Process for the photoprotective treatment of artificially dyed keratin fibres by application of a liquid water/steam mixture
Abstract
Procedure for treating artificially dyed keratin fibers by direct coloring or by oxidation coloring, in particular of human hair, characterized in that it consists of applying, on said keratin fibers, a composition that does not contain oxidation coloring agent or agent oxidizing and comprising, in a physiologically acceptable medium, at least one protective agent selected from the water-soluble or fat-soluble organic UV filters whose log P is less than or equal to 6, and then applied to the fibers a mixture of liquid water / water vapor whose temperature is between 40 and 75 ° C; said organic filters being selected between the cinnamic derivatives and the benzophenone derivatives.

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6 claims: 6 independent, 0 dependent
- 1ES 2 345 503 T3 ES 2 345 503 T3 CLAIMS REIVINDICACIONES 1. Procedure for treating artificially dyed keratin fibers by direct coloring or by oxidation coloring, in particular human hair, characterized in that it consists of applying, on said keratin fibers, a composition that does not contain oxidation coloring agent or oxidation agent. oxidant and comprising, in a physiologically acceptable medium, at least one protective agent selected from the water-soluble or fat-soluble organic UV filters whose log P is less than or equal to 6, and after applying a liquid water / water vapor mixture to the fibers whose temperature is between 40 and 75 ° C ; said organic filters being selected from the cinnamic derivatives and benzophenone derivatives. 1. Procedimiento de tratamiento de las fibras de queratina teñidas artificialmente mediante coloración directa o mediante coloración de oxidación, en particular del cabello humano, caracterizado por que consiste en aplicar, sobre dichas fibras de queratina, una composición que no contiene agente de coloración de oxidación ni agente oxidante y que comprende, en un medio fisiológicamente aceptable, al menos un agente protector seleccionado entre los filtros UV orgánicos hidrosolubles o liposolubles cuyo log P es inferior o igual a 6, y después en aplicar sobre las fibras una mezcla de agua líquida/vapor de agua cuya temperatura está comprendida entre 40 y 75°C; seleccionándose dichos filtros orgánicos entre los derivados cinámicos y los derivados de benzofenona. 2. Process according to claim 1, in which the liquid water / steam mixture also contains one or more different gases or vaporizable compounds. 2. Procedimiento de acuerdo con la reivindicación 1, en la que la mezcla de agua líquida/vapor de agua contiene además uno o más gases o compuestos vaporizables diferentes. 3. Process according to any one of claims 1 or 2, in which the liquid water / steam mixture is brought into contact with the fibers for a period ranging from 1 second to 1 hour. 3. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 ó 2, en el que la mezcla de agua líquida/vapor de agua se pone en contacto con las fibras durante un periodo que varía entre 1 segundo y 1 hora. 4. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 3, en el que la mezcla de agua líquida/vapor de agua se pone en contacto con las fibras durante un periodo que varía entre 5 minutos y 15 minutos. Four. Process according to any one of claims 1 to 3, in which the liquid water / steam mixture is brought into contact with the fibers for a period ranging from 5 minutes to 15 minutes. 5. Process according to any one of claims 1 to 4, which consists of cooling the fibers treated with the liquid water / water vapor mixture by passing a stream of cold air or a stream of air at room temperature over or through them . 5. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 4, que consiste en enfriar las fibras tratadas con la mezcla de agua líquida/vapor de agua haciendo pasar sobre o a través de éstas una corriente de aire frío o una corriente de aire a temperatura ambiente. 6. Process according to any one of claims 1 to 5, in which the cinnamic derivatives are selected from:6. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 5, en el que los derivados cinámicos se seleccionan entre: Ethylhexyl Methoxycinnamate, Ethylhexyl Methoxycinnamate, Isopropyl Methoxy cinnamate, Isopropyl Methoxy cinnamate, Isoamyl Methoxy cinnamate, Isoamyl Methoxy cinnamate, Cinoxate, Cinoxate, DEA Methoxycinnamate, DEA Methoxycinnamate, Diisopropyl Methylcinnamate. Diisopropyl Methylcinnamate. 7. Process according to any one of claims 1 to 5, in which the benzophenone derivatives are selected from 7. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 5, en el que los derivados de benzofenona se seleccionan entre Benzophenone-1, Benzophenone-1, Benzophenone-2, Benzophenone-2, Benzophenone-3, Benzophenone-3, Benzophenone-4, Benzophenone-4, Benzophenone-5, Benzophenone-5, Benzophenone-6, Benzophenone-6, Benzophenone-8, Benzophenone-8, Benzophenone-9. Benzophenone-9. 8. Process according to any one of claims 1 to 7, in which the fat-soluble organic UV filters are selected from 8. