Patent Application
20050166938
The present invention pertains to the field of keratin fiber treatment. In particular, the invention concerns a treatment device for treating keratin fibers, a method for treating keratin fibers, the use of a treatment device for dyeing or bleaching a person's hair, and preparations for dyeing or bleaching keratin fibers.
The treatment of keratin fibers, especially hair, can have various objectives. For one thing, the treatment can have the purpose of shaping the keratin fibers. For example, the keratin fibers can be shaped into waves, or wavy keratin fibers can be straightened by suitable treatment. Human hair is now being treated in many different ways with hair cosmetic products, such as hair dyes, blond-bleaching preparations, waving lotions, straightening agents, hair treatments, and other hair-care preparations. In this regard, products for changing the color of hair are becoming increasingly important. So-called oxidation dyes are used for long-lasting intensive dyeing with suitable fastness properties. Dyes of this type usually contain oxidation dye intermediates, so-called developer components. Active substances of these kinds, in combination with a developer lotion, produce long-lasting color changes in the hair by oxidation. Ammonia in the dyeing cream loosens the hair structure and allows the dye products to penetrate the interior of the hair (cortex). The oxidation process causes physically small compounds to become large-molecular compounds, which become firmly coupled in the hair structure.
For temporary dyeing, customary dyeing or tinting agents are used, which contain so-called direct dyes as the dyeing components. These dyes comprise dye molecules that are directly absorbed by the hair and do not require an oxidation process to develop the dye. The dyeing intensity and the stability of these products depend on the number of hair washings. It is the nature of this product category that continuous color loss occurs.
The mechanism of action of blond-bleaching preparations is fundamentally different from that of the aforementioned dyes. A decolorizing bleaching process is initiated by the application to the hair of products that contain persulfates to the hair. They decolorize the natural pigment molecules, such as melanin, as well as any synthetic dyes that may already be present in the hair. The persulfate-containing preparations are activated by a developer lotion, which is added immediately before application. The desired degree of brightening can be varied by the length of time the preparation is allowed to act.
To intensify the treatment or to accelerate it, it is well known, for example, that heat can be used during the treatment. In this regard, there are heating hoods, which, for example, are lowered over the head of a person whose hair is being treated.
In addition, WO 03/049712 and WO 03/020070 describe a comb-like ultrasonic device for treating hair or other fibers. An ultrasonic device of this type comprises an ultrasonic generator and a comb connected with the ultrasonic generator. To use this device, the ultrasonic generator is turned on, and the individual strands of hair to be treated are combed with the comb. This means, for example, that if a dyeing process is to be improved through the use of this ultrasonic device, a hairdresser or the person handling the ultrasonic device repeatedly combs through the strands of hair to be dyed with the comb.
The use of an ultrasonic device of this type presents certain problems in a modern salon operation, since it takes the person handling the ultrasonic device a very long time to repeatedly go over all of the person's hair one tuft at a time. Especially in the case of long hair, the time required for this is considerable.
The objective of the present invention is to specify an improved treatment device.
This objective is achieved by a specific embodiment of the invention, as specified in claim 1.
Additional embodiments and refinements of the present invention are objects of the dependent claims.
In accordance with an advantageous embodiment of the present invention, a treatment device for treating keratin fibers is specified, which has a vibration generator for generating vibrations and a vibration transmitter, which is connected with the vibration generator, for transmitting vibrations to the keratin fibers. The vibration transmitter has sections that can be brought into a treatment position, in which the keratin fibers are secured between the sections. For example, the vibration transmitter can be realized in the form of a metal clip or clamp. The keratin fibers are preferably secured in such a way that the vibration transmitter does not slip from the keratin fibers during the treatment, i.e., in such a way that it does not slip, e.g., due to its own weight, from the clamped keratin fibers, such as tufts of hair.
This device has the advantage that it is merely necessary for the person operating it, for example, for the purpose of treating a person's hair, to apply the vibration transmitter to the hair to be dyed. The treatment can then be performed without the person operating the device having to carry out any other action. After the treatment, the vibration transmitter is removed from the hair and, for example, hung on a suitable holder. Preferably, several vibration transmitters are provided.
In accordance with another advantageous embodiment of the present invention, a treatment device for treating hair is specified, which comprises a hood that is suitable for at least partially enclosing regions of the head of a person whose hair is to be treated. In addition, a vapor generator is provided for producing vapor. The vapor generator is connected with the hood in such a way that the vapor that is generated is fed into the hood and conveyed to the hair through small holes provided in the hood. Furthermore, a vibration generator is provided, which causes the vapor to vibrate, so that the vibrations are transmitted to the hair in the area of the hood.
In accordance with this embodiment, vibrations are transmitted to the hair in an advantageous way without contact via a medium, namely, the vapor. The micromovements of the hair caused by the vibrations allow a better hair treatment. For example, improved hair dyeing can be achieved in this way, as well as better shaping or straightening of the hair. Especially the combination of the vapor heat and the micromovement produced in the hair can be advantageous.
In accordance with another advantageous embodiment of the present invention, a treatment device is specified, which has means for transmitting vibrations, which are formed as partially elastic fingers, which at least partially surround the area of the head in which the hair is located.
This makes a very easily handled hair treatment device available. During treatment, for example, the device can be supported on a holder, while the vibration transmitter is being used on the hair.
The use of the treatment device of the invention for hair dyeing or bleaching is especially advantageous. The use of vibrations or waves in the ultrasonic range or even in the audible range, for example, kHz, allows the active substance combinations of the hair treatment preparation to penetrate the hair faster. Furthermore, deeper penetration of the active substances into the fiber sheath of the hair and thus improved stability of the products produced by the dyeing process can be achieved. In addition, a significant increase in color intensity can be achieved. The power of a vibration generator of the type that can be used in the treatment device of the present invention is, for example, in the range of 5 to 200 watts. The power is preferably on the order of 100 watts. Examples of vibration generators that can be used are resonators or multivibrators, such as those used, for example, in power whistles and sirens. In addition, it is possible to use, for example, magnetostrictive transducers, piezoelectric transducers, and piezomagnetic transducers, for example, nickel-copper-cobalt ferrites.
