Title:
Device for treating keratin fibers
Kind Code:
A1


Abstract:
Device for treating keratin fibers, which comprises a vibration generator and a vibration transmitter, in which the vibration transmitter is secured on the hair during the treatment, and in which vibrations are transmitted to the keratin fibers in this clamped position during the treatment.



Inventors:
Hoepfl, Helmut (Hamburg, DE)
Wolff, Wolfgang (Bargteheide, DE)
Akram, Mustafa (Hamburg, DE)
Application Number:
11/047330
Publication Date:
08/04/2005
Filing Date:
01/31/2005
Assignee:
HOEPFL HELMUT
WOLFF WOLFGANG
AKRAM MUSTAFA
Primary Class:
International Classes:
A45D2/00; A45D2/36; A45D4/18; A45D6/14; A45D7/00; A45D7/06; A45D19/00; A45D19/04; A45D19/16; A45D44/04; A45D4/08; A45D7/02; (IPC1-7): A45D24/00
View Patent Images:
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Primary Examiner:
DOAN, ROBYN KIEU
Attorney, Agent or Firm:
PAUL & PAUL (PHILADELPHIA, PA, US)
Claims:
1. A device for treating keratin fibers, which comprises a vibration generator for generating vibrations; and a vibration transmitter, which is connected with the vibration generator, for transmitting vibrations to the keratin fibers; wherein the vibration transmitter has a first section and a second section; wherein the first section and the second section can be brought into a treatment position, in which the keratin fibers are secured between the first section and the second section; and wherein, during the treatment, the vibrations are transmitted to the keratin fibers by at least one of the two sections in the clamped position.

2. The device in accordance with claim 1, wherein the first and second sections of the vibration transmitter have surfaces that are arranged essentially parallel to each other in the clamped position.

3. The device in accordance with claim 1 wherein the vibration transmitter has the form of a clip or clamp.

4. The device in accordance with claim 1 wherein the first and second sections of the vibration transmitter have dimensions such that a tuft of keratin fibers wrapped in foil is enclosed by the first and second sections essentially along a length of the keratin fibers.

5. The device in accordance with claim 1 wherein the first or the second section of the vibration transmitter consists essentially of an aluminum material.

6. The device in accordance with claim 1 wherein the first and second sections of the vibration transmitter consist of wire-like elements.

7. The device in accordance with claim 6 wherein the vibration transmitter is stationary relative to the keratin fibers arranged in the vibration transmitter during the treatment.

8. The device in accordance with claim 1 wherein the keratin fibers are human hair.

9. The device in accordance with claim 8 wherein a large number of vibration transmitters is provided, each of which is connected with the vibration generator; wherein a stand is provided, on which the vibration transmitters can be placed in a resting position in such a way that they are arranged near the head of a person whose hair is to be treated; wherein the vibration transmitters can each be attached to a tuft of hair of a person during a treatment; and wherein the vibration generator is installed on the stand.

10. The device in accordance with claim 1 wherein the vibration generator is designed to generate at least one vibration with a frequency in the range of about 3 kHz to about 200 kHz.

11. The device in accordance with claim 1 wherein the vibration generator is designed to generate at least one vibration in the ultrasonic range.

12. The device in accordance with claim 11 wherein the vibration generator is designed to generate at least one vibration with a frequency in the range of about 3 kHz to about 20 kHz.

13. The device in accordance with claim 12 wherein the vibration generator is designed to generate at least one vibration with a frequency on the order of 5 kHz.

14. The device in accordance with claim 1 wherein the keratin fibers are secured in such a way between the first and second sections of the vibration transmitter that the vibration transmitter does not slip from the keratin fibers during the treatment due to its own weight.

15. A method for treating keratin fibers, which comprises the following steps: attaching a vibration transmitter, which is connected with a vibration generator and is designed for transmitting vibrations to keratin fibers, to the keratin fibers in such a way that the keratin fibers are arranged between a first and second section of the vibration transmitter, wherein the keratin fibers are secured between the first and second sections; and transmission of the vibrations from at least one of the two sections to the keratin fibers by the vibration transmitter.

16. The method in accordance with claim 15 wherein the keratin fibers are hair; wherein a large number of vibration transmitters is arranged on the hair, and each vibration transmitter is connected with the vibration generator; and wherein the large number of vibration transmitters is mounted in a resting position on a stand in such a way that the vibration transmitters are arranged near the head of a person whose hair is to be treated and can be removed from the stand and attached to individual tufts of hair.

17. The method in accordance with claim 15 wherein an agent for changing the color of the keratin fibers, which contains no chelates, is applied to the keratin fibers.

18. The method in accordance with claim 16 wherein the agent helps transmit vibrations from the vibration transmitter to the keratin fibers.

19. The method in accordance with claim 15 wherein the vibrations have a frequency in the range of about 3 kHz to about 200 kHz.

20. The method in accordance with claim 18 wherein the vibrations have a frequency in the ultrasonic range.

21. The method in accordance with claim 19 wherein the vibrations have a frequency in the range of about 3 kHz to about 20 kHz.

22. The method in accordance with claim 20 wherein the vibrations have a frequency on the order of 5 kHz.

23. A device for treating hair, which comprises: a hood that is designed to at least partially enclose regions of the head of a person whose hair is to be treated; a vapor generator for producing vapor, wherein the vapor generator is connected with the hood; wherein the hood has holes to apply the vapor to regions of the head; a vibration generator for generating vibrations; wherein the vibration generator acts together with the vapor generator in such a way that the vibrations are transmitted to the vapor or through the vapor; wherein the vapor, to or through which the vibrations have been at least partially transmitted, is applied through the hood to hair in the corresponding regions of the head.

24. The device in accordance with claim 22 wherein the vibration generator is designed to generate at least one vibration with a frequency in the range of about 3 kHz to about 200 kHz.

25. The device in accordance with claim 22 wherein the vibration generator is designed to generate at least one vibration in the ultrasonic range.

26. The device in accordance with claim 22 wherein the vibration generator is designed to generate at least one vibration with a frequency in the range of about 3 kHz to about 20 kHz.

27. The device in accordance with claim 25 wherein the vibration generator is designed to generate at least one vibration with a frequency on the order of 35 kHz.

28. A method for treating keratin fibers, which comprises the following step: transmission of the vibrations to the keratin fibers by means of vapor.

29. The method in accordance with claim 27 wherein a first agent for changing the color of the keratin fibers, which contains no chelates, is applied to the keratin fibers.

30. The method in accordance with claim 27 further comprising a second agent, which supports the transmission of vibrations from the vapor to the keratin fibers, is applied to the keratin fibers.

31. The method in accordance with claim 27 wherein the vibrations have a frequency in the range of about 3 kHz to about 200 kHz.

32. The method in accordance with claim 27 wherein the vibrations have a frequency in the ultrasonic range.

33. The method in accordance with claim 31 wherein the vibrations have a frequency in the range of about 3 kHz to about 20 kHz.

34. The method in accordance with claim 27 wherein the vibrations have a frequency on the order of 35 kHz.

35. A device for treating hair, which comprises vibration transmission means, which surround large portions of the hair region of a person's head; wherein the vibration transmission means transmit vibrations to the hair.

36. The device in accordance with claim 34 wherein the vibration transmission means are formed as partially elastic fingers so as to at least partially surround the region of the head that is covered with hair.

37. The device in accordance with claim 34 wherein the vibrations have a frequency in the range of about 3 kHz to about 200 kHz.

38. The device in accordance with claim 34 wherein the vibrations have a frequency in the ultrasonic range.

39. The device in accordance with claim 37 wherein the vibrations have a frequency in the range of about 3 kHz to about 20 kHz.

40. The device in accordance with claim 38 wherein the vibrations have a frequency on the order of 5 kHz.

41. A method for treating keratin fibers, which comprises the step of transmitting vibrations to the keratin fibers.

42. The method in accordance with claim 40 wherein a first agent for changing the color of the keratin fibers, which contains no chelates, is applied to the keratin fibers.

43. The method in accordance with claim 40 further comprising a second agent, which supports the transmission of vibrations to the keratin fibers, is applied to the keratin fibers.

44. The method in accordance with claim 40 wherein the vibrations have a frequency in the range of about 3 kHz to about 200 kHz.

45. The method in accordance with claim 43 wherein the vibrations have a frequency in the ultrasonic range.

46. The method in accordance with claim 40 wherein the vibrations have a frequency in the range of about 3 kHz to about 20 kHz.

47. The method in accordance with claim 45 wherein the vibrations have a frequency on the order of 5 kHz.

48. An agent for changing the color of keratin fibers, wherein the agent contains no chelating agents.

Description:

CROSS REFERENCE TO RELATED APPLICATIONS

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.

BACKGROUND OF THE INVENTION

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.

SUMMARY OF THE INVENTION

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.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a three-dimensional view of a first embodiment of a treatment device in accordance with the present invention.

FIG. 2 shows a three-dimensional view of the treatment device of FIG. 1 during its use.

FIG. 3 shows a three-dimensional detail view of the treatment device of FIG. 1.

FIG. 4 shows a top view of an embodiment of a vibration transmitter in accordance with the present invention, of a type which can be used, for example, in the first embodiment of the treatment device in FIG. 1.

FIG. 5 shows a top view of another embodiment of a vibration transmitter in accordance with the present invention, of a type which can be used, for example, in the first embodiment of the treatment device in FIG. 1.

FIG. 6 shows a sectional view of another embodiment of a vibration transmitter with a tuft of hair wrapped in foil, of a type which can be used, for example, in the first embodiment of the treatment device in FIG. 1.

FIG. 7 shows a top view of the vibration transmitter of FIG. 6.

FIG. 8 shows a side sectional view of a second embodiment of a treatment device for treating keratin fibers in accordance with the present invention.

FIG. 9 shows a simplified view of a third embodiment of a treatment device for treating hair in accordance with the present invention.

FIG. 10 shows a simplified view of a fourth embodiment of a treatment device for treating hair in accordance with the present invention.