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 7, en el que los filtros UV orgánicos liposolubles se seleccionan entre Ethylhexyl Methoxycinnamate, Ethylhexyl Methoxycinnamate, Benzophenone-3. Benzophenone-3. 9. Process according to any one of claims 1 to 8, in which the keratin fiber protective agent (s) have a log P lower than 4.5 and more preferably lower than 2. 9. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 8, en el que el o los agentes protectores de las fibras de queratina tienen un log P inferior a 4,5 y más preferiblemente inferior a 2. ES 2 345 503 T3 ES 2 345 503 T3 10. Process according to any one of claims 1 to 9, in which the protective agent (s) are soluble at least 0.5% in water or lower C alcohols.1-C4 at 25 ° C. 10. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 9, en el que el o los agentes protectores son solubles a al menos el 0,5% en agua o alcoholes inferiores de C1-C4 a 25°C. 11. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 10, en el que el o los agentes protectores presentan, en su estructura, al menos una función ácida en forma libre o parcial o totalmente salificada. eleven. Process according to any one of claims 1 to 10, in which the protective agent (s) have, in their structure, at least one acid function in free or partially or totally salified form. 12. Process according to claim 11, in which the protective agents have, in their structure, at least one sulfonic acid function in free or partially or totally salified form. 12. Procedimiento de acuerdo con la reivindicación 11, en el que los agentes protectores presentan, en su estructura, al menos una función ácido sulfónico en forma libre o parcial o totalmente salificada. 13. Process according to any one of claims 1 to 12, in which the protective agent (s) are water-soluble organic UV filters. 13. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 12, en el que el o los agentes protectores son filtros UV orgánicos hidrosolubles. 14. Process according to claim 13, in which the water-soluble organic UV filters are selected from 14. Procedimiento de acuerdo con la reivindicación 13, en el que los filtros UV orgánicos hidrosolubles se seleccionan entre Benzophenone-4 Benzophenone-4 Benzophenone-5 Benzophenone-5 Benzophenone-9 o sus mezclas. Benzophenone-9 or its mixtures. 15. Procedimiento de acuerdo con la reivindicación 14, en el que el agente protector es Benzophenone-4. fifteen. Process according to claim 14, in which the protective agent is Benzophenone-4. 16. Process according to any one of claims 1 to 15, in which the protective agent (s) for the keratin fibers represent 0.15% to 50% by weight, preferably 0.35% to 30% by weight and more particularly from 0.5 to 20% by weight relative to the total weight of the composition. 16. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 15, en el que el o los agentes protectores de las fibras de queratina representan del 0,15% al 50% en peso, preferiblemente del 0,35% al 30% en peso y más particularmente del 0,5 al 20% en peso con respecto al peso total de la composición. 17. Process according to any one of claims 1 to 16, in which the physiologically acceptable medium is constituted by water or by a mixture of water and at least one cosmetically acceptable organic solvent. 17. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 16, en el que el medio fisiológicamente aceptable está constituido por agua o por una mezcla de agua y de al menos un disolvente orgánico cosméticamente aceptable. 18. Process according to claim 17, in which the organic solvents are selected from lower alkanols of C1-C4;polyols and polyol ethers and mixtures thereof. 18. Procedimiento de acuerdo con la reivindicación 17, en el que los disolventes orgánicos se seleccionan entre alcanoles inferiores de C1-C4;polioles y éteres de polioles y sus mezclas. 19. Process according to any one of claims 1 to 18, in which the composition comprises one or more additives selected from anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or their mixtures, anionic, cationic, nonionic, amphoteric polymers , zwitterionic or their mixtures, mineral or organic thickening agents, and in particular associative thickeners of anionic, cationic, nonionic and amphoteric polymers, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile, modified or unmodified silicones, film-forming agents, ceramides, preserving agents, and opacifying agents. 19. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 18, en el que la composición comprende uno o más aditivos seleccionados entre agentes tensioactivos aniónicos, catiónicos, no iónicos, anfóteros, zwitteriónicos o sus mezclas, polímeros aniónicos, catiónicos, no iónicos, anfóteros, zwitteriónicos o sus mezclas, agentes espesantes minerales u orgánicos, y en particular los espesantes asociativos de polímeros aniónicos, catiónicos, no iónicos y anfóteros, agentes de penetración, agentes secuestradores, perfumes, tampones, agentes dispersantes, agentes de acondicionamiento tales como, por ejemplo, siliconas volátiles o no volátiles, modificadas o sin modificar, agentes formadores de películas, ceramidas, agentes conservantes y agentes opacificantes. 20. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 19, en el que la composición comprende al menos un alcohol aromático y al menos un ácido aromático carboxílico. twenty. Process according to any one of claims 1 to 19, in which the composition comprises at least one aromatic alcohol and at least one aromatic carboxylic acid. 21. Procedimiento de acuerdo con la reivindicación 20, en el que el o los alcoholes aromáticos representan del 0,01% al 50% en peso, preferiblemente del 0,1% al 30% en peso y, más particularmente, del 1 al 20% en peso con respecto al peso total de la composición. twenty-one. Process according to claim 20, in which the aromatic alcohol (s) represent from 0.01% to 50% by weight, preferably from 0.1% to 30% by weight and, more particularly, from 1 to 20% by weight. weight relative to the total weight of the composition. 22. Process according to claim 21, in which the aromatic alcohol (s) are present at concentrations greater than 1% by weight. 22. Procedimiento de acuerdo con la reivindicación 21, en el que el o los alcoholes aromáticos están presentes a concentraciones superiores al 1% en peso. 2. 3. Process according to any one of claims 20 to 21, in which the aromatic alcohol is benzyl alcohol. 23. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 20 a 21, en el que el alcohol aromático es alcohol bencílico. 24. Process according to any one of claims 19 to 23, in which the aromatic acid (s) or their salts represent from 0.001% to 30% by weight, preferably from 0.01% to 20% by weight and, more particularly, 0.1 to 10% by weight relative to the total weight of the composition. 24. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 19 a 23, en el que el o los ácidos aromáticos o sus sales representan del 0,001% al 30% en peso, preferiblemente del 0,01% al 20% en peso y, más particularmente, del 0,1 al 10% en peso con respecto al peso total de la composición. 25. Process according to any one of claims 19 to 24, in which the aromatic acid is benzoic acid. 25. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 19 a 24, en el que el ácido aromático es ácido benzoico. 26. Process according to any one of claims 1 to 25, in which the composition further comprises at least one conditioning agent. 26. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 25, en el que la composición comprende además al menos un agente acondicionador. 27. Process according to claim 26, in which the conditioning agent (s) represent from 0.001% to 20% by weight, preferably from 0.01% to 10% by weight and more particularly from 0.1 to 3% by weight with with respect to the total weight of the final composition. 27. Procedimiento de acuerdo con la reivindicación 26, en el que el o los agentes acondicionadores representan del 0,001% al 20% en peso, preferiblemente del 0,01% al 10% en peso y más particularmente del 0,1 al 3% en peso con respecto al peso total de la composición final. ES 2 345 503 T3 ES 2 345 503 T3 28. Process according to any one of claims 1 to 27, in which the composition is presented in the form of an aqueous or hydroalcoholic lotion;gel, milk, cream, emulsion or foam. 28. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 27, en el que la composición se presenta en forma de loción acuosa o hidroalcohólica;de gel, de leche, de crema, de emulsión o de espuma. 29. Process according to any one of claims 1 to 28, in which the composition is packaged in the form of a vaporizer, a measuring bottle or in an aerosol container. 29. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 28, en el que la composición se envasa en forma de vaporizador, de frasco dosificador o en un recipiente de aerosol. 30. Process according to any one of claims 1 to 29, in which the pH of the composition applied to the keratin fibers varies generally between 1 and 11 and preferably between 2 and 6. 30. Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 a 29, en el que el pH de la composición aplicada sobre las fibras de queratina varía generalmente entre 1 y 11 y preferiblemente entre 2 y 6. 31. Use of the method as defined according to one of claims 1 to 30, for the protection of keratin fibers, in particular human hair, against the action of atmospheric agents and particularly against the action of light. 31. Utilización del procedimiento tal como se define de acuerdo con una de las reivindicaciones 1 a 30, para la protección de las fibras de queratina, en particular del cabello humano, contra la acción de los agentes atmosféricos y particularmente contra la acción de la luz. 32. Use of the method as defined according to one of Claims 1 to 30, subsequent to the treatment of an oxidation coloring or a direct coloring of keratin fibers and, more particularly, of human hair. 32. Utilización del procedimiento tal como se define de acuerdo con una de las reivindicaciones 1 a 30, de forma posterior al tratamiento de una coloración de oxidación o de una coloración directa de las fibras de queratina y, más particularmente, del cabello humano. 