专利摘要:
A multi-component packaging unit (kit-of-parts) for bleaching by reduction of colored keratin fibers, which comprises - a container (A) containing a cosmetic agent (a) and - a container (B) containing a cosmetic agent (b), which are made separately from one another, - the agent (a) in the container (A) (a1) contains one or more derivatives of sulfinic acid of a given group, (a2) contains one or more fatty components selected from the group consisting of C12 to C30 alcohols, C12 to C30 fatty acid triglycerides, C12 to C30 fatty acid monoglycerides, C12 fatty acid diglycerides. at C30, C12-C30 fatty acid esters, hydrocarbons and / or silicone oils, (a3) has a water content of 10.0% by weight maximum, based on the total weight of the agent (a), the agent (b) in the container (B) (b1) has a water content of at least 30.0% by weight, based on the total weight of the agent (b). Another object of the invention is a process for bleaching by the eduction of colored keratin fibers using a multi-component packaging unit.
公开号:FR3043328A1
申请号:FR1660663
申请日:2016-11-04
公开日:2017-05-12
发明作者:Jurgen Schopgens；Burkhard Muller
申请人:Henkel AG and Co KGaA；
IPC主号:

专利说明:

The present invention relates to multi-component packaging units (kit-of-parts) for keratin fiber reduction bleaching and contains separately manufactured containers (A) and (B). The container (A) contains a cosmetic agent (a), formulated substantially without water, which contains at least one sulphinic acid derivative of a given group and one or more fatty components. The container (B) contains a cosmetic agent (b) which has an aqueous formulation. Another object of the present invention is a stained keratin fiber reduction staining method in which the multi-component packaging unit described above is used.
Dyeing and hair coloring preparations are an important type of cosmetic agents. They can be used to shade the natural color of the hair slightly or more strongly according to the wish of the person concerned, to obtain totally different hair colors or to cover unwanted hair colors, such as gray tones. The usual hair coloring agents are formulated according to the desired color or the permanence of the color, either on the basis of oxidation dyes or on the basis of direct dyes. Combinations of oxidation dyes and direct dyes are also frequently used to obtain special grades.
Coloring agents based on oxidation dyes give brilliant and long-lasting color shades. However, they require the use of strong oxidants such as hydrogen peroxide solutions. These coloring agents contain oxidation dye precursors, called developer components and copulatory components. The developer components form, under the influence of oxidants or oxygen of the air between them or by coupling with one or more copulatory components the dyes themselves.
Direct dye-based coloring agents are frequently used for temporary coloring. Direct dyes are dye molecules that attach directly to the hair and do not require any oxidation process to develop the color. Important representatives of this class of dyes are, for example, triphenylmethane dyes, azo dyes, anthraquinone dyes or nitrobenzene dyes which may each carry cationic or anionic groups.
In all these coloring processes, it may happen that, for various reasons, the coloring fades completely or partially. Partial disappearance of the color appears, for example, when the resulting coloring on the fibers is darker than expected. On the other hand, a complete disappearance of the coloring may be desired in some cases. Thus, it is for example conceivable to color or shades the hair for a specific reason in a given shade and to return to the original color after a few days.
Various means and methods of bleaching are already known in the literature. One method, sufficiently known in the state of the art, for staining the coloring, is the oxidative discoloration of the colored hair, for example with the aid of a common brightening agent. In this process, however, the fibers can be damaged by the use of strong oxidants.
In addition, reduction bleaching processes have already been described. Thus, for example, the European patent application EP 1 300 136 A2 discloses hair treatment processes in which the hair is colored in a first step and again discolored by reduction in a second step. Reduction discoloration is effected by application of a formulation containing a dithionite salt and a surfactant. In WO 2008/055756 A2, keratin fiber reduction bleaching is performed using a mixture of a reducing agent and an absorbing agent.
In WO 2012/069599, WO 2014/174230 and WO 2013/017862, various sulfinic acid derivatives are disclosed in hair reduction coloring agents. However, the resulting garment and fading process obtained with the agents described in the aforementioned documents can not yet be designated as optimal.
When using reducing discoloration agent, the discoloration is carried out by reducing the dyes which are on the keratin fibers or on the hair. The reduction transforms the dyes usually into their reduced leucoforms. In this process, the double bonds present in the dyes are reduced, the chromophore system of the dyes is thereby interrupted and the dye is converted to a colorless form.
In order to reduce the dyes it is generally necessary to use strong reducing agents which can undesirably react with oxidizing agents such as oxygen in the air. In an aqueous solution, the reducing agents are also often very unstable and decompose more or less rapidly depending on the pH value of the solution. For example, the sodium dithionite reduction bleaching agent known in the state of the art is sensitive to oxygen in the atmosphere and decomposes slowly in an aqueous solution. Increasing the pH value may delay these decomposition reactions. Adjustment to a slightly alkaline pH value stabilizes the aqueous dithionite solutions so that the solution can be stored, protected from oxygen, for several weeks to several months. However, if the reducing bleaching agent has to store longer, if the absence of air can not be reliably guaranteed or if high temperatures prevail in the storage conditions, the solution formulation, particularly in aqueous solution, is not method of choice. To avoid this problem, the documents of the state of the art often recommend using the reducing agents themselves in solid form, for example in powder form. This procedure, however, has various disadvantages.
The reducing agents must be dissolved before the user in a cosmetic medium. If they are for that incorporated in pure form, for example in powder form, in the cosmetic support, dust can be generated which can irritate, if inhaled, the respiratory tract of the user. If the particle size of the pulverulent reducing agent is chosen to be larger, there is a risk that the reducing agent will not dissolve sufficiently, and thus result in uneven and unsightly resulting discoloration. In the case of an incomplete solution, the amount of reducing agent in the bleaching process is not available so that the resulting discoloration may be lower than expected.
If the solubility of the reducing agent in particulate form in the cosmetic carrier is poor, the user is still obliged to mix the solid reducing agent and the cosmetic carrier for a very long time. This procedure is not convenient for the user, takes time and is therefore very undesirable.
An object of the present invention is therefore to provide a bleaching agent of colored keratin fibers which bleaches the keratin fibers in the most uniform and effective manner possible. The bleaching agent must be characterized by high storage stability and still have a high discoloration force even after long periods of storage at elevated temperatures. The ready-to-use bleaching agent should be easy to prepare and convenient to apply to the user. In particular, no dust should be generated during use. Furthermore, the consistency of the bleaching agent must be optimized so that it can both be easily applied and well distributed on the head of the user, without dripping on the other hand keratin fibers. Finally, the discoloration must also be improved over the bleaching agents known from the state of the art.
Surprisingly, it has now been found that the above-mentioned object can be perfectly achieved when the reducing bleaching agent is made in the form of a multi-component packaging unit (kit-of-parts) which comprises two containers (A). and (B), made separately, the containers (A) and (B) containing respectively the cosmetic agents (a) and (b). Here, the agent (a) contains at least one sulfinic acid derivative which is selected from representatives of a specific group, and one or more fatty components. The agent (a) is made substantially without water. Agent (b) is a cosmetic carrier containing water. To effect bleaching by reducing colored keratin fibers, the user mixes the agents (a) and (b) shortly before use and thereby makes the bleaching agent ready for use.
A first object of the present invention is a multicomponent packaging unit (kit-of-parts) for the reduction bleaching of colored keratin fibers, which comprises a container (A) containing a cosmetic agent (a) and a container (B) containing a cosmetic agent (b), which are made separately from one another, the agent (a) in the container (A) (a1) contains one or more derivatives of sulfinic acid of the group having - (H2N) (NH) C (SO2H) formamidine-sulfinic acid, - HN (CH2SO2Na) 2, [(sulfinatomethyl) amino] methanesulfinate disodium - HN (CH2SO2K) 2, [(sulfinatomethyl) amino] methane -sulfinate dipotassium - HN (CH 2 SO 2 H) 2, [(sulfinomethyl) amino] methanesulfinic acid - N (CH 2 SO 2 Na) 3, [bis (sulfinatomethyl) amino] methanesulfinate trisodium - N (CH 2 SO 2 K) 3, [bis (sulfinatomethyl) amino] methanesulfinate tripotassium - N (CH2SO2H) 3, [bis (sulfinomethyl) amino] methanesulfinic acid - H2NCH (CH3) SO2Na, 1-aminoethane-1-sul sodium finate - H2NCH (CH3) SO2K, potassium 1-aminoethan-1-sulfinate - H2NCH (CH3) SO2H, 1-amino-ethane-1-sulfinic acid, - HN (CH (CH3) SO2Na) 2, 1- Disodium [(1-sulfinatoethyl) amino] ethan-1-sulfinate - HN (CH (CH 3) SO 2 K) 2, 1 - [(1-sulfinatoethyl) amino] ethane-1-sulphinate dipotassium - HN (CH (CH 3) SO 2 H) 2j 1 - [(1-sulfinoethyl) amino] ethane-1-sulfinic acid - N (CH (CH3) SO2Na) 3I 1 - [bis (1-sulfinatoethyl) amino] ethan-1-sulfinate trisodium - N (CH (CH 3 ) S02K) 3i 1- [bis (1-sulfinatoethyl) amino] ethane-1-sulfinate tripotassium and / or - N (CH (CH3) SO2H) 3i 1- [bis (1-sulfinoethyl) amino] ethane-1- acid sulfinic acid, (a2) contains one or more fatty components selected from the group of C12-C30 alcohols, triglycerides of C12-C30 fatty acids, monoglycerides of C12-C30 fatty acids, diglycerides of fatty acids C 12 -C 30 fatty acid esters of C 12 to C 30, hydrocarbons and / or silicone oils (a 3) have a water content of 10.0% by weight maximum, by weight to the total weight of the agent (a), the agent (b) in the container (B) (b1) has a water content of at least 30.0% by weight, relative to the total weight of the agent (b).
The agents (a) and (b), which are contained in the containers (A) and (B) of the multi-component packaging unit of the invention, are characterized by extraordinarily good storage stability, even at high temperatures. In addition, it has been found in the course of the work which led to this invention that the two agents (a) and (b) can be mixed together very quickly and very easily and that the ready-to-use bleaching agent obtained after mixing, provides a very uniform resultant discoloration. When mixing agents (a) and (b), no dust is generated. In addition, it has been found that the damage to the hair upon application of the bleaching agent of the invention (i.e., when using the mixture of the agents (a) and (b) )) could be reduced. Surprisingly, the resulting discoloration has also been improved over the agents known in the state of the art.
By keratin fibers, keratinous fibers or fibers containing keratin means skins, wool, feathers and hair, particularly human. Although the agents of the invention are particularly suitable for lightening and coloring keratin fibers or human hair, there are in principle no obstacles to using them in other fields.
By the term "stained keratin fibers" is meant keratin fibers which have been stained with conventional coloring agents known to those skilled in the art. In particular, "colored keratin fibers" are understood to mean fibers which have been colored with oxidation dyes known in the state of the art and / or with direct dyes. In this respect, one refers explicitly to known monographs, for example Kh. Schrader, Grundlagen und Rezepturen, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, which reproduces the corresponding knowledge of those skilled in the art.