Preferred embodiments of the present invention are described below with reference to the drawings.
In the following description of the drawings, the same reference numbers are used for elements which are the same or which correspond to each other.
As
The vibration transmitters can be designed, for example, as light-weight hair clips, which are applied by hand to the person's hair, where they then remain during the entire treatment, for example, for the entire reaction time of the dye or bleach used in the dyeing or bleaching process.
A vibration generator is housed in the control unit 16. The vibration generator may be, for example, a piezomagnetic or piezoelectric vibration generator that is capable of producing frequencies on the order of, for example, 5 kHz. However, the vibration generator can also be designed to generate frequencies in the ultrasonic range. The vibration generator is preferably designed to generate frequencies in the power range of 5 to 200 watts. The vibration generator preferably generates a power of 100 watts.
In a variant of this embodiment, instead of one vibration generator being provided in the control unit 16, a large number of small vibration generators can be provided in or on the vibration transmitters 12. In this way, it is not necessary to transmit the vibration energy from the vibration generator in the control unit 16 to the vibration transmitters 12, but rather the vibrations are produced directly on the vibration transmitters 12, which, for example, are designed as hair clips.
The control unit 16 has means for adjusting the display and the settings, so that, for example, the frequency generated by the vibration generator can be adjusted, a treatment time can be set, and/or the power setting of the vibration transmitters can be adjusted.
To carry out a treatment, the vibration transmitters 12 are applied by hand to the person's hair, for example, by a hairdresser, where they then remain, for example, during a hair dyeing treatment, for the entire reaction time of the dye or bleach used in the dyeing or bleaching process. Usually, the hair to be dyed is treated in tufts with the dyeing or bleaching agent. The tufts of hair are then wrapped, for example, in aluminum foil, the corners of which are folded down to produce a small pocket. This pocket prevents the dyeing or bleaching agent from running out during the application. Instead of aluminum foil, it is also possible to use wax foil or PE foil.
Naturally, the treatment device in accordance with the present invention can also be used without foil pockets of this type.
The vibration transmitters, i.e., the clips, are clipped onto the individual foil pockets. About 60 foil pockets are usually needed for this type of hair treatment. If each vibration transmitter or clip is clipped onto two foil pockets, it is thus advantageous for 30 vibration transmitters 12 to be available.
Since each vibration transmitter 12 is connected by vibration transmission lines 14 (when the vibration generator is installed in the control unit 16) or power supply lines 14 (when the vibration generators are provided directly on the power transmitters 12), it is advantageous for the freedom of movement of the person, i.e., for example, a hair salon customer, not to be overly restricted and for the person to be allowed to assume a comfortable, usually seated, position.
The clip is preferably designed in such a way that it can be easily applied to and removed from the foil-wrapped tufts of hair by hand. To this end, the clip may, for example, be provided with a spring, which ensures a firm grip of the clip on the foil pocket or on the tuft of hair, but prevents strong squeezing of the foil or the tuft of hair. The basic dimensions of the clip are, for example 3 cm by 8 cm, which thus essentially correspond to the basic dimensions of a customary foil pocket.
Furthermore, as
It is also possible for there to be only one small aluminum plate 50 instead of two and for the other plate 50 to be made of plastic.
As noted earlier, it is also possible to provide a vibration generator, for example, in the grip section 54 of the vibration transmitter. This vibration generator generates vibrations, which are then applied to the air through the small plates 50. Furthermore, it is possible, for example, to provide a vibration generator on one or both of the small plates 50. The vibration transmitter can be connected to the treatment device, especially to the control unit 16, by a vibration transmission line or power supply line 14.
As noted above, in the present invention, vibrations are transmitted to the hair to be treated. These vibrations are, for example, in the audible range or in the ultrasonic range. These vibrations produce, for example, micromovements of the hair. For example, a cavitation effect can also be produced by these vibrations. The application of the vibrations to the hair also often leads to a temperature increase. In any case, it can be stated that, for example, this type of application of vibrations to the hair significantly reduces the amount of time the active hair-dyeing or hair-bleaching agents must act on the hair. In addition, more intensive and longer-lasting dyeing can be achieved, since the active agent can penetrate the fiber sheath more deeply. The application of vibrations can also lead to a definite increase in color intensity. These positive effects can advantageously reduce, e.g., the proportions of oxidation dye intermediates or ammonia in the hair-dyeing or hair-bleaching agents, which, for example, reduces the annoyance of strong odors for persons who come in contact with these agents. It is also possible to achieve an advantageous reduction of the amounts of active substances and agents. Furthermore, subtler dyeing can be achieved.
The vapor can be provided with vibrations, for example, in such a way that the particles of liquid experience slight vibration, for example, a microvibration, and in such a way that molecular vibration is produced in the liquid droplets that form the vapor. When water vapor is used, it is possible, for example, to produce a dipole vibration.
For example, the vibration element 100 can be refined in such a way that the vibration element 100 brings about atomization of a liquid to produce an aerosol. For example, by dropping a liquid onto the vibration element 100, fine atomization can be produced in such a way that a very fine aerosol is produced.
In accordance with a variation of this second embodiment (
These sound generators preferably consist of a radiating surface, one or more resonators and an electromechanical transducer. In accordance with the invention, the electromechanical transducer is preferably a piezoelectric transducer or a magnetostrictive transducer.
The radiating surface is preferably made of stainless steel or titanium and preferably has a surface area of 100 to 10,000 mm2, especially 1000 to 8000 mm2. A surface area of 7000 mm2 can be especially preferred in accordance with the invention. A rectangular geometry of the radiating surface is preferred in accordance with the invention, but any other geometry is also possible, for example, square or circular. The radiating surface can be mounted, for example, on a cylindrical attachment with a diameter of 10-100 mm, especially 35-65 mm and most especially 45-55 mm. This cylindrical attachment is constructed of several disks with a piezoelectric transducer preferably located in the center and with a resonator on each side. With an arrangement of this type, the radiating surface is preferably mounted on one of the two resonators. As a result of this vibration of the piezoelectric transducer, the whole cylindrical attachment in this refinement is subject to a change in length and transmits this vibration to the radiating surface. The piezoelectric transducer is excited by a high-frequency generator, preferably in the region of its resonance frequency. Preferred frequencies to be used in accordance with the invention are 20-50 kHz, especially 30-40 kHz and most preferably in the area of 35 kHz.