FIG. 11 shows a simplified view of a fifth embodiment of a treatment device for treating hair in accordance with the present invention.

FIG. 12 shows a three-dimensional view of a clip for transmitting vibrations in the fifth embodiment of the treatment device of FIG. 11.

FIG. 13 shows a side sectional view of a second variant of the second embodiment of a treatment device for treating keratin fibers in accordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION

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.

FIG. 1 shows a three-dimensional view of a first embodiment of a treatment device in accordance with the present invention. As FIG. 1 shows the treatment device has three operating arms 2, 4, and 6, which are preferably movably mounted on a stand 8. The operating arms 2, 4, and 6 are preferably movably mounted on the stand 8 in a way that allows each of them to be moved in three dimensions. Each operating arm 2, 4, and 6 is provided with recesses or projections, on which several vibration transmitters 12 can be removably placed. The vibration transmitters 12 are used to transmit vibrations, for example, in the audible frequency range or in the ultrasonic range, to keratin fibers, such as a person's hair. The vibration transmitters 12 are connected to a control unit 16 by cables or suitable vibration transmission lines. The stand 8 is preferably supported on a foundation 10 that is fitted with rollers.

As FIG. 1 shows, the vibration transmitters 12 are equally distributed on the three operating arms 2, 4, and 6. In FIG. 1, eleven vibration transmitters 12 are provided per operating arm, so that a total of 33 vibration transmitters 12 are provided. Naturally, a larger or smaller number of vibration transmitters can be provided in accordance with the present invention. For example, nine to twelve vibration transmitters are sufficient for certain applications. For applications in which a large amount of hair, e.g., very long hair, is to be dyed, a total of sixty vibration transmitters, for example, may be advantageous.

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.

FIG. 2 shows the treatment device of FIG. 1 during its use. As the drawing shows, the outer dimensions of the stand 8 and the operating arms 2, 4, and 6 are preferably such that they are arranged to the left of, the right of, and above the head of a seated person 22, so that the distance between each operating arm 2, 4, and 6 and the head of the person 22 is about 10-30 cm. This ensures that the person 22 has sufficient freedom of movement during the treatment. In FIG. 2, foil pockets 20 are shown in the hair of the person 22, and the vibration transmitters 12 can now be clipped onto the foil pockets.

FIG. 3 shows a three-dimensional detail view of the treatment device of FIG. 1. As the drawing shows, the operating arms 4 and 6 are arranged opposite each other and essentially horizontally. Mounting devices, such as projections, on which the vibration transmitters 12 are clipped, can be provided on the upper side of the operating arms 2, 4, and 6. It is also possible to provide recesses in the operating arms 2, 4, and 6, into which the vibration transmitters 12 are inserted. This makes it possible for them be held in a resting position on the operating arms 2, 4, and 6, so that, for example, the treatment device can be rolled to a different place without the vibration transmitters 12 falling off.

Furthermore, as FIG. 3 shows, a hand grip 30 can be provided on the control unit 16 to simplify the handling of the treatment device.

FIG. 4 shows a top view of a vibration transmitter 12, as it can be used, e.g., in the treatment device shown in FIG. 1. The vibration transmitter 12 shown in FIG. 4 comprises two flat elements 50, which in the closed state are arranged a small distance apart and essentially parallel to each other, and these flat elements 50 are preferably designed as small aluminum plates. For example, these small aluminum plates have dimensions of 5 cm by 8 cm. The small aluminum plates 50 are joined by a spring 52 at one of their two shorter ends. The spring 52 exerts a force on the plates 50 in such a way that the plates 50 are lightly pressed together in the closed state. The spring tension is preferably of sufficient magnitude that, when the spring-tensioned plates 50 are slipped onto the foil pockets, sufficient spring tension is applied to prevent the vibration transmitter 12 from slipping off the foil pocket under its own weight, but not so much pressure is applied to the foil pocket that an active agent applied to the hair in the foil pocket is squeezed out. In addition, the vibration transmitter 12 has a grip section 54, which serves both to press the plates 50 together and to allow the vibration transmitter 12 to be handled. Basically, this vibration transmitter 12 can be designed like a clothespin or a hair clip.

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.

FIG. 5 shows a top view of another embodiment of a vibration transmitter in accordance with the present invention. The vibration transmitter 12 shown in FIG. 5 is essentially the same as the vibration transmitter 12 shown in FIG. 4, except that the plates 50 are provided with cut-out sections 56, so that the plates 50 have the shape of a fork in the top view. In this way, it is possible, for example, to reduce the weight of the vibration transmitters but nevertheless to transmit the vibrations to the hair or the foil pocket. Instead of the cut-out section 56, the small plates 50 can be provided with holes.

FIG. 6 shows a sectional side view of another embodiment of a vibration transmitter 12 in accordance with the present invention. As the drawing shows, the vibration transmitter 12 has a spring 52, which presses the regions 74 against each other. In the view shown in FIG. 6, a foil packet 70 with a tuft of hair 72 is held between the regions 74. As FIG. 6 shows, the vibration transmitter 12 is preferably designed in such a way that a major portion of the foil packet or foil pocket 70 is enclosed by the regions 74.

FIG. 7 shows a top view of the vibration transmitter 12 arranged on the foil pocket 70. As the drawing shows, the regions 74 are designed as a U-shaped section of wire.

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.

FIG. 8 shows a side view of a second embodiment of a treatment device of the present invention. As the drawing shows, this treatment device has a hood 90, which is designed to surround regions of a person's head. For example, the hood 90 has essentially the dimensions of a conventional commercial drying hood. The hood 90 can be made, for example, of a plastic material. The hood 90 has an inner side 92 and an outer side 94. A large number of small holes 96 are provided on the inner side, i.e., the side of the hood 90 that faces the hair to be treated. Instead of holes, it is also possible to provide slits or openings of other, types. The hood 90 is connected to a vapor generator 98. The vapor generator 98 is connected with the hood 90 in such a way that vapor produced in the vapor generator 98 is introduced into a space between the inner side 92 and the outer side 94 of the hood 90 and is then conveyed through the holes 96 to the hair of the person to be treated. In addition, a vibration generator 102 is provided, which transmits vibrations, for example, via a vibration element 100, to the vapor or to a liquid, which is evaporated. The vibration generator 102 can be provided with adjusting devices 104 for adjusting the power and/or frequency of the generated vibrations.

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 (FIG. 13), one or more sound generators (also known as vibration elements) can be mounted on the inner side (92) of the hood, independently of the holes (96); the sound generators arranged in this way transfer the vibrations through the vapor phase to the hair to be treated. Although it is sufficient, in accordance with the invention, to mount only a single sound generator on the inner side of the hood, the mounting of several sound generators on the inner side (92) of the hood can be preferred. Furthermore, it is preferred if these sound generators are uniformly distributed over the inner side of the hood to allow uniform transmission of the vibrations to the vapor around the head of the person whose hair is to be treated.

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.

FIG. 9 shows a simplified view of a third embodiment of a treatment device of the present invention. The treatment device shown in FIG. 9 comprises vibration transmitters 120, which are formed as partially elastic fingers, which can be flipped from a resting position, in which they are shown in FIG. 9, into an operating position in such a way that the fingers 120 rest on an individual's hair. To this end, the vibration transmitters, which are movably mounted, for example, on a wall, by a mounting device 122, are moved up to the head of, for example, a seated person, in such a way that a center 126, at which the vibration transmitters 120 come together and are attached to the mounting device 122, rests on the person's hair basically near the whorl of hair at the rear of the head. The fingers 120 flipped onto the hair can then be made to conform to the shape of the person's head or hair, so that the fingers 120 are in contact with large areas of or a large portion of the hair to be treated. The fingers 120 can be made, for example, of plastic materials, such as PE, covered with metal foil. As FIG. 9 shows, a vibration generator 124 is provided, which can be mounted in a suitable place in the treatment device and transmits the vibrations to the fingers 120, through which the vibrations are in turn transmitted to the hair.

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.

FIG. 10 shows a fourth embodiment of a treatment device in accordance with the present invention. The treatment device shown in FIG. 10 is essentially the same as the treatment device shown in FIG. 9, except that a vibration transmission plate 130 that conforms to the curvature of the head is provided instead of a large number of fingers. This slightly curved vibration transmission plate 130 is flexibly attached by the mounting device 122, for example, to a stand or to a wall. To perform the treatment, the vibration transmission plate 130 can be applied to regions of the person's hair. This treatment device can be used, for example, in conjunction with a treatment device of the type shown in FIG. 9 if a person has very long hair. The treatment device shown in FIG. 9 can be used in the immediate vicinity of the head for the hair on the head down to about the neck region. For longer hair that reaches, for example, to the lower back, the treatment device shown in FIG. 10 can be used by placing the vibration transmission plate 130 on the hair in the region between the person's neck and lower back. In this way, an efficient treatment can be ensured even for long hair.

FIG. 11 shows a simplified view of a fifth embodiment of a treatment device in accordance with the present invention. As the drawing shows, this treatment device has a basically chair-like configuration with a base 140, which can be equipped with rollers, a seat 142, on which a person can sit, and a back support 144, which is designed in such a way that a person can lean back against it. A large number of vibration transmitters 146 is provided on the back support 144. A vibration generator can be provided, for example, in the seat 142 and can be connected by suitable vibration transmission lines with the vibration transmitters 146. It is also possible to provide individual vibration generators in, on or near the vibration transmitters 146.

FIG. 12 shows a three-dimensional view of an embodiment of a vibration transmitter 146 that can be used, for example, in the treatment device illustrated in FIG. 11. The vibration transmitter 146 is connected with the treatment device by a suitable line 148. The mechanical function of the vibration transmitter is essentially the same as that of a clothespin. When an operator presses the two handling regions 150 together, the two clip regions 152 are opened or moved apart. Between the handling regions 150 and the clip regions 152, there is a spring 154, which, when the handling regions 150 are not being pressed together, forces the clip regions 152 to come together in a position in which they are essentially parallel to each other. A foil packet that encloses hair and is arranged between the clip regions is thus held between the clip regions 152. The spring tension of the spring 154 is preferably strong enough that, when the vibration transmitter 146 is attached to a foil pocket, the weight of the vibration transmitter 146 itself is supported on the foil packet or on the hair. On the other hand, the spring tension of the spring 154 is weak enough to ensure that the foil packet is not pressed together to strongly, so that, for example, an active substance that has been applied to the hair is not squeezed out of the foil packet. The regions 152 and 150 can be alternately connected like a clothespin.