Agents (a) and (b) contain the essential ingredients for the invention present each time in a cosmetic support which is substantially free of water in the case of agent (a) and which contains water in the case of agent (b). The agent (a) is made substantially without water and can be present here in solid form, in powder form or in paste form. Making the agent (a) in the form of a paste is preferred. Agent (a) may further contain a solvent-containing carrier. In addition, the fatty component content of the group (a2) can also be selected to be high in the agent (a) so that the fat constituents function as a carrier of the agent (a) and thus represent, in addition to derivatives of sulfinic acid (a1), the main constituent of agent (a). The aqueous cosmetic agent (b) may be, for example, an agent containing a suitable aqueous or aqueous-alcoholic carrier. To carry out the reduction bleaching, such carriers may be for example creams, emulsions, gels or even surfactant foaming solutions, such as shampoos, aerosol foams, foam formulations or other preparations which are suitable for application on the hair. In a particularly preferred manner, the keratin fiber reduction bleaching agents are in the form of creams, emulsions or fluid gels. In a particularly preferred manner, the agent (b) is formulated in the form of an emulsion.
Agent (a) in the container fA) The multi-component packaging unit (kit-of-parts) of the invention contains a first container (A) which contains a cosmetic agent (a). Agent (a) is characterized by its content of one or more sulfinic acid derivatives (a1) which is selected from the group consisting of - (H2N) (NH) C (SO2H) formamidine-sulfinic acid, - HN ( CH2SO2Na) 2, [(sulfinatomethyl) amino] methanesulfinate disodium - HN (CH2SO2K) 2, [(sulfinatomethyl) amino] methanesulphinate dipotassium - HN (CH2SO2H) 2, [(sulfinomethyl) amino] methanesulfinic acid - N (CH2SO2Na) 3, [bis (sulfinatomethyl) amino] methanesulfinate trisodium - N (CH2SO2K) 3, [bis (sulfinatomethyl) amino] methanesulfinate tripotassium - N (CH2SO2H) 3, [bis (sulfinomethyl) amino] methane -sulfinic acid - H2NCH (CH3) SO2Na, sodium 1-aminoethane-1-sulfinate - H2NCH (CH3) SO2K, potassium 1-aminoethan-1-sulfinate - H2NCH (CH3) SO2H, 1-amino-ethane-1-amino acid sulfinic acid, - HN (CH (CH3) SO2Na) 2] 1 - [(1-sulfinatoethyl) amino] ethane-1-sulfinate disodium - HN (CH (CH3) SO2K) 2, 1 - [(1-sulfinatoethyl) amino] ethane Dipotassium -1-sulfinate - HN (CH (CH3) SO2H) 2, 1 - [(1-sulfinoethyl) amino] acid thane-1-sulfinic acid - N (CH (CH3) SO2Na) 3I 1 - [bis (1-sulfinatoethyl) amino] ethane-1-sulfinate trisodium - N (CH (CH3) SO2K) 3, 1- [bis (1- tripotassium sulfinatoethyl) amino] ethane-1-sulfinate and / or - N (CH (CH 3) SO 2 H) 3, 1- [bis (1-sulphoethyl) amino] ethane-1-sulfinic acid. Formamidinsulfinic acid is also alternatively referred to as thiourea dioxide or aminoiminomethansulfinic acid. Formamidinsulfinic acid has the structure of formula (I) but may also be in the form of its tautomers. Formamidinsulfonic acid has CAS No. 1758-73-2 and can be obtained commercially from various suppliers, such as Sigma Aldrich. (I)
Disodium [(sulfinatomethylamino) methanesulphinate is the disodium salt of [(sulfinomethyl) amino] methanesulfinic acid and has the structure of formula (II).
Dipotassium [(sulfinatomethyl) amino] methanesulphinate is the dipotassium salt of [(sulfinomethyl) amino] methanesulfinic acid and has the structure of formula (III). (III) [(Sulfinomethyl) amino] methanesulfinic acid has the structure of formula (IV).
(IV)
Trisodium [bis (sulfinatomethyl) amino] methanesulfinate is the trisodium salt of [bis (sulfinomethyl) amino] methanesulfinic acid and has the structure of formula (V). (V)
Tripotassium [bis (sulfinatomethyl) amino] methanesulfinate is the tripotassium salt of [bis (sulfinomethyl) amino] methanesulfinic acid and has the structure of formula (VI).
(VI) [Bis (sulfinomethyl) amino] methanesulphinic acid having the structure of formula (VII).
(VII)
Sodium 1-aminoethane-1-sulfinate is the sodium salt of 1-aminoethane-1-sulfinic acid, and has the structure of formula (VIII).
(VIII)
Potassium 1-aminoethan-1-sulfinate is the potassium salt of 1-aminoethane-1-sulfinic acid and has the structure of formula (IX).
(IX) 1-Aminoethane-1-sulfinic acid has the structure of formula (X).
(X)
The disodium 1 - [(1-sulfinatoethyl) amino] ethane-1-sulfinate is the disodium salt of 1 - [(1-sulfinoethyl) amino] ethane-1-sulfinic acid and has the structure of formula (XI) . (XI)
Dipotassium 1 - [(1-sulfinatoethyl) amino] ethane-1-sulfinate is the dipotassium salt of 1 - [(1-sulfinoethyl) amino] ethane-1-sulfinic acid and has the structure of formula (XII) .
(XII)
1 - [(1-sulfinoethyl) amino] ethane-1-sulfinic acid has the structure of formula (XIII).
I (XIII)
Trisodium 1- [bis (1-sulfinatoethyl) amino] ethan-1-sulfinate is the trisodium salt of 1- [bis (1-sulfinoethyl) amino] ethane-1-sulfinic acid and has the structure of the formula ( XIV). (XIV)
1- [bis (1-sulfinatoethyl) amino] ethane-1-sulfinate is the tripotassium salt of 1- [bis (1-sulfinoethyl) amino] ethane-1-sulfinic acid and has the structure of the formula (XV ). (XV)
1- [bis (1-sulfinoethyl) amino] ethane-1-sulfinic acid has the structure of formula (XVI). (XVI)
The preparation of the compounds of formulas (II) to (XVI) is described for example in EP 0914516 B1.
It is best to have been able to make formamidinsulfinic acid in paste form because the formamidinsulfinic acid could be finely dispersed in the carrier containing fatty substances and was very stable in storage in this form. In addition, the use of formamidinsulfinic acid has resulted in extraordinarily good resultant discoloration.
When applying the ready-to-use bleaching agent, i.e. after mixing the agent (a), containing the formamidinsulfinic acid, with the aqueous carrier (b), the Odor release was also particularly weak.
A particularly preferred multi-component packaging unit (kit-of-parts) is therefore characterized in that the agent (a) in the container (A) contains (a1) a derivative of sulfinic acid (H2N) ( NH) C (SO2H) formamidinsulfinic acid.
In addition, the sulfinic acid derivative (s) of group (a1) are preferably used in certain quantitative ranges. Preferably, the agent
(a), substantially made without water, contains the sulfinic acid derivative (s) of group (a1) in a total amount of 0.1 to 50.0% by weight, preferably from 1.0 to 30.0 % by weight, more preferably from 1.5 to 20.0% by weight and particularly preferably from 2.5 to 10.5% by weight. All quantitative data herein refer to the total amount of all sulfinic acid derivatives contained in agent (a) of group (a1) which is related to the total weight of the agent.
A particularly preferred multi-component packaging unit (kit-of-parts) is characterized in that the agent (a) in the container (A) contains, based on the total weight of the agent (a), one or more sulfinic acid derivatives of group (a1) in a total amount of 0.1 to 50.0% by weight, preferably 1.0 to 30.0% by weight, more preferably 1.5 20.0% by weight and particularly preferably 2.5 to 10.5% by weight.
A particularly preferred multi-component packaging unit (kit-of-parts) for reduction-bleaching of colored keratin fibers is characterized in that the agent (a) in the container (A) contains (a1) from 0.1 to 50.0% by weight of formamidinesulfinic acid (other name thiourea dioxide).
A particularly preferred multi-component packaging unit (kit-of-parts) for reduction-bleaching of colored keratin fibers is characterized in that the agent (a) in the container (A) contains (a1) from 1.0 to 30.0% by weight of formamidinesulfinic acid (other name thiourea dioxide).
A particularly preferred multi-component packaging unit (kit-of-parts) for reduction-bleaching of colored keratin fibers is characterized in that the agent (a) in the container (A) contains (a1) from 1.5 to 20.0% by weight of formamidinesulfinic acid (other name thiourea dioxide).
A particularly preferred multi-component packaging unit (kit-of-parts) for reduction-bleaching of colored keratin fibers is characterized in that the agent (a) in the container (A) contains (a1) from 2.5 to 10.5% by weight of formamidinesulfinic acid (other name thiourea dioxide).
In principle, the agent (a) may contain, in addition to derivatives of the sulfinic acid of the group (a1), also other reducing agents. However, it has been found that certain reducing agents are not compatible with the sulfinic acid derivatives of group (a1) because they degrade storage stability or surprisingly damage the hair. More particularly, as for example sodium sulphite (Na 2 SO 3), potassium sulphite (K 2 SO 3), ammonium sulphite ((NH 4 SO 3) or bisulphites, have proved to be of little advantage when used in combination with the sulfinic acid derivatives of the formula (a1) because, when using these combinations, the hair became brittle and dry after fading.
For this reason, a preferred multicomponent packaging unit (kit-of-parts) for the reduction bleaching of colored keratin fibers is characterized in that the agent (a) in the container (A) contains, on the basis of the total weight of the agent (a), (a1) sulfites in a total amount of less than 1.0% by weight, preferably less than 0.5% by weight, more preferably less than 0 , 1% by weight.
In other words, a preferred multi-component packaging unit (kit-of-parts), intended for reduction-bleaching of colored keratin fibers, is characterized in that the agent (a) in the container ( A) contains, based on the total weight of agent (a), (a1) sulphites of the group comprising sodium sulphite (Na2SO3), potassium sulphite (K2SO3) and ammonium sulphite ((NH4) ) 2SO3) in a total amount of less than 1.0% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight. Agent (a) contains, as the second component (a2) essential for the invention, at least one or more fatty components of the group of C12 to C30 fatty alcohols, triglycerides of C12 to C30 fatty acids, monoglycerides. of C12 to C30 fatty acids, C12 to C30 fatty acid diglycerides, C12 to C30 fatty acid esters, hydrocarbons and / or silicone oils.
The term "fatty constituents" within the meaning of the invention is understood to mean organic compounds having a solubility in water at ambient temperature (22 ° C.) and at atmospheric pressure (760 mmHg) of less than 1% by weight. weight, preferably less than 0.1% by weight.
The definition of fat constituents only explicitly includes uncharged (ie, nonionic) compounds. The fatty components have at least one saturated or unsaturated alkyl group having at least 12 carbon atoms. The molecular weight of the fatty constituents is 5000 g / mol maximum, preferably 2500 g / mol maximum and particularly preferably 1000 g / mol maximum. The fatty constituents of the compounds which are neither polyoxyalkyl nor polyglycerylated. In this regard, the polyalkoxylated compounds are the compounds whose production requires the reaction of at least 2 alkylene oxide units. Similarly, the polyglyceryl compounds are the compounds whose production requires the reaction of at least two glycerol units. Since, within the meaning of the present invention, only nonionic substances are expressly considered to be fat constituents, the charged compounds, such as, for example, fatty acids and fatty acid salts, do not fall into the group of fatty constituents.
The preferred fatty components are the components of the C 12 to C 30 fatty acid triglyceride group, C 12 to C 30 fatty acid monoglycerides, C 12 to C 30 fatty acid diglycerides, C 12 fatty acid esters. at C30 and hydrocarbons.
The C 12 to C 30 fatty alcohols can be saturated, monounsaturated or polyunsaturated, linear or branched fatty alcohols having 12 to 30 carbon atoms.
Examples of preferred saturated linear C12 to linear fatty alcohols are dodecan-1-ol (dodecyl alcohol, lauryl alcohol), tetradecan-1-ol (tetradecyl alcohol, myristyl alcohol), hexadecan-1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol), octadecan-1-ol (octadecyl alcohol, stearyl alcohol), arachyl alcohol (eicosane-1-ol), henicosyl alcohol (heneicosan-1-ol) and / or behenyl alcohol (docosan-1-ol).
Preferred linear unsaturated fatty alcohols are (9Z) -octadec-9-en-1-ol (oleic alcohol), (9) -octadec-9-en-1-ol (elaidyl alcohol), (9Z, 12Z) -octadeca-9,12-dien-1-ol (linoleic alcohol), (9Z, 12Z, 15Z) -octadeca-9,12,15-trien-1-ol (linolenoyl alcohol), gadoleic alcohol (9Z) -Eicos-9-en-1-ol), arachidonic alcohol ((5Z, 8Z, 11Z, 14Z) -icosa-5,8,11,14-tetraen-1-ol), alcohol erucyl ((13Z) -docos-13-en-1-ol) and / or brassidyl alcohol ((13E) -docosen-1-ol).
Preferred representatives of the branched fatty alcohols are 2-octyl-dodecanol, 2-hexyl-dodecanol and / or 2-butyl-dodecanol.
For the purposes of the present invention, the term "triglyceride" of C 12 -C 30 fatty acids is intended to mean the triester of the trivalent alcohol glycerol with three equivalents of fatty acids. Fatty acids of the same structure and different fatty acids in a triglyceride molecule participate in the formation of esters.
The term "fatty acids" according to the invention means saturated or unsaturated, branched or unbranched, substituted or unsubstituted C12 to C30 carboxylic acids. Unsaturated fatty acids can be monounsaturated or polyunsaturated. In the case of an unsaturated fatty acid, its carbon-carbon double bond (s) has the cis or trans configuration.