In addition, it can also be preferred in accordance with the invention not to drive the piezoelectric transducer at a constant frequency, but rather to vary the frequency in a range of several hundred Hz (the frequency is wobbled). IN this process, the high frequency is varied by 0.1 to 1 kHz, preferably several times per second and especially 10 times per second. At a basic frequency of, for example, 35 kHz, this variation causes the frequency to vary in a range of about 34 to 36 kHz. This modification produces a more uniform result on the fibers to be treated.
In accordance with the invention, it can also be preferred to use mechanical movement of the entire sound generator inside the vapor hood to achieve a more uniform result. For example, the sound generator as a whole can be slowly moved back and forth or can also revolve in cyclical paths inside the hood. This can occur, for example, with a frequency on the order of about 1 revolution per 10-300 seconds and preferably about 1 revolution per 10 seconds. When several sound generators are used, it is also possible for all of them to be integrated in a motion of this type. In accordance with the invention, it is also possible to combine frequency wobbling with simultaneous mechanical movement of the entire sound generator. In this regard, the system is preferably optimized in such a way that it allows maximum sound emission in a gaseous medium.
Methods and devices in which, for example, vibrations, such as ultrasonic waves, can be transmitted to vapor are described in U.S. Pat. No. 3,211,159 and U.S. Pat. No. 4,085,893, which are herewith incorporated in the present disclosure by reference.
Instead of a central vibration generator 124, one or more vibration generators can also be mounted on the fingers 120.
To distribute the vibrations as uniformly as possible to the hair, the hair can be pretreated with, for example, a vibration-conducting substance. For example, a good distribution of the vibrations around each of the fingers 120 can be achieved by applying an aqueous liquid or gel to the hair.
Vibrations can be transmitted to keratin fibers, for example, hair, by means of the embodiments described above. As described above, the treatment devices are preferably designed in such a way that no attendance by the operator is necessary during the treatment. That is, the treatment device is set up, for example, vibration transmitters are applied to the hair. The treatment is then begun. During the treatment, no attendance or supervision by, for example, a hairdresser or assistant is necessary. As soon as the treatment is finished, the vibration transmitters can then be removed. This simplifies the handling of the device and allows efficient treatment of a large number of persons in the everyday routine of the hair salon.
As noted earlier, a treatment can involve the shaping of hair, the dyeing of hair, the bleaching of hair or the application of hair treatment agents or hair-care preparations.
The vibrations transmitted to the keratin fibers can be in the audible range or even in the ultrasonic range. For example, an improved treatment can be achieved at a frequency of 5 kHz. However, it is also possible to obtain good results with frequencies in the range of 20 kHz to 200 kHz. Good results can also be achieved in higher frequency ranges. The power of the vibration generators that are used can vary from 5 to 200 watts. More powerful vibration transmitters are also conceivable. The total power of the vibration transmitters of a treatment device is advantageously on the order of 100 watts.
The treatment devices described above can be advantageously used for hair dyeing or bleaching. For example, agents for dyeing or bleaching keratin fibers can be used which contain no chelant or chelating agent. A standard function of chelating agents or chelants is reduction of visible fiber damage caused by the simultaneous or subsequent use of oxidative treatment steps involving bleaching or dyeing of the hair. Chelating agents accomplish this by fixing minerals that are bound in the hair. To this end, it is necessary for the chelating agents to be brought into contact with the hair as effectively as possible, so that preferably they quickly get into or penetrate the hair. Chelants or chelating agents (also known as chelants) pertain to a molecule that has two or more electron donor atoms, so that coordinate bonds can be formed with a single ion. This results in the formation of a cyclic structure known as a chelate. In particular, these are understood to mean diamines or monoamine dipole acids or the like. Amine-based chelating agents are also known, which supposedly improve the effectiveness of an oxidizing agent.
Described in a general way, chelating agents are always so-called, at least bidentate molecules that form a ring or the like with the metal ion to be formed.
Complexing agents of this type can also be used to bind or capture metal ion impurities in water.
Accordingly, embodiments of agents for dyeing or bleaching keratin fibers in accordance with the present invention are specified or described, which do not have to contain a chelant or chelating agent or in which chelants or chelating agents can be left out. These agents can be advantageously used in conjunction with the treatment devices that were described earlier.
For the dyeing of keratin fibers, especially human hair, the so-called oxidation dyes play a preferred role due to their intensive dyeing and good fastness properties. Dyes of this type contain oxidation dye intermediates, so-called developer components and coupler components. The developer components form the actual dyestuffs among themselves under the influence of oxidizing agents or atmospheric oxygen or by coupling with one or more coupler components.
Primary aromatic amines with an additional free or substituted hydroxyl or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives, and 2,4,5,6-tetraminopyrimidine and its derivatives are usually used as developer components.
Specific members of these groups are p-phenylenediamine, p-toluylenediamine, 2,4,5,6-tetraminopyrimidine, p-aminophenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenyl)ethanol, 2-(2,5-diaminophenoxy)ethanol, 1-phenyl-3-carboxyamido-4-aminopyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine, and 1,3-N,N′-bis(2-hydroxyethyl)-N,N′-bis(4-aminophenyl)diaminopropan-2-ol.
Good oxidation dye intermediates should satisfy the following requirements above all: During the oxidative coupling, they must develop the desired color shades in sufficient intensity and fastness. In addition, they must have a good capacity for absorption on the fibers, and, especially in the case of human hair, there may be no appreciable differences between frayed hair and hair that has recently grown in (leveling capacity). They should be resistant to light, heat, sweat, friction and the action of chemical reducing agents, e.g., permanent wave liquids. Finally, if used as hair dyes, they should not stain the scalp very much, and, above all, they should be toxicologically and dermatologically safe. Furthermore, the dyeing produced by blond-bleaching should be readily removable from the hair if it turns out that it does not conform to the desires of the individual person and is to be reversed.
In accordance with the invention, keratin fibers are understood to mean furs, wool, feathers and especially human hair.
