose sind besonders bevorzugt;
• - Onsäuren, insbesondere Gluconsäure, Glucuronsäure;
• - Polyole, wie z. B. Glucamine, Glycerin, Mono- oder Diglyceride, 2-Ethyl-1,3- hexandiol, 2-Hydroxymethylpropantriol, Glycole wie Ethylenglykol, Diethylenglykol, Triethylenglykol, Propylenglykol, Dipropylenglykol, 1,3- Butandiol;
• - Polyhydroxysäuren, wie z. B. Pentahydroxyhexansäure, Tetrahydroxypentansäure und/oder deren Derivate, wie z. B. Ether, Ester und/oder Amide, z. B. Pentahydroxyhexansäureamid und/oder deren physiologisch verträglichen Salzen; weitere Beispiele: Zitronensäure, Äpfelsäure oder Weinsäure.
• - Silikone, wie z. B. Cyclomethicone (Octamethylcyclotetrasiloxan, Decamethylcyclopentasiloxan, Dodecamethylcyclohexasiloxan), Hexamethyldisiloxan, Dimethicon-Copolymere, Polysiloxane sowie quaternierte Polysiloxane;
• - Esterquats und/oder deren Derivate, z. B. Halogenide, Methylsulfate, wobei unter Esterquats quaternierte Estersalze von Fettsäuren z. B. mit Triethanolamin, mit Diethanolalkylaminen oder mit 1,2-Dihydroxypropyldialkylaminen verstanden werden; es kann bevorzugt sein, quaternierte Estersalze von linear und/oder verzweigten aliphatischen gesättigten und/oder ungesättigten C₁-C₂₀-Fettsäuren mit den o. g. Alkanolaminen einzusetzen
• - Pantolacton
• - Panthenol und/oder dessen Derivate;
• - Hydroxysäuren, wie z. B. α-, β-Hydroxyfettsäuren bzw. Ketofeusäuren und/oder deren physiologisch verträglichen Salzen; wie beispielsweise Salicylsäure oder Milchsäure, Glyoxylsäure, Glycolsäure.
• - bevorzugte Vitamine sind die Vitamine, Provitamine und Vitaminvorstufen der Vitamin-Gruppen A, B₃, B₅, B₆, C, E, F und H
• - Pflanzenextrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmann, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel.

Restructuring active substances preferably used according to the invention in the context of this embodiment are derived from a number of compound classes, in particular from:

• linear and / or branched fatty acids, preferably C ₂ -C ₃₀ fatty acids, particularly preferably C ₄ -C ₁₈ fatty acids, most preferably C ₆ -C ₁₀ fatty acids and / or their physiologically tolerable salts; Further examples are derived from the carboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, lactic acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, acic acid, sorbic acid, sorbic acid, sorbic acid, sorbic acid, sorbic acid, sorbic acid , Crotonic acid, isocrotonic acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoyl acid, hydratropic acid, atropic acid, cinnamic acid, isonicotinic acid, 4,4'-nicotinic acid, bicinic acid, bicinic acid, Dicyano-6,6'-binicotinic acid, 8-carbamoyloctanoic acid, 1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1,2,4,6,7-naphthalenpentaacetic acid, malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazole carboxylic acid, gallic acid or propane tricarboxylic acid, and of the dicarboxylic acids selected from the group that is formed ch compounds of the general formula (I),
  
  
  in the Z stands for a linear or branched alkyl or alkenyl group with 4 to 12 carbon atoms, n for a number from 4 to 12 and one of the two groups X and Y for a COOH group and the other for hydrogen or a methyl or Ethyl radical, dicarboxylic acids of the general formula (II) which additionally carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring and dicarboxylic acids which formally form from the dicarboxylic acids of the formula (II) by addition of a molecule of water to the double bond in the cyclohexene ring.
• linear and / or branched and saturated and / or unsaturated alcohols, preferably C ₂ -C ₃₀ alcohols, particularly preferably C ₄ -C ₂₄ alcohols, most preferably C ₆ -C ₂₂ alcohols; such as ethanol, butanol, hexanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol;
• Alkylamidoamines, e.g. B. Tego Amid® S 18 (stearylamidopropyldimethylamine);
• - Amino acids and their derivatives, e.g. B. amino acid amides, especially di-, tri- or tetra-peptides, amino acid esters and / or phosphorylated amino acids and / or their physiologically tolerable salts; such as alanine, arginine, cysteine, glutamine, glycine, histidine, lysine, leucine, ornithine, isoleucine, serine, tyrosine, tryptophan, valine and phenylalanine;
• - Peptides, especially oligopeptides, such as. B. protein hydrolyzates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, peptides with a mass M <1000 being particularly preferred;
• - polyhydroxy compounds; this should be mentioned in particular
• - Sugar with 5 and / or 6 carbon atoms, in particular as mono- and / or oligosaccharides, for example glucose, fructose, galactose, lactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose and / or their derivatives, e.g. B. ether derivatives, amino derivatives and / or acetyl derivatives such as acetylated glucose, e.g. B. tetraacetylglucose, pentaacetylglucose and / or 2-acetamido-2-deoxyglucose. Preferred sugars are glucose, fructose, galactose, allose, lactose, arabinose and sucrose; Glucose, galactose and lactose are particularly preferred;
• - On acids, especially gluconic acid, glucuronic acid;
• - Polyols, such as B. glucamines, glycerol, mono- or diglycerides, 2-ethyl-1,3-hexanediol, 2-hydroxymethylpropane triol, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol;
• - Polyhydroxy acids, such as. B. pentahydroxyhexanoic acid, tetrahydroxypentanoic acid and / or their derivatives, such as. B. ethers, esters and / or amides, e.g. B. pentahydroxyhexanoic acid amide and / or its physiologically tolerable salts; further examples: citric acid, malic acid or tartaric acid.
• - Silicones, such as B. cyclomethicones (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane), hexamethyldisiloxane, dimethicone copolymers, polysiloxanes and quaternized polysiloxanes;
• - Esterquats and / or their derivatives, e.g. B. halides, methyl sulfates, wherein quaternized ester salts of fatty acids z. B. with triethanolamine, with diethanolalkylamines or with 1,2-dihydroxypropyldialkylamines; it may be preferred to use quaternized ester salts of linear and / or branched aliphatic saturated and / or unsaturated C ₁ -C ₂₀ fatty acids with the abovementioned alkanolamines
• - pantolactone
• - panthenol and / or its derivatives;
• - Hydroxy acids, such as. B. α-, β-hydroxy fatty acids or keto acids and / or their physiologically tolerable salts; such as salicylic acid or lactic acid, glyoxylic acid, glycolic acid.
• - Preferred vitamins are the vitamins, provitamins and vitamin precursors of vitamin groups A, B ₃ , B ₅ , B ₆ , C, E, F and H
• - Plant extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needles, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi, mel , Orange, grapefruit, sage, rosmann, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root.

• - Oxidationsfarbstoffvorprodukte vom Entwickler- und/oder Kuppler-Typ, und
• - Vorstufen naturanaloger Farbstoffe, wie Indol- und Indolin-Derivate,

sowie Mischungen von Vertretern dieser Gruppen enthalten. In a further embodiment, the shaped body according to the invention can be used to formulate a colorant for coloring keratin fibers, in particular hair. For this purpose, the molded body contains oxidation dye precursors. With regard to the dye precursors which can be used in the moldings according to the invention, the present invention is in principle not subject to any restrictions. The colorants according to the invention can be used as further dye precursors

• - Oxidation dye precursors of the developer and / or coupler type, and
• Precursors of nature-analogous dyes, such as indole and indoline derivatives,

as well as mixtures of representatives of these groups.

The colorant can contain at least one developer component. As Developer components are usually primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives are used.

• - G¹ steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄- Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)- Alkoxy-(C₁- bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen C₁- bis C₄- Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'- Aminophenylrest substituiert ist;
• - G² steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄- Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)- Alkoxy-(C₁- bis C₄)-alkylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
• - G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, Iod- oder Fluoratom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Acetylaminoalkoxyrest, einen C₁- bis C₄-Mesylaminoalkoxyrest oder einen C₁- bis C₄-Carbamoylaminoalkoxyrest;
• - G⁴ steht für ein Wasserstoffatom, ein Halogenatom oder einen C₁- bis C₄-Alkylrest oder
• - wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.