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.

    • m-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are usually used as coupler components. The following substances are especially suitable as coupler substances: 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-methylpyrazol-5-one, 2,4-dichloro-3-aminophenol, 1,3-bis(2,4-diaminophenoxy)propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methyl resorcinol, and 2-methyl-4-chloro-5-aminophenol.

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 embedded image
in which

    • G1 stands for a hydrogen atom, a C1 to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a (C1 to C4)-alkoxy-(C1 to C4)-alkyl group, a 4′-aminophenyl group, or a C1 to C4 alkyl group substituted with a nitrogen-containing group, a phenyl group, or a 4′-aminophenyl group;
    • G2 stands for a hydrogen atom, a C1 to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a (C1 to C4)-alkoxy-(C1 to C4)-alkyl group, or a C1 to C4 alkyl group substituted with a nitrogen-containing group;
    • G3 stands for a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine, or fluorine atom, a C1 to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a C1 to C4 hydroxyalkoxy group, a C1 to C4 acetylaminoalkoxy group, a C1 to C4 mesylaminoalkoxy group, or a C1 to C4 carbamoylaminoalkoxy group;
    • G4 stands for a hydrogen atom, a halogen atom, or a C1 to C4 alkyl group, or if G3 and G4 are in the ortho position relative to each other, together they can form a bridging α,β)-alkylenedioxo group, for example, an ethylenedioxy group.

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.

    • p-Phenylenediamines of formula (E1) that are especially preferred are p-phenylenediamine, p-toluylenediamine, 2-(β-hydroxyethyl)-p-phenylenediamine, 2-(α,β-dihydroxyethyl)-p-phenylenediamine, and N,N-bis(β-hydroxyethyl)-p-phenylenediamine.

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: embedded image
in which

    • Z1 and Z2, independently of each other, stand for a hydroxyl or NH2 group, which is possibly substituted by a C1 to C4 alkyl group, by a C1 to C4 hydroxyalkyl group, and/or by a bridge Y, or which is possibly part of a bridging ring system,
    • the bridge Y stands for an alkylene group with 1 to 14 carbon atoms, for example, a linear or branched alkylene chain or an alkylene ring, which alkylene group can be interrupted or terminated by one or more nitrogen-containing groups and/or one or more hetero atoms, such as oxygen, sulfur, or nitrogen atoms, and can possibly be substituted by one or more hydroxyl or C1 to C8 alkoxy groups, or a direct linkage,
    • G5 and G6, independently of each other, stand for a hydrogen or halogen atom, a C1 to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a C1 to C4 aminoalkyl group, or a direct linkage to the bridge Y,
    • G7, G8, G9, G10 G11 and G12, independently of one another, stand for a hydrogen atom, a direct linkage to the bridge Y or a C1 to C4 alkyl group, subject to the conditions that the compounds of formula (E2) contain only one bridge Y per molecule, and the compounds of formula (E2) contain at least one amino group, which bears at least one hydrogen atom.

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 embedded image
in which

    • G13 stands for a hydrogen atom, a halogen atom, a C1 to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a (C1 to C4)-alkoxy-(C1 to C4)-alkyl group, a C1 to C4 aminoalkyl group, a hydroxy-(C1 to C4)-alkylamino group, a C1 to C4 hydroxyalkoxy group, a C1 to C4 hydroxyalkyl-(C1 to C4)-aminoalkyl group, or a (di-C1 to C4-alkylamino)-(C1 to C4)-alkyl group,
    • G14 stands for a hydrogen or halogen atom, a C1 to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a (C1 to C4)-alkoxy-(C1 to C4)-alkyl group, a C1 to C4 aminoalkyl group, or a C1 to C4 cyanoalkyl group,
    • G15 stands for hydrogen, a C1 to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a phenyl group, or a benzyl group, and
    • G16 stands for hydrogen or a halogen atom.

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 embedded image
in which

    • G17, G18, G19 and G20, independently of one another, stand for a hydrogen atom, a C1 to C4 alkyl group, an aryl group, a C1 to C4 hydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a (C1 to C4)-alkoxy-(C1 to C4)-alkyl group, a C1 to C4 aminoalkyl group, which may possibly be protected by an acetylureid group or a sulfonyl group, a (C1 to C4)-alkylamino-(C1 to C4)-alkyl group, a di-[(C1 to C4)-alkyl]-(C1 to C4)-aminoalkyl group, in which the dialkyl groups possibly form a carbon ring or a heterocyclic ring with 5 or 6 chain members, a C1 to C4 hydroxyalkyl, or a di-(C1 to C4)-[hydroxyalkyl]-(C1 to C4)-aminoalkyl group,
    • the X groups, independently of one another, stand for a hydrogen atom, a C1 to C4 alkyl group, an aryl group, a C1 to C4 hydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a C1 to C4 aminoalkyl group, (C1 to C4)-alkylamino-(C1 to C4)-alkyl group, a di-[(C1 to C4)-alkyl]-(C1 to C4)— aminoalkyl group, in which the dialkyl groups possibly form a carbon ring or a heterocyclic ring with 5 or 6 chain members, C1 to C4 hydroxyalkyl or a di-(C1 to C4)-[hydroxyalkyl]-(C1 to C4)-aminoalkyl group, an amino group, a C1 to C4 alkyl or di-(C1 to C4 hydroxyalkyl)-amino group, a halogen atom, a carboxylic acid group, or a sulfonic acid group,
    • i has a value of 0, 1, 2, or 3,
    • p has a value of 0 or 1,
    • q has a value of 0 or 1, and
    • n has a value of 0 or 1,
      subject to the conditions that
    • the sum of p+q is not equal to 0,
    • if p+q is equal to 2, n has a value of 0, and the groups NG17G18 and NG19G20 occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7).

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: embedded image

Especially the following pyrazole-[1,5-a]-pyrimidines of formula (E4) above can be cited:

  • 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]-pyrimidine-7-ol;
  • 3-aminopyrazole-[1,5-a]-pyrimidine-5-ol;
  • 2-(3-aminopyrazole-[1,5-a]-pyrimidine-7-ylamino)ethanol;
  • 2-[(2-(7-aminopyrazole-[1,5-a]-pyrimidine-3-ylamino)ethanol;
  • 2-[(3-aminopyrazole-[1,5-a]-pyrimidine-7-yl)-(2-hydroxyethyl)-amino]ethanol;
  • 2-[(7-aminopyrazole-[1,5-a]-pyrimidine-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;
    and their physiologically tolerated salts and their tautomeric forms if a tautomeric equilibrium is present.

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.

    • m-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, and m-aminophenol derivatives are usually used as coupler components. The following substances are especially suitable as coupler substances: 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-methylpyrazol-5-one, 2,4-dichloro-3-aminophenol, 1,3-bis(2′,4′-diaminophenoxy)propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methyl resorcinol, 5-methyl resorcinol, and 2-methyl-4-chloro-5-aminophenol.

The following are preferred coupler components in accordance with the invention:

    • m-aminophenol and its derivatives, for example, 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, 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, for example, 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-diaminobenzene and its derivatives, for example, 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
    • di- and trihydroxybenzene derivatives, for example, resorcinol, resorcinol monomethyl ether, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol, and 1,2,4-trihydroxybenzene,
    • pyridine derivatives, for example, 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, for example, 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, for example, 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
    • quinoxaline derivatives, for example, 6-methyl-1,2,3,4-tetrahydroquinoxaline,
    • pyrazole derivatives, for example, 1-phenyl-3-methyl-pyrazol-5-one,
    • indole derivatives, for example, 4-hydroxyindole, 6-hydroxyindole, and 7-hydroxyindole,
    • pyrimidine derivatives, for example, 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, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene, and 1-(2′-hydroxyethyl)-amino-3,4-methylenedioxybenzene.

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 embedded image
in which, independently of one another,

    • R1 stands for hydrogen, a C1-C4 alkyl group, or a C1-C4 hydroxyalkyl group,
    • R2 stands for hydrogen or a —COOH group, such that the —COOH group can also be present in the form of a salt with a physiologically tolerated cation,
    • R3 stands for hydrogen or a C1-C4 alkyl group,
    • R4 stands for hydrogen, a C1-C4 alkyl group, or a —CO—R6 group, in which R6 stands for a C1-C4 alkyl group, and
    • R5 stands for one of the groups specified for R4,
      and physiologically tolerated salts of these compounds with an organic or inorganic acid.

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. embedded image
in which, independently of one another,

    • R1 stands for hydrogen, a C1-C4 alkyl group, or a C1-C4 hydroxyalkyl group,
    • R2 stands for hydrogen or a —COOH group, such that the —COOH group can also be present in the form of a salt with a physiologically tolerated cation,
    • R3 stands for hydrogen or a C1-C4 alkyl group,
    • R4 stands for hydrogen, a C1-C4 alkyl group, or a —CO—R6 group, in which R6 stands for a C1-C4 alkyl group, and
    • R5 stands for one of the groups specified for R4,
      and physiologically tolerated salts of these compounds with an organic or inorganic acid.

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

    • (a) cationic triphenylmethane dyes, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2, and Basic Violet 14,
    • (b) aromatic systems substituted with a quaternary nitrogen group, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16, and Basic Brown 17, and
    • (c) direct dyes that contain a heterocyclic ring that has at least one quaternary nitrogen atom, such as those specified in EP 998 908 A2, claims 6 to 11, to which explicit reference is herewith made.