Primary aromatic amines with an additional free or substituted hydroxyl or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives, and 2,4,5,6-tetraminopyrimidine and its derivatives are usually used as developer components.
The use of a p-phenylenediamine derivative or one of its physiologically tolerated salts can be preferred in accordance with the invention. p-Phenylenediamine derivatives of formula (E1) are especially preferred
in which
Examples of the C1 to C4 alkyl groups specified as substituents in the compounds in accordance with the invention are the groups methyl, ethyl, propyl, isopropyl, and butyl. Ethyl and methyl are preferred alkyl groups. Examples of preferred C1 to C4 alkoxy groups in accordance with the invention are the methoxy group and the ethoxy group. Examples of preferred C1 to C4 hydroxyalkyl groups are the hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, and 4-hydroxybutyl groups. A 2-hydroxyethyl group is especially preferred. An especially preferred C2 to C4 polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms that can be used in accordance with the invention are F, Cl, or Br atoms. Cl atoms are especially preferred. Other terms used in accordance with the invention are derived from the definitions given here. Examples of nitrogen-containing groups in formula (E1) include especially amino groups, C1 to C4 monoalkylamino groups, C1 to C4 dialkylamino groups, C1 to C4 trialkylammonium groups, C1 to C4 monohydroxyalkylamino groups, imidazolinium, and ammonium.
Especially preferred p-phenylenediamines of formula (E1) are selected from among p-phenylenediamine, p-toluylenediamine, 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-(α,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 physiologically tolerated salts.
In accordance with the invention, compounds that contain at least two aromatic nuclei that are substituted with amino and/or hydroxyl groups can also be preferred for use as the developer component.
Binuclear developer components that can be used in the dye compositions in accordance with the invention include especially compounds of formula (E2) below and their physiologically tolerated salts:
in which
In accordance with the invention, the substituents used in formula (E2) are defined analogously to the details specified above.
Preferred binuclear developer components of formula (E2) are especially the following: N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropan-2-ol, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine, N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)tetramethylenediamine, N,N′-bis(4-methylaminophenyl)tetramethylenediamine, N,N′-diethyl-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine, bis(2-hydroxy-5-aminophenyl)methane, 1,3-bis(2,5-diaminophenoxy)propan-2-ol, 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 physiologically tolerated salts.
Binuclear developer components of formula (E2) that are especially preferred are N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropan-2-ol, bis(2-hydroxy-5-aminophenyl)methane, 0,1,3-bis(2,5-diaminophenoxy)propan-2-ol, N,N′-bis(4′-aminophenyl)-1,4-diazacycloheptane, and 1,10-bis(2′,5′-diaminophenyl)-1,4′,7,10-tetraoxadecane, or one of their physiologically tolerated salts.
In accordance with the invention, bis(2-hydroxy-5-aminophenyl)methane is an especially preferred binuclear developer component of formula (E2).
In addition, in accordance with the invention, it can be preferred to use a p-aminophenol derivative or one of its physiologically tolerated salts as the developer component. p-Amino-phenol derivatives of formula (E3) are especially preferred
in which
In accordance with the invention, the substituents used in formula (E3) are defined analogously to the details specified above.
Preferred p-aminophenols of formula (E3) are especially 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-(hydroxyethoxy)phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol, 4-amino-2-(α,β-dihydroxyethyl)phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2-(diethylaminomethyl)phenol, and their physiologically tolerated salts.
Compounds of formula (E3) that are especially preferred are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(α,β-dihydroxyethyl)phenol, and 4-amino-2-(diethylaminomethyl)phenol.
Furthermore, the developer component can be selected from among o-aminophenol and its derivatives, for example, 2-amino-4-methylphenol, 2-amino-5-methylphenol, or 2-amino-4-chlorophenol.
In addition, the developer component can be selected from among heterocyclic developer components, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives, and their physiologically tolerated salts.
Preferred pyridine derivatives are especially the compounds described in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2-(4′-methoxyphenyl)-amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(β-methoxyethyl)-amino-3-amino-6-methoxypyridine, and 3,4-diaminopyridine.
Preferred pyrimidine derivatives are especially the compounds described in German Patent DE 2 359 399, Japanese Early Disclosure JP 02019576 A2, or Early Disclosure WO 96/15765, such as 2,4,5,6-tetraminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethyl-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, and 2,5,6-triaminopyrimidine.
Preferred pyrazole derivatives are especially the compounds described in the patents DE 3 843 892 and DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP 740 931, and DE 195 43 988, 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.
Preferred pyrazole-pyrimidine derivatives are especially the derivatives of pyrazole-[1,5-a]-pyrimidine of formula (E4) below and its tautomeric forms if a tautomeric equilibrium exists
in which
In accordance with the invention, the substituents used in formula (E4) are defined analogously to the details specified above.
If the pyrazole-[1,5-a]-pyrimidine of formula (E4) above contains a hydroxyl group in one of the positions 2, 5, or 7 of the ring system, a tautomeric equilibrium exists, which is described, for example, by the following equilibrium equation:
Especially the following pyrazole-[1,5-a]-pyrimidines of formula (E4) above can be cited:
The pyrazole-[1,5-a]-pyrimidines of formula (E4) above can be prepared, as described in the literature, by cyclization, starting from an aminopyrazole or from hydrazine.
In another preferred embodiment, the dyes of the invention contain at least one other coupler component.
The following are preferred coupler components in accordance with the invention:
Coupler components that are especially preferred in accordance with 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-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, and 2,6-dihydroxy-3,4-dimethylpyridine.
The hair dyes of this embodiment of the invention contain both the developer components and the coupler components, preferably in an amount of 0.005 to 20 wt. %, and especially in an amount of 0.1 to 5 wt. %, in each case based on the total amount of oxidation dye. In this regard, developer components and coupler components are generally used in approximately equimolar amounts. Although the use of equimolar amounts has been found to be advantageous, a certain excess of individual oxidation dye intermediates is not disadvantageous, so that developer components and coupler components can be present in a molar ratio of 1:0.5 to 1:3, and especially 1:1 to 1:2.