It may be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as the developer component. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred


in which

• G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl, a 4'-aminophenyl or a C ₁ to C ₄ alkyl which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl group;
• G ² represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C _4- polyhydroxyalkyl, a C ₁ to C ₄ hydroxyalkoxy, a C ₁ to C ₄ acetylaminoalkoxy, a C ₁ to C ₄ mesylaminoalkoxy or a C ₁ to C ₄ carbamoylaminoalkoxy;
• - G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or
• - If G ³ and G ⁴ are ortho to each other, they can together form a bridging α, ω-alkylenedioxo group, such as an ethylenedioxy group.

Examples of the C ₁ to C ₄ alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C ₁ to C ₄ hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ - to C ₄ -polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are in particular the amino groups, C ₁ - to C ₄ -monoalkylamino groups, C ₁ - to C ₄ -dialkylamino groups, C ₁ - to C ₄ -trialkylammonium groups, C ₁ - to C ₄ - monohydroxyalkylamino groups, Imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p- Phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p- phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5- Dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p- phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) - aniline; N, N-bis (β-hydroxyethyl) p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino 2-methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p- phenylenediamine, 2- (a, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2- Isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl- p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β- hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'- Aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p- phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p- phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiological tolerable salts.

According to the invention, particularly preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (a, β- Dihydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

According to the invention, it can also be preferred as the developer component To use compounds that contain at least two aromatic nuclei with Amino and / or hydroxyl groups are substituted.

• - Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄- Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• - die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈- Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• - G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄- Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• - G⁷, G⁸, G⁹, G¹⁰, G¹¹ und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C₁- bis C₄-Alkylrest,

mit den Maßgaben, dass

• - die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
• - die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

Among the binuclear developer components which can be used in the moldings according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:


in which:

• - Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical, which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridging Y. is or is possibly part of a bridging ring system,
• - The bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring which is interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms and may be substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals, or a direct bond,
• G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ aminoalkyl radical or a direct connection to the bridge Y,
• G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridging Y or a C ₁ to C ₄ alkyl radical,

with the proviso that

• - The compounds of formula (E2) contain only one bridging Y per molecule and
• - The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

According to the invention, the substituents used in formula (E2) are analogous to the above Executions defined.

Preferred dinuclear developer components of the formula (E2) are in particular:
N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl ) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis (β-hydroxyethyl) -N, N ' -bis- (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-diethyl-N, N'-bis- (4'-amino-3 ' -methylphenyl) ethylenediamine, bis- (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis- (2- hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiological tolerable salts.

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis- (2- hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiological tolerable salts.

• - G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, einen Hydroxy-(C₁- bis C₄)-alkylaminorest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Hydroxyalkyl-(C₁-bis C₄)-aminoalkylrest oder einen (Di-C₁- bis C₄- Alkylamino)-(C₁- bis C₄)-alkylrest, und
• - G¹⁴ steht für ein Wasserstoff oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkykest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest oder einen C₁- bis C₄-Cyanoaikylrest,
• - G¹⁵ steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄- Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• - G¹⁶ steht für Wasserstoff oder ein Halogenatom.

Furthermore, it can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as developer component. P-Aminophenol derivatives of the formula (E3) are particularly preferred


in which:

• G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) Alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a hydroxy- (C ₁ - to C ₄ ) -alkylamino radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C aminoalkyl -C ₄ hydroxyalkyl (C ₁ to C _4), or (di-C ₁ - - to C ₄ - alkylamino) - ₁ (C ₁ - to C ₄₎ alkyl, and
• G ¹⁴ represents a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) Alkoxy (C ₁ to C ₄ ) alkyl radical, a C ₁ to C ₄ aminoalkyl radical or a C ₁ to C ₄ cyanoalkyl radical,
• - G ¹⁵ represents hydrogen, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ represents hydrogen or a halogen atom.

According to the invention, the substituents used in formula (E3) are analogous to the above Executions defined.

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N- Methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2- Hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (β- hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4- Amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β- hydroxyethyl aminomethyl) phenol, 4-amino-2- (a, ßdihydroxyethyl) phenol, 4-amino-2- fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and its physiologically tolerable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4- Amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (a, β- dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol.

Furthermore, the developer component can be selected from o-aminophenol and its Derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2- Amino-4-chlorophenol.

Furthermore, the developer component can be selected from heterocyclic Developer components such as the pyridine, pyrimidine, pyrazole, pyrazole Pyrimidine derivatives and their physiologically acceptable salts.

Preferred pyridine derivatives are especially the compounds described in the patents GB 1 026 978 and GB 1 153 196 can be described, such as 2,5-diamino-pyridine, 2- (4'- Methoxyphenyl) amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2- (β- Methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent DE 23 59 399, the Japanese patent application JP 02019576 A2 or in the Published patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2- Dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- Triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 38 43 892, DE 41 33 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988 can be described, such as 4,5-diamino-1-methylpyrazole, 4,5- Diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'- chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1- phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5- hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1- methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β- hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1- ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5- Diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1- isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) - amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5- Diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1- methylpyrazole.

• - G¹⁷, G¹⁸, G¹⁹ und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)- alkylrest, einen Di-[(C₁- bis C₄)-alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl- Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄)- [Hydroxyalkyl]-(C₁- bis C₄)-aminoalkylrest,
• - die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁- bis C₄- Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄- Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest, einen (C₁- bis C₄)- Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)alkyl]- (C₁- bis C₄)- aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄- Hydroxyalkyl- oder einen Di-(C₁- bis C₄-hydroxyalkyl)-aminoalkylrest, einen Aminorest, einen C₁- bis C₄-Alkyl- oder Di-(C₁- bis C₄-hydroxyalkyl)-aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• - i hat den Wert 0, 1, 2 oder 3,
• - p hat den Wert 0 oder 1,
• - q hat den Wert 0 oder 1 und
• - n hat den Wert 0 oder 1,
  mit der Maßgabe, dass
• - die Summe aus p + q ungleich 0 ist,
• - wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G¹⁸ und NG¹⁹G²⁰ belegen die Positionen (2, 3); (5, 6); (6, 7); (3, 5) oder (3,7);
• - wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G¹⁸ (oder NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2, 3); (5, 6); (6, 7); (3, 5) oder (3, 7);

Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazole- [1,5-a] pyrimidine of the following formula (E4) and its tautomeric forms, provided there is a tautomeric equilibrium:


in which:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -Polyhydroxyalkylrest a (C ₁ - to C ₄ ) -alkoxy- (C ₁ - to C ₄ ) -alkyl residue, a C ₁ - to C ₄ -aminoalkyl residue, optionally protected by an acetyl-ureide or a sulfonyl residue can be a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl radical, a di - [(C ₁ - to C ₄ ) -alkyl] - (C ₁ - to C ₄ ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical,
• - The X radicals independently of one another represent a hydrogen atom, a C ₁ to C ₄ alkyl radical, an aryl radical, a C ₁ to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ aminoalkyl, a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) - aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a C ₁ - to C ₄ - hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical , an amino radical, a C ₁ to C ₄ alkyl or di (C ₁ to C ₄ hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1,
  with the proviso that
• - the sum of p + q is not equal to 0,
• - if p + q is 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2, 3); (5, 6); (6, 7); (3, 5) or (3.7);
• - if p + q is 1, n has the value 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2, 3); (5, 6); (6, 7); (3, 5) or (3, 7);

According to the invention, the substituents used in formula (E4) are analogous to the above Executions defined.