The triglycerides of fatty acid are distinguished by a particular ability in that at least one of the ester groups is formed from glycerol with a fatty acid selected from dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid ), hexadecanoic acid (palmitic acic acid), tetracosanoic acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidonic acid), docosanoic acid (behenic acid), acid petoselinic [Z (6) -6-octadecenoic acid], palmitoleic acid [9 (9Z) -hexadec-9-enoic acid], oleic acid [9 (9Z) -octadecen-9-enoic acid], elaidinic acid [acid (9E) -octadec-9-enoic], erucic acid [13Z) -docos-13-enoic acid], linoleic acid [9Z, 12Z) -Octadeca-9,12-dienoic acid, [9Z, 12Z, 15Z) -octadeca- 9,12,15-triene, linolenic acid, elaeostearinic acid [9Z, 11E, 13E) -octadeca-9,11,3-trienic acid], ac arachidonic acid [(5Z, 8Z, 11Z, 14Z) -icosa-5,8,11,14,14-tetrenic acid] and / or nervonic acid [15Z-tetracos-15-enoic acid].
Triglycerides of fatty acids can be of natural origin, triglycerides of fatty acids, which are found in soybean oil, peanut oil, olive oil, sunflower oil macadamia oil, walnut oil, moringa oil, apricot kernel oil, marula oil and / or possibly hydrogenated castor oil or mixtures thereof are particularly suitable for use in the agent (a).
The term monoglycerides of C12 to C30 fatty acids is the monoester of trivalent glycerol fatty alcohol with one equivalent of fatty acid. The mid-hydroxy group of glycerol or the terminal hydroxy group of glycerol can here be esterified with the fatty acid.
The fatty acid monoglycerides are distinguished by a particular ability in that at least one of the ester groups is formed from glycerol with a fatty acid selected from dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid ), hexadecanoic acid (palmitic acic acid), tetracosanoic acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidonic acid), docosanoic acid (behenic acid), acid petoselinic [Z (6) -6-octadecenoic acid], palmitoleic acid [9 (9Z) -hexadec-9-enoic acid], oleic acid [9 (9Z) -octadecen-9-enoic acid], elaidinic acid [9E] -octadec-9-enoic acid], erucic acid [13Z) -docos-13-enoic acid], linoleic acid [9Z, 12Z) -Octadeca-9,12-dienoic acid, [(9Z, 12Z, 15Z) -octadeca-9,12,15-triene, linolenic acid, elaeostearinic acid [(9Z, 11E, 13E) -octadeca-9,11,3-trienic acid], arachidonic acid [(5Z, 8Z, 11Z, 14Z) -icosa-5,8,11,14,14-tetrenic acid] and / or nervonic acid [15Z-tetracos-15-enoic acid].
By diglycerides of C12 to C30 fatty acids is meant the diester of the trivalent fatty alcohol glycerol with two equivalents of fatty acid. The mid-hydroxy group or a terminal hydroxy group of the glycerol can here be esterified with two equivalents of fatty acid or the end groups of the glycerol are each esterified with a fatty acid. Glycerol can be esterified with two fatty acids of the same structure and two different fatty acids
The fatty acid diglycerides are distinguished by a particular ability in that at least one of the ester groups is formed from glycerol with a fatty acid selected from dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid ), hexadecanoic acid (palmitic acic acid), tetracosanoic acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidonic acid), docosanoic acid (behenic acid), acid petoselinic [Z (6) -6-octadecenoic acid], palmitoleic acid [9 (9Z) -hexadec-9-enoic acid], oleic acid [9 (9Z) -octadecen-9-enoic acid], elaidinic acid [9E] -octadec-9-enoic acid], erucic acid [13Z) -docos-13-enoic acid], linoleic acid [9Z, 12Z) -Octadeca-9,12-dienoic acid, [(9Z, 12Z, 15Z) -octadeca- 9,12,15-triene, linolenic acid, elaeostearinic acid [9Z, 11E, 13E) -octadeca-9,11,3-trienic acid ], arachidonic acid [(5Z, 8Z, 11Z, 14Z) -icosa-5,8,11,14,14-tetraenic acid] and / or nervonic acid [(15Z) -tetracos-15-enoic acid].
For the purposes of the present invention, the term "C12 to C30 fatty acid ester" is understood to mean the monoester of a fatty acid and of an aliphatic monovalent alcohol, the alcohol containing up to 6 carbon atoms. Suitable alcohols are, for example, ethanol, n-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, n-pentanol, iso-pentanol or n-hexanol. Suitable alcohols are ethanol and isopropanol.
The preferred C 12 to C 30 fatty acid monoesters are the esters which are formed during the esterification of the ethanol and / or isopropanol alcohols with one of the fatty acids of the group comprising dodecanoic acid (lauric acid), the tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acique), tetracosanoic acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidonic acid), docosanoic acid (behenic acid) ), petroselinic acid [(Z) -6-octadecenoic acid], palmitoleic acid [(9Z) -hexadec-9-enoic acid], oleic acid [(9Z) -octadecen-9-enoic acid] , elaidinic acid [9E] -octadec-9-enoic acid], erucic acid [13Z) -docos-13-enoic acid], linoleic acid [9Z, 12Z) -Octadeca-9 acid , 12-dienoic, [(9Z, 12Z, 15Z) -octadeca-9,12,15-triene, linolenic acid, elaeostearinic acid [9Z, 11E, 13E) -octadeca-9 acid , 11,3-trienic], arachidonic acid [(5Z, 8Z, 11Z, 14Z) -icosa-5,8,11,14-tetraenic acid] and / or nervonic acid [15Z-tetracos-15-acid] -énoïque]. Of the fatty acid esters, isopropyl myristate is particularly preferred.
Hydrocarbons are compounds consisting exclusively of carbon and hydrogen atoms, with 8 to 250 carbon atoms, preferably 8 to 150 carbon atoms. In this context, particularly preferred are aliphatic hydrocarbons such as mineral oils, liquid paraffin oils (for example Paraffinium Liquidum Paraffinum or Perliquidum), isoparaffin oils, semi-solid paraffin oils, paraffin waxes. solid paraffin (Paraffinum Solidum), petrolatum and polydecene.
In this context, liquid paraffins (Paraffinum Liquidum and Paraffinium Perliquidum) have proved particularly suitable. Most preferably, the hydrocarbon is Paraffinum Liquidum, also known as white oil. Paraffinum Liquidum is a mixture of saturated and purified aliphatic hydrocarbons that consists essentially of hydrocarbon chains with a carbon chain distribution of 25 to 35 carbon atoms.
Silicone oils within the meaning of the invention are understood to mean hydrophobic compounds which contain at least one Si atom, preferably several silicon atoms, having a molecular weight of up to 5000 g / mol and which are liquid at room temperature ( 22 ° C) and at atmospheric pressure (760 mm Hg), i.e., the melting point of the silicone oils (at atmospheric pressure) is below 22 ° C.
A particularly preferred multi-component packaging unit (kit-of-parts) for the reduction bleaching of colored keratin fibers is characterized in that - the agent (a) in the container (A) contains (a2) a or more fatty components of the group consisting of C12 to C30 fatty alcohols of C12 to C30 fatty acid triglycerides, C12 to C30 fatty acid monoglycerides, C12 to C30 fatty acid diglycerides, esters of C12 to C30 fatty acids, and / or hydrocarbons.
A also preferred multicomponent packaging unit (kit-of-parts) for the reduction bleaching of colored keratin fibers is characterized in that - the agent (a) in the container (A) contains (a2) a one or more fatty components of the group consisting of dodecan-1-ol (dodecyl alcohol, lauryl alcohol), tetradecan-1-ol (tetradecyl alcohol, myristyl alcohol), hexadecan-1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol), octadecan-1-ol (octadecyl alcohol, stearyl alcohol), arachyl alcohol (eicosan-1-ol), henicosyl alcohol (heneicosan-1-ol) and / or behenyl alcohol (docosan 1-ol). (9Z) -octadec-9-en-1-ol (oleic alcohol), (9E) -octadec-9-en-1-ol (elaidyl alcohol), (9Z, 12Z) -octadeca-9,12-dien-1-ol (linoleic alcohol), (9Z, 12Z, 15Z) -octadeca- 9,12,15-trien-1-ol (linolenoyl alcohol), gadoleic alcohol {9Z ) -Eicos-9-èn-Ιοί), alcohol ar achidonic acid ((5Z, 8Z, 11Z, 14Z) -icosa-5,8,11,14-tetraen-1-ol), erucyl alcohol ((13Z) -docos-13-en-1-ol) and / or brassidyl alcohol ((13E) -docosen-1-ol), 2-octyl-dodecanol, 2-hexyl-dodecanol and / or 2-butyl-dodecanol.
A also preferred multicomponent packaging unit (kit-of-parts) for the reduction bleaching of colored keratin fibers is characterized in that - the agent (a) in the container (A) contains (a2) a or more fatty components of the group of triglycerides of fatty acids wherein at least one of the ester groups is formed from glycerol with a fatty acid which is selected from dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid ), hexadecanoic acid (palmitic acic acid), tetracosanoic acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidonic acid), docosanoic acid (behenic acid), acid petoselinic [Z (6) -6-octadecenoic acid], palmitoleic acid [9 (9Z) -hexadec-9-enoic acid], oleic acid [9 (9Z) -octadecen-9-enoic acid], elaidinic acid [acid (9E) -octadec-9-enoic], erucic acid [ac ide ((13Z) -docos-13-enoic], linoleic acid [(9Z, 12Z) -Octadeca-9,12-dienoic acid, linolenic acid [(9Z, 12Z, 15Z) -octadeca-9, 12,15-triene, elaeostearinic acid [9Z, 11E, 13E) -octadeca-9,11,3-trienoic acid], arachidonic acid [5Z, 8Z, 11Z, 14Z) -icosa-5 acid , 8,11,14-tetrenic] and / or nervonic acid [15Z-tetracos-15-enoic acid].
A also preferred multicomponent packaging unit (kit-of-parts) for the reduction bleaching of colored keratin fibers is characterized in that - the agent (a) in the container (A) contains (a2) a or more fatty components of the hydrocarbon group consisting of mineral oils, liquid paraffin oils, isoparaffin oils, semi-solid paraffin oils, paraffin waxes and / or hard paraffin (Paraffinum Solidum) Vaseline and polydecenes.
The total content of fatty components (a2) in agent (a) has been shown to be a key control variable for reducing dust formation. The reduction of dust is already done when using small amounts of fat constituents. However, to ensure the most complete dedusting possible, it has been shown that it is optimal to use the fatty components (a2) in a total amount of at least 10% by weight. For this reason, it is particularly preferred that the agent (a) contain the fatty components (a2) in a total amount of 10.0 to 90.0% by weight, preferably 20.0 to 86.0% by weight. weight, more preferably from 25.0 to 84.0% by weight and particularly preferably from 30.0 to 80.0% by weight. When the fat constituents (a2) were used in the total preferred and particularly preferred amount indicated in the agent (a), the reducing agent could further be effectively protected against atmospheric oxygen influences and the stability at storage could be significantly improved in this way.
A specifically preferred multi-component packaging unit (kit-of-parts) for the reduction bleaching of colored keratin fibers is characterized in that - the agent (a) in the container (A) contains, on the base of the total weight of the agent (a), one or more fatty components selected from the group (a2) in a total amount of 10.0 to 90.0% by weight, preferably from 20.0 to 86, 0% by weight, more preferably 25.0 to 84.0% by weight and particularly preferably 30.0 to 80.0% by weight.
To reduce the formation of dust and to render the reducing agent inert to oxygen in the air, the use of hydrocarbons has proved particularly effective. In particular, paraffin oils and paraffin waxes are particularly suitable for coating the sulfinic acid derivatives of group (a1) in the form of pulp, and then converting them into a very stable paste form. For this reason, it is explicitly most particularly preferred to use one or more hydrocarbons as the reducing agent (a2) in a total amount of 15.0 to 90.0% by weight, preferably 20.0 to 85.0%. by weight, more preferably from 25.0 to 80.0% by weight and particularly preferably from 30.0 to 75.0% by weight. All data by weight are still based on the total weight of all hydrocarbons contained in the agent (a), which is related to the total weight of the agent (a).
A specifically preferred multi-component packaging unit (kit-of-parts) for the reduction bleaching of colored keratin fibers is characterized in that the agent (a) in the container (A) contains (a2) one or more hydrocarbons in a total amount of from 15.0 to 90.0% by weight, preferably from 20.0 to 85.0% by weight, more preferably from 25.0 to 80.0% by weight, and particularly preferably from 30.0 to 75.0% by weight, based on the total weight of the agent (a).
It is furthermore essential and essential for the invention that agent (a) be present (a3) substantially free of water. The term "substantially water-free" is intended to mean that the water content of the agent (a) is 10.0% by weight maximum. Preferably, however, the water content of the agent (a) is less than 10.0% by weight and is preferably 8.0% by weight maximum, more preferably 5.0% by weight maximum, more preferably preferably 3.0% by weight maximum and most preferably 1.0% by weight maximum. All data in percent by weight refer to the total weight of agent (a).
A low water content in the agent (a) may be desired to incorporate in the agent, in addition to the derivatives of sulfinic acid (a1) and fatty constituents (a2), various hydrophilic ingredients (for example perfumes or hydrophilic care substances). These hydrophilic ingredients may for example first be pre-dissolved in water and then are emulsified or dispersed with the aid of surfactants in the fatty constituents (a2). In this case, the fatty components (a2) serve at the same time as a support, and an W / O emulsion is formed.
In the agent (a) it is also possible to use other ingredients or active substances which contain a certain percentage of water. It has been found in this context that a water content of up to 10% by weight does not affect to a relatively large extent the storage stability of the agent (a).