In another embodiment of the present invention, the dyes can contain at least one precursor of a natural analogue dyestuff. Indoles and indolines that have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of natural analogue dyestuffs. These groups can have further substituents, e.g., in the form of an etherification or esterification of the hydroxyl group or an alkylation of the amino group. In a second preferred embodiment, the dyes contain at least one indole and/or indoline derivative.
Derivatives of 5,6-dihydroxyindoline of formula (IIa) are especially well suited as precursors of natural analogue hair dyes
in which, independently of one another,
Especially 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, as well as 6-hydroxyindoline, 6-aminoindoline, and 4-aminoindoline.
Especially preferred compounds 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.
In addition, derivatives of 5,6-dihydroxyindole of formula (IIb) are extremely well suited as precursors of natural analogue hair dyes.
in which, independently of one another,
Especially 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.
Especially preferred compounds 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 be used in the dyes of the invention both as free bases and in the form of their physiologically tolerated salts with inorganic or organic acids, e.g., the hydrochlorides, sulfates, and hydrobromides. The indole or indoline derivatives are usually present in the dyes in amounts of 0.05 to 10 wt. %, and preferably 0.2 to 5 wt. %.
In accordance with another embodiment of the invention, it can be preferred for the indoline or indole derivative to be present in the dyes in combination with at least one amino acid or one oligopeptide. It is advantageous for the amino acid to be an α-amino acid; especially preferred α-amino acids are arginine, ornithine, lysine, serine, and histidine, especially arginine.
In addition to the m-phenylenediamine derivatives of formula (E1) in accordance with the invention, in another preferred embodiment of the present invention, the dyes of the invention can contain one or more direct dyes to obtain the desired shading. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, or indophenols. Preferred direct dyes are the following compounds known by their international designations or trade names: HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57:1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52, as well as 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-tetrahydroxyquinoxaline, 2-hydroxy-1,4-naphthoquinone, 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, the preparations of the invention can contain a cationic direct dye. Especially preferred compounds of this type are
Preferred cationic direct dyes of group (c) include especially the following compounds:
The compounds of formulas (DZ1), (DZ3), and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31, and Basic Red 51, are especially preferred cationic direct dyes of group (c).
The cationic direct dyes sold under the trade name Arianor® are also especially preferred cationic direct dyes in accordance with the invention.
The preparations in accordance with this embodiment of the invention preferably contain the direct dyes in an amount of 0.01 to 20 wt. %, based on the total dye.
In addition, the preparations of the invention can also contain naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile blossom, sandalwood, black tea, alder buckthorn (Rhamnus frangula) bark, sage, logwood, madder root, catechu, sedre, and alkanet root.
It is not necessary for the oxidation dye intermediates or the direct dyes to be homogeneous compounds, but rather the hair dyes in accordance with the invention can contain minor amounts of other components originating from the production processes for the individual dyes, provided that these other components do not adversely affect the dyeing result or have to be excluded for other reasons, e.g., toxicological reasons.
With respect to the dyestuffs that can be used in the hair dyeing and tinting agents in accordance with the invention, explicit reference is additionally made to the monograph C. Zviak, The Science of Hair Care, Chapter 7 (pp. 248-250; direct dyes) and Chapter 8 (pp. 264-267; oxidation dye intermediates), published as Volume 7 of the series Dermatology (Edited by C. Culnan and H. Maibach), Verlag Marcel Dekker, Inc., New York, Basel, 1986, and “European Inventory of Cosmetic Raw Materials”, published by the European Union and available on floppy disk from the Bundesverband Deutscher Industrie- und Handelsunternehmen für Arzneimittel, Reformwaren und Körperpflegemittel e.V. [German National Industrial and Commercial Association for Drugs, Health Products, and Toiletries], Mannheim.
The dyes of the invention can also contain all active substances, additives, and adjuvants known for preparations of this type. In many cases, the dyes contain at least one surfactant. It is basically possible to use not only anionic surfactants, but also zwitterionic, ampholytic, nonionic, and cationic surfactants. In many cases, however, it has been found to be advantageous to select the surfactants from among anionic, zwitterionic or nonionic surfactants.
All anionic surface-active substances suitable for use on the human body are suitable for use as anionic surfactants in preparations in accordance with the invention. These substances are characterized by an anionic group that makes the substance soluble in water, e.g., a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group with about 10-22 C atoms. In addition, the molecule can contain glycol ether groups or polyglycol ether groups, ester, ether and amide groups, and hydroxyl groups. The following are examples of suitable anionic surfactants, each in the form of the sodium, potassium, ammonium and mono-, di-, and trialkanol ammonium salts with 2 or 3 C atoms in the alkanol group,
Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates, and ether carboxylic acids with 10-18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and especially salts of saturated and especially unsaturated C8-C22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid, and palmitic acid.
Nonionic surfactants contain as the hydrophilic group, e.g., a polyol group, a polyalkylene glycol ether group, or a combination of polyol and polyglycol ether groups. The following are examples of compounds of this type:
Preferred nonionic surfactants are alkyl polyglycosides with the general formula R1O-(Z)x. These compounds are characterized by the following parameters.
The alkyl group R1 contains 6-22 carbon atoms and can be both linear and branched. Primary linear and 2-methyl-branched aliphatic groups are preferred. Examples of alkyl groups of this type are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl, and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, and 1-myristyl are especially preferred. When so-called “oxo alcohols” are used as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.
The alkyl polyglycosides that can be used in accordance with the invention may contain, for example, only one specific alkyl group R1. However, these compounds are usually produced with natural fats and oils or mineral oils as the starting materials. In this case, the alkyl groups R comprise mixtures corresponding to the starting compounds or corresponding to the given processing of these compounds.
Alkyl polyglycosides that are especially preferred are those in which R1 comprises
Any desired mono- or oligosaccharides can be used as the sugar building block Z. Sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of sugars of this type are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose, and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose, and sucrose; glucose is especially preferred.
The alkyl polyglycosides that can be used in accordance with the invention contain, on average, 1.1 to 5 sugar building blocks. Alkyl polyglycosides with values of x of 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are especially preferred.
The alkyl glycosides can be used not only for their surfactant effect but also to improve the fixation of fragrant components on the hair. Thus, when it is desired that an effect of a perfume oil on the hair extend beyond the duration of the hair treatment, the expert will preferably fall back on this class of substances as a further ingredient of the preparations of the invention.