If the pyrazole [1,5-a] pyrimidine of the formula (E4) above contains a hydroxy group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is illustrated, for example, in the following scheme:

• - Pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - 2,5-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - Pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• - 2,7-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• - 3-Aminopyrazol-[1,5-a]-pyrimidin-7-ol;
• - 3-Aminopyrazol-[1,5-a]-pyrimidin-5-ol;
• - 2-(3-Aminopyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• - 2-(7-Aminopyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• - 2-[(3-Aminopyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• - 2-[(7-Aminopyrazol-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino)-ethanol;
• - 5,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - 2,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - 3-Amino-7-dimethylamino-2,5-dimethylpyrazol-[1,5-a]-pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomeres Gleichgewicht vorhanden ist. Among the pyrazole- [1,5-a] pyrimidines of the above formula (E4), one can mention in particular:

• - pyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 2,5-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 2,7-dimethylpyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 3-aminopyrazole- [1,5-a] pyrimidin-7-ol;
• - 3-aminopyrazole- [1,5-a] pyrimidin-5-ol;
• - 2- (3-aminopyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-aminopyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazole- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;
• - 2 - [(7-aminopyrazole- [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino) ethanol;
• - 5,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 2,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 3-amino-7-dimethylamino-2,5-dimethylpyrazole [1,5-a] pyrimidine;

as well as their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

The pyrazole- [1,5-a] pyrimidines of the above formula (E4) can be as in the literature described by cyclization starting from an aminopyrazole or from hydrazine getting produced.

Such indoles and indolines are preferred as precursors of nature-analogous dyes used, the at least one hydroxyl or amino group, preferably as a substituent on Six ring. These groups can carry further substituents, e.g. B. in the form an etherification or esterification of the hydroxy group or an alkylation of the Amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

• - R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄ -Hydroxyalkylgruppe,
• - R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiolugisch verträglichen Kation vorliegen kann,
• - R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• - R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• - R⁵ steht für eine der unter R⁴ genannten Gruppen,

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure. Derivatives of 5,6-dihydroxyindoline of the formula (IIa) are particularly suitable as precursors of naturally analogous hair dyes,


in the independently of each other

• R ¹ represents hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
• R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
• R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
• - R ⁴ stands for hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C ₁ -C ₄ alkyl group, and
• R ⁵ stands for one of the groups mentioned under R ⁴ ,

as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6- dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and that 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5,6-dihydroxyindoline.

• - R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄ -Hydroxyalkylgruppe,
• - R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• - R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• - R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• - R⁵ steht für eine der unter R⁴ genannten Gruppen,

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure. Derivatives of 5,6-dihydroxyindole of the formula (IIb) are also outstandingly suitable as precursors of nature-analogous hair dyes,


in the independently of each other

• R ¹ represents hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
• R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
• R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
• - R ⁴ stands for hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C ₁ -C ₄ alkyl group, and
• R ⁵ stands for one of the groups mentioned under R ⁴ ,

as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4- Aminoindole.

Of particular note within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6- dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and especially 5,6-dihydroxyindole.

The indoline and indole derivatives can both in the moldings according to the invention as free bases as well as in the form of their physiologically tolerable salts with inorganic or organic acids, e.g. B. the hydrochloride, sulfate and hydrobromide, be used. The indole or indoline derivatives are usually in these Contain amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In a further embodiment, it may be preferred according to the invention that the indoline or indole derivative in combination with at least one amino acid or one Use oligopeptide. The amino acid is advantageously an α-amino acid; all particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, especially arginine.

In a particularly preferred embodiment, the inventive Shaped body at least one coupler component. It is again preferred that To formulate shaped bodies so that it is free of developer components and Indoline or indole derivatives.

As coupler components, m-phenylenediamine derivatives, naphthols, Resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are used. As Coupler substances are particularly suitable 1-naphthol, 1,5-, 2,7- and 1,7- Dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, Resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3- aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5- Methyl resorcinol and 2-methyl-4-chloro-5-aminophenol.

• - m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N- Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4- aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor- 6-methylphenol, 5-Amino-4-chlor-2-methylphenol, 5-Amino-4-methoxy-2- methylphenol, 5-(2'-Hydroxyethyl)-amino-2-methylphenol, 3-(Diethylamino)-phenol, N-Cyclopentyl-3-aminophenol, 1,3-Dihydroxy-5-(methylamino)-benzol, 3- Ethylamino-4-methylphenol und 2,4-Dichlor-3-aminophenol,
• - o-Aminophenol und dessen Derivate,
• - m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4- Diaminophenoxyethanol, 1,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino- 4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2',4'-diaminophenyl)-propan, 2,6-Bis-(2'- hydroxyethylamino)-1-methylbenzol und 1-Amino-3-bis-(2'-hydroxyethyl)- aminobenzol,
• - o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• - Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,
• - Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6- Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• - Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2- Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6-Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7- Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• - Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Aminobenzomorpholin,
• - Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• - Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• - Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7- Hydroxyindol,
• - Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amino-2,6- dihydroxypyrimidin, 2,4-Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2- Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin und 4,6- Dihydroxy-2-methylpyrimidin, oder
• - Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4- methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)- amino-3,4-methylendioxybenzol.

Coupler components preferred according to the invention are

• - m-Aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl -3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) - amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro- 3-aminophenol,
• o-aminophenol and its derivatives,
• - m-Diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 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'-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) - aminobenzene,
• o-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-methylbenzene,
• Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• - Pyrimidine derivatives, such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino -4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• - Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) - amino-3,4-methylenedioxybenzene.

Coupler components which are particularly preferred according to the invention are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3- hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

According to the invention, direct dyes can be used as cosmetic active ingredients in the Moldings are integrated. Nitro dyes 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, the at least one nitro group wearing.

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- (β-hydroxyethyl) amino-2-nitrobenzene, 3- Nitro-4- (β-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 its 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, there are also the azo dyes, anthraquinones or Naphthoquinones preferred synthetic direct dyes according to the invention. Preferred direct 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 2-hydroxy-1,4-naphthoquinone.

• a) kationische Triphenylmethanfarbstoffe,
• b) aromatische Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, und
• c) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist.

Furthermore, it can be preferred according to the invention if the synthetic direct dye carries a cationic group. Are particularly preferred

• a) cationic triphenylmethane dyes,
• (b) aromatic systems substituted with a quaternary nitrogen group, and
• c) direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom.

Examples of dyes of class (i) are in particular Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14.

Examples of dyes of class (ii) are in particular Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17.

Examples of dyes of class (iii) are described in particular in EP-A2-998 908 which is explicitly referred to at this point, disclosed in claims 6 to 11.

Preferred cationic direct dyes of group (iii) are in particular the following compounds:

The compounds of the formulas (DZ1), (DZ3) and (DZ5) are very particularly preferred cationic direct dyes of group (iii).

Furthermore, the moldings according to the invention can also occur in nature Dyes such as those in henna red, henna neutral, henna black, Chamomile flower, sandalwood, black tea, sapwood, sage, blue wood, Madder root, catechu, sedre and alkanna root are included.

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

In the molded article according to the invention, furthermore, cosmetic active ingredients can be used Oxidizing agents may be included. On the one hand, the oxidizing agent can on the one hand Brightening keratin fibers, e.g. B. in bleaching agents but also in hair dyes, serve. The addition of an oxidizing agent, on the other hand, causes the development of the actual dye from the dye precursors.

Although the choice of the oxidizing agent is in principle not subject to any restrictions it may be preferred according to the invention to use addition products of oxidizing agents Use hydrogen peroxide, especially on urea, melamine or sodium borate. The use of percarbamide is particularly preferred.

It is also possible to carry out an oxidation with the aid of enzymes, the Enzymes can be used both for the generation of oxidizing per compounds also to enhance the effect of a small amount of oxidizing agents present.

So the enzymes (enzyme class 1: oxidoreductases) can remove electrons from suitable Transfer developer components (reducing agents) to atmospheric oxygen. Are preferred oxidases such as tyrosinase and laccase but also glucose oxidase, uricase or Pyruvate. The procedure should also be mentioned, the effect of small amounts (e.g. 1% and less, based on the total agent) hydrogen peroxide by peroxidases to reinforce.

The formation of oxidative colorations can also be supported and increased by adding certain metal ions to the shaped body. 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⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. In principle, the metal ions can 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 formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner. However, it has also proven practical to use the metal ions in the form of their complexes or also attached to zeolites to increase the coloring power.

Although the moldings according to the invention in their dissolution Application preparations can result in being slightly acidic, neutral or even alkaline are set, the moldings contain in a preferred embodiment at least one alkalizing agent.