In order to obtain optimum storage stability, even at high temperatures, it has been found advantageous that the water content of the agent (a) has a value of up to 8.0% by weight, preferably of 5.0% by weight. maximum weight, more preferably 3.0% by weight maximum and more preferably 1.0% by weight maximum, relative to the total weight of the agent (a).
Another particularly preferred multi-component packaging unit (kit-of-parts) for color reduction of colored keratin fibers is characterized in that the agent (a) in the container (A) has a3) a water content of not more than 8.0% by weight, preferably not more than 5.0% by weight, more preferably not more than 3.0% by weight and more preferably not more than 1.0% by weight; , based on the total weight of agent (a). Agent (a) may further contain other ingredients or active substances as well. In particular, the use of nonionic surfactants (a4) in agent (a) has been found to be particularly advantageous. It has been found that the nonionic surfactants have a very good compatibility with the derivatives of sulfinic acid (a1) as well as in particular with the fatty constituents (a2) so that the agent (a) can be produced easily and in a manner reproducible and does not separate during storage. The use of one or more nonionic surfactants makes it possible to obtain optimum miscibility with the agent (b).
Nonionic surfactants may be used, for example, in total amounts of from 0.1 to 15.0% by weight, preferably from 0.5 to 12.5% by weight, more preferably from 1.0 to 10% by weight. and particularly preferably from 1.5 to 8.0% by weight, based on the total weight of the agent (a).
In addition, a multi-component packaging unit (kit-of-parts) thus also preferred for the reduction bleaching of colored keratin fibers is characterized in that - the agent (a) in the container (A) contains in addition to (a4) one or more nonionic surfactants in a total amount of 0.1 to 15.0% by weight, preferably 0.5 to 12.5% by weight, more preferably 1.0 to 10, 0% by weight and particularly preferably from 1.5 to 8.0% by weight, relative to the total weight of the agent (a).
The term "surfactants" means amphiphilic compounds (bifunctional) comprising at least one hydrophobic radical and at least one hydrophilic molecular part. The hydrophobic molecular part is generally a hydrocarbon chain having 10 to 30 carbon atoms. In the case of nonionic surfactants, the hydrophilic molecular part comprises a strongly polar non-charged structural unit.
The nonionic surfactants contain as hydrophilic group for example a polyol group, a polyalkylene glycol or a combination of polyol ether group and polyglycol ether. Such compounds are, for example, adducts of from 2 to 50 moles of ethylene oxide and / or from 2 to 50 moles of propylene oxide to linear and branched fatty alcohols having 12 to 30 carbon atoms, polyglycol ethers of fatty alcohol or polypropylene glycol ethers of fatty alcohols or polyether of mixed fatty alcohols, adducts of 2 to 50 moles of ethylene oxide and / or 2 to 50 moles of propylene oxide to linear and branched fatty acids having 6 to 30 carbon atoms, polyglycol ethers of fatty acids or polypropylene glycol ethers of fatty acids or polyether of mixed fatty acids, adducts of 2 to 50 mols of ethylene and / or from 2 to 50 moles of propylene oxide to linear and branched alkylphenols having 8 to 15 carbon atoms in the alkyl group, alkylphenol polyglycol ethers or alkylphenol polypropyleneglycol ethers or mixed alkylphenol polyether Adducts, end-capped with a methyl or C2-C6 alkyl radical, 2 to 50 moles of ethylene oxide and / or 2 to 50 moles of propylene oxide are linear and branched fatty alcohols having 8 to 30 carbon atoms, fatty acids having 8 to 30 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group, for example the types available under the trade names Dehydrol® * LS, DehydroKDLT (Cognis), monoesters and diesters of C12 to C30 fatty acids of adducts of 2 to 30 moles of ethylene oxide to glycerol, adducts from 5 to 60 moles of ethylene oxide to castor oil and hydrogenated castor oil, fatty acid polyolsters such as for example the commercial product Hydagen®HSP (Cognis) or SOVERMOL types ® * (Cognis), polyalkoxylated triglycerides, alkyl esters of polyacoxylated acids of the formula (Tnio-1) R1CO- (OCH2CHR2) wOR3 (Tnio-1) in which R1CO represents a linear or branched, saturated and / or unsaturated acyl radical having from 6 to 22 carbon atoms, R2 represents an atom of hydrogen or a methyl group, R3 represents linear or branched alkyl radicals having 1 to 4 carbon atoms, and w represents a number from 2 to 20, the amine oxides, the mixed hydroxyethers, as described for example in the document DE OS-19736866, sorbitan fatty acid esters and ethylene oxide adducts to sorbitan fatty acid esters such as, for example, polysorbates. fatty acid esters and ethylene oxide adducts on sugar fatty acid esters, ethylene oxide adducts to fatty acid alkanolamides and fatty amines, sugar surfactants of the type of alkyl and alkenyl oligoglycosides, or sugar surfactants of the type of N-alkylpolyhydroxyalkyl fatty acid amides.
C 12 to C 30 fatty alcohols, C 12 to C 30 fatty acid triglycerides, C 12 to C 30 fatty acid monoglycerides, C 12 to C 30 fatty acid diglycerides, C 12 to C 30 fatty acid esters , do not have a strongly polar end group (which also results from the low HLB values of the compounds of this group). For the purposes of the present invention, they are considered to be fatty constituents and therefore do not represent nonionic surfactants according to the definition of the present invention.
In addition, agents (a) may additionally contain one or more nonionic polymers (a5). The nonionic polymer (s) may be used, for example, in total amounts of 0.1 to 15.0% by weight, preferably 0.2 to 10.5% by weight, more preferably 0.25 to 7% by weight. , 5% by weight, and particularly preferably from 0.3 to 5.0%, relative to the total weight of the agent (a).
A particularly preferred multicomponent packaging unit (kit-of-parts) for the reduction bleaching of colored keratin fibers is characterized in that - the agent (a) in the container (A) additionally contains (a5 ) one or more nonionic polymers in a total amount of 0.1 to 15.0% by weight, preferably 0.2 to 10.5% by weight, more preferably 0.25 to 7.5% by weight and particularly preferably from 0.3 to 5.0% by weight, based on the total weight of the agent (a).
By polymers is meant macromolecules having a molecular weight of at least 1000 g / mol, preferably at least 2500 g / mol, particularly preferably at least 5000 g / mol, which consist of organic units identical repetitive. The polymers are produced by polymerization of a single type of monomer or by polymerization of different types of monomers of different structures. If the polymer is produced by polymerization of a type of monomer, it is called homopolymer. If several types of monomers of different structures are used during the polymerization, those skilled in the art speak of copolymers.
The maximum molecular weight of the polymer depends on the degree of polymerization (the number of polymerized monomers) and is also determined by the polymerization process. For the purpose of the present invention, it is preferred that the maximum molecular weight of the zwitterionic polymer (d) is not greater than 107 g / mol, preferably not greater than 106 g / mol and particularly preferably no greater than 105 g / mol. mol.
The nonionic polymers are characterized in that they have no charges, that is to say that the nonionic polymers in the sense of the present invention are produced by homo- or copolymerization of uncharged monomers.
Examples of suitable nonionic polymers are vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidinone, vinylpyrrolidone / vinyl acetate copolymers, polyethylene glycols, ethylene / propylene / styrene copolymers and / or butylene / ethylene / styrene copolymers.
Agent (B) in the Container (B) The multicomponent packaging unit of the invention comprises a second container (B) which contains an agent (b) This agent (b) is a cosmetic carrier formulation which has a water content of at least 30.0% by weight relative to the total weight of the agent (b).
In a preferred embodiment, the agent (b) is made so that its water content has a value of at least 40.0% by weight, preferably at least 50.0% by weight, more preferably at least 55.0% by weight and most preferably at least 60.0% by weight, based on the total weight of the agent (b).
In addition, a preferred multi-component packaging unit (kit-of-parts) for the reduction bleaching of colored keratin fibers is characterized in that - the agent (b) in the container (B) a (b1 ) a water content of at least 40.0% by weight, preferably at least 50.0% by weight, more preferably at least 55.0% by weight and most preferably from minus 60.0% by weight based on the total weight of agent (b).
In the course of the work which has led to the present invention, it has been found that the pH of the bleaching agent ready for use for optimum bleaching is preferably alkaline. At a pH value of 7.0 to 13.0, the derivatives of sulfinic acid (a1) showed their best effect. It has furthermore been found particularly advantageous that the alkalizing agent necessary for adjusting the pH is present in the aqueous agent (b). In this way, it can be reliably guaranteed that the contact between derivatives of the sulfinic acid (a1) and the alkalinizing agent is only a short time before use after the mixing of the agents (a). and B). The adjustment of the alkaline pH value can be carried out in principle by means of various alkalinizing agents. Suitable alkalisers are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate. In this respect it has been found, however, that the derivatives of sulfinic acid, effecting the reduction discoloration (a1), can best diffuse into the hair fiber when the alkalinization agent is used for nitrogen compounds such as ammonia. alkanolamines and / or basic amino acids.
In addition, a multicomponent packaging unit (kit-of-parts) therefore also preferred for the reduction bleaching of colored keratin fibers is characterized in that - the agent (b) in the container (B) contains (b2) one or more alkalinizing agents of the group comprising ammonia, alkanolamines and / or basic amino acids.
The pH values of the present invention were measured at a temperature of 22 ° C with an N-type glass electrode 61 from Schott.
The alkanolamines which can be used in the agent (b) of the invention are preferably chosen from primary amines having a C2-C6 alkyl base body which carries at least one hydroxyl group. Preferred alkanolamines are selected from the group consisting of 2-amino-ethan-1-ol (monoethanolamine), 3-aminopropane-1-ol, 4-aminobutan-1-ol, 5-amino pentan 1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3- diol.
Particularly preferred alkanolamines according to the invention are chosen from 2-aminoethane-1-ol and / or 2-amino-2-methylpropan-1-ol. A particularly preferred embodiment is therefore characterized in that the agent (b) according to the invention contains as alkalinizing agent is an alkanolamine chosen from 2-amino-ethan-1-ol and / or 2-amino -2-methylpropan-1-ol.
An amino acid suitable for the purposes of the invention is an organic compound which contains in its structure at least one protonable amino group and at least one -COOH- or -SO3H- group. Preferred amino acids are aminocarboxylic acids, particularly α- (alpha) -aminocarboxylic acids and ω-aminocarboxylic acids, with α-aminocarboxylic acids being particularly preferred.
The term "basic amino acids" according to the invention means amino acids which have an isoelectric point greater than 7.0.
The basic α-aminocarboxylic acids contain at least one asymmetric carbon atom. In the context of the present invention, the two possible enantiomers can be used as the specific compound or mixtures thereof, in particular in the form of racemates. However, it is particularly advantageous to use the isomeric form preferably of natural origin, usually in the L configuration.
The basic amino acids are preferably selected from the group consisting of arginine, lysine, ornithine and histidine, more preferably arginine and lysine. In another particularly preferred embodiment, an agent of the invention is therefore characterized in that the alkalinization agent is a basic amino acid chosen from the group formed by arginine, lysine, ornithine and / or or histidine.
In addition, a multi-component packaging unit (kit-of-parts) therefore also preferred for the reduction-bleaching of colored keratin fibers is characterized in that - the agent (b) in the container (B) contains (b2) one or more alkalinizing agents selected from the group consisting of ammonia, 2-amino-ethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 3-amino-2 methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-amino-propan-1,2-diol, 2-amino-2-methylpropan-1,3-diol, arginine, lysine, ornithine and / or histidine