The alkoxylated homologues of the specified alkyl polyglycosides can also be used in accordance with the invention. These homologues can contain, on average, up to 10 ethylene oxide and/or propylene oxide units per alkyl glycoside unit.
In addition, zwitterionic surfactants can be used, especially as co-surfactants. Zwitterionic surfactants are surface-active compounds that have at least one quaternary ammonium group and at least one —COO(−) or —SO3(−) group in the molecule. Especially well-suited zwitterionic surfactants are the so-called betaines, such as N-alkyl-N,N-dimethylammonium glycinates, for example, cocoalkyl dimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, such as cocoacylaminopropyl dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl imidazolines with 8-18 C atoms in the alkyl or acyl group, as well as cocoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name cocamidopropyl betaine.
Ampholytic surfactants are also suitable, especially as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C8-C18 alkyl or acyl group, contain at least one free amino group and at least one —COOH or —SO3H group in the molecule and are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids, and alkylaminoacetic acids with 8-18 C atoms in the alkyl group. Especially preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate, and C12-18-acylsarcosine.
Cationic surfactants that can be used in accordance with the invention include especially those of the following types: quaternary ammonium compounds, esterquats, and amidoamines.
Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyl trimethylammonium chlorides, dialkyl dimethylammonium chlorides, and trialkyl methylammonium chlorides, e.g., cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and tricetylmethylammonium chloride, as well as the imidazolium compounds known by the INCI names quaternium-27 and quaternium-83. The long alkyl chains of the aforementioned surfactants preferably have 10-18 carbon atoms.
Esterquats are well-known substances that contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanol alkylamines, and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Products of this type are sold, for example, under the trade names Stepantex®, Dehyquart®, and Armocare®. The products Armocare® VGH-70, an N,N-bis(2-palmitoyloxyethyl)dimethylammonium chloride, and Dehyquart® F-75, and Dehyquart® AU-35 are examples of these esterquats.
The alkyl amidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkyl aminoamines. A compound in this group of substances that is especially suitable in accordance with the invention is stearylamidopropyl dimethylamine, which is commercially available under the trade name Tegoamid® S 18.
Other cationic surfactants that can be used in accordance with the invention are quaternized protein hydrolysates.
Cationic silicone oils are also suitable in accordance with the invention, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone, which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker), and Abil®-Quat 3270 and 3272 (manufacturer: T. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).
An example of a quaternary sugar derivative that can be used as a cationic surfactant is the commercial product Glucquat® 100, which in INCI nomenclature is a “lauryl methyl gluceth-10 hydroxypropyldimonium chloride”.
The compounds with alkyl groups that are used as the surfactant can be homogeneous substances. However, it is generally preferred to produce these substances from natural raw materials of animal or vegetable origin, so that mixtures of substances are obtained that have different alkyl chain lengths, depending on the particular raw material.
The surfactants that are addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of these addition products may either be products with a “normal” homologue distribution or products with a restricted homologue distribution. “Normal” homologue distributions are understood to mean mixtures of homologues obtained in the reaction of fatty alcohols and alkylene oxides with the use of alkali metals, alkali-metal hydroxides, or alkali-metal alcoholates as catalysts. Restricted homologue distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline-earth-metal salts of ether carboxylic acids, alkaline-earth-metal oxides, hydroxides, or alcoholates are used as catalysts. The use of products with restricted homologue distributions can be preferred.
In many cases the hair treatment preparations additionally contain at least one conditioning polymer.
Cationic polymers are a first group of conditioning polymers. Within the context of the invention, cationic polymers are understood to be polymers whose main chain and/or side chain contains a group that can be “temporarily” cationic or “permanently” cationic. “Permanently cationic” polymers in accordance with the invention are polymers that have a cationic group, independently of the pH of the preparation. These are generally polymers that contain a quaternary nitrogen atom, for example, in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, polymers in which the quaternary ammonium group is linked to a polymer main chain consisting of acrylic acid, methacrylic acid or their derivatives via a C1-4 hydrocarbon group have proven especially suitable.
Especially preferred cationic polymers are homopolymers of general formula (G1-I)
in which R=—H or —CH3; R2, R3, and R4 are selected, independently of one another, from C1-4 alkyl, alkenyl, or hydroxyalkyl groups; m=1, 2, 3, or 4; n is a natural number; and X− is a physiologically tolerated organic or inorganic anion; and copolymers that consist essentially of the monomer units specified in formula (G1-I) and nonionic monomer units. Among these polymers, polymers which are preferred in accordance with the invention are those for which one of the following conditions applies:
Suitable physiologically tolerated anions X− include, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions, and organic ions, such as lactate, citrate, tartrate, and acetate ions. Halide ions are preferred, especially chloride.
An especially suitable homopolymer is poly(methacryloyloxyethyltrimethylammonium chloride), which may be crosslinked, if so desired. The INCI name of the compound is polyquaternium-37. If desired, the crosslinking can be carried out with multiply olefinically unsaturated compounds, for example, divinylbenzene, tetrallyloxyethane, methylenebisacrylamide, diallyl ether, polyallyl polyglyceryl ether, or allyl ethers of sugars or sugar derivatives, such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose, or glucose. Methylenebisacrylamide is a preferred crosslinking agent.
The homopolymer is preferably used in the form of a nonaqueous polymer dispersion, which should have a polymer content of not less than 30 wt. %. Polymer dispersions of this type are commercially available under the names Salcare® SC 95 (ca. 50% polymer component; other components: mineral oil (INCI name: mineral oil) and tridecyl polyoxypropylene/polyoxyethylene ether (INCI name: PPG-1 trideceth-6)) and Salcare® SC 96 (ca. 50% polymer component; other components: mixture of diesters of propylene glycol with a mixture of caprylic acid and capric acid (INCI name: propylene glycol dicaprylate/dicaprate) and tridecyl polyoxypropylene/polyoxyethylene ether (INCI name: PPG-1 trideceth-6)).