In principle, the alkalizing agents are not subject to any restrictions. suitable Alkalizing agents are, for example, ammonium salts, carbonates, hydrogen carbonates, Phosphates, amino acids, alkali or alkaline earth hydroxides and organic amines.

In a preferred embodiment of the present invention come solid Alkalizing agent used.

In a further embodiment of the present invention, it may be preferred Use alkalizing agents that are characterized by good water solubility. According to the invention, compounds of which at least 5 g are readily soluble in water are Dissolve 100 ml of water at 15 ° C. Compounds with a are particularly preferred Water solubility of more than 7.5 g in 100 ml of water at 15 ° C.

Furthermore, the alkalizing agents have proven to be particularly preferred, the following their incorporation into the moldings according to the invention only a low partial pressure develop outside the molded body.

In a preferred embodiment of the present invention, as Alkalizing agent amino acids or oligopeptides with at least one amino group and a carboxy or a sulfo group, the 2.5% aqueous solution of which pH of greater than 9.0.

In this embodiment, aminocarboxylic acids are particularly preferred in particular α-aminocarboxylic acids and ω-aminocarboxylic acids. Among the Again, α-aminocarboxylic acids are particularly preferred lysine and especially arginine.

The amino acids of the shaped bodies according to the invention can preferably be in free form be added. However, in a number of cases it is also possible to use the amino acids use in salt form. Preferred salts are then the compounds with Hydrogen halide acids, especially the hydrochlorides and the hydrobromides.

Furthermore, the amino acids can also be in the form of oligopeptides and Protein hydrolyzates are used if it is ensured that the required amounts of Amino acids used according to the invention are contained therein. In this Context is made to the disclosure of DE-OS 22 15 303, to which expressly Reference is made.

A very particularly preferred alkalizing agent is arginine, especially free one Form, but also used as hydrochloride because it is in addition to its alkaline properties the penetration capacity of the dyes also increased significantly.

The alkalizing agent is preferably in amounts in the shaped bodies according to the invention from 0.5 to 20% by weight, in particular from 5 to 15% by weight, based on the total Means included.

The consumer may be particularly impressed with the perception of the shaped bodies by a spherical shape of the shaped body, optionally in conjunction with aromatic fragrances, the colorant according to the invention with a stimulant such as z. B. Connect confectionery. Through this association, especially with Children, oral intake or swallowing of the forked body in principle cannot be excluded. In a preferred embodiment, the Shaped body according to the invention a bitter substance to swallow or a to prevent accidental ingestion. Bitter substances are preferred according to the invention, at least 5 g / l soluble in water at 20 ° C.

With regard to an undesirable interaction with possibly in the molded body contained fragrance components, especially a change in the consumer perceived fragrance, the ionogenic bitter substances have the non-ionic as proven superior. Ionogenic bitter substances, preferably consisting of organic (n) Cation (s) and organic anion (s) are therefore for the invention Preparations preferred.

Quaternary are particularly suitable as bitter substances according to the invention Ammonium compounds that contain an aromatic group in both the cation and the anion. A such connection is the commercial z. B. under the trademarks Bitrex® and Indigestin® available benzyldiethyl ((2,6-xylylcarbamoyl) methyl) ammonium benzoate. This Compound is also known as Denatonium Benzoate.

The bitter substance is in the shaped bodies according to the invention in amounts of 0.0005 to 0.1 % By weight, based on the shaped body. Amounts of are particularly preferred 0.001 to 0.05% by weight.

Other components

In addition to the ingredients mentioned, the moldings according to the invention can also contain all active ingredients, additives and auxiliary substances known for such preparations. As other components can use both solids and liquids come. If liquids as a further component of the invention Shaped body are selected, the dosage is to be chosen such that before Tableting is a flowable powder. The liquid others are preferred Components before tabletting through a suitable device spraying tabletting powder. Another way to put liquid components in the Incorporate molded body according to the invention offers z. B. the previous removal of Solvents so that the originally liquid component can be used as a solid.

In many cases, the moldings contain at least one surfactant, in principle both anionic as well as zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proven advantageous to remove the surfactants select anionic, zwitterionic or nonionic surfactants.

• - lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• - Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• - Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• - lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• - lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• - Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• - Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• - Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030,
• - sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354,
• - Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344,
• - Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

Suitable anionic surfactants in preparations 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. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, glycol 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 as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• Acyl taurides with 10 to 18 carbon atoms in the acyl group,
• Acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Monosulfonic acid and dialkyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• linear alkanesulfonates with 12 to 18 carbon atoms,
• linear alpha olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,
• Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
• - Esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as stearic acid, oleic acid, isostearic acid and palmitic acid ,

• - Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C- Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• - C₁₂-C₂₂-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• - C₈-C₂₂-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga sowie
• - Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl.

Non-ionic surfactants contain z. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

• Addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,
• C ₁₂ -C ₂₂ fatty acid monoesters and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,
• - C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues as well
• - Adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These compounds are available, for example, from Henkel under the trade name Plantacare® and are characterized by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R ¹ . Usually, however, these compounds are made from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.

• - im wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• - im wesentlichen aus C₁₂- und C₁₄-Alkylgruppen,
• - im wesentlichen aus C₈- bis C₁₆-Alkylgruppen oder
• - im wesentlichen aus C₁₂- bis C₁₆-Alkylgruppen besteht.

Alkylpolyglycosides in which R ¹

• essentially from C ₈ and C ₁₀ alkyl groups,
• essentially from C ₁₂ and C ₁₄ alkyl groups,
• - essentially from C ₈ - to C ₁₆ alkyl groups or
• - consists essentially of C ₁₂ - to C ₁₆ alkyl groups.

Any mono- or oligosaccharides can be used as the sugar building block Z. Usually sugar with 5 or 6 carbon atoms and the corresponding Oligosaccharides used. Examples of such sugars are glucose, fructose, Galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar components are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 Sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. All alkyl glycosides in which x is 1.1 to 1.4 are particularly preferred.

In addition to their surfactant action, the alkyl glycosides can also serve for fixation of fragrance components to improve hair. The specialist is therefore in the event that an effect of the perfume oil beyond the duration of the hair treatment the hair is desired, preferably to this class of substances as an additional ingredient of the preparations according to the invention. A particularly inventive preferred alkyl glucoside is the commercial product Plantacare® 1200G.

The alkoxylated homologs of the alkyl polyglycosides mentioned can also are used according to the invention. These homologues can average up to 10 Contain ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^(-) - or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammonium glycinate, and 2 -Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₁₈ -alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acyl sarcosine.

According to the invention, cationic surfactants are in particular those of the type of quaternary ammonium compounds, the esterquats and the amidoamines used.

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, Dialkyldimethylammoniumchloride and Trialkylmethylammoniumchloride, e.g. B. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and Tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above The surfactants mentioned preferably have 10 to 18 carbon atoms.

Esterquats are known substances that both have at least one Contain ester function as well as at least one quaternary ammonium group as a structural element. Preferred ester quats 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-dihydroxypropyl dialkylamines. Such products will be for example under the trademarks Stepantex®, Dehyquart® and Armocare® distributed. The products Armocare® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart® F-75 and Dehyquart® AU-35 Examples of such ester quats.

The alkylamidoamines are usually made more natural or by amidation synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A According to the invention, this compound is particularly suitable from this group of substances the name Tegoamid® S 18 commercially available stearamidopropyl-dimethylamine represents.

Other quaternized cationic surfactants that can be used according to the invention are the quaternized ones Protein hydrolyzates.

Also suitable according to the invention are cationic silicone oils such as those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized Trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (Manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

An example of a quaternary sugar derivative that can be used as a cationic surfactant is provided the commercial product Glucquat® 100, according to INCI nomenclature a "Lauryl Methyl Gluceth-10 hydroxypropyl dimonium chloride ".

The compounds with alkyl groups used as surfactant can in each case be act uniform substances. However, it is usually preferred in manufacturing these substances from natural vegetable or animal raw materials, so that one Mixtures of substances with different, depending on the respective raw material Maintains alkyl chain lengths.