33. Procedure for coloring keratin fibers, in particular human hair, which comprises at least the following steps a), b) and c): 33. Procedimiento de coloración de las fibras de queratina, en particular del cabello humano, que comprende al menos las siguientes etapas a), b) y c): a) a direct coloring or oxidation of said fibers is carried out, a) se realiza una coloración directa o de oxidación de dichas fibras, b) a composition comprising at least one protective agent and containing no oxidation coloring agent or oxidizing agent is applied to said fibers, as defined in any one of the preceding claims;b) se aplica sobre dichas fibras una composición que comprende al menos un agente protector y que no contiene agente de coloración de oxidación ni agente oxidante, tal como se define en una cualquiera de las reivindicaciones anteriores;c) a liquid water / water vapor mixture is applied to said fibers, as defined in any one of the preceding claims. c) se aplica sobre dichas fibras una mezcla de agua líquida/vapor de agua, tal como se define en una cualquiera de las reivindicaciones anteriores. 3. 4. Procedure for coloring keratin fibers, in particular human hair, characterized in that it comprises the following steps: 34. Procedimiento de coloración de las fibras de queratina, en particular del cabello humano, caracterizado por que comprende las siguientes etapas: 1) a) a direct dye or oxidation composition (A) is applied to said fibers for a sufficient time to develop the color, 1) se aplica sobre dichas fibras a) una composición (A) colorante directa o de oxidación durante un tiempo suficiente para desarrollar el color,
- 22) eventualmente, se realiza a continuación un aclarado y/o un lavado con champú y/o un secado parcial o total de dichas fibras, 2) optionally, a rinsing and / or shampooing and / or partial or total drying of said fibers is then carried out,
- 33) a composition (B) is applied that comprises at least one protective agent and that does not contain an oxidation coloring agent or an oxidizing agent, as defined in any one of the preceding claims;3) se aplica una composición (B) que comprende al menos un agente protector y que no contiene agente de coloración de oxidación ni agente oxidante, tal como se define en una cualquiera de las reivindicaciones anteriores;
- 44) eventualmente, se realiza a continuación un aclarado y/o un lavado con champú y/o un secado parcial o total de dichas fibras, 4) optionally, a rinsing and / or shampooing and / or partial or total drying of said fibers is then carried out,
- 55) a liquid water / water vapor mixture is applied to the fibers, as defined in any one of the preceding claims;5) se aplica sobre las fibras una mezcla de agua líquida/vapor de agua, tal como se define en una cualquiera de las reivindicaciones anteriores;
- 66) eventualmente, se realiza a continuación un aclarado y/o un lavado con champú y/o un secado parcial o total de dichas fibras. 6) optionally, a rinsing and / or shampooing and / or partial or total drying of said fibers is then carried out. 35. Procedure for coloring keratin fibers, in particular human hair, characterized in that it comprises the following steps:35. Procedimiento de coloración de las fibras de queratina, en particular del cabello humano, caracterizado por que comprende las siguientes etapas: 1) a composition (B) is applied which comprises a protective agent and which does not contain an oxidation coloring agent or an oxidizing agent, as defined in any one of the preceding claims;1) se aplica una composición (B) que comprende un agente protector y que no contiene agente de coloración de oxidación ni agente oxidante, tal como se define en una cualquiera de las reivindicaciones anteriores;2) optionally a rinsing and / or washing with shampoo and / or partial or total drying of said fibers is carried out, 2) se realiza eventualmente un aclarado y/o un lavado con champú y/o un secado parcial o total de dichas fibras, 3) a liquid water / water vapor mixture is applied to the fibers, as defined in any one of the preceding claims;3) se aplica sobre las fibras una mezcla de agua líquida/vapor de agua, tal como se define en una cualquiera de las reivindicaciones anteriores;4) a direct dye or oxidation composition (A) is applied to said fibers for a sufficient time to develop the color, 4) se aplica sobre dichas fibras a) una composición (A) colorante directa o de oxidación durante un tiempo suficiente para desarrollar el color, ES 2 345 503 T3 ES 2 345 503 T3 5) optionally a rinsing and / or shampooing and / or partial or total drying of said fibers is carried out. 5) se realiza eventualmente un aclarado y/o un lavado con champú y/o un secado parcial o total de dichas fibras. 6) eventualmente, se realiza a continuación un aclarado y/o un lavado con champú y/o un secado parcial o total de dichas fibras. 6) optionally, a rinsing and / or shampooing and / or partial or total drying of said fibers is then carried out.