Preferred cationic direct dyes of group (c) include especially the following compounds: embedded image embedded image

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,

    • linear fatty acids with 10-22 C atoms (soaps),
    • ether carboxylic acids with the formula R—O—(CH2—CH2O)x—CH2—COOH, in which R is a linear alkyl group with 10-22 C atoms and x=0 or 1 to 16,
    • acyl sarcosides with 10-18 C atoms in the acyl group,
    • acyl taurides with 10-18 C atoms in the acyl group,
    • acyl isethionates with 10-18 C atoms in the acyl group,
    • sulfosuccinic monoalkyl and dialkyl esters with 8-18 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters with 8-18 C atoms in the alkyl group and 1-6 oxyethyl groups,
    • linear alkane sulfonates with 12-18 C atoms,
    • linear α-olefin sulfonates with 12-18 C atoms,
    • α-sulfo fatty acid methyl esters of fatty acids with 12-18 C atoms,
    • alkyl sulfates and alkyl polyglycol ether sulfates with the formula R—O—(CH2—CH2O)x—SO3H, in which R is a preferably linear alkyl group with 10-18 C atoms and x=0 or 1 to 12,
    • mixtures of surface-active hydroxysulfonates in accordance with DE 37 25 030 A,
    • sulfated hydroxyalkyl polyethylene glycol ethers and/or hydroxyalkylene propylene glycol ethers in accordance with DE 37 23 354 A,
    • sulfonates of unsaturated fatty acids with 12-24 C atoms and 1-6 double bonds in accordance with DE 39 26 344 A,
    • esters of tartaric acid and citric acid with alcohols that are addition products of about 2-15 molecules of ethylene oxide and/or propylene oxide to fatty alcohols with 8-22 C atoms.

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:

    • addition products of 2-30 moles of ethylene oxide and/or 0-5 moles of propylene oxide to linear fatty alcohols with 8-22 C atoms, to fatty acids with 12-22 C atoms, and to alkyl phenols with 8-15 C atoms in the alkyl group,
    • C12-C22 fatty acid monoesters and diesters of addition products of 1-30 moles of ethylene oxide to glycerol,
    • C8-C22 alkyl monoglycosides and oligoglycosides and their ethoxylated analogues, and
    • addition products of 5-60 moles of ethylene oxide to castor oil and hydrogenated castor oil.

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

    • essentially C8 and C10 alkyl groups,
    • essentially C12 and C14 alkyl groups,
    • essentially C8 to C16 alkyl groups, or
    • essentially C12 to C16 alkyl groups.

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) embedded image
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:

    • R1 stands for a methyl group
    • R2, R3, and R4 stand for methyl groups
    • m has a value of 2.

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:

    • quaternized cellulose derivatives, such as those which 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,
    • cationic alkyl polyglycosides as described in German Patent DE 44 13 686,
    • cationized honey, for example, the commercial product Honeyquat® 50,
    • cationic guar derivatives, especially products sold under the trade names Cosmedia® Guar and Jaguar
    • polysiloxanes with quaternary groups, such as 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),
    • polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid; examples of cationic polymers of this type are the commercially available products Merquat® 100 (poly(dimethyldiallylammonium chloride)) and Merquat® 550 (dimethyldiallylammonium chloride/acrylamide copolymer),
    • copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkylacrylate and methacrylate, for example, vinylpyrrolidone/-dimethylaminoethylmethacrylate copolymer quaternized with diethyl sulfate; compounds of this type are commercially available under the names Gafquat® 734 and Gafquat® 755,
    • vinylpyrrolidone/vinylimidazoliummethochloride copolymers, such as those sold under the names Luviquat® FC 370, FC 550, FC 905, and HM 552,
    • quaternized polyvinyl alcohol, and
    • the polymers known by the names polyquaternium 2, polyquaternium 17, polyquaternium 18, and polyquaternium 27, which have quaternary nitrogen atoms in the main chain of the polymer.

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

    • (a) monomers with quaternary ammonium groups of general formula (II),
      R1—CH═CR2—CO-Z—(CnH2n)—N(+)R3R4R5A(−) (II)
    • in which R1 and R2, independently of each other, stand for hydrogen or a methyl group, R3, R4 and R5, independently of one another, stand for alkyl groups with 1 to 4 carbon atoms, Z stands for an NH group or an oxygen atom, n is a whole number from 2 to 5, and A(−) is the anion of an organic or inorganic acid, and
    • (b) monomeric carboxylic acids of general formula (III),
      R6—CH═CR7—COOH (III)
    • in which R6 and R7, independently of each other, are hydrogen or a methyl group.

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

    • nonionic polymers, such as vinylpyrrolidone/vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone/vinyl acetate copolymers, and polysiloxanes,
    • cationic polymers, such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide/dimethyldiallylammonium chloride copolymers, dimethylaminoethylmethacrylate/vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidone/imidazoliniummethochloride copolymers, and quaternized polyvinyl alcohol,
    • zwitterionic and amphoteric polymers, such as acrylamidopropyltrimethylammonium chloride/acrylate copolymers and octyl acrylamide/methyl methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers,
    • anionic polymers, such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers, and acrylic acid/ethyl acrylate/N-tert-butyl acrylamide terpolymers,
    • thickening agents, such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean flour, linseed gums, dextrans, cellulose derivatives, e.g. methyl cellulose, hydroxyalkyl cellulose, and carboxymethyl cellulose, starch fractions and derivatives, such as amylose, amylopectin, and dextrins, clays, e.g. bentonite, or fully synthetic hydrocolloids, such as polyvinyl alcohol,
    • structuring agents, such as maleic acid and lactic acid,
    • hair-conditioning compounds, such as phospholipids, for example, soy lecithin, egg lecithin, and cephalins,
    • protein hydrolysates, especially elastin, collagen, keratin, milk protein, soy protein, and wheat protein hydrolysates, their condensation products with fatty acids, and quaternized protein hydrolysates,
    • perfume oils, dimethyl isosorbitol, and cyclodextrins,
    • solvents and solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, and diethylene glycol,
    • active substances that improve fiber structure, especially mono-, di-, and oligosaccharides, such as glucose, galactose, fructose, levulose, and lactose,
    • quaternized amines, such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate,
    • antifoaming agents, such as silicones,
    • dyes for coloring the preparation itself,
    • anti-dandruff active ingredients, such as piroctone olamine, zinc omadine, and climbazole,
    • light stabilizers, especially derivatized benzophenones, cinnamic acid derivatives, and triazines,
    • substances for adjusting pH, such as customary acids, especially acidulants, and bases,
    • active substances such as allantoin, pyrrolidone carboxylic acids and their salts, and bisabolol,
    • vitamins, provitamins, and vitamin precursors, especially those that are members of the groups A, B3, B5, B6, C, E, F, and H,
    • plant extracts, such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, lappa, horsetail, hawthorn, linden flower, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lemon, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckooflower, wild thyme, yarrow, thyme, balm, restharrow, coltsfoot, marsh mallow, meristem, ginseng, and ginger root,
    • cholesterol,
    • consistency regulators, such as sugar esters, polyol esters, or polyol alkyl ethers,
    • fats and waxes, such as spermaceti, beeswax, montan wax, and paraffins,
    • fatty acid alkanolamides,
    • complexing agents, such as EDTA, NTA, β-alanine diacetic acid, and phosphonic acids (can be left out in accordance with one embodiment of the present invention),
    • swelling and penetration agents, such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas, and primary, secondary, and tertiary phosphates,
    • opacifiers, such as latex, styrene/PVP and styrene/acrylamide copolymers,
    • pearlizing agents, such as ethylene glycol mono- and distearate and PEG-3 distearate,
    • pigments,
    • stabilizers for hydrogen peroxide and other oxidizing agents,
    • propellants, such as propane-butane mixtures, N2O, dimethyl ether, CO2, and air, and
    • antioxidants.

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.:

    • pyranose oxidase and, e.g., D-glucose or galactose,
    • glucose oxidase and D-glucose,
    • glycerol oxidase and glycerol,
    • pyruvate oxidase and pyruvic acid or its salts,
    • alcohol oxidase and alcohol (MeOH, EtOH),
    • lactate oxidase and lactic acid and its salts,
    • tyrosinase oxidase and tyrosine,
    • uricase and uric acid or its salts,
    • choline oxidase and choline,
    • amino acid oxidase and amino acids.

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.

EXAMPLES

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.

1. Formulation 1

Raw MaterialWt. %
Stenol ® 16183.5
Kokoslorol ®1.5
behenyl alcohol1.0
Eumulgin ® B 10.3
Eumulgin ® B 20.3
Texapon ® NSO10.0
Dehyton ® K5.0
Polymer JR ® 4000.3
Gafquat ® 7550.3
Celquat ® L 2000.1
ascorbic acid0.2
sodium metabisulfite0.3
ammonium sulfate0.4
hydroxyethanediphosphonic acid (can also be0.2
omitted from this embodiment of the present
invention)
water glass solution, 40%0.5
perfume oil0.3
p-phenylenediamine dihydrochloride0.058
p-toluylenediamine sulfate0.17
N,N-bis(2′-hydroxyethyl)-p-phenylenediamine1.45
sulfate
2-(2′-hydroxyethyl)-p-phenylenediamine sulfate0.17
1,3-N,N′-bis(2′-hydroxyethyl)-N,N′-bis(4′-0.073
aminophenyl)diaminopropan-2-ol tetrahydrochloride
1,10-bis(2,5-diaminophenyl)-1,4,7,10-0.029
tetraoxadecane tetrahydrochloride
4,5-diamino-2-(2′-hydroxyethyl)pyrazole sulfate1.20
3,5-diamino-2-(2-methoxyethoxy)toluene0.25
3,5-diamino-4-(2-methoxyethoxy)toluene0.07
3,5-bis[(2-hydroxyethyl)amino]-2-(2-1.31
methoxyethoxy)toluene
resorcinol0.023
2-methyl resorcinol0.035
4-chlororesorcinol0.023
5-amino-2-methylphenol0.011
5-(2′-hydroxyethyl)amino-2-methylphenol0.058
5-amino-4-chloro-2-methylphenol0.28
3-amino-2-chloro-6-methylphenol0.08
1-naphthol0.011
1,5-dihydroxynaphthalene0.058
2,6-bis[(2′-hydroxyethyl)amino]toluene0.17
5,6-dihydroxyindoline hydrobromide0.05
HC Red 10.03
4-amino-2-nitrodiphenylamine-2′-carboxylic acid0.02
HC Red BN0.03
HC Red B 540.03
Basic Red 510.02
ammonia, 25%To pH 10
waterto 100