Copolymers with monomer units of formula (G1-I) preferably contain acrylamide, methacrylamide, acrylic acid C1-4 alkyl esters, and methacrylic acid C1-4 alkyl esters as nonionic monomer units. Of these nonionic monomers, acrylamide is especially preferred. As in the case of the homopolymers described above, these copolymers can also be crosslinked. A copolymer that is preferred in accordance with the invention is crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer. Copolymers of this type, in which the monomers are present in a ratio by weight of about 20:80, are commercially available as a ca. 50% nonaqueous polymer dispersion under the name Salcare® SC 92.
Examples of other preferred cationic polymers are:
Other cationic polymers that can be used are polymers known by the name polyquaternium-24 (commercial product, e.g., Quatrisoft® LM 200). The copolymers of vinylpyrrolidone can also be used in accordance with the invention, e.g., those which are commercially available under the trade names Copolymer 845 (manufacturer: ISP), Gaffix® VC 713 (manufacturer: ISP), Gafquat® ASCP 1011, Gafquat® HS 110, Luviquat® 8155, and Luviquat® MS 370.
Other cationic polymers in accordance with the invention are the so-called “temporarily cationic” polymers. These polymers usually contain an amino group, which at certain pH's is present as a quaternary ammonium group and is thus cationic. Preferred polymers of this type include, for example, chitosan and its derivatives, such as the commercially available products Hydagen® CMF, Hydagen® HCMF, Kytamer® PC, and Chitolam® NB/101.
Preferred cationic polymers in accordance with the invention are cationic cellulose derivatives and chitosan and its derivatives, especially the commercial products Polymer® JR 400, Hydagen® HCMF, and Kytamer® PC, cationic guar derivatives, cationic honey derivatives, especially the commercial product Honeyquat® 50, cationic alkyl polyglycosides as described in German Patent DE 44 13 686, and polymers of the type polyquaternium-37.
In addition, the cationic polymers include cationized protein hydrolysates. The underlying protein hydrolysate can be derived from animals, for example, from collagen, milk or keratin, from plants, for example, from wheat, corn, rice, potatoes, soybeans, or almonds, or from marine life forms, for example, from fish collagen or algae, or it can be obtained by bioengineering methods. The protein hydrolysates on which the cationic derivatives of the invention are based can be obtained from the corresponding proteins by a chemical hydrolysis, especially an alkaline or acid hydrolysis, by an enzymatic hydrolysis and/or by a combination of the two types of hydrolysis. The hydrolysis of proteins generally yields a protein hydrolysate with a molecular-weight distribution from about 100 daltons to several thousand daltons. Preferred cationic protein hydrolysates are those whose underlying protein component has a molecular weight of 100 to 25,000 daltons, and preferably 250 to 5,000 daltons. Cationic protein hydrolysates are also understood to mean quaternized amino acids and their mixtures. The protein hydrolysates or the amino acids are often quaternized by means of quaternary ammonium salts, for example, N,N-dimethyl-N-(n-alkyl)-N-(2-hydroxy-3-chloro-n-propyl) ammonium halides. Moreover, the cationic protein hydrolysates can also be further derivatized. Typical examples of cationic protein hydrolysates and derivatives in accordance with the invention are the commercially available products listed by the INCI names in “International Cosmetic Ingredient Dictionary and Handbook”, (Seventh Edition 1997, The Cosmetic, Toiletry, and Fragrance Association, 1101 17th. Street, N.W., Suite 300, Washington, D.C. 20036-4702): cocodimonium hydroxypropyl hydrolyzed collagen, cocodimonium hydroxypropyl, hydrolyzed casein, cocodimonium hydroxypropyl hydrolyzed collagen, cocodimonium hydroxypropyl hydrolyzed hair keratin, cocodimonium hydroxypropyl hydrolyzed keratin, cocodimonium hydroxypropyl hydrolyzed rice protein, cocodimonium hydroxypropyl hydrolyzed soy protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyl arginine lauryl/myristyl ether HCl, hydroxypropyltrimonium gelatin, hydroxypropyltrimonium hydrolyzed casein, hydroxypropyltrimonium hydrolyzed collagen, hydroxypropyltrimonium hydrolyzed conchiolin protein, hydroxypropyltrimonium hydrolyzed keratin, hydroxypropyltrimonium hydrolyzed rice bran protein, hydroxypropyltrimonium hydrolyzed soy protein, hydroxypropyl hydrolyzed vegetable protein, hydroxypropyltrimonium hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed wheat protein/siloxysilicate, laurdimonium hydroxypropyl hydrolyzed soy protein, laurdimonium hydroxypropyl hydrolyzed wheat protein, laurdimonium hydroxypropyl hydrolyzed wheat protein/siloxysilicate, lauryldimonium hydroxypropyl hydrolyzed casein, lauryldimonium hydroxypropyl hydrolyzed collagen, lauryldimonium hydroxypropyl hydrolyzed keratin, lauryldimonium hydroxypropyl hydrolyzed soy protein, steardimonium hydroxypropyl hydrolyzed casein, steardimonium hydroxypropyl hydrolyzed collagen, steardimonium hydroxypropyl hydrolyzed keratin, steardimonium hydroxypropyl hydrolyzed rice protein, steardimonium hydroxypropyl hydrolyzed soy protein, steardimonium hydroxypropyl hydrolyzed vegetable protein, steardimonium hydroxypropyl hydrolyzed wheat protein, steardimonium hydroxyethyl hydrolyzed collagen, quaternium-76 hydrolyzed collagen, quaternium-79 hydrolyzed collagen, quaternium-79 hydrolyzed keratin, quaternium-79 hydrolyzed milk protein, quaternium-79 hydrolyzed soy protein, and quaternium-79 hydrolyzed wheat protein.
The plant-based cationic protein hydrolysates and derivatives are especially preferred.
Other conditioning polymers that can be used in accordance with the invention are the amphoteric compounds specified in British Early Disclosure 2 104 091, European Early Disclosure 47 714, European Early Disclosure 217 274, European Early Disclosure 283 817, and German Early Disclosure 28 17 369.