The agents (b) that are preferred according to the invention may also contain mixtures of alkalinity agents such as, for example, a mixture of different alkanolamines, a mixture of basic amino acids and / or a mixture of alkanolamines and amino acids. basic. The alkalizing agents are particularly preferably used in certain combinations: 2-aminoethane-1-ol / 2-amino-2-methylpropan-1-ol; 2-aminoethan-1-ol / arginine; 2-amino-ethan-1-ol / lysine; 2-aminoethan-1-ol / omithine; 2-aminoethan-1-ol / histidine; 2-amino-2-methylpropan-1-ol / arginine; 2-amino-2-methylpropan-1-ol / lysine; 2-amino-2-methylpropan-1-ol / omithine; 2-amino-2-methylpropan-1-ol / histidine; arginine / lysine; arginine / ornithine; arginine / histidine; lysine / ornithine; lysine / histidine and / or orithine / histidine.
In addition, the agent may contain a plurality of alkalizing agents, in particular inorganic alkalinizing agents. The inorganic alkalinization agents which can be used according to the invention are preferably chosen from the group which is formed by sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and sodium phosphate. potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.
Although the preferred pH value of the agent (b) is in the alkaline range, the agents (b) could contain, in addition to the alkalinizing agent, also small amounts of acidifying agents for one or more alkaline agents. fine adjustment of the desired pH. The preferred acidifying agents according to the invention are food acids, for example citric acid, acetic acid, malic acid or tartaric acid, as well as dilute mineral acids.
To make a fine adjustment of the desired pH value, one or more acids from the group including citric acid, tartaric acid, malic acid, lactic acid, acetic acid, sulfuric acid, lactic acid, Hydrochloric acid, phosphoric acid, methanesulfonic acid, benzoic acid, malonic acid, oxalic acid and / or 1-hydroxyethane-1,1-diphosphonic acid have been found to be suitable. The acid or acids are preferably chosen from the group consisting of citric acid, tartaric acid, malic acid, lactic acid, methanesulfonic acid, oxalic acid, malonic acid, benzoic acid, hydrochloric acid, sulfuric acid, phosphoric acid and / or 1-hydroxyethan-1,1-diphosphonic acid.
The pH value of the aqueous agent (b) is preferably adjusted to 7.5 to 12.5, preferably 8.0 to 12.0, more preferably 8.5 to 11.5, and particularly preferably from 9.0 to 11.0.
A particularly preferred multi-component packaging unit (kit-of-parts) is characterized in that the agent (b) in the container (B) has b3) a pH value of 7.5 to 12.5, preferably from 8.0 to 12.0, more preferably from 8.5 to 11.5, and most preferably from 9.0 to 11.0. Agent (b) is produced as a liquid preparation to which other surfactants can be added. They are preferably chosen from anionic, zwitterionic, amphoteric and nonionic surfactants. Agent (b) contains as anionic surfactants, for example, fatty acids, alkyl sulfates, alkyl ether sulfates and ether carboxylic acids having 10 to 20 carbon atoms in the alkyl group and up to 16 glycol ether groups in the alkyl group. the molecule. The agent (B) may also contain one or more zwitterionic surfactants, for example betaines, N-alkyl-N, N-dimethylammonium glycinates, N-acylaminopropyl-NN-dimethylammonium glycinates and 2-alkyl-3 carboxymethyl-3-hydroxyethyl imidazolines.
Suitable agents (b) according to the invention are further characterized in that the agent (b) additionally contains at least one amphoteric surfactant. The preferred amphoteric surfactants are N-alkylglycines, N-alkylproprionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkyliaminopropionic acids and alkylaminoacetic acids. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, such as cocoacylaminoethyl aminopropionate and C12-C18 acylsarcosine.
It has been found particularly advantageous that the agent (b) additionally contain nonionic surfactants (b4). Preferred nonionic surfactants are alkylpolyglycosides alkylene oxide adducts to fatty alcohols and fatty acids each having 10 to 60 moles of ethylene oxide per mole of fatty alcohol or fatty acid and triglycerides of fatty acids which are ethoxylated with 10 to 60 ethylene oxide units.
A particularly preferred multi-component packaging unit (kit-of-parts) is characterized in that the agent (b) in the container (B) additionally contains one or more nonionic surfactants from the group comprising the alcohols. C12 to C30 fatty acids that are ethoxylated with 10 to 60 ethylene oxide units and / or fatty acid triglycerides that are ethoxylated with 10 to 60 ethylene oxide units.
The nonionic, zwitterionic, amphoteric and / or anionic surfactants may be used in amounts of 0.1 to 25.0% by weight, preferably 0.3 to 15.0% by weight and most preferably 0.5 to 5.0% by weight relative to the total weight of the composition (b).
In the optimally prepared ready-to-use bleaching agent, the viscosity has been adjusted so that the agent is on the one hand sufficiently fluid to ensure adequate diffusion of all the active substances of the agent into the hair fiber but on the other hand is sufficiently viscous not to dribble during application. For this reason, ready-to-use bleaching agents preferably contain a thickener. In a particularly preferred manner, the thickener is incorporated in the aqueous agent (b).
According to another preferred embodiment, the thickener is an anionic synthetic polymer. Preferred anionic groups are carboxylate and sulfonate groups.
Examples of anionic monomers, of which polymeric anionic thickeners may be constituted, are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride and 2-acrylamido-2-acid. methylpropanesulfonic acid. The acidic groups may be totally or partially present in the form of sodium, potassium, ammonium, mono- or triethanolammonium salt. The preferred monomers are maleic anhydride and in particular 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.
Preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allylethers of pentaerythritol, sucrose and propylene are preferred crosslinking agents. Such compounds are commercially available for example under the trademark Carbopol®. The homopolymer of 2-acrylamido-2-methylpropanesulphonic acid, which can be obtained in the control, for example under the trade name Rheothik®11-80, is also preferred.
In this first embodiment, it may also be preferred to use copolymers consisting of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. The preferred nonionic monomers are acrylamide, methacrylamide, esters of acrylic acid, methacrylic acid esters, monoesters and diesters of itaconic acid, vinylpyrrolidone, vinyl ethers and vinyl esters .
Preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C 1 -C 6 alkyl esters, such as those sold under the name INCI Acrylates Copolymers. A preferred commercial product is, for example, Aculyn®33 from Rohm & Haas. In addition, copolymers of acrylic acid, methacrylic acid or their C1-C6 alkyl esters and esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol are preferred. Suitable ethylenically unsaturated acids include acrylic acid, methacrylic acid and itaconic acid; the appropriate alkoxylated fatty alcohols are in particular Steareth-20 or Ceteth-20. These copolymers are sold by Rohm & Haas under the trade name Aculyn®22 and by the company National Starch under the trade names Structure®2001 and Structure®3001.
The preferred anionic copolymers are, in addition, the acrylic acid-acrylamide copolymers, and in particular the copolymers of polyacrylamide with monomers containing sulfonic acid groups. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, the sulfonic acid group being completely or partially present in the form of sodium, potassium, ammonium, mono- or triethanolammonium salt. This copolymer may also be present in crosslinked form, the preferred crosslinking agents being polyolefinically unsaturated compounds such as tetraallyloxythane, allylsucrose, allylpentaerythritol and methylenebisacrylamide. Such a polymer is contained in the commercial products Sepigel®305 and Simulgel®600 from Seppic. The use of these compounds, which additionally contain polymer components, a mixture of hydrocarbons (isoparaffin or isohexadecane C13 to C14) and a nonionic emulsifier (Laureth-7 or polysorbate-80), has proved particularly advantageous in the context of the teaching of the invention.
In addition, polymers of maleic anhydride and methyl vinyl ether, particularly those having crosslinks, are preferred thickeners. A maleic acid-methylvinyl ether copolymer, cross-linked with 1,9-decadiene, is commercially available under the name StabilezeOQM.
Preferably, the agent of the invention may further contain at least one polymer or copolymer of acrylic acid and / or anionic methacrylic acid. Preferred polymers of this type are the following: polymers consisting for example of at least 10% by weight of lower alkyl and acrylic acid, 25 to 70% by weight of methacrylic acid and possibly up to 40% by weight of another comonomer, copolymers consisting of 50 to 75% by weight of ethyl acrylate, 25 to 35% by weight of acrylic acid and 0 to 25% by weight of other comonomers.
Suitable dispersions of this type are available commercially, for example under the trade name LatekolKDD (BASF), copolymers consisting of 50 to 60% by weight of ethyl acrylate, 30 to 40% by weight of methacrylic acid and to 15% by weight of acrylic acid, crosslinked with ethylene.
According to another embodiment, the thickener is a cationic synthetic polymer. Preferred cationic groups are quaternary ammonium groups. In particular, the polymers, in which the quaternary ammonium groups are linked, via a C 1 -C 4 hydrocarbon group, to a polymer backbone consisting of acrylic acid, methacrylic acid or their derivatives, are have proven to be particularly appropriate.
Homopolymers of the general formula (HP-1),
(HP-1) wherein R 1 = -H or -CH 3, R 2, R 3 and R 4 are independently selected from hydroxyalkyl, alkenyl or C 1 -C 4 alkyl, m = 1, 2, 3 or 4, n is a number and X 'is a physiologically acceptable organic or inorganic anion, and copolymers, consisting essentially of the monomeric units of the formula (HP-1), and the nonionic monomeric units, are particularly preferred cationic polymeric gelling agents. In the context of these polymers, those which are preferred according to the invention satisfy at least one of the following conditions: R1 represents a methyl group, R2, R3 and R4 represent methyl groups, M has a value of 2.
Suitable physiologically acceptable counterions X are, for example, halide ions, sulphate ions, phosphate ions, methosulphate ions and organic ions such as lactate, citrate, tartrate and acetate ions. especially chloride, are preferred.
A particularly suitable homopolymer is methacryloxyethyltrimethylammonium polychloride, optionally cross-linked, with the INCI name Polyquatemium-37. The crosslinking can optionally be carried out using olefinically polyunsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyglycerol polyallylether 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 non-aqueous polymer dispersion which should not have a polymer content of less than 30% by weight. These polymer dispersions can be obtained commercially under the names Salcare®SC 95 (about 50% polymer content, other components: mineral oil (INCI name: Ore Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG). -1-Trideceth-6)) and Salcare®SC 96 (about 50% polymer content, other components: mixture of propylene glycol diesters with a mixture of caprylic and capric acids (INCI designation: Propylen Glycol Dicaprylate / Dicaprate) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1-Trideceth-6).
The copolymers comprising monomeric units according to the formula (HP-1) contain, as non-ionogenic monomer units, preferably acrylamide, methacrylamide, C 1 -C 4 alkyl esters and acrylic acid and esters of C1-C4 alkyl and methacrylic acid. Among these nonionic monomers, acrylamide is particularly preferred. These copolymers can also be crosslinked, as in the case of the homopolymers above. A preferred copolymer according to the invention is the acrylamide-methacroyloxyethylthmethylammonium chloride copolymer. Such copolymers, in which the monomers are present in a weight ratio of about 20:80, are available commercially in the form of a 50% aqueous dispersion of non-aqueous polymer under the designation Salcare®SC 92.
In another preferred embodiment, natural thickeners are used. Preferred thickeners of this embodiment are, for example, nonionic guar gums. According to the invention, unmodified and modified guar gums can be used. The unmodified guar gums are sold for example under the trade name Jaguar®C by the Rhône Poulenc company. Preferred modified guar gums according to the invention contain C1-C6 hydroxyalkyl groups. Hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl are preferred. Such modified guar gums are known in the state of the art and can be prepared for example by reaction of the guar gum with alkylene oxides. The degree of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed in proportion to the number of free hydroxy groups of the guar gum, is preferably between 0.4 and 1.2. Such modified guar gums are commercially available under the trade names Jaguar®HP8, Jaguar®HP60, Jaguar®HP120, Jaguar®DC 293 and Jaguar®HP105 from the company Rhône-Poulenc. Other suitable natural thickeners are also already known from the state of the art.