Independent claims6
506 paragraphs in 27 sections, as filed
ES 2 345 503 T3
DESCRIPTION
Photoprotective treatment procedure for artificially dyed keratin fibers by applying a liquid water / water vapor mixture.
The subject of the present invention is a process for treating artificially dyed keratin fibers by direct coloring or by oxidation coloring, in particular of human hair, comprising the application on said keratin fibers of a composition that does not contain oxidation coloring agent or oxidizing agent and that comprises at least one protective agent selected from the water-soluble or fat-soluble organic UV filters whose log P is less than or equal to 6, and then the application on the fibers of a liquid water / steam mixture whose temperature is between 40 ° and 75 ° C; said filters being selected from the cinnamic derivatives and the benzophenone derivatives.
The present invention also has as its object the use of said process to protect artificially dyed keratin fibers by direct coloring or by oxidation coloring, in particular human hair, against the action of atmospheric agents and particularly against the action of light. .
It is well known that hair is sensitized or brittle to varying degrees by the action of atmospheric agents and particularly light. Numerous publications report that natural light destroys some amino acids in hair. By altering these attacks on the hair fiber, its mechanical properties such as tensile strength, the load before breaking and elasticity, or its resistance to swelling in an aqueous medium, decrease. The hair is then dull, rough and brittle.
It is also known that, in particular, light tends to attack natural hair color as well as artificial color of colored hair. Hair color gradually weakens or turns towards unsightly or undesirable nuances.
The effect of light is even more visible on dyed hair by artificial coloring, in particular oxidation coloring or direct coloring. In this case, exposure to light leads to degradation of the colorants present both in the hair and on its surface. This results in a significant fading and / or change in hair color.
For many years, the cosmetic industry has been searching for substances that protect hair from degradation caused by atmospheric aggressions, such as light. In particular, products are sought that protect the integrity of keratin fibers, that is, their composition, their surface condition, their natural or artificial color, their intrinsic mechanical properties (tensile strength, load before breakage and elasticity, or its resistance to swelling in an aqueous medium).
To combat these degradations of hair keratin, it has already been proposed to use protective agents such as organic UV filters, anti-oxidants, chelators or anti-free radical agents.
Thus, some substances capable of filtering light radiation have been proposed, such as 2-hydroxy-4-methoxy benzophenone-5-sulfonic acid or its salts (FR-A-2 627 085) or 4- (2 -oxo-3-bornedilibdenum methyl) benzene sulfonic acid or its salts (EP-A-329 032) or also lactoferrin (FR-A-2 673 839).
Coloring compositions containing 2-hydroxy-4-methoxy benzophenone-5-sulfonic acid or its salts, an aromatic alcohol and an acid direct dye are known from Japanese patent application JP05-043437.
However, current cosmetic compositions containing protective agents do not provide complete satisfaction and in particular on hair dyed with blue oxidation dyes such as those obtained with couplings comprising meta-phenylenediamines.
It has already been proposed to treat oxidation-dyed hair with a gas comprising water vapor (application of a composition comprising at least one oxidation coloring precursor and of a composition comprising at least one oxidizing agent) to accelerate the process of coloring in patent FR-1011151 or to reduce hair selectivity after coloring in patent EP0659396.
It has already been proposed in patent FR2713929 to treat hair that has undergone bleaching with a gas comprising water vapor by applying a composition containing an oxidizing agent to obtain a rapid bleaching that does not generate any red reflection.
The Applicant has now surprisingly discovered a new method for treating artificially dyed keratin fibers by direct coloring or by oxidation coloring, in particular of human hair, comprising the application on said keratin fibers of a composition that does not contain oxidation coloring agent or oxidizing agent and that comprises at least one protective agent selected from the water-soluble or fat-soluble organic UV filters whose log P is less than or equal to 6, and then the application on the fibers of a liquid water / steam mixture whose temperature is between 40 and 75 ° C; said filters being selected from the cinnamic derivatives and the benzophenone derivatives.
ES 2 345 503 T3
This procedure makes it possible to obtain a better protection of said fibers against the action of atmospheric agents and particularly against the harmful effects of light.
In particular, thanks to this treatment method, an improvement in the resistance to light of the coloring of the dyed hair is obtained by direct coloring or oxidation coloring. The treatment method according to the invention also makes it possible to provide a light protection effect resistant to several shampooing.