In the case of surfactants, the addition products of ethylene and / or propylene oxide Fatty alcohols or derivatives of these addition products can represent both products with a "normal" homolog distribution as well as those with a narrowed Homolog distribution can be used. Under "normal" homolog distribution Mixtures of homologs understood, which one in the implementation of fatty alcohol and Alkylene oxide using alkali metals, alkali metal hydroxides or Alkali metal alcoholates obtained as catalysts. Narrowing homolog distributions will be on the other hand, if, for example, hydrotalcites, alkaline earth metal salts of Ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates as catalysts be used. The use of products with a narrow homolog distribution can be preferred.

In a preferred embodiment of the present invention, Dissolving the shaped body in water is a gel. For this, the molded body Thickeners such as agar-agar, guar-gum, alginates, xanthan-gum, rubber arabicum, karaya-guni, locust bean gum, linseed gums, dextrans, cellulose Derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, Starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as B. Bentonite, silicates, such as those sold under the trade names Optigel® (South Chemistry) or Laponite® (Solvay), or fully synthetic hydrocolloids such as B. added polyvinyl alcohol. Thickeners are particularly preferred Xanthans, alginates and highly substituted carboxymethyl celluloses.

• - zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyltrimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• - anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacryiat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid- Terpolymere,
• - Strukturanten wie Maleinsäure und Milchsäure,
• - Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• - Parfümöle, Dimethylisosorbid und Cyclodextrine,
• - Lösungsmittel und -vermittler wie Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• - faserstrukturverbessemde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose und Fruchtzucker,
• - quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• - Entschäumer wie Silikone,
• - Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• - Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• - Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• - Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• - Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• - Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmann, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,
• - Cholesterin,
• - Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• - Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• - Fettsäurealkanolamide,
• - Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• - Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• - Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• - Stabilisierungsmittel für das Oxidationsmittel,
• - Antioxidantien.

Other active ingredients, auxiliaries and additives are, for example

• - zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• - anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / Vinylacryiat copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,
• - structurants such as maleic acid and lactic acid,
• Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• Solvents and mediators such as ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose and fructose,
• - Quaternized amines such as methyl 1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• - defoamers like silicones,
• - anti-dandruff agents such as piroctone olamine, zinc omadine and climbazol,
• Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,
• Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosmann, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root,
• - cholesterol,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as walrus, beeswax, montan wax and paraffins,
• - fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• - opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Stabilizing agent for the oxidizing agent,
• - antioxidants.

Shaped body geometries

The moldings according to the invention can take on any geometric shape, such as for example concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five-, seven- and octagonal-prismatic and rhombohedral shapes. Completely irregular too Base areas such as arrow or animal shapes, trees, clouds etc. can be realized. The training as a board, the shape of bars or bars, cubes, cuboids and the like Room elements with flat side surfaces and in particular cylindrical ones Designs with circular or oval cross-section and molded body with spherical geometry are preferred according to the invention. Are particularly preferred Shaped body in the form of spherical geometry.

The cylindrical design covers the form of presentation from the tablet to 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. As an additional optical differentiation, an embodiment with rounded Corners and chamfered ("chamfered") edges preferred.

In addition to a spherical shape, the spherical configuration preferably comprises one Hybrid of spherical and cylindrical shape, each base of the cylinder with one Hemisphere is capped. The hemispheres preferably have a radius of approximately 4 mm and the entire molded body of this embodiment has a length of 12-14 mm.

A shaped body according to the invention with a spherical configuration can according to the known methods can be produced. It is possible to pass through the shaped body Extrusion of a premix with subsequent shaping to produce it Example in WO-A-91/02047 is described in more detail in the context of this Registration is expressly referred to.

In a further preferred embodiment, they are therefore almost spherical Moldings, in particular by extrusion and subsequent rounding to Shaping, manufactured.

In a further preferred embodiment, the portioned compacts can each be formed as separate individual elements that the predetermined Dosage amount of the cosmetic active ingredients corresponds. However, it is also possible to use compacts to train that connect a plurality of such mass units in a compact, the ease of separation, in particular by predetermined predetermined breaking points portioned smaller units is provided. Training the portioned Compacts as tablets in cylindrical or cuboid form can be useful, with a Diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable Devices in particular for the production of such compacts.

Another possible three-dimensional shape of the moldings according to the invention has one rectangular base, the height of the molded body being smaller than the smaller one Rectangular side of the base. Rounded corners are with this offer form prefers.

Another preferred molded body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin Represent segments, can be broken off and used in such portions. This principle of the "bar-shaped" shaped body can also be used in other geometrical shapes Shapes, for example vertical triangles, only on one of their sides are connected alongside each other, can be realized.

If the shaped bodies according to the invention contain at least two cosmetic active ingredients, it can be advantageous in a further embodiment, the different Do not compress components exclusively into a single tablet. In the In this embodiment, tablets are obtained which have several tablets Have layers, that is, at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous performance properties of the shaped bodies result. If, for example, components are contained in the moldings, the affect each other negatively, so it is possible to have one component in the faster integrate soluble layer and the other component into a slower soluble Work in layer so that the components are not already during the dissolving process react with each other.

The layer structure of the moldings can be made in a stack-like manner, with a The process of dissolving the inner layer (s) on the edges of the molded body already then takes place when the outer layers have not yet been completely dissolved. In the stacked arrangement, the stacking axis can be arranged as desired to the tablet axis his. In the case of a cylindrical tablet, for example, the stacking axis can be parallel or perpendicular to the height of the cylinder.

However, it can also be preferred according to a further embodiment if one complete covering of the inner layer (s) by the outer layer (s) Layer (s) is reached, which prevents the early release of Components of the inner layer (s) leads. Shaped bodies in which the Coat layers with the different active ingredients. For example, be one Layer (A) completely from the layer (B) and this in turn completely from the Layer (C) wrapped. Shaped bodies may also be preferred in which, for. B. the Layer (C) completely from the layer (B) and this in turn completely from the Layer (A) is covered.

Similar effects can also be achieved by coating individual components the composition to be pressed or the entire molded body. For this can the body to be coated, for example with aqueous solutions or Emulsions are sprayed, or a process of melt coating Received coating.

The (trough) moldings produced according to the invention can be wholly or partly with be provided with a coating. Procedures in which post-treatment in Applying a coating layer on the molded body surface (s) in which the filled trough (s), or by applying a coating layer on the whole Shaped bodies are preferred according to the invention.

The molded body according to the invention has a preferred breaking hardness of 30-100 N, particularly preferably from 40-80 N, very particularly preferably from 50-60 N (measured according to the European Pharmacopoeia 1997, 3rd edition, ISBN 3-7692-2186-9, "2.9.8 Breaking strength of tablets "; Page 143-144 with a tablet hardness tester Schleuniger 6D).

Furthermore, the moldings according to the invention can be made from one with the term "Base moldings" described, manufactured per se by known tabletting processes Shaped body consist of a trough. Preferably the Base molding first produced and the further pressed part in another Work step on or introduced into this basic molded body. The resulting Product is referred to below with the generic term "trough shaped body" or Inscribed "trough tablet".

In principle, the basic shaped body can, according to the invention, all realizable spatial shapes accept. The spatial shapes already mentioned are particularly preferred. Form the trough can be chosen freely, molded bodies being preferred according to the invention, in which at least one hollow is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five-, seven- and can take octagonal-prismatic and rhombohedral shape. Completely too irregular trough shapes such as arrow or animal shapes, trees, clouds, etc. will be realized. As with the basic shaped bodies, the troughs are rounded Corners and edges or with rounded corners and chamfered edges preferred.

The size of the trough in comparison to the entire molded body depends on the desired use of the molded body. Depending on whether pressed in the second Part of a smaller or larger amount of active substance should be included The size of the trough varies. Shaped bodies are independent of the intended use preferred, in which the weight ratio of base molding to trough filling in Range from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, particularly preferably from 3: 1 to 50: 1 and in particular from 4: 1 to 30: 1.

Similar statements can be made about the surface proportions that the Basic molded body or the trough filling on the entire surface of the molded body turn off. Shaped bodies are preferred in which the surface of the pressed-in Well filling 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular accounts for 4 to 10% of the total surface area of the filled base molding.

If, for example, the overall shaped body has dimensions of 20 × 20 × 40 mm and thus a total surface area of 40 cm ² , trough fillings are preferred which have a surface area of 0.4 to 10 cm ² , preferably 0.8 to 8 cm ² , particularly preferably of Have 1.2 to 6 cm and in particular from 1.6 to 4 cm ² .