According to this preferred embodiment, the biosaccharide gum of microbial origin, such as scleroglucan gums or xanthan gums, are gums obtained from plant exudates such as gum arabic, gum ghatti, karaya gum. gum tragacanth, carrageenan gum, agar-agar, locust bean meal, pectins, alginates, starch fractions and derivatives such as amylose, amylopectin and dextrins, derivatives thereof cellulose, such as methylcellulose, carboxyalkylcellulose and hydroxyalkylcelluloses.
Preferred hydroxyalkylcelluloses are in particular hydroxyethylcelluloses which are sold under the names Cellosize® from Amerchol and Natrosol® from Hercules. Suitable carboxyalkylcelluloses are, in particular, carboxymethylcelluloses, such as those sold under the names Blanose® by Aqualon, Aquasorb® and Ambergum® by Hercules and Cellgon® by Montello. Starch and its derivatives are also preferred. Starch is a plant storage substance that is found mainly in tubers and roots, in cereal seeds and in fruits and can be obtained from a variety of high yielding plants. The polysaccharide which is insoluble in cold water and which forms a colloidal solution in boiling water, can be obtained for example potatoes, cassava, sweet potato, marantine, corn, cereals, rice, legumes such as peas and beans, bananas or medulla from certain types of palm (eg sago palm). According to the invention, it is possible to use natural starches of plant origin and / or chemically or physically modified starches. Modification can be achieved for example by introducing different functional groups onto one or more of the hydroxyl groups of the starch. Usually, they are esters, ethers or amides of starch having optionally substituted C1-C40 radicals. Particularly advantageous is commercially available corn starch etherified with a 2-hydroxypropyl group, for example from National Starch under the brand name Amaze®.
However, commercially available non-ionic, all-synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidinone, non-ionic, all-synthetic, preferred polymers are sold, for example, by BASF under the trade name Luviskol®. Particularly suitable are copolymers of butylene, ethylene and styrene or copolymers of propylene, ethylene and styrene as the nonionic thickener according to the invention.
Such nonionic polymers provide, in addition to their excellent thickening properties, also a significant improvement in the feel of the resulting formulations.
Phyllosilicates (polymer, crystalline sodium disilicate) have proved particularly suitable as mineral thickeners within the meaning of the present invention. In particular, it is possible to use clays, in particular magnesium and aluminum silicates such as bentonite, in particular smectites such as montmorillonite or hectorite, which may also optionally be modified appropriately, and synthetic phyllosilicates. , such as the magnesium phyllosilicate sold by Sud Chemie under the trade name Optigel®, are preferred.
The most suitable thickeners are the thickeners of the group of celluloses, hydroxy-C2-C6 alkyl-celluloses, carboxymethyl-celluloses, alginic acid, (meth) acrylic polymers and / or xanthan gum. Therefore, it is particularly preferred to incorporate one or more thickeners of this group in the agent (b) of the invention.
A particularly preferred multi-component package (kit-of-parts) is characterized in that the agent (b) in the container (B) additionally contains (b4) one or more thickeners of the group of celluloses, hydroxy C 2 -C 6 alkylcelluloses, carboxymethylcelluloses, alginic acid, (meth) acrylic polymers and / or xanthan gum.
In another particularly preferred embodiment, the agent (b) is in the form of a clear gel formulation and therefore does not contain any fat ingredients.
If the agent (a), which contains one or more fatty ingredients (a2), is mixed with the agent (b), preferably in the form of a clear gel, an emulsion is produced which may be in the form of a O / W emulsion.
A particularly preferred multi-component packaging unit (kit-of-parts) is characterized in that the agent (b) in the container (B) contains, based on the total weight of the agent (b), fatty components of the group of C12 to C30 alcohols, triglycerides of C12 to C30 fatty acids, monoglycerides of C12 to C30 fatty acids, diglycerides of C12 to C30 fatty acids, esters of fatty acids at C12 to C30, hydrocarbons and / or silicone oils in a total amount of less than 2.5% by weight, preferably less than 1.0% by weight, more preferably less than 0.5% by weight, and particularly preferably less than 0.1% by weight.
The definitions of the fat constituents correspond to the definition of the fatty constituents (a2) in the agent (a). Discoloration of colored keratin fibers The multi-component packaging unit of the invention is a system comprising the means (a), (b) and (c) which is used for the bleaching of previously colored keratin fibers, particular human hair. The colored keratin fibers are usually fibers that have been previously stained with oxidation dyes and / or standard direct dyes known to those skilled in the art.
The bleaching agents are suitable for removing stains that have been produced with developers-based and copulatory-based dyes on keratin fibers. If the following compounds have been used as a developer, the colorations produced can be removed with the decolorizing agent in a correct, effective manner and practically without any subsequent sinking: p-phenylenediamine, p-toluylendiamine-N, N-bis (B- hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino-2-methyl-aniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (a, 3-dihydroxyethyl) p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, bis (2-hydroxy-5-aminophenyl) methane, p-aminophenol, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy -2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine and / or 4,5-diamino-1- (β-hydroxyethyl) pyrazole.
If the following compounds have been used as copulators, the dyes produced can also be removed with a very good decolorization result: m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives. Suitable copulators are in particular 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, m-phenylenediamine, 1-phenyl-3-methyl-pyrazoton-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4-diaminophenoxy) -propane, 2-chloro-resorcin, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcin, 5-methylresorcin, 2-methyl-4-chloro-5- aminophenol and 2,6-dihydroxy-3,4-dimethylpyridine.
The substrate to be bleached may also have been stained with direct dyes. Direct dyes include nitrophenylenediamine, nitroaminophenols, azo dyes, anthraquinones or indophenols. The multi-component packaging units of the invention (kit-of-parts) make it possible to bleach, for example, keratin fibers which have been colored with the dyes known under the international names or the trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yeltow 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, Blue HC 2, Blue HC 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Component 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, Acid Black 52, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-Bis- ( 3-hydroxyethyl) -amino-2-nitrobenzene, 3-nitro-4- (3-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-tetrahydrochinoxaline, 2-hydroxy-1,4-naphthochinone, pikraminic acid and their salts, 2-amino 6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoyl and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.
In addition, the substrates to be decolorized can also be colored with naturally occurring natural dyes, such as, for example, those contained in red henna, neutral henna, black henna, chamomile flowers, sandalwood, black tea, buckthorn bark, sage, logwood, madder root, cachou, cedar and alkanna roots.
The bleaching agents of the invention are intended to remove these dyes and therefore preferably do not contain any dyes, i.e., no developer and copulatory type oxidation dye precursors and also no direct dyes.
In another preferred embodiment, a multi-component packaging unit of the invention (kit-of-parts) is therefore characterized in that the total amount of all the oxidation dye dyes and precursors contained in agent (a) has a maximum value of 0.2% by weight, preferably 0.1% by weight, more preferably 0.05% by weight and particularly preferably 0.01% by weight relative to the total weight of the agent (a) and the total amount of all oxidation dye dyes and precursors contained in the agent (b) has a maximum value of 0.2% by weight, preferably 0, 1% by weight, more preferably 0.05% by weight and particularly preferably 0.01% by weight relative to the total weight of the agent (b). The multicomponent packaging unit of the invention is used to decolorize by reducing the colored keratin fibers. Agents (a) and (b) together form the ready-to-use bleaching agent which contains a reducing agent. Therefore, the agents (a) and (b) preferably do not contain any oxidation agent for reasons of incompatibility and to avoid uncontrollable exothermic reactions.
By oxidation agents is meant here in particular oxidation agents also used for oxidative decolorization such as hydrogen peroxide and persulfates (potassium persulfate (alternatively, potassium peroxodisulfate), sodium persulfate ( sodium peroxodisulfate) and ammonium persulfate (alternatively ammonium peroxodisulfate) Preferably, none of the agents (a), (b) and (c) therefore contain the above-mentioned oxidation agent.
In another preferred embodiment, a multi-component packaging unit of the invention (kit-of-parts) is thus characterized in that the total amount of all oxidation agents contained in the agent ( a), the group of peroxides and persulfates has a maximum value of 0.2% by weight, preferably 0.1% by weight, more preferably 0.05% by weight and particularly preferably 0.01% by weight; by weight relative to the total weight of the agent (a), the total amount of all the oxidation agents contained in the agent (b) of the group of peroxides and persulfates has a maximum value of 0.2% by weight, preferably 0.1% by weight, more preferably 0.05% by weight and particularly preferably 0.01% by weight relative to the total weight of the agent (b)
In addition, the agents of the invention (a) and (b) may contain other active ingredients, auxiliaries and additives such as for example nonionic polymers such as for example vinylpyrrolidinone / vinyl acetate copolymers, polyvinylpyrrolidinone, vinylpyrrolidinone vinyl acetate, polyethylene glycols and polysiloxanes; additional silicones such as volatile or non-volatile polyalkylsiloxanes, linear, branched or cyclic, crosslinked or non-crosslinked (such as dimethicone or cyclomethicone), polyarylsiloxanes and / or polyalkylarylsiloxanes, in particular polysiloxanes comprising organofunctional groups, such as substituted or unsubstituted amines (Amodimethicone), carboxyl, alkoxy and / or hydroxyl groups (dimethiconcopolyols), linear polysiloxane (A) -polyoxyalkylene (B) block copolymers, grafted silicone polymers; cationic polymers such as quaternized cellulose ethers, polysiloxanes containing quaternary groups, chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidinone-imidazolinium-methochloride copolymers and quaternized polyvinyl alcohol; zwitterionic and amphoteric polymers; anionic polymers such as, for example, polyacrylic acids or crosslinked polyacrylic acids; structuring agents such as glucose, hair conditioning compounds such as phospholipids, for example lecitin and cephalins; perfume oils, dimethyliso-sorbide and cyclodextrin; active substances for improving the structure of the fibers, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose and lactose; dyes intended to color the agent; anti-dandruff substances such as piroctone olamine, zinc omadine and climbazol; amino acids and oligopeptides; protein hydrolysates of animal and / or vegetable origin, and in the form of their fatty acid condensation products or optionally the anionically or cationically modified derivatives; vegetable oils; stabilizers of the effects of light and UV light inhibitors; active substances such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinone carboxylic acids and their salts and bisabolol; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycumarines, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidines, anthocyanidins, flavanones, flavones and flavonols; ceramides or pseudoceramides; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes such as fatty alcohols, beeswax, mineral wax and paraffins; swelling and penetration substances such as glycerol, propylene glycol, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates; opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers; pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate; pigments and propellants such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air. In this respect, one refers explicitly to known monographs, for example Kh. Schrader, 'Grundlagen und Rezepturen des Kosmetika', 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, which reflect the relevant knowledge of those skilled in the art.
As already described, the ready-to-use bleaching agent is produced by mixing agents (a) and (b). In principle, the agents (a) and (b) are mixed in various mixing ratios such as for example (a) / (b) from 20: 1 to 1:20. The agent (a) is preferably a solid, powdery agent, in particular preferably a pasty agent. In order to be able to completely transform into a solution when mixing with the agent (b), it is however advantageous to use the agent (b) in at least the same amount as the agent (a). In addition, it is preferred to use the agent (b) in excess.