Preferred amphoteric polymers are polymers that are composed essentially of
In accordance with the invention, these compounds can be used both directly and in the form of their salts, which are obtained by neutralization of the polymers, for example, with an alkali hydroxide. In regard to the details of the preparation of these polymers, explicit reference is made to the contents of German Early Disclosure 39 29 973. Especially preferred polymers of this type are those in which the monomers of type (a) are characterized by the fact that R3, R4, and R5 are methyl groups, Z is an NH group, and A(−) is a halide, methoxysulfate, or ethoxysulfate ion; acrylamidopropyl trimethylammonium chloride is an especially preferred monomer (a). The use of acrylic acid as monomer (b) in the aforesaid polymers is preferred.
The hair-care preparations preferably contain the conditioning polymers in an amount of 0.01 to 5 wt. %, and especially in an amount of 0.1 to 2 wt. %, based on the total applied preparation.
Other suitable hair-conditioning compounds are phospholipids, for example, soy lecithin, egg lecithin, and cephalins, and the substances known by the following INCI names: linoleamidopropyl PG-dimonium chloride phosphate, cocamidopropyl PG-dimonium chloride phosphate, and stearamidopropyl PG-dimonium chloride phosphate. These compounds are sold, for example, by the company Mona, under the trade names Phospholipid EFA®, Phospholipid PTC®, and Phospholipid SV®.
The preparations of the invention preferably contain the lipids in amounts of 0.01 to 10 wt. %, and especially 0.1 to 5 wt. %, based on the total applied preparation.
In addition, the dyes of the invention can contain other active substances, adjuvants, and additives, for example
With respect to other optional components and the amounts of these components to be used, reference is explicitly made to handbooks on this subject, with which the expert is already familiar, e.g., K. Schrader, Grundlagen und Rezepturen der Kosmetika [Principles and Formulations of Cosmetics], Second Edition, Hüthig Buch Verlag, Heidelberg, 1989.
The preparations of the invention preferably contain the dye intermediates in a suitable aqueous, alcoholic, or aqueous/alcoholic vehicle. For purposes of hair dyeing, these vehicles are, for example, creams, emulsions, gels, or surfactant-containing, foaming solutions, for example, shampoos, foaming aerosols, or other preparations that are suitable for application to the hair. However, it is also possible to integrate the dye precursors in a powdered or tableted formulation.
In the context of the present invention, aqueous/alcoholic solutions are understood to mean aqueous solutions that contain 3-70 wt. % of a C1-C4 alcohol, especially ethanol or isopropanol. The preparations of the invention can also contain other organic solvents, for example, methoxybutanol, benzyl alcohol, ethyl diglycol, or 1,2-propylene glycol. In this regard, all water-soluble organic solvents are preferred.
In principle, the actual oxidative dyeing of the fibers can be accomplished with atmospheric oxygen. However, the use of a chemical oxidizing agent is preferred, especially when a lightening effect on human hair is desired in addition to the dyeing. Suitable oxidizing agents are persulfates, chlorites, and especially hydrogen peroxide or its addition products with urea, melamine, and sodium borate. However, in accordance with the invention, it is also possible for the oxidation dye to be applied to the hair together with a catalyst, which activates the oxidation of the dye intermediates, e.g., by atmospheric oxygen. Suitable catalysts for this purpose include, for example, metal ions, iodides, quinones, or certain enzymes.
Examples of suitable metal ions are Zn2+, Cu2+, Fe2+, Fe3+, Mn2+, Mn4+, Li+, Mg2+, Ca2+, and A3+. Of these metal ions, Zn2+, Cu2+ and Mn2+ are especially suitable. The metal ions can be used basically in the form of any desired, physiologically tolerated salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates, and tartrates. The use of these salts can both accelerate the development of the dye and systematically influence the shade of color.
Suitable enzymes are, for example, peroxidases, which can significantly intensify the activity of small amounts of hydrogen peroxide. In addition, suitable enzymes in accordance with the invention are those which, with the assistance of atmospheric oxygen, directly oxidize the oxidation dye intermediates, for example, the laccases, or those which produce small amounts of hydrogen peroxide in situ and in this way biocatalytically activate the oxidation of the dye intermediates. Especially suitable catalysts for the oxidation of the dye intermediates are the so-called two-electron oxidoreductases in combination with the substrates specific for them, e.g.:
It is advantageous to prepare the actual hair dye immediately before application by mixing the preparation of the oxidizing agent with the preparation that contains the dye intermediates. The resulting ready-to-use hair dye preparation preferably has a pH in the range of 6-12. The application of the hair dye in a weakly alkaline environment is especially preferred. The application temperatures can be in a range of 15-40° C. After the hair dye has been allowed to act for 5-45 minutes, it is removed from the hair that is being dyed by rinsing it out. Subsequent washing with a shampoo is unnecessary if a vehicle with a high surfactant content, e.g., a dyeing shampoo, was used.
However, especially in the case of hair that is difficult to dye, the preparation that contains the dye intermediates can be applied to the hair without first being mixed with the oxidation component. After it has been allowed to act for 20-30 minutes, the oxidation component is then applied, possibly after an intermediate rinsing of the hair. After this preparation has been allowed to act for another 10-20 minutes, the hair is rinsed and, if desired, shampooed. In a first variant of this embodiment, in which the previous application of the dye intermediates is intended to effect better penetration of the hair, the preparation in question is adjusted to a pH of about 4-7. In accordance with a second variant, oxidation with air is strived for first, in which the applied preparation preferably has a pH of 7-10. In the subsequent accelerated oxidation, the use of acid-adjusted peroxydisulfate solutions as the oxidizing agent is preferred.
The following dyeing creams are suitable especially for a dye treatment with the treatment devices of the invention.
The specified quantities are understood to be in wt. % unless otherwise noted.
The formulations 1 to 8 are preferably allowed to dye completely with the following oxidizing agent preparation:
The formulations 9 to 16 are preferably allowed to dye completely with the following oxidizing
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2004 005 092.9 | Feb 2004 | DE | national |
This application claims benefit under 35 U.S.C. §119(e) of U.S. Provisional Application No. 60,541,123, filed Feb. 2, 2004. This application also claims priority under 35 U.S.C. § 120 of German Application DE 10 2004 005 092.9, filed Feb. 2, 2004.
| Number | Date | Country | |
|---|---|---|---|
| 60541123 | May 2004 | US |