The trough filling and the base molding are preferably optically distinguishable inked. In addition to the optical differentiation, trough tablets show application technology advantages on the one hand through different solubilities of the different areas on the other hand but also by the separate storage of Active substances in the different shaped body areas.

Shaped bodies in which the pressed-in trough filling dissolves more slowly than that Base moldings are preferred according to the invention. By incorporating certain The solubility of the trough filling can be specifically varied on the one hand, on the other hand, the release of certain ingredients from the well filling can Advantages in the application process.

tableting

It can be preferred according to the invention to add individual active ingredients before they are incorporated to encapsulate the molded article separately; for example, it is conceivable, especially reactive To use components or the fragrances in encapsulated form.

The moldings according to the invention are first produced by dry Mixing of the components, which can be partially or fully pre-granulated, and Subsequent information, in particular pressing into tablets, referring to known Procedure can be used. For the production of the invention The premix is molded in a so-called die between two stamps compacted into a solid compressed. This process, briefly referred to below as Tableting is called, is divided into four sections: dosage, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body by the position of the lower one Stamp and the shape of the press tool can be determined. The constant one Dosage even at high molding throughputs is preferably over a volumetric dosage of the premix reached. In the further course of tableting the upper stamp touches the premix and continues to lower towards the Lower stamp. With this compression, the particles of the premix become closer pressed together, the void volume within the filling between the Stamping decreases continuously. From a certain position of the upper stamp (and the plastic begins at a certain pressure on the premix Deformation in which the particles flow together and it to form the molded body comes. Depending on the physical properties of the premix, a part also becomes the premixed particles are crushed, and there is a pressure at even higher pressures Sintering the premix. With increasing press speed, i.e. high Throughput quantities, the phase of elastic deformation is shortened more and more, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is made using the lower stamp pressed out of the die and by subsequent transport devices carried away. At this point, only the weight of the molded body is final determined because the compacts due to physical processes (stretching, crystallographic effects, cooling etc.) can still change their shape and size.

Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only the Upper stamp used to build up pressure, the lower stamp also moves during of the pressing process towards the upper punch, while the upper punch presses down. Eccentric tablet presses are preferably used for small production quantities, where the stamp or stamps are attached to an eccentric disc, which in turn an axis with a certain rotational speed is mounted. The movement this ram is comparable to the way a conventional four-stroke engine works. The pressing can be done with an upper and lower stamp, but it can also several stamps can be attached to an eccentric disc, the number of Die holes are expanded accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, on which one so-called die table a larger number of dies is arranged in a circle. The number of matrices varies between 6 and 55, depending on the model, with larger ones as well Matrices are commercially available. Each die on the die table is a top and Assigned lower stamp, whereby again the pressure is active only by the upper or Lower stamp, but can also be built up by both stamps. The matrix table and the stamps move about a common vertical axis, the Stamp with the help of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and discharge. To the Places where there is a particularly serious increase or decrease in the stamp is necessary (filling, compacting, ejecting), these cam tracks are additional low-pressure pieces, pull-down rails and lifting tracks supported. The The die is filled via a rigidly arranged feed device so-called filling shoe, which is connected to a storage container for the premix. The pressure on the premix is via the press paths for upper and lower punches individually adjustable, the pressure build-up by rolling the Stamp shaft heads happen on adjustable pressure rollers.

Rotary presses can also be used with two filling shoes to increase the throughput be provided, with only a semicircle to produce a tablet must become. Several are used to produce two- and multi-layer moldings Filling shoes arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected. Appropriate process management is based on this Way to produce coated and dot tablets that have an onion skin-like Have structure, whereby in the case of the point tablets the top of the core or Core layers are not covered and thus remain visible. Also Rotary tablet presses can be equipped with single or multiple tools, so that for example, an outer circle with 50 and an inner circle with 35 holes can be used for pressing at the same time. The throughputs are more modern Rotary tablet presses are over a million tablets per hour.

When tableting with rotary presses, it has proven to be advantageous Perform tableting with the smallest possible fluctuations in the weight of the tablet.

• - Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• - Geringe Umdrehungszahl des Rotors
• - Große Füllschuhe
• - Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• - Füllschuh mit konstanter Pulverhöhe
• - Entkopplung von Füllschuh und Pulvervorlage

The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations in weight can be achieved in the following ways:

• - Use of plastic inserts with small thickness tolerances
• - Low number of revolutions of the rotor
• - Big filling shoes
• - Matching the filler paddle speed to the speed of the rotor
• - Filling shoe with constant powder height
• - Decoupling of filling shoe and powder feed

All of the technology is available to reduce the build-up of stamps known non-stick coatings. Plastic coatings are particularly advantageous, Plastic inlays or plastic stamps. Rotating stamps also turned out to be proven to be advantageous, the upper and lower punches being rotatable if possible should be. With rotating stamps, a plastic insert can usually be used to be dispensed with. The stamp surfaces should be electropolished here.

It was also shown that long pressing times are advantageous. You can use Pressure rails, several pressure rollers or low rotor speeds can be set. Because the fluctuations in hardness of the tablet due to the fluctuations in the pressing forces systems should be used that limit the pressing force. Here can elastic stamps, pneumatic compensators or spring elements in the Kraftweg be used. The pressure roller can also be designed to be resilient.

Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Fann Instruments Company, Houston, Texas (USA), Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AT), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). Particularly suitable is for example the hydraulic double pressure press HPF 630 from LAEIS, D.

Tableting tools are, for example, from Adams companies tableting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Sons GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharmatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Toolmaking, Tamm available. Other providers are e.g. B. Senss AG; Reinach (CH) and the Medicopharm, Kamnik (SI).

The process for the production of the shaped bodies is, however, not restricted to the fact that only a particulate premix is pressed into a shaped body. Much more the method can also be expanded in such a way that it is known per se produces multilayered molded articles by preparing two or more premixes, which are pressed together. This makes the pre-filled premix easy pre-pressed to a smooth and parallel to the top of the molded body top get, and after filling the second premix to the finished molded article final compression. In the case of three-layer or multi-layer moldings, after each premix Add another pre-compression before adding the last pre-mix Shaped body is finally pressed.

The compression of the particulate composition into the well can be analogous to The base moldings are produced on tablet presses. One is preferred Procedure in which the base molding is first produced with a trough, then filled and are then pressed again. This can be done by ejecting the base molding a first tablet press, filling and transport into a second tablet press happen in which the final pressing takes place. Alternatively, the final compression can also be done by pressure rollers that roll over the molded articles on a conveyor belt, respectively. But it is also possible to use a rotary tablet press with different To provide stamp sets, so that a first stamp set recesses in the molded body presses in and the second set of stamps after refilling by pressing for a tarpaulin Molded surface ensures.

packaging

The moldings according to the invention can be packaged after production, with the use of certain packaging systems has proven to be particularly useful as these Packaging systems on the one hand increase the storage stability of the ingredients, on the other hand if necessary, however, also significantly improve the long-term adherence of the depression. The The term “packaging system” in the context of the present invention always the primary packaging of the moldings, d. H. the packaging that is on the inside is in direct contact with the molded body surface. An optional Secondary packaging has no requirements, so all the usual ones Materials and systems can be used.

Packaging systems which have only a low moisture permeability are preferred according to the invention. In this way, the coloring capacity of the shaped bodies according to the invention can be maintained over a longer period of time, even if, for example, hygroscopic components are used in the shaped bodies. Packaging systems which have a moisture vapor permeability rate of 0.1 g / m ² / day to less than 20 g / m ² / day are particularly preferred if the packaging system is stored at 23 ° C. and a relative equilibrium moisture content of 85%. The specified temperature and humidity conditions are the test conditions that are mentioned in DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature an Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested. The moisture vapor permeability rate can be determined from the surface of the container which is closed with the material to be tested (permeation surface), the weight gain of the calcium chloride and the exposure time


calculate, where A is the area of the material to be tested in cm ² , x is the weight gain of calcium chloride in g and y is the exposure time in h.