In another preferred embodiment, a multi-component packaging unit of the invention is therefore characterized in that the amounts of agent (a) in the container (A) and agent (b) in the container (B) are chosen so that, during the production of the application mixture, that is to say during the mixing of the agents (a) and (b), the mixing ratio (a) / (b) at a value of from 1: 5 to 5: 1, preferably from 1: 3 to 3: 1, more preferably from 1: 2 to 2: 1.
To produce the mixture, the agent (a) of the container (A) may, for example, be completely transferred to the container (B) which already contains the agent (b). In this case, the size of the container (B) is chosen so that the container (B) can contain the total amount of the agent (a) and (b) and also allows a mixture of the two agents (a) and (b), for example by succussion or agitation.
Similarly, the production of the mixture can also be carried out by complete transfer of the agent (b) from the container (B) to the container (A) which already contains the agent (a). In this case, the size of the container (A) must be chosen so that the container (a) can receive the total amount of the agents (a) and (b) and that it also allows a mixture of the two agents (a). ) and (b), for example by succussion or stirring.
Another possibility of preparing the application mixture is the complete transfer of the two agents (a) and (b) from the containers (A) and (B) into a third container (C) which then allows the two agents to be mixed together by example by succussion or agitation.
For example, a multi-component packaging unit of the invention contains 25 g of the agent (a) in the container (A) 100 grams of the agent (b) in the container (B)
To produce the mixture, the agent (b) is completely transferred from the container (B) into the container (A). The agents (a) and (b) are then shaken or agitated. The mixing ratio of the agents (a) / (b) is at a value of (25 g / 100 g) = 0.25.
For example, a multi-component packaging unit of the invention contains 100 g of the agent (a) in the container (A) 100 grams of the agent (b) in the container (B)
To produce the mixture, the agent (b) is completely transferred from the container (B) into the container (A). The agents (a) and (b) are then shaken or agitated. The mixing ratio of the agents (a) / (b) is at a value of (100 g / 100 g) = 1.0. The multi-component packaging unit according to the invention may also contain one or more other agents in separately made containers. For example, the multi-component packaging unit according to the invention may also comprise a container (C) containing a cosmetic agent (c). The agent (c) may be, for example, a pretreatment agent, a post-treatment agent or a care agent.
processes
The multi-component packaging units of the invention (kit-of-parts) described above can be used in reduction bleaching processes.
A second object of the present invention is therefore a process of bleaching by reducing colored keratin fibers, in particular human hair, comprising the following steps, in the order indicated, consisting of (I) producing a bleaching agent ready to the use by mixing an agent (a) as defined in the description of the first subject of the invention with an agent (b) as defined in the description of the first subject of the invention, (II) applying the bleaching agent ready for use on the keratin fibers, (III) allowing the bleaching agent to act for a period of 5 to 60 minutes, preferably 10 to 55 minutes, more preferably 20 to 50 minutes 30 to 45 minutes, (IV) rinsing off the keratin fiber bleaching agent, (V) optionally applying a post-treatment agent to the keratin fibers, the post-treatment agent containing an am surfactant photeur, zwitterionic and / or anionic, (VI) optionally rinse off the post-treatment agent of keratin fibers.
Steps (I), (II), (III) and (IV) of the process constitute the process of bleaching keratin fibers, and are thus carried out one after the other in a direct time course. With regard to the course of steps (IV) and (V), there is in principle no time limit. Thus, step (v) can be performed hours, days or for example up to two weeks after the end of step (IV).
It is also possible and according to the invention to perform the fading steps (I) to (IV) are performed several times successively.
As described above, the agents (a) and (b) are preferably used in an amount ratio (a) / (b) which is preferably 1: 5 to 5: 1, more preferably 1: 3 to 3: 1 and most preferably 1: 2 to 2: 1.
Accordingly, preferably, a method of bleaching colored keratin fibers is characterized in that the production of the bleaching agent ready for use in step (I) is carried out by mixing the agent (a). ) with the agent (b), the two agents are used in an amount ratio (a) / (b), the value of which is from 1: 5 to 5: 1, more preferably from 1: 3 to 3: 1 and particularly preferably from 1: 2 to 2: 1. The post-treatment agent optionally used in process steps (V) and (VI) may be, for example, a shampoo, a conditioner, a gel or a solution.
A post-treatment agent may be used in particular to avoid re-foaming or re-oxidation which may occur by the action of oxygen from the air on the discolored keratin fibers. To effectively avoid this reoxidation, the post-treatment must be performed before the oxygen in the air has time to act on the reduced keratin fibers. For this reason, the post-treatment should be carried out as much as possible immediately after the decolorization (i.e., in time directly after the end of the process step (IV)). It is therefore preferred to allow a maximum duration of 12 hours, preferably 6 hours maximum, more preferably 1 hour maximum and particularly preferably 30 minutes maximum, between the end of the process step (IV). ) and the beginning of the process step (V).
A preferred method according to the invention is therefore characterized in that a maximum duration of 12 hours, preferably 6 hours maximum, more preferably 1 hour maximum and particularly preferably 30 minutes maximum, is left between the steps of process (IV) and (V). The application of the post-treatment agent may also be repeated several times, for example if the post-treatment agent is a shampoo which is applied regularly after the bleaching. If the post-treatment is repeated, that is to say the completion of steps (V) to (VII), it becomes possible to suppress the re-oxidation over a period of time.
Particularly preferably, a staining process by reduction of stained keratin fibers therefore comprises, in the given order, the following steps of (I) producing a ready-to-use bleaching agent by mixing an agent (a) with an agent (b), the agent (a) being an agent, as defined in the description of the first subject of the invention, and the agent (b) being an agent, as defined in the description of the first subject of the invention, (II) applying the bleaching agent ready for use on the colored keratin fibers, (III) allowing the bleaching agent to act for a period of 5 to 60 minutes, preferably from 10 to 55 minutes, more preferably from 20 to 50 minutes, and particularly preferably from 30 to 45 minutes, (IV) rinsing off the keratin fiber bleaching agent, (V) applying a post agent -treatment on keratin fibers, the agent of after-treatment containing at least one amphoteric, zwitterionic and / or anionic surfactant, (VI) rinsing off the keratin fiber post-treatment agent, (VII) applying a post-treatment agent to the keratin fibers, the post-treatment agent containing at least one amphoteric, zwitterionic and / or anionic surfactant, (VIII) rinse off the post-treatment agent of the keratin fibers.
To prevent re-oxidation and re-faking, the post-treatment agent applied in process step (V) preferably additionally contains at least one acid from the group comprising citric acid, tartaric acid and , malic acid, lactic acid, acetic acid, hydroxyethan-1,1-diphosphonic acid, methanesulfonic acid, benzoic acid, hydrochloric acid, sulfuric acid, phosphoric acid, malonic acid, maleic acid, succinic acid and / or oxalic acid.
A particularly preferred method of discoloration by reducing colored keratin fibers is therefore further characterized in that the post-treatment agent applied in step (V) contains at least one acid from the group comprising citric acid. tartaric acid, malic acid, lactic acid, acetic acid, hydroxyethan-1,1-diphosphonic acid, methanesulfonic acid, malonic acid, maleic acid, acid fumaric acid, benzoic acid, hydrochloric acid, sulfuric acid, phosphoric acid, malonic acid, maleic acid and / or oxalic acid.
In other words, most preferably, a color reduction keratin fiber reduction bleaching method comprises, in the order indicated, the following steps: (I) producing a bleaching agent ready to use by blending an agent (a) with an agent (b), the agent (a) being an agent, as defined in the description of the first subject of the invention, and the agent (b) being an agent, such defined in the description of the first subject of the invention, (II) applying the bleaching agent ready for use on the colored keratin fibers, (III) allowing the bleaching agent to act for a period of 5 to 60 minutes, preferably 10 to 55 minutes, more preferably 20 to 50 minutes, and particularly preferably 30 to 45 minutes, (IV) rinse off the bleaching agent of keratin fibers, (V) apply a post-treatment agent on keratin fibers, ag after-treatment with at least citric acid, tartaric acid, malic acid, lactic acid, acetic acid, hydroxyethan-1,1-diphosphonic acid, methanesulfonic acid , benzoic acid, hydrochloric acid, sulfuric acid, phosphoric acid, malonic acid, maleic acid, succinic acid and / or oxalic acid, (VI) rinse off l post-treatment agent of keratin fibers.
With respect to other preferred embodiments of the method of the invention, what has just been said about the agents of the invention apply mutatis mutandis.
Examples 1.1 Coloring
The following formulations were prepared (all data are percentages by weight):
Coloring cream (F1)
Oxidizing agent (Οχ)
The coloring cream (F1) and the oxidizing agent (Ox) were mixed in a ratio of 1: 1 and applied to locks of hair (natural hair Kerling Euro White). The weight ratio of the hair application mixture was 4: 1, the action time was 30 minutes at a temperature of 32 degrees Celsius. The braids were then rinsed with water, dried and allowed to stand for at least 24 hours at room temperature. The locks were stained in a dark brown color.
The hair measured by colorimetry and the L value was determined.
1.2. Discoloration
The following bleaching agent was produced (all data are percent by weight of active substance):
Agent (a)
1) INCI: Paraffinium Liquidum (mineral oil), ethylene / propylene / styrene copolymer, butylene / ethylene / styrene copolymer (2) INCI: Cetearyl Alcohol (about 90%) and Sodium Cetearyl Sulfate (about 10.0%)
Agent (b)
(3) CETEARYL ALCOHOL, PEG-40 CASTOR OIL, SODIUM SULPHATE CETEARYL
Agents (aV) and (b1) were stirred together in the weight ratio (Av) / (b1) of 1: 1 (i.e., 100 g of agent (aV). ) and 100 g of agent (b1) The two agents could be mixed without generating dust.
The agents (aE) and (b1) were stirred with each other in the quantitative ratio (aE) / (b1) of 1: 1 (ie 100 g of agent (aE) and 100 g agent (b1)). Both agents can be mixed with each other without generating dust.
The ready-to-use bleaching agents thus produced were each applied to the colored hair at 1.1 and allowed to act for 30 minutes at a temperature of 20 ° C. Then, the locks were rinsed for 20 seconds with water and allowed to dry.
The hair was again measured by colorimetry and the L value was determined.
To determine the effect of the discoloration, the AL value was determined using the following formula. AL = L (after fading) - L (after coloring)
In the Lab color space, the L axis describes the brightness of a color (L = 0 means black, L = 100 means white). The higher the AL value, the greater the difference in brightness of the color and the greater the discoloration of the hair. The higher the AL value, the better the fading agent.
Similarly, the agents (aV) and (b2) were stirred with each other in the quantitative ratio (aV) / (b2) of 1: 1 (i.e. 100 g of (aV) and 100 g agent (b2)) and were applied. The two agents could be mixed one to
the other without generating dust. Staining was performed as described above.
Similarly, the agents (aV) and (b2) were stirred with each other in the quantitative ratio (aE) / (b2) of 1: 1 (i.e., 100 g of (aE) and 100 g of agent (b2)) and were applied. Both agents could be mixed together without generating dust. Staining was performed as described above.
1.3. Post treatment
The locks of hair discolored in 1.2 were treated with the following post-treatment agents N1 to N6.
Post-processing agent (N) (all data is in percent by weight)
N4 N5 N6
Cetearyl alcohol 2.00 4.50 4.50 Sodium cetearyl sulphate 0.50 0.60 0.60
Hydrogenated castor oil PEG-40 0.40 0.60 0.60
Succinic acid - - 1.80
Malic acid 1.80
Oxalic acid - 2.50
Sulfuric acid (20% aqueous solution) 0.50
Monoethanolamine - - 0,20 qsp for qs for
Water qs for 100 100 100