2. Formulation 2

Raw MaterialWt. %
Stenol ® 16183.5
Kokoslorol ®1.5
behenyl alcohol1.0
Eumulgin ® B 10.3
Eumulgin ® B 20.3
Texapon ® NSO10.0
Dehyton ® K5.0
Polymer JR ® 4000.3
Gafquat ® 7550.3
Celquat ® L 2000.1
ascorbic acid0.2
sodium metabisulfite0.3
ammonium sulfate0.4
hydroxyethanediphosphonic acid (can also be0.2
omitted from this embodiment of the present
invention)
water glass solution, 40%0.5
perfume oil0.3
p-toluylenediamine sulfate0.18
2-(2′-hydroxyethyl)-p-phenylenediamine sulfate0.18
4-aminophenol0.02
4-amino-3-methylphenol0.02
4-amino-2-aminomethylphenol dihydrochloride0.05
4-amino-2-[(diethylamino)methyl]phenol0.03
dihydrochloride
bis-(5-amino-2-hydroxyphenyl)methane0.61
dihydrochloride
2,4,5,6-tetraaminopyrimidine sulfate0.24
3,5-diamino-2-(2-methoxyethoxy)toluene0.02
3,5-diamino-2-[2-(2-methoxyethoxy)ethoxy]toluene0.02
3,5-diamino-4-(2-methoxyethoxy)toluene0.06
3,5-bis[(2-hydroxyethyl)amino]-2-(2-1.11
methoxyethoxy)toluene
3,5-bis[(2-hydroxyethyl)amino]-4-(2-0.03
methoxyethoxy)toluene
resorcinol0.03
resorcinol monomethyl ether0.04
2-ethylamino-4-nitro-6-chlorophenol0.03
4-amino-3-nitrophenol0.02
1,4-diamino-2-nitrobenzene0.05
Basic Yellow 870.01
Basic Orange 310.03
ammonia, 25%to pH 10
waterto 100

3. Formulation 3

Raw MaterialWt. %
fatty alcohol mixture C10-C2210.0
Texapon ® K 14 S 70 C2.5
Plantaren ® 1200 UP2.0
Akypo Soft ® 45 NV12.0
Eutanol ® G1.0
Eumulgin ® B 10.5
Eumulgin ® B 20.5
Polymer W ® 371942.0
Cosmedia Guar ® C 2610.2
Mirapol ® A 150.5
Promois ® WK2.0
Dow Corning ® Q2-14010.2
Gluadin ® WQ1.0
ascorbic acid0.2
EDTA disodium salt (can also be omitted from this0.1
embodiment of the present invention)
sodium metabisulfite0.3
ammonium sulfate0.5
perfume oil0.4
p-phenylenediamine dihydrochloride0.14
2-(2′-hydroxyethyl)-p-phenylenediamine sulfate0.91
4-aminophenol0.18
4-amino-3-methylphenol0.05
4-amino-2-[(diethylamino)methyl]phenol0.11
dihydrochloride
2,4,5,6-tetraaminopyrimidine sulfate1.21
4-hydroxy-2,5,6-triaminopyrimidine sulfate0.17
3,5-diamino-2-(2-methoxyethoxy)toluene0.012
3,5-diamino-2-[2-(2-methoxyethoxy)ethoxy]toluene0.020
3,5-diamino-4-(2-methoxyethoxy)toluene0.040
3,5-bis[(2-hydroxyethyl)amino]-2-(2-0.28
methoxyethoxy)toluene
3,5-bis[(2-hydroxyethyl)amino]-4-(2-0.014
methoxyethoxy)toluene
resorcinol0.11
2-methyl resorcinol0.66
4-chlororesorcinol0.04
3-aminophenol0.004
5-amino-2-methylphenol0.033
3-amino-2-chloro-6-methylphenol0.033
3-amino-2,4-dichlorophenol0.10
2-amino-3-hydroxypyridine0.26
2,6-dihydroxy-3,4-dimethylpyridine0.11
2,7-dihydroxynaphthalene0.02
l-phenyl-3-methylpyrazol-5-one0.02
ammonia, 25%to pH 10
waterto 100

4. Formulation 4

Raw MaterialWt. %
fatty alcohol mixture C10-C2210.0
Texapon ® K 14 S 70 C2.5
Plantaren ® 1200 UP2.0
Akypo Soft ® 45 NV12.0
Eutanol ® G1.0
Eumulgin ® B 10.5
Eumulgin ® B 20.5
Polymer W ® 371942.0
Cosmedia Guar ® C 2610.2
Mirapol ® A 150.5
Promois ® WK2.0
Dow Corning ® Q2-14010.2
Gluadin ® WQ1.0
ascorbic acid0.2
EDTA disodium salt (can also be omitted from this0.1
embodiment of the present invention)
sodium metabisulfite0.3
ammonium sulfate0.5
perfume oil0.4
N-[2-(4-aminophenylamino)ethyl]-N′-phenylurea0.14
dihydrochloride
p-phenylenediamine dihydrochloride0.14
p-toluylenediamine sulfate0.62
N,N-bis(2′-hydroxyethyl)-p-phenylenediamine0.10
sulfate
4-amino-3-methylphenol0.35
3,5-diamino-2-(2-methoxyethoxy)toluene0.01
3,5-bis[(2-hydroxyethyl)amino]-2-(2-0.03
methoxyethoxy)toluene
resorcinol0.07
5-(2′-hydroxyethyl)amino-2-methylphenol0.03
5-amino-4-chloro-2-methylphenol0.02
3-amino-2-chloro-6-methylphenol0.58
2,4-diaminophenoxyethanol sulfate0.001
2-amino-4-(2′-hydroxyethyl)anisole sulfate0.001
1,3-bis(2′,4′-diaminophenoxy)propane0.001
tetrahydrochloride
2-amino-3-hydroxypyridine0.15
2-methylamino-3-amino-6-methoxypyridine0.001
1-naphthol0.02
2-methyl-1-naphthol0.03
1,5-dihydroxynaphthalene0.05
2,6-bis[(2′-hydroxyethyl)amino]toluene0.05
4-amino-2-nitro-diphenylamine-2′carboxylic acid0.05
Basic Orange 310.05
ammonia, 25%to pH 10
waterto 100

5. Formulation 5

Raw MaterialWt. %
fatty alcohol mixture C10-C2210.0
Texapon ® K 14 S 70 C2.5
Plantaren ® 1200 UP2.0
Akypo Soft ® 45 NV12.0
Eutanol ® G1.0
Eumulgin ® B 10.5
Eumulgin ® B 20.5
Polymer W ® 371942.0
Cosmedia Guar ® C 2610.2
Mirapol ® A 150.5
Promois ® WK2.0
Dow Corning ® Q2-14010.2
Gluadin ® WQ1.0
ascorbic acid0.2
EDTA disodium salt (can also be omitted from this0.1
embodiment of the present invention)
sodium metabisulfite0.3
ammonium sulfate0.5
perfume oil0.4
p-toluylenediamine sulfate0.91
N,N-bis(2′-hydroxyethyl)-p-phenylenediamine0.05
sulfate
2-(2′-hydroxyethyl)-p-phenylenediamine sulfate0.25
1,3-N,N′-bis(2′-hydroxyethyl)-N,N′-bis(4′-0.01
aminophenyl)diaminopropan-2-ol tetrahydrochloride
1,10-bis(2,5-diaminophenyl)-1,4,7,10-0.01
tetraoxadecane tetrahydrochloride
4-amino-2-[(diethylamino)methyl]phenol0.10
dihydrochloride
3,5-diamino-2-(2-methoxyethoxy)toluene0.10
3,5-bis[(2-hydroxyethyl)amino]-2-(2-0.14
methoxyethoxy)toluene
resorcinol0.35
3-aminophenol0.10
1,3-bis(2′,4′-diaminophenoxy)propane0.005
tetrahydrochloride
2-methylamino-3-amino-6-methoxypyridine0.020
3,5-diamino-2,6-dimethoxypyridine0.005
4-hydroxyindole0.01
6-hydroxyindole0.01
5,6-dihydroxyindoline hydrobromide0.10
ammonia, 25%to pH 10
waterto 100

6. Formulation 6

Raw MaterialWt. %
Stenol ® 16184.5
Behenyl alcohol1.0
Kokoslorol ®2.5
Texapon ® NSO2.0
Dehyton ® K1.0
potassium oleate2.0
potassium isostearate2.0
potassium myristate1.0
Westvaco Diacid ® H 240 K salt2.0
Merquat ® 5500.2
Luviquat ® FC 3700.1
Merquat ® 2800.1
Gafquat ® HS 1000.1
ascorbic acid0.4
hydroxyethanediphosphonic acid (can also be0.2
omitted from this embodiment of the present
invention)
perfume oil0.4
4-aminophenol0.02
4-amino-2-aminomethylphenol dihydrochloride0.04
4-amino-2-[(diethylamino)methyl]phenol0.04
dihydrochloride
bis-(5-amino-2-hydroxyphenyl)methane1.00
dihydrochloride
2,4,5,6-tetraaminopyrimidine sulfate0.27
3,5-bis[(2-hydroxyethyl)amino]-2-(2-1.17
methoxyethoxy)toluene
1,2,3,4-tetrahydro-6-nitroquinoxaline0.04
HC Yellow 50.02
HC Red BN0.03
2-ethylamino-4-nitro-6-chlorophenol0.01
4-amino-3-nitrophenol0.01
HC Red B 540.03
Acid Red 520.05
Acid Red 330.05
ammonia, 25%to pH 10
waterto 100