The relative equilibrium humidity, often referred to as "relative humidity", is 85% at 23 ° C. when measuring the moisture vapor transmission rate in the context of the present invention. The absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is given in g / m ³ . For example, 1 m ^{3 of} air at 17 ° is saturated with 14.4 g of water vapor; at a temperature of 11 ° there is saturation with just 10 g of water vapor. The relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air contains 17 ° 12 g / m ³ water vapor, then the relative humidity = (12 / 14.4) .100 = 83%. If this air is cooled, then the saturation (100% r.L.) is reached at the so-called dew point (in the example: 14 °), ie, if it cools further, a precipitate is formed in the form of fog (dew). Hygrometers and psychrometers are used for the quantitative determination of moisture.

The relative equilibrium humidity of 85% at 23 ° C can be found, for example, in Laboratory chambers with humidity control to +/- 2% r. Depending on the device type. L. exactly to adjust. Even over saturated solutions of certain salts form in closed Systems at a given temperature constant and well-defined relative Humidities based on the phase balance between the partial pressure of the Water, saturated solution and soil body are based.

The combinations of molded body and packaging system can of course in turn, packaged in secondary packaging, such as cardboard boxes or trays with no further requirements being placed on the secondary packaging have to. Secondary packaging is therefore possible, but not necessary.

Depending on the embodiment of the invention, the packaging system encloses one or several moldings. It is preferred according to the invention, either a shaped body to be designed so that it comprises an application unit of the colorant, and this Pack the moldings individually, or the number of moldings in one Pack packaging unit, which in total comprises an application unit. This The principle can of course be expanded, so that combinations according to the invention also contain three, four, five or even more molded articles in one packaging unit can. Of course, two or more moldings can be in one package have different compositions. In this way it is possible to spatially separate certain components, for example To avoid stability problems.

The packaging system of the combination according to the invention can be from the different materials exist and take any external shape. Out economic reasons and for reasons of easier processability, however Packaging systems preferred in which the packaging material is light in weight has, easy to process and is inexpensive and ecologically compatible.

In a first preferred combination according to the invention, this consists Packing system consisting of a sack or bag made of single-layer or laminated Paper and / or plastic film. The moldings can be unsorted, i. H. as loose Fill, be filled into a bag from the materials mentioned. But it's over aesthetic reasons and for sorting the combinations in secondary packaging preferred to sort the shaped bodies individually or in groups in sacks or bags to fill. These packaging systems can then - again preferably sorted - optionally packed in outer packaging, which is the compact offer form of the Shaped body underlines.

The sacks or bags made of single-layer or laminated paper or plastic film, which are preferably used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam, which is sealed by heat (hot fusion), adhesives or adhesive tapes become. Single-layer bag or sack materials are the known papers, which may or may not be impregnated, and plastic films, which may or may not be co-extruded. Plastic films which can be used as a packaging system in the context of the present invention are specified, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf, 1988, page 193. Fig. 111 shown there also provides information on the water vapor permeability of the materials mentioned.

Although it is possible, wax-coated in addition to the films or papers mentioned To use paper in the form of cardboard boxes as a packaging system for the shaped articles, it is preferred in the context of the present invention if the packaging system does not include boxes made of wax coated paper.

No requirements are placed on the optional secondary packaging, so that all common materials and systems can be used here.

Also preferred are embodiments in which the packaging system is resealable. It has proven practical, for example, as Packaging system a reclosable tube made of glass, plastic or To use metal. In this way it is possible to adjust the meterability To optimize hair dye products so that consumers can be guided, for example can use one shaped body for each defined hair length unit. Also Packaging systems that have a microperforation can be made according to the invention implement with preference.

• A) ein oder mehrere erfindungsgemäße Formkörper in einem Medium M unter Bildung der Zubereitung A gelöst werden,
• B) die resultierende Zubereitung A mit einer Zubereitung B zu einer gebrauchsfertigen Anwendungsmischung AN vermischt wird,
• C) die Anwendungsmischung AN auf die Fasern aufgetragen und
• D) nach einer Einwirkzeit wieder abgespült wird.

A second subject of the invention is a method for the cosmetic treatment of fibers containing keratin, in which

• A) one or more shaped bodies according to the invention are dissolved in a medium M to form preparation A,
• B) the resulting preparation A is mixed with a preparation B to form a ready-to-use application mixture AN,
• C) the application mixture AN applied to the fibers and
• D) is rinsed off again after a contact time.

• A) mindestens einen Auflösungsbeschleuniger und
• B) mindestens ein Perlglanzpigment

enthält. It is of course also possible within the scope of the method to use a powder or granules instead of the shaped body according to the invention which contains at least one cosmetic active ingredient and additionally in a cosmetically acceptable carrier

• A) at least one dissolution accelerator and
• B) at least one pearlescent pigment

contains.

In one embodiment of the invention, the medium M has a viscosity of 500-100000 mPa.s, preferably 3000-70000 mPa.s, particularly preferably 6000-50000 mPa.s and very particularly preferably 10000-30000 mPa.s. The viscosities are measured with a Brookfield RVT viscometer at a temperature of 20 ° C at 4 rpm with spindle No. 4. However, the choice of the spindle for measuring the above-mentioned viscosities is preferably made according to the viscosity range (measured under the above-mentioned test conditions) according to Table 1. Table 1 Spindle number Viscosity range [mPa.s] 1 -2500 2 > 2500-10000 3 > 10000-25000 4 > 25000-50000 5 > 50000-100000

In a special embodiment, the medium M has a viscosity of 500-50000 mPa.s, particularly preferably from 500-25000 mPa.s, very particularly preferably from 500-15000 mPa.s. The measurement of the viscosities of this special embodiment is carried out with a Brookfield RVT viscometer at 20 ° C with the spindle 4 and 20 rpm carried out.

Preparation B can contain at least one oxidizing agent. This is particularly so then the case if the method according to the invention is a Hair coloring process or a process for lightening or bleaching hair. The The addition of an oxidizing agent causes the development of the in the hair dyeing process actual dye from the dye precursors. In addition, that can Oxidizing agents serve to lighten the fibers to be treated, both in the process the hair coloring, as well as in

The actual oxidative coloring of the fibers can basically be done with atmospheric oxygen respectively. However, a chemical oxidizing agent is preferably used, especially when if, in addition to the coloring, a lightening effect on human hair is desired. As Oxidizing agents are persulfates, chlorites and especially hydrogen peroxide or its adducts with urea, melamine and sodium borate in question. According to the invention, however, the oxidation coloring agent can also be used together with a Catalyst is applied to the hair, which prevents the oxidation of the dye precursors, z. B. activated by atmospheric oxygen. Such catalysts are e.g. B. metal ions, iodides, Quinones or certain enzymes.

The formation of the color can also be supported and increased by adding certain metal ions to the shaped body. 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⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. In principle, the metal ions can 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 formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner. However, it has also proven practical to use the metal ions in the form of their complexes or also attached to zeolites to increase the coloring power.

• - Pyranose-Oxidase und z. B. D-Glucose oder Galactose,
• - Glucose-Oxidase und D-Glucose,
• - Glycerin-Oxidase und Glycerin,
• - Pyruvat-Oxidase und Benztraubensäure oder deren Salze,
• - Alkohol-Oxidase und Alkohol (MeOH, EtOH),
• - Lactat-Oxidase und Milchsäure und deren Salze,
• - Tyrosinase-Oxidase und Tyrosin,
• - Uricase und Harnsäure oder deren Salze,
• - Cholinoxidase und Cholin,
• - Aminosäure-Oxidase und Aminosäuren.

Suitable enzymes are e.g. B. peroxidases, which can significantly enhance the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as for example the laccases, or generate small amounts of hydrogen peroxide in situ and in this way activate the oxidation of the dye precursors biocatalytically. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the substrates specific for them, e.g. B.

• - Pyranose oxidase and z. B. D-glucose or galactose,
• Glucose oxidase and D-glucose,
• Glycerin oxidase and glycerin,
• Pyruvate oxidase and pyruvic acid or its salts,
• - alcohol oxidase and alcohol (MeOH, EtOH),
• Lactate oxidase and lactic acid and their salts,
• Tyrosinase oxidase and tyrosine,
• Uricase and uric acid or its salts,
• Choline oxidase and choline,
• - Amino acid oxidase and amino acids.