权利要求:
Claims (15)
[1" id="c-fr-0001]
claims
1. Multi-component packaging unit (kit-of-parts) for bleaching by reduction of colored keratin fibers, which comprises - a container (A) containing a cosmetic agent (a) and - a container (B) containing a cosmetic agent (b), which are made separately from each other, - the agent (a) in the container (A) (a1) contains one or more sulfinic acid derivatives of the group comprising (H2N) (NH) C (SO2H) formamidine-sulfinic acid, - HN (CH2SO2Na) 2, [(sulfinatomethyl) amino] methanesulfinate disodium - HN (CH2SO2K) 2 [[sulfinatomethyl) amino] methanesulphinate dipotassium - HN (CH 2 SO 2 H) 2, [(sulfinomethyl) amino] methanesulfinic acid - N (CH 2 SO 2 Na) 3, [bis (sulfinatomethyl) amino] methanesulfinate trisodium - N (CH 2 SO 2 K) 3, [bis (sulfinatomethyl) amino] methanesulfinate tripotassium - N (CH2SO2H) 3, [bis (sulfinomethyl) amino] methanesulfinic acid - H2NCH (CH3) SO2Na, sodium 1-aminoethane-1-sulfinate - H2NCH (CH3) SO2K, 1-amino potassium ethane-1-sulfinate - H2NCH (CH3) SO2H, 1-amino-ethane-1-sulfinic acid, - HN (CH (CH3) SO2Na) 2, 1 - [(1-sulfinatoethyl) amino] ethane-1 disodium sulfinate - HN (CH (CH 3) SO 2 K) 21 - [(1-sulfinatoethyl) amino] ethane-1-sulphinate dipotassium - HN (CH (CH 3) SO 2 H) 2, 1 - [(1-sulfinoethyl) amino] acid ethane-1-sulfinic acid - N (CH (CH3) SO2Na) 3, 1 - [bis (1-sulfinatoethyl) amino] ethane-1-sulfinate trisodium - N (CH (CH3) SO2K) 3, 1- [bis (1 Tripotassium and / or - N (CH (CH 3) SO 2 H) 3> 1- [bis (1-sulfinoethyl) amino] ethane-1-sulfinic acid, (a2) contains one or more fatty components selected from the group of C12-C30 alcohols, C12-C30 fatty acid triglycerides, C12-C30 fatty acid monoglycerides, C12-C30 fatty acid diglycerides, C12-C30 fatty acid C12 to C30 fatty acids, hydrocarbons and / or silicone oils, (a3) has a water content of not more than 10.0% by weight, based on the total weight of the agent (a), - agent (b) in the container (B) (b1) has a water content at least of 30.0% by weight, based on the total weight of the agent (b).
[2" id="c-fr-0002]
2. Multi-component packaging unit (kit-of-parts) according to claim 1, characterized in that the agent (a) in the container (A) contains (a1) a derivative of sulfinic acid (H2N ) (NH) C (SO2H) formamidinsulfinic acid.
[3" id="c-fr-0003]
A multi-component packaging unit (kit-of-parts) according to claim 1, characterized in that the agent (a) in the container (A) contains, on the basis of the total weight of the agent ( a), one or more derivatives of the sulfinic acid of group (a1) in a total amount of 0.1 to 50.0% by weight, preferably from 1.0 to 30.0% by weight, more preferably from 1.5 to 20.0% by weight and particularly preferably 2.5 to 10.5% by weight.
[4" id="c-fr-0004]
4. Multi-component packaging unit (kit-of-parts) according to one of claims 1 to 3, characterized in that the agent (a) in the container (A) contains, on the basis of the total weight agent (a), one or more fatty components selected from group (a2) in a total amount of 10.0 to 90.0% by weight, preferably 20.0 to 86.0% by weight, more preferably from 25.0 to 84.0% by weight and particularly preferably from 30.0 to 80.0% by weight.
[5" id="c-fr-0005]
5. Multi-component packaging unit (kit-of-parts) according to one of claims 1 to 4, characterized in that the agent (a) in the container (A) contains (a2) one or more hydrocarbons in a total amount of 15.0 to 90.0% by weight, preferably 20.0 to 85.0% by weight, more preferably 25.0 to 80.0% by weight and particularly preferably 30.0 to 80.0% by weight. 0 to 75.0% by weight, based on the total weight of agent (a).
[6" id="c-fr-0006]
6. Multi-component packaging unit (kit-of-parts) according to one of claims 1 to 5, characterized in that the agent (a) in the container (A) has (a3) a water content a maximum of 8.0% by weight, preferably not more than 5.0% by weight, more preferably not more than 3.0% by weight, and more preferably not more than 1.0% by weight, based on the weight total of agent (a).
[7" id="c-fr-0007]
7. Multi-component packaging unit (kit-of-parts) according to one of claims 1 to 6, characterized in that the agent (a) in the container (A) contains (a4) one or more surfactants nonionics in a total amount of from 0.1 to 15.0% by weight, preferably from 0.5 to 12.5% by weight, more preferably from 1.0 to 10.0% by weight and most preferably from 1.5 to 8.0% by weight, based on the total weight of the agent (a).
[8" id="c-fr-0008]
8. Multi-component packaging unit (kit-of-parts) according to one of claims 1 to 7, characterized in that the agent (a) in the container (A) additionally contains (a5) one or several nonionic polymers in a total amount of from 0.1 to 15.0% by weight, preferably from 0.2 to 10.5% by weight, more preferably from 0.25 to 7.5% by weight, and particularly preferably from 0.3 to 5.0% by weight, based on the total weight of the agent (a).
[9" id="c-fr-0009]
9. Multi-component packaging unit (kit-of-parts) according to one of claims 1 to 8, characterized in that the agent (b) in the container (B) has (b1) a water content at least 40.0% by weight, preferably at least 50.0% by weight, more preferably at least 55.0% by weight and most preferably at least 60.0% by weight by weight based on the total weight of the agent (b).
[10" id="c-fr-0010]
10. Multi-component packaging unit (kit-of-parts) according to one of claims 1 to 9, characterized in that the agent (b) in the container (B) contains (b2) one or more agents alkalinization of the group comprising ammonia, alkanolamines and / or basic amino acids.
[11" id="c-fr-0011]
11. Multi-component packaging unit (kit-of-parts) according to one of claims 1 to 10, characterized in that the agent (b) in the container (B) has (b3) a pH value. from 7.5 to 12.5, preferably from 8.0 to 12.0, more preferably from 8.5 to 11.5, and most preferably from 9.0 to 11.0.
[12" id="c-fr-0012]
12. Multi-component packaging unit (kit-of-parts) according to one of claims 1 to 11, characterized in that the agent (b) in the container (B) additionally contains (b4) one or several thickeners of the group of celluloses, hydroxy-C 2 -C 6 alkyl-celluloses, carboxymethylcelluloses, alginic acid, (meth) acrylic polymers and / or xanthan gum.
[13" id="c-fr-0013]
13. Multi-component packaging unit (kit-of-parts) according to one of claims 1 to 12, characterized in that the agent (b) in the container (B) contains, relative to the total weight of agent (b), fatty components of the group of C 12 to C 30 alcohols, triglycerides of C 12 to C 30 fatty acids, monoglycerides of C 12 to C 30 fatty acids, diglycerides of C 12 to C 12 fatty acids. C 30, C 12 to C 30 fatty acid esters, hydrocarbons and / or silicone oils in a total amount of less than 2.5% by weight, preferably less than 1.0% by weight, more preferably less than 0.5% by weight and particularly preferably less than 0.1% by weight.
[14" id="c-fr-0014]
14. A method of bleaching by reducing keratinous stained fibers, comprising the following steps, in the order indicated, of (I) producing a ready-to-use bleaching agent by blending an agent (a) with a agent (b), - agent (a) being an agent as defined in claims 1, 2, 3, 4, 5, 6, 7 and / or 8, - agent (b) being an agent such as as defined in claims 1, 9, 10, 11, 12 and / or 13, (I) applying the ready-to-use bleaching agent to the keratin fibers, (II) allowing the bleaching agent to remain a period of 5 to 60 minutes, preferably 10 to 55 minutes, more preferably 20 to 50 minutes, and most preferably 30 to 45 minutes, (III) rinsing off the bleaching agent of keratin fibers, ( IV) optionally applying a post-treatment agent to the keratin fibers, the post-treatment agent containing an amphoteric, zwitterionic surfactant and / or anionic, (V) optionally rinse off the post-treatment agent of the keratin fibers.
[15" id="c-fr-0015]
15. Process according to claim 14, characterized in that the post-treatment agent applied in step (V) contains at least one acid from the group comprising citric acid, tartaric acid, malic lactic acid, acetic acid, hydroxyethan-1,1-diphosphonic acid, methanesulfonic acid, malonic acid, maleic acid, fumaric acid, benzoic acid, acid hydrochloric acid, sulfuric acid, phosphoric acid, malonic acid, maleic acid and / or oxalic acid.

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同族专利:

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公开号 | 公开日

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DE102015222216A1|2017-05-11|

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US10493010B2|2019-12-03|

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GB2550227A|2017-11-15|

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GB2550227B|2020-05-13|

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FR3043328B1|2020-06-19|

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US20170128342A1|2017-05-11|

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法律状态:
2017-11-21| PLFP| Fee payment|Year of fee payment: 2 |

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2019-11-20| PLFP| Fee payment|Year of fee payment: 4 |

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2020-01-03| PLSC| Publication of the preliminary search report|Effective date: 20200103 |

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2020-11-20| PLFP| Fee payment|Year of fee payment: 5 |

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2021-11-22| PLFP| Fee payment|Year of fee payment: 6 |

优先权:

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申请号 | 申请日 | 专利标题

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DE102015222216.0A|DE102015222216A1|2015-11-11|2015-11-11|Reductive color print with sulfinic acid derivatives in paste form|

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DE102015222216.0|2015-11-11|

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