All of these discoveries are at the basis of the present invention.
Thus, according to the present invention, a process for treating artificially dyed keratin fibers by direct coloring or by oxidation coloring, in particular of human hair, has now been proposed, characterized in that it consists in applying on said fibers keratin a composition without oxidizing coloring agent and without oxidizing agent comprising, in a physiologically acceptable medium, at least one protective agent selected from water-soluble or fat-soluble organic UV filters whose log P is less than or equal to 6; said filters being selected from the cinnamic derivatives and benzophenone derivatives, and then applying a liquid water / steam mixture whose temperature is between 40 and 75 ° C on the fibers.
By "containing no oxidation coloring agent" is meant that it does not contain any oxidation coloring precursors such as bases or couplers in an amount sufficient to allow keratin fibers to be oxidatively dyed in contact with an oxidizing agent.
By "containing no oxidizing agent" is meant that it does not contain any oxidizing agent in an amount that allows keratin fibers to discolor by oxidation.
Another object of the invention consists in the use of said process for the protection of keratin fibers against the action of atmospheric agents and particularly against the action of light.
An object of the invention consists in the use of said method after the treatment of an oxidation coloring or a direct coloring of the keratin fibers and more particularly of the hair.
Another object of the invention relates to a process for coloring keratin fibers, in particular human hair, which comprises at least the following steps a), b) and c):
a) a direct coloring or oxidation of said fibers is carried out;
b) a composition containing no oxidation coloring agent or oxidizing agent is applied to said fibers and which comprises, in a physiologically acceptable and in particular cosmetically acceptable medium, at least one protective agent selected from the water-soluble or fat-soluble organic UV filters whose log P is less than or equal to 6;
c) a liquid water / water vapor mixture is applied to said fibers, the temperature of which is between 40 and 75 ° C; said filters being selected from the cinnamic derivatives and the benzophenone derivatives.
Although the following discussion essentially revolves around the particular case of hair treatment, it will be noted in this case that the process according to the invention is applicable to any human keratin fiber in general, particularly eyelashes, mustaches, hairs and others.
The different objects of the invention will be detailed below. The set of meanings and definitions of the compounds used in the present invention that are given below are valid for all the objects of the invention.
In the context of the invention, the value of log P represents in a conventional way the partition coefficient of the dye between octanol and water. The log P value can be calculated according to the method described in the article by Meylan and Howard "Atom / Fragment contribution method for estimating octanol-water partition coefficient", J. Pharm. Sci. 84: 83-92, 1995. This value can also be calculated from numerous commercially available computer programs that determine the value of logP based on the structure of a molecule. As an example, mention may be made of the Epiwin program of the United States environmental agency as well as the Virtual Computational Chemistry Laboratory program.
The liquid water / water vapor mixture forms a mist. Said mixture can also contain at least one other gas such as oxygen or nitrogen, gas mixtures such as air or other vaporizable compounds.
ES 2 345 503 T3
Preferably, the liquid water / steam mixture is contacted with the fiber for a period ranging from 1 second to 1 hour, and even more preferably from 5 minutes to 15 minutes. Of course, the application of said mixture can be repeated several times on the same fiber, each operation being carried out according to a period as indicated above.
A preferred embodiment of the process according to the invention consists in first applying a composition containing the photoprotective agents to the hair, and then subjecting these strands impregnated in this way to the action of the liquid water / steam mixture. water according to the conditions mentioned above, and after cooling the locks treated in this way, for example by passing over or through them a stream of cold air or air at room temperature.
The production of the liquid water / steam mixture used according to the invention can be carried out with the aid of any apparatus known per se and provided for this purpose. However, according to the present invention, preferably an apparatus is used comprising at least one steam generator connected directly to a helmet that diffuses the liquid water / steam mixture over the keratin fibers, in particular human hair. Water. As a type of apparatus, the one marketed under the name ®MICROMIST by the company TAKARA BELMONT will be used more particularly.