7. Formulation 7

Raw Materialwt. %
Stenol ® 16186.0
behenyl alcohol1.5
Kokoslorol ®6.0
Eumulgin ® B 13.0
Eumulgin ® B 23.0
Eumulgin ® HRE 401.0
Polydiol ® 4005.0
Aminoxyd ® WS 351.0
EDTA disodium salt (can also be omitted from this0.1
embodiment of the present invention)
Natrosol ® 250 HHR1.0
ammonium sulfate0.4
ascorbic acid0.1
Hydroxyethanediphosphonic acid0.2
perfume oil0.3
p-phenylenediamine dihydrochloride0.06
p-toluylenediamine sulfate0.20
N,N-bis(2′-hydroxyethyl)-p-phenylenediamine0.18
sulfate
2-(2′-hydroxyethyl)-p-phenylenediamine sulfate0.29
1,3-N,N′-bis(2′-hydroxyethyl)-N,N′-bis(4′-0.03
aminophenyl)diaminopropan-2-ol tetrahydrochloride
1,10-bis(2,5-diaminophenyl)-1,4,7,10-0.06
tetraoxadecane tetrahydrochloride
bis-(5-amino-2-hydroxyphenyl)methane0.20
dihydrochloride
3,5-bis[(2-hydroxyethyl)amino]-2-(2-0.70
methoxyethoxy)toluene
3,5-bis[(2-hydroxyethyl)amino]-4-(2-0.08
methoxyethoxy)toluene
HC Red 10.02
HC Red BN0.05
HC Red B 540.05
Basic Yellow 870.02
Basic Orange 310.10
Basic Red 510.15
ammonia, 25%to pH 10
waterto 100

8. Formulation 8

Raw MaterialWt. %
Edenor ® PK 18057.0
Texapon ® NSO4.0
coco fatty alcohol7.5
Dehydol ® LS 28.0
Isopropanol14.5
sodium metabisulfite0.1
ascorbic acid0.1
hydroxyethanediphosphonic acid (can also be0.1
omitted from this embodiment of the present
invention)
L-arginine1.0
Monoethanolamine8.0
Salcare ® SC 960.1
perfume oil0.3
p-phenylenediamine dihydrochloride0.07
p-toluylenediamine sulfate0.09
N,N-bis(2′-hydroxyethyl)-p-phenylenediamine0.05
sulfate
2-(2′-hydroxyethyl)-p-phenylenediamine sulfate0.05
2,4,5,6-tetraaminopyrimidine sulfate0.50
4-hydroxy-2,5,6-triaminopyrimidine sulfate0.04
3,5-bis[(2-hydroxyethyl)amino]-2-(2-0.96
methoxyethoxy)toluene
1,2,3,4-tetrahydro-6-nitroquinoxaline0.10
HC Yellow 50.02
HC Red 10.01
HC Red BN0.01
2-ethylamino-4-nitro-6-chlorophenol0.03
4-amino-3-nitrophenol0.04
HC Red B 540.02
1,4-diamino-2-nitrobenzene0.05
Acid Red 520.03
Acid Red 330.03
ammonia, 25%to pH 10
waterto 100

The formulations 1 to 8 are preferably allowed to dye completely with the following oxidizing agent preparation:

dipicolinic acid0.1wt. %
sodium pyrophosphate0.03wt. %
Turpinal ® SL (can also be omitted from1.50wt. %
this embodiment of the present invention)
Texapon ® N282.00wt. %
Acrysol ® 220.60wt. %
hydrogen peroxide, 50%2.00wt. %
sodium hydroxide, 45%0.80wt. %
waterto 100wt. %

9. Example 9

Raw MaterialAmount
aqueous ammonium Carbopol solution (1%)15.0
Lanette ® E0.70
lauryl ether sulfate (27% aqueous solution)4.40
PEG 4000.60
potassium oleate (12.5% aqueous solution)3.00
titanium dioxide0.50
cetylstearyl alcohol 50/5012.00
Eumulgin ® B23.00
Eutanol ® G2.00
Cutina ® AGS2.00
Cutina ® GMS-SE2.00
XF42-B19891.50
potassium hydroxide (50% in water)0.48
tetrasodium EDTA (can also be omitted from this0.40
embodiment of the present invention)
sodium sulfite0.10
ascorbic acid0.05
Merquat Plus ® 33302.00
perfume0.50
ammonia (25% aqueous solution)6.00
Aerosil ® 2000.25
p-toluylenediamine sulfate0.460
resorcinol0.200
m-aminophenol0.026
2,6-diaminopyridine0.010
2,4-diaminophenoxyethanol dihydrochloride0.012
waterto 100

10. Example 10 to 12

Example
101112
Raw MaterialAmountAmountAmount
aqueous ammonium Carbopol15.0015.0015.00
solution (1%)
Lanette ® E0.700.700.70
lauryl ether sulfate (27%4.404.404.40
aqueous solution)
PEG 4000.604.604.60
potassium oleate (12.5% aqueous3.003.003.00
solution)
titanium dioxide0.500.500.50
cetylstearyl alcohol 50/5012.0012.0012.00
Eumulgin ® B23.003.003.00
Eutanol ® G2.002.002.00
Cutina ® AGS2.002.002.00
Cutina ® GMS-SE2.002.002.00
XF42-B19891.501.501.50
Potassium hydroxide (50% in1.00
water)
tetrasodium EDTA (can also be0.400.400.40
omitted from this embodiment of
the present invention)
sodium sulfite0.15
ascorbic acid0.100.050.05
Merquat Plus ® 33302.002.002.00
perfume0.500.500.60
AMP-1003.947.80
ammonia (25% aqueous solution)6.006.007.50
Aerosil ® 2000.250.250.25
p-aminophenol0.200
p-toluylenediamine sulfate0.960
resorcinol0.450
m-aminophenol0.030
5-amino-2-methylphenol0.060
1,2-diamino-4-nitrobenzene0.3500.400
waterto 100to 100to 100

11. Example 13

Raw MaterialAmount
aqueous ammonium Carbopol solution (1%)15.0
Lanette ® E0.70
lauryl ether sulfate (27% aqueous solution)4.40
PEG 4000.60
potassium oleate (12.5% aqueous solution)3.00
titanium dioxide0.50
cetylstearyl alcohol 50/5012.00
Eumulgin ® B23.00
Eutanol ® G2.00
Cutina ® AGS2.00
Cutina ® GMS-SE2.00
XF42-B19891.50
potassium hydroxide (50% in water)0.28
tetrasodium EDTA (can also be omitted from this0.40
embodiment of the present invention)
sodium sulfite0.10
ascorbic acid0.05
Merquat Plus ® 33302.00
perfume0.50
AMP-1005.00
ammonia (25% aqueous solution)6.50
Aerosil ® 2000.25
p-aminophenol0.015
p-toluylenediamine sulfate0.260
5-amino-2-methylphenol0.250
2,4-diaminophenoxyethanol dihydrochloride0.020
waterto 100

Examples 14 to 16

Example
141516
Raw MaterialAmountAmountAmount
aqueous ammonium Carbopol15.0015.0015.00
solution (1%)
Lanette ® E0.700.700.70
lauryl ether sulfate (27%4.404.404.40
aqueous solution)
PEG 4000.600.600.60
potassium oleate (12.5% aqueous3.003.003.00
solution)
titanium dioxide0.500.500.50
cetylstearyl alcohol 50/5012.0012.0012.00
Eumulgin ® B23.003.003.00
Eutanol ® G2.002.002.00
Cutina ® AGS2.002.002.00
Cutina ® GMS-SE2.002.002.00
XF42-B19891.501.501.50
potassium hydroxide (50% in1.000.600.28
water)
tetrasodium EDTA (can also be0.400.400.40
omitted from this embodiment of
the present invention)
sodium sulfite0.100.100.08
ascorbic acid0.100.100.05
Merquat Plus ® 33302.002.002.00
perfume0.500.500.50
ammonia (25% aqueous solution)6.006.006.00
Aerosil ® 2000.250.250.25
p-aminophenol0.0700.0350.024
p-phenylenediamine0.7800.5100.220
dihydrochloride
resorcinol0.5400.3300.140
m-aminophenol0.0850.0290.011
waterto 100to 100to 100

The formulations 9 to 16 are preferably allowed to dye completely with the following oxidizing

Raw MaterialAmount
stearyl trimethylammonium chloride0.75
Eumulgin ® B21.20
Lanette ® O4.00
propylene glycol0.50
liquid paraffin0.50
Turpinal ® SL (can also be omitted from this0.20
embodiment of the present invention)
sodium benzoate0.10
phenacetin0.10
Na2HPO40.04
hydrogen peroxide (35% in water)17.00
waterto 100
PH3.0

12. Examples 17 to 19

DyeingDyeingDyeing
CreamCreamCream
Raw Material171819
1,2-propylene glycol6.86.86.8
tetrasodium EDTA (can also be0.30.30.3
omitted from this embodiment of
the present invention)
ascorbic acid0.10.10.1
sodium sulfite0.30.30.3
perfume0.50.50.5
ammonia, 25%6.06.06.0
myristyl alcohol0.90.90.9
cetearyl alcohol7.17.17.1
hydrogenated castor oil0.70.70.7
glyceryl stearate1.21.21.2
laureth-230.30.30.3
ceteareth-300.90.90.9
cetrimonium chloride2.12.12.1
isopropyl myristate3.03.03.0
p-toluylenediamine sulfate1.845.2
m-aminophenol0.240.360.36
resorcinol0.661.76
2-amino-4-(2-0.040.18
hydroxyethyl) aminoanisole
sulfate
1-(2-hydroxyethyl)-4,5-1.35
diaminopyrazole
4-amino-3-methylphenol0.14
5-amino-2-methylphenol0.41
KOH, aqueousto pHto pHto pH
10.310.610.0
water, demineralizedto 100to 100to 100
shade of the dyeinglightfieryblack
brownred