Regarding other optional components and the amounts used Components is expressly referred to the relevant manuals known to the expert, z. B. Kh. Schrader, basics and formulations of cosmetics, 2nd edition, Hüthig book Verlag, Heidelberg, 1989.

Methods are preferred according to the invention in which the preparation B is at least an oxidizing agent and the medium M at least one oxidation dye intermediate included (hair coloring). In a further embodiment, such Shaped body preferably used, the at least one as a cosmetic active ingredient Coupler component included. In this embodiment of the invention Process, the medium M preferably contains at least one Oxidation dye intermediate of the developer type and / or at least one precursor natural dyes, such as indole and / or indoline derivatives. It is according to the invention preferably to use such developer components as described above were.

In this embodiment, the medium M can be in addition to the developer components at least one coupler component and / or at least one substantive dye contain. The coupler components preferably used in this embodiment or direct dyes correspond to those already mentioned above were. What has been said in the corresponding sections applies.

It is not necessary that those used in medium M. Oxidation dye precursors or the substantive dyes are uniform Represent connections. Rather, in the moldings according to the invention, due to the manufacturing process for the individual dyes, in subordinate Amounts of other components may be included, provided that these do not affect the coloring result adversely affect or for other reasons, e.g. B. toxicological, excluded Need to become.

The oxidation dye precursors in the medium M are preferably in amounts of 0.01 to 20 wt .-%, preferably 0.5 to 5 wt .-%, each based on the total Medium M included.

In a method of this second embodiment, preparation A and Preparation B preferably mixed in a weight ratio of 1: 1. The ready to use Mixture of applications in this embodiment should preferably have a pH value in Range from 6 to 12. The use of is particularly preferred Hair dye in a weakly alkaline environment. The application temperatures can be in a range between 15 and 40 ° C, preferably at the temperature of the scalp. The exposure time is usually about 5 to 45, in particular 15 to 30, minutes. Unless a high tenside carrier was used, it may be preferred to use such then clean treated hair with a shampoo.

A third object of the present invention is a kit for use in the method according to the invention. The kit according to the invention contains three contains separately assembled components in containers K1, K2 and K3, whereby Container K1 the medium M, container K2 one or more according to the invention Shaped body and container K3 contains the preparation B.

Examples

The following hair dye molded articles with a mass of 0.4 g and a breaking hardness of 60 to 80 N were produced. The tablets were pressed with a force of 3.5 kN during manufacture. example 1

Example 2

Example 3

Example 4

Claims (25)

1. Shaped body containing at least one cosmetic active ingredient in a cosmetically acceptable carrier, characterized in that the shaped body A) at least one dissolution accelerator and B) at least one pearlescent pigment contains. 2. Shaped body according to claim 1, characterized in that the Dissolution accelerator is a disintegration aid. 3. Shaped body according to claim 2, characterized in that the disintegrant is based on cellulose. 4. Shaped body according to one of claims 1-3, characterized in that the Shaped body additionally a mixture consisting of starch and at least one Contains saccharide. 5. Shaped body according to claim 4, characterized in that the saccharide Is disaccharide. 6. Shaped body according to claim 5, characterized in that the disaccharide is selected from the group which is formed from lactose, maltose, sucrose, Trehalose, turanose, gentiobiose, melibiose and cellobiose. 7. Shaped body according to claim 6, characterized in that the disaccharide is selected from the group consisting of lactose, maltose and sucrose. 8. Shaped body according to claim 7, characterized in that the disaccharide lactose is. 9. Shaped body according to one of claims 4-8, characterized in that the strength and the saccharides used in a weight ratio of 1:10 to 10: 1 are included. 10. Shaped body according to claim 9, characterized in that the strength and the used saccharides in a weight ratio of 1: 1 to 1:10 are. 11. Shaped body according to claim 10, characterized in that the strength and the saccharides used are contained in a weight ratio of 1: 4 to 1: 7. 12. Shaped body according to one of claims 4-11, characterized in that the Dissolution accelerator and the mixture consisting of starch and at least a saccharide in a weight ratio of 1: 1 to 1: 2 are contained. 13. Shaped body according to one of claims 1-12, characterized in that the Shaped body a pearlescent agent based on mica and / or on mica / metal oxide Base contains. 14. Shaped body according to claim 13, characterized in that the pearlescent agent based on mica / metal oxide is a metal oxide selected from Colorona® red-brown (47-57 wt .-% Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ), 43- 50% by weight Fe ₂ O ₃ (INCI: Iron Oxides CI 77491), <3% by weight TiO ₂ (INCI: Titanium Dioxide CI 77891), Colorona® Blackstar Blue (39-47% by weight Muscovit Mica ( KH ₂ (AlSiO ₄ ) ₃ ), 53-61% by weight Fe ₃ O ₄ (INCI: Iron Oxides CI 77499)), Colorona® Siena Fine (35-45% by weight Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ), 55-65% by weight Fe ₂ O ₃ (INCI: Iron Oxides CI 77491)), Colorona® Aboriginal Amber (50-62% by weight Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ), 36 -44% by weight Fe ₃ O ₄ (INCI: Iron Oxides CI 77499), 2-6% by weight TiO ₂ (INCI: Titanium Dioxide CI 77891)), Colorona® Patagonian Purple (42-54% by weight Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ), 26-32% by weight Fe ₂ O ₃ (INCI: Iron Oxides CI 77491), 18-22% by weight TiO ₂ (INCI: Titanium Dioxide CI 77891), 2-4% by weight Prussian Blue (INCI: Ferric Ferrocyanide CI 7751 0)), Colorona® Chameleon (40-50% by weight Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ), 50-60% by weight Fe ₂ O ₃ (INCI: Iron Oxides CI 77491)) and Silk® Mica (> 98 wt .-% Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ )) contains. 15. Shaped body according to one of claims 1-14, characterized in that the Shaped body contains an alkalizing agent. 16. Shaped body according to one of claims 1-15, characterized in that the Shaped body contains at least one bitter substance. 17. Shaped body according to one of claims 1-16, characterized in that the cosmetic active ingredient is selected from conditioning active ingredients, restructuring agents, oxidation dye precursors and substantive Dyes. 18. Shaped body according to one of claims 1-17, characterized in that individual Components of the composition to be pressed or the entire molded body is coated. 19. Shaped body according to one of claims 1 to 18, characterized in that the Shaped bodies a Brueb hardness of 30-100 N, preferably 40-80 N, particularly preferably of 50-60 N, (measured according to European Pharmacopoeia 1997, 3. Edition, ISBN 3-7692-2186-9, "2.9.8 Breaking strength of tablets"; Page 143-144 with a Schleuniger 6D tablet hardness tester). 20. Shaped body according to one of claims 1-19, characterized in that the Shaped body is enveloped by a primary packaging. 21. A method for the cosmetic treatment of keratin fibers, characterized in that A) one or more shaped bodies according to one of claims 1 to 20 are dissolved in a medium M to form preparation A, B) the resulting preparation A is mixed with a preparation B to form a ready-to-use application mixture AN, C) the application mixture AN applied to the fibers and D) is rinsed off again after a contact time. 22. The method according to claim 21, characterized in that the medium M is a gel or is a W / O emulsion or an O / W emulsion. 23. The method according to any one of claims 21 or 22, characterized in that the Medium M has a viscosity of 500-100000 mPa.s, preferably 3000-70000 mPa.s, particularly preferably from 6000-50000 mPa.s and very particularly preferred of 10000-30000 mPa.s (Brookfield RVT viscometer at a temperature of 20 ° C at 4 rpm with spindle no.4). 24. The method according to any one of claims 21 to 23, characterized in that the Preparation B is an oxidizing agent and the medium M is at least one Oxidation dye intermediate of the developer type and / or at least one precursor contains natural dyes, such as indole and / or indoline derivatives. 25. Kit for use in a method according to any one of claims 21-24, characterized characterized in that there are three separately assembled components in the containers K1, K2 and K3 contains, with container K1 the medium M, container K2 one or several moldings according to one of claims 1-20 and container K3 Preparation B contains.