As examples of water-soluble or fat-soluble organic UV filters whose log P is less than or equal to 6, those designated below with the INCI name can be mentioned:
Cinnamic derivatives:
Ethylhexyl Methoxycinnamate marketed particularly under the trade name "PARSOL MCX" by HOFFMANN LA ROCHE,
Isopropyl Methoxy cinnamate,
Isoamyl Methoxy cinnamate marketed under the trade name "NEO HELIOPAN E 1000" by HAARMANN and REIMER,
Cinoxate,
DEA Methoxycinnamate,
Diisopropyl Methylcinnamate,
Derivatives of benzophenone:
Benzophenone-1 sold under the trade name "UVINUL 400" by BASF,
Benzophenone-2 sold under the trade name "UVINUL D50" by BASF
Benzophenone-3 or Oxybenzone, marketed under the trade name "UVINUL M40" by BASF,
Benzophenone-4 sold under the trade name "UVINUL MS40" by BASF,
Benzophenone-5
Benzophenone-6 sold under the trade name "Helisorb 11" by Norquay, Benzophenone-8 sold under the trade name "Spectra-Sorb UV-24" by American Cyanamid
Benzophenone-9 sold under the trade name "UVINUL DS-49" by BASF.
As fat-soluble (or lipophilic) organic UV filters suitable for use in the present invention, there may be mentioned more particularly:
Ethylhexyl Methoxycinnamate
Benzophenone-3,
According to the invention, the protective agent (s) of the keratin fibers will preferably be at concentrations ranging between 0.05% and 50% by weight, preferably between 0.35% and 30% by weight and more. particularly between 0.5 and 20% by weight with respect to the total weight of the composition.
ES 2 345 503 T3
According to a preferred embodiment of the invention, protective agents having a logP (octanol / water partition coefficient) of less than 4.5 and more preferably less than 2 will be used.
According to a particularly preferred embodiment of the invention, protective agents soluble in the aqueous medium of the composition will be used, in particular protective agents soluble at 25 ° C to at least 0.5% in water or lower C-alcohols. C<sub>4</sub> like ethanol.
According to a particularly preferred embodiment of the invention, protective agents will be used which possess in their chemical structure at least one acid function in free or partially or totally salified form such as carboxylic acid or sulfonic acid. Even more particularly, protective agents will be used which possess in their chemical structure at least one sulfonic acid function in free or partially or totally salified form.
And more particularly, water-soluble organic UV filters selected from among
Benzophenone-4
Benzophenone-5
Benzophenone-9 or its mixtures
Among these filters Benzophenone-4 will be used more particularly.
The physiologically and, in particular, cosmetically acceptable medium is preferably constituted by water or by a mixture of water and at least one cosmetically acceptable organic solvent. As the organic solvent, there may be mentioned, for example, the lower alkanols of C<sub>1</sub>-C<sub>4</sub>, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether and mixtures thereof.
The solvents are preferably present in proportions preferably between 1 and 40% by weight approximately relative to the total weight of the dyeing composition, and even more preferably between 3 and 30% by weight approximately.
The composition according to the invention containing the protective agent or agents may also contain various adjuvants conventionally used in hair treatment compositions, such as anionic, cationic, non-ionic, amphoteric, zwitterionic surfactants or their mixtures, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents and, in particular, the associative thickeners of anionic, cationic, nonionic and amphoteric polymers, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile, modified or unmodified silicones, forming agents of films, ceramides, preservatives and opacifying agents.
According to a preferred embodiment of the invention, the hair compositions according to the invention containing the protective agent or agents further comprise at least one aromatic alcohol and at least one aromatic carboxylic acid.
By the term "aromatic alcohol" is meant any compound liquid at room temperature and atmospheric pressure that comprises at least one benzene or naphthalene ring and at least one alcohol (OH) function directly attached to the ring or attached to at least one substituent of said ring. Preferably, the alcohol function will be on a benzene or naphthalene ring substituent.
Among the aromatic alcohols usable in the composition according to the invention, there may be mentioned in particular
- benzyl alcohol
- benzoyl isopropanol
- benzyl glycol
- phenoxyethanol
- di-chloro-benzyl alcohol
ES 2 345 503 T3
- methylphenylbutanol
- phenoxyisopropanol
- phenylisohexanol
- phenylpropanol
- phenylethyl alcohol
- their mixtures.
Benzyl alcohol will be selected more particularly.
According to the invention, the aromatic alcohol (s) may represent from 0.01% to 50% by weight, preferably from 0.1% to 30% by weight and more particularly from 1 to 20% by weight with respect to the total weight. of the composition. Preferably, they will be used at concentrations greater than 1% by weight.
The hair compositions according to the invention also comprise at least one optionally salified aromatic carboxylic acid.
By the term "aromatic carboxylic acid", is meant any compound that comprises at least one benzene or naphthalene ring and at least one carboxylic acid (COOH) function, in free or salified form, attached directly to the ring or attached in at least one substituent. of said ring. Preferably, the acid function will be directly attached to the benzene or naphthalene ring.