13. Example 20

Ammonium Carbopol solution, 1% in water17.25
Ammonium Rohagit solution, 6% in water5.25
Oleth-75.70
potassium olein soap, 12.5% in water12.75
potassium castor oil soap, 12.5% in water3.45
Plantaren ® 20000.53
titanium dioxide anatase, type AS 050.48
Cetiol ® V3.45
cetyl alcohol16.80
glycerol monostearate NSE2.85
Phospholipid EFA0.85
tetrasodium EDTA (can also be omitted from0.46
this embodiment of the present invention)
silicic acid, highly disperse, pyrogenic0.11
p-toluylenediamine2.41
resorcinol0.86
3-aminophenol0.26
1-methoxy-2-amino-4-(2-hydroxyethylamino)0.11
benzene
1,2-propylene glycol USP1.05
methoxybutanol1.43
ammonia, 25% in waterto pH 9.0
ascorbic acid0.06
Mirapol ® A150.19
perfume0.43
waterto 100.00

14. Example 21

Ammonium Carbopol solution, 1% in water17.25
Ammonium Rohagit solution, 6% in water5.25
Oleth-75.70
potassium olein soap, 12.5% in water12.75
potassium castor oil soap, 12.5% in water3.45
Plantaren ® 20000.53
titanium dioxide anatase, type AS 050.48
Cetiol ® V3.45
cetyl alcohol16.80
glycerol monostearate NSE2.85
Phospholipid EFA0.85
tetrasodium EDTA (can also be omitted from0.46
this embodiment of the present invention)
silicic acid, highly disperse, pyrogenic0.11
p-toluylenediamine2.12
resorcinol0.63
3-aminophenol0.20
1-methoxy-2-amino-4-(2-hydroxyethylamino)0.05
benzene
1,2-propylene glycol USP1.05
methoxybutanol1.43
ammonia, 25% in waterto pH 10.0
ascorbic acid0.06
cetyltrimethylammonium bromide0.50
perfume0.43
waterto 100.00

15. Example 22

Ammonium Carbopol solution, 1% in water17.25
Ammonium Rohagit solution, 6% in water5.25
Oleth-75.70
potassium olein soap, 12.5% in water12.75
potassium castor oil soap, 12.5% in water3.45
Plantaren ® 20000.53
titanium dioxide anatase, type AS 050.48
Cetiol ® V3.45
cetyl alcohol16.80
glycerol monostearate NSE2.85
Phospholipid EFA0.85
tetrasodium EDTA (can also be omitted from0.46
this embodiment of the present invention)
silicic acid, highly disperse, pyrogenic0.11
p-toluylenediamine0.84
resorcinol0.21
3-aminophenol0.05
4-chlororesorcinol0.15
1,2-propylene glycol USP1.05
methoxybutanol1.43
ammonia, 25% in waterto pH 10.5
ascorbic acid0.06
Rewoquat ® W 75 PG0.30
perfume0.43
waterto 100.00

16. Example 23

Ammonium Carbopol solution, 1% in water17.25
Ammonium Rohagit solution, 6% in water5.25
Oleth-75.70
potassium olein soap, 12.5% in water12.75
potassium castor oil soap, 12.5% in water3.45
Plantaren ® 20000.53
titanium dioxide anatase, type AS 050.48
Cetiol ® V3.45
cetyl alcohol16.80
glycerol monostearate NSE2.85
Phospholipid EFA0.85
tetrasodium EDTA (can also be omitted from0.46
this embodiment of the present invention)
silicic acid, highly disperse, pyrogenic0.22
p-toluylenediamine1.33
resorcinol0.48
3-aminophenol0.10
1-methoxy-2-amino-4-(2-hydroxyethylamino)0.02
benzene
1,2-propylene glycol USP1.05
methoxybutanol1.43
ammonia, 25% in waterto pH 9.5
ascorbic acid0.06
Polymer JR ® 4001.00
perfume0.43
waterto 100.00

17. Example 24

Ammonium Carbopol solution, 1% in water17.25
Ammonium Rohagit solution, 6% in water5.25
Oleth-75.70
potassium olein soap, 12.5% in water12.75
potassium castor oil soap, 12.5% in water3.45
Plantaren ® 20000.53
titanium dioxide anatase, type AS 050.48
Cetiol ® V3.45
cetyl alcohol16.80
glycerol monostearate NSE2.85
Phospholipid SV0.85
tetrasodium EDTA (can also be omitted from0.46
this embodiment of the present invention)
silicic acid, highly disperse, pyrogenic0.11
p-toluylenediamine2.41
resorcinol0.86
3-aminophenol0.26
1-methoxy-2-amino-4-(2-hydroxyethylamino)0.11
benzene
1,2-propylene glycol USP1.05
methoxybutanol1.43
ammonia, 25% in waterto pH 9.0
ascorbic acid0.06
Gafquat ® 755N0.50
perfume0.43
waterto 100.00

18. Example 25

Ammonium Carbopol solution, 1% in water17.25
Ammonium Rohagit solution, 6% in water5.25
Oleth-75.70
potassium olein soap, 12.5% in water12.75
potassium castor oil soap, 12.5% in water3.45
Plantaren ® 20000.53
titanium dioxide anatase, type AS 050.48
Cetiol ® V3.45
cetyl alcohol16.80
glycerol monostearate NSE2.85
Phospholipid SV0.85
tetrasodium EDTA (can also be omitted from0.46
this embodiment of the present invention)
silicic acid, highly disperse, pyrogenic0.11
p-toluylenediamine2.12
resorcinol0.63
3-aminophenol0.20
1-methoxy-2-amino-4-(2-hydroxyethylamino)0.05
benzene
1,2-propylene glycol USP1.05
methoxybutanol1.43
ammonia, 25% in waterto pH 8.9
ascorbic acid0.06
Crotein ® C0.30
perfume0.43
waterto 100.00

19. Example 26

Ammonium Carbopol solution, 1% in water17.25
Ammonium Rohagit solution, 6% in water5.25
Oleth-75.70
potassium olein soap, 12.5% in water12.75
potassium castor oil soap, 12.5% in water3.45
Plantaren ® 20000.53
titanium dioxide anatase, type AS 050.48
Cetiol ® V3.45
cetyl alcohol16.80
glycerol monostearate NSE2.85
Phospholipid SV0.85
tetrasodium EDTA (can also be omitted from0.46
this embodiment of the present invention)
Silicic acid, highly disperse, pyrogenic0.11
p-toluylenediamine0.84
resorcinol0.21
3-aminophenol0.05
4-chlororesorcinol0.16
1,2-propylene glycol USP1.05
methoxybutanol1.43
ammonia, 25% in waterto pH 9.0
ascorbic acid0.06
Gluadin ® WK0.70
perfume0.43
waterto 100.00

20. Example 27

Ammonium Carbopol solution, 1% in water17.25
Ammonium Rohagit solution, 6% in water5.25
Oleth-75.70
potassium olein soap, 12.5% in water12.75
potassium castor oil soap, 12.5% in water3.45
Plantaren ® 20000.53
titanium dioxide anatase, type AS 050.48
Cetiol ® V3.45
cetyl alcohol16.80
glycerol monostearate NSE2.85
Phospholipid PTC0.85
tetrasodium EDTA (can also be omitted from0.46
this embodiment of the present invention)
silicic acid, highly disperse, pyrogenic0.11
p-toluylenediamine2.41
resorcinol0.86
3-aminophenol0.26
1-methoxy-2-amino-4-(2-hydroxyethylamino)0.11
benzene
1,2-propylene glycol USP1.05
methoxybutanol1.43
ammonia, 25% in waterto pH 9.1
ascorbic acid0.06
Merquat ® 2800.20
perfume0.43
waterto 100.00

21. Example 28

Ammonium Carbopol solution, 1% in water17.25
Ammonium Rohagit solution, 6% in water5.25
Oleth-75.70
potassium olein soap, 12.5% in water12.75
potassium castor oil soap, 12.5% in water3.45
Plantaren ® 20000.53
titanium dioxide anatase, type AS 050.48
Cetiol ® V3.45
cetyl alcohol16.80
glycerol monostearate NSE2.85
Phospholipid PTC0.85
tetrasodium EDTA (can also be omitted from0.46
this embodiment of the present invention)0.46
silicic acid, highly disperse, pyrogenic0.11
p-toluylenediamine2.12
resorcinol0.63
3-aminophenol0.20
1-methoxy-2-amino-4-(2-hydroxyethylamino)0.05
benzene
1,2-propylene glycol USP1.05
methoxybutanol1.43
ammonia, 25% in waterto pH 9.1
ascorbic acid0.06
Jaguar ® C-170.30
perfume0.43
waterto 100.00

22. Example 29

Ammonium Carbopol solution, 1% in water17.25
Ammonium Rohagit solution, 6% in water5.25
Oleth-75.70
potassium olein soap, 12.5% in water12.75
potassium castor oil soap, 12.5% in water3.45
Plantaren ® 20000.53
titanium dioxide anatase, type AS 050.48
Cetiol ® V3.45
cetyl alcohol16.80
glycerol monostearate NSE2.85
Phospholipid PTC0.85
tetrasodium EDTA (can also be omitted from0.46
this embodiment of the present invention)
silicic acid, highly disperse, pyrogenic0.22
p-toluylenediamine1.33
resorcinol0.48
3-aminophenol0.10
1-methoxy-2-amino-4-(2-hydroxyethylamino)0.02
benzene
1,2-propylene glycol USP1.05
methoxybutanol1.43
ammonia, 25% in waterto pH 9.0
ascorbic acid0.06
Mirapol ® A150.19
perfume0.43
waterto 100.00

23. List of Commercial Products Used

The commercial products used in the examples are defined as follows:
Acid Red 33C.I. 17200
Acid Red 52C.I. 45100
Acrysol ® 22Acrylic polymer (ca. 29.5-30.5% solids
in water; INCI name: Acrylates/Steareth-20
Methacrylate Copolymer)
Aerosil ® 200Pyrogenic silicic acid (INCI name: Silica)
(Degussa)
Akypo Soft 45 NV ®Lauryl alcoho1-4.5-EO-acetic acid sodium
salt (at least 21% active substance
content; INCI name: Sodium Laureth-6
Carboxylate) (Chem-Y)
Aminoxyd ® WS 35N,N-dimethyl-N(C8-18
cocoacylamidopropyl)amine-N-oxide (ca. 35%
active substance in water; INCI name:
Cocamidopropylamine Oxide) (Goldschmidt)
Ammonium CarbopolSolution of an ammonium salt of a
methacrylic acid/methacrylate copolymer
(INCI name: Ammonium Polyacrylate) (Röhm
GmbH)
Ammonium RohagitSolution of an ammonium salt of an acrylic
acid polymer (INCI name: Ammonium Acrylate
Copolymer) (Goodrich)
Basic Orange 31Azo dye (CIBA)
Basic Red 51Azo dye (CIBA)
Basic Yellow 87Methine dye (CIBA)
Celquat ® L 200Quaternized cellulose derivative (INCI
name: Polyquaternium-4) (National Starch)
Cetiol ® VDecyl oleate (INCI name: Decyl Oleate)
(Henkel)
Cosmedia Guar ®Guar hydroxypropyltrimethylammonium
C 261chloride (at least 93% solids; INCI name:
Guar Hydroxypropyltrimonium Chloride)
(Cognis Corporation Cosmedia)
Crotein ® CGelatin hydrolysate (ca. 93% active
substance; INCI name: Hydrolyzed Collagen)
(Croda)
Cutina ® ACSEthylene glycol distearate (INCI name:
Glycol Distearate) (Cognis)
Cutina ® GMS-SEGlycerol monodistearate/potassium stearate
mixture of plant origin (INCI name:
Glyceryl Stearates SE) (Cognis)
Dehydol ® LS 2C12-14 fatty alcohol with ca. 2 EO units
(INCI name: Laureth-2) (Cognis Pulcra)
Dehyton ® KN,N-Dimethyl-N—(C8-18
cocamidopropyl)ammonium acetobetaine (ca.
30% active substance; INCI name: Aqua
(Water), Cocamidopropyl Betaine) (Cognis)
Dow CorningDimethylcyclosiloxane/dimethylpolysiloxanol
Q2-1401 ®mixture (ca. 13% solids; INCI name:
Cyclomethicone, Dimethiconol) (Dow Corning)
Edenor ® PK 1805Oleic acid (INCI name: Oleic Acid) (Cognis)
Eumulgin ® B1Cetylstearyl alcohol with ca. 12 EO units
(INCI name: Ceteareth-12) (Cognis)
Eumulgin ® B2Cetylstearyl alcohol with ca. 20 EO units
(INCI name: Ceteareth-20) (Cognis)
Eumulgin ® HRE 40Hydrogenated castor oil with ca. 40 EO
units (INCI name: PEG-40 Hydrogenated
Castor Oil) (Cognis)
Eutanol ® G2-Octyldodecyl alcohol (INCI name:
Octyldodecanol) (Cognis)
Gafquat ® 755Dimethylaminoethyl
methacrylate/vinylpyrrolidone copolymer,
quaternized with diethyl sulfate (ca. 19%
solids in water; INCI name:
Polyquaternium-11) (ISP)
Gafquat ® HS 100Vinylpyrrolidone/methacrylamidopropyltrimethyl-
ammonium chloride copolymer (19-21% active
substance in water; INCI name: Polyquaternium-
28) (ISP)
Gluadin ® WKWheat protein hydrolysate-fatty acid
condensate (ca. 30% active substance; INCI
name: Sodium Cocoyl Hydrolyzed Wheat
Protein) (Henkel)
Gluadin ® WQWheat protein hydrolysate (ca. 31-35%
solids; INCI name: Aqua (Water),
Laurdimonium Hydroxypropyl Hydrolyzed
Wheat Protein, Ethylparaben,
Methylparaben) (Cognis)
Glycerol mono-NSE (INCI name: Glyceryl Stearate)
stearate(Oleofina)
HC Red 12-Amino-2-nitrodiphenylamine
HC Red B 544-[(2-hydroxyethyl)amino]-3-nitrophenol
(INCI name: 3-nitro-p-
hydroxyethylaminophenol)
HC Red BN4-[(3-hydroxypropyl)amino]-3-nitrophenol
HC Yellow 5N1-(2-hydroxyethyl)-4-nitro-1,2-
phenylenediamine
Hydrenol ® DC16-18 fatty alcohol (INCI name: Cetearyl
Alcohol) (Cognis)
Jaguar ® C-17Guar hydroxypropyltrimethylammonium chloride
(INCI name: Guar Hydroxypropyltrimonium
Chloride) (Rhodia Inc.)
Kokosloral ®C12-18 fatty alcohol (INCI name: Coconut
Alcohol) (Cognis)
Lanette ® ECetylstearyl alcohol sulfate sodium salt
(INCI name: Sodium Cetearyl Sulfate)
(Cognis)
Lanette ® OC16-18 fatty alcohol (INCI name: Cetearyl
Alcohol) (Cognis)
Lorol ® tech.C12-18 fatty alcohol (INCI name: Coconut
Alcohol) (Cognis)
Luviquat ®Vinylimidazoliummethyl
FC 370chloride/vinylpyrrolidone copolymer (30:70)
(38-42% solids in water; INCI name:
Polyquaternium-16) (BASF)
Merquat ® 280Dimethyldiallylammonium chloride/acrylic
acid copolymer (ca. 35% active substance
in water; INCI name: Polyquaternium-22)
(Ondeo-Nalco)
Merquat ® 550Dimethyldiallylammonium
chloride/acrylamide copolymer (ca. 8.1-
9.1% active substance in water; INCI name:
Polyquaternium-7) (Ondeo-Nalco)
Merquat Plus ®Dimethyldiallylammonium chloride/acrylic
3330acid/acrylamide terpolymer (ca. 9.5%
active substance content; INCI name:
Polyquaternium-39) (Ondeo-Nalco)
Mirapol ® A 15Poly[N-(3-(dimethylammonium)propyl]-N′-[3-
ethyleneoxyethylenedimethylammonium)propyl]-
urea dichloride (ca. 64% solids in water;
INCI name: Polyquaternium-2) (Rhodia)
Natrosol ® 250Hydroxyethyl cellulose (INCI name:
HHRhydroxyethylcellulose) (Hercules)
Oleth-7Oleyl alcohol with 7 EO units (Henkel)
Phospholipid EFA(ca. 30% active substance; INCI name:
Linoleamidopropyl PG-Dimonium Chloride
Phosphate) (Mona)
Phospholipid PTC(ca. 47% active substance; INCI name:
Cocamidopropyl PG-Dimonium Chloride
Phosphate) (Mona)
Phospholipid SV(ca. 41.5% active substance; INCI name:
Stearamidopropyl PG-Dimonium Chloride
Phosphate (and) Cetyl Alcohol) (Mona)
Plantaren ®C12-C16 fatty alcohol-1,4-glucoside
1200 UPunpreserved, boron-free (ca. 50-53% active
substance) (Cognis Corporation (Emery))
Plantaren ® 2000C8-18-alkyl-1,4-polyglucoside (ca. 51%
active substance; INCI name: Decyl
Glucoside) (Henkel)
Polydiol ® 400Polyethylene glycol (INCI name: PEG-8)
(Cognis)
Polymer JR ® 400Quaternized hydroxyethyl cellulose (INCI
name: Polyquaternium-10) (Amerchol)
Polymer ® Wca. 20 wt. % active substance content in
37194water; INCI name: Acryamidopropyltrimonium
Chloride/Acrylates Copolymer (Stockhausen)
Promois ® WKKeratin hydrolysate (INCI name: Aqua
(Water), Hydrolyzed Keratin,
Methylparaben, Propylparaben) (Seiwa
(Interorgana))
Rewoquat ® W1-Methyl-2-nortallow alkyl-3-tallow fatty
75 PGacidamidoethylimidazolinium methosulfate
(ca. 75% active substance in propylene
glycol; INCI name: Quaternium 27) (Witco
Surfactants GmbH)
Salcare ® SC 96ca. 50% active substance content; INCI
name: Polyquaternium-37, Propylene Glycol
Dicaprylate/Dicaprate, PPG-1 Trideceth-6
(CIBA)
Stenol ® 1618C16-18 fatty alcohol (INCI name: Cetearyl
Alcohol) (Cognis)
Texapon ® EVRLauryl ether sulfate sodium salt with
special additives (ca. 34-37% active
substance content; INCI name: Sodium
Lauryl Sulfate, Sodium Laureth Sulfate,
Lauramide MIPA, Cocamide MEA, Glycol
Stearate, Laureth-10) (Cognis)
Texapon ® K 14Laurylmyristyl ether sulfate sodium salt
S 70 C(ca. 68-73% active substance content; INCI
name: Sodium Myreth Sulfate) (Cognis)
Texapon ® N28Lauryl ether sulfate sodium salt (at least
26.5% active substance content; INCI name:
Sodium Laureth Sulfate) (Cognis)
Texapon ® NSOLauryl ether sulfate sodium salt (ca.
27.5% active substance content; INCI name:
Sodium Laureth Sulfate) (Cognis)
Turpinal ® SL1-Hydroxyethane-1,1-diphosphonic acid (ca.
58-61% active substance content; INCI
name: Etidronic Acid, Aqua. (Water))
(Solutia)
Westvaco Diacid ®4-Hexyl-5(6)-carboxy-2-cyclohexene-1-
H 240octanoic acid potassium salt (ca. 41%
active substance in water) (Westvaco
Chemicals)
XF42-B1989amino-functional silicone (INCI name:
Amodimethicone) (GE-Toshiba Silicones)