The salts of the aromatic carboxylic acids can be selected in particular from alkali metal (sodium, potassium), alkaline earth metal (calcium, magnesium) salts or organic amine or ammonium salts.
Among the aromatic carboxylic acids usable in the composition according to the invention, there may be mentioned in particular
- benzoic acid
- para-anisic acid
- diphenolic acid
- ferulic acid
- hippuric acid
- 3-hydroxybenzoic acid
- 4-hydroxybenzoic acid
- phenylthioglycolic acid
- acetylsalicylic acid
- para, meta or ortho-phthalic acid as well as their salified forms and their mixtures.
Benzoic acid will be selected more particularly.
According to the invention, the aromatic acid (s) or their salts may represent from 0.001% to 30% by weight, preferably from 0.01% to 20% by weight and more particularly from 0.1 to 10% by weight with respect to to the total weight of the composition.
Compositions according to the invention may further contain one or more conditioning agents.
Within the framework of the present invention, "conditioning agent" is understood to be any agent whose function is to improve the cosmetic properties of the hair, in particular softness, looseness, feel, straightening and static electricity.
ES 2 345 503 T3
The conditioning agents can be in liquid, semi-solid or solid form such as for example oils, waxes or gums.
According to the invention, the conditioning agents can be selected from synthetic oils such as polyolefins, vegetable oils, fluorinated or perfluorinated oils, natural or synthetic waxes, silicones, non-polysaccharide cationic polymers, ceramide-type compounds, cationic surfactants, fatty amines. , fatty acids and their derivatives as well as mixtures of these different compounds.
Synthetic oils are, in particular, polyolefins, in particular polyolefins, and more particularly:
- of the polybutene type, hydrogenated or unhydrogenated, and preferably polyisobutene, hydrogenated or unhydrogenated.
Isobutylene oligomers of molecular weight less than 1000 and their mixtures with polyisobutylenes of molecular weight greater than 1000 and preferably between 1000 and 15000 are preferably used.
As examples of poly-α-olefins which can be used in the context of the present invention, mention may be made more particularly of the polyisobutenes sold under the name PERMETHYL 99 A, 101 A, 102 A, 104 A (n = 16) and 106 A (n = 38) by the company PRESPERSE Inc, or also the products marketed under the name ARLAMOL HD (n = 3) by the company ICI (n designating the degree of polymerization),
- of the polydecene type, hydrogenated or unhydrogenated.
Said products are marketed, for example, under the names ETHYLFLO by the company ETHYL CORP., And ARLAMOL PAO by the company ICI.
Animal or vegetable oils are preferably selected from the group consisting of sunflower, corn, soybean, avocado, jojoba, pumpkin, grape seed, sesame, hazelnut, fish oils, glycerol tricaprocaprylate oils , or vegetable or animal oils of formula R<sub>9</sub>COOR<sub>!0</sub> in which R<sub>9</sub> represents the remainder of a higher fatty acid comprising 7 to 29 carbon atoms and R<sub>w</sub> represents a straight or branched hydrocarbon chain containing from 3 to 30 carbon atoms in particular alkyl or alkenyl, for example Purcellin's oil or liquid jojoba wax;
Natural or synthetic essential oils such as, for example, eucalyptus, bleach, lavender, vetiver, Litsea cubeba, lemon, sandalwood, rosemary, chamomile, savory, nutmeg oils can also be used. , cinnamon, hyssop, caraway, orange, geraniol, juniper and bergamot;
Waxes are natural (animal or vegetable) or synthetic substances that are solid at room temperature (20 ° -25 ° C). They are insoluble in water, soluble in oils and are capable of forming a water-repellent film.
On the definition of waxes, there may be mentioned, for example, PD Dorgan, Drug and Cosmetic Industry, December 1983, pages 30-33.
The wax or waxes are particularly selected from Carnauba wax, Candelilla wax, and Alpha wax, paraffin wax, ozokerite, vegetable waxes such as olive wax, rice wax, hydrogenated jojoba wax or the absolute flower waxes such as essential blackcurrant flower wax marketed by the BERTIN company (France), animal waxes such as beeswax, or modified beeswax (cerabeline); Other waxes or waxy raw materials that can be used according to the invention are particularly marine waxes such as that marketed by the company SOPHIM under the reference M82, polyethylene waxes or polyolefin waxes in general.
Preferred conditioning agents according to the invention are cationic polymers and silicones.
The non-saccharide cationic polymers that can be used according to the present invention can be selected from all those already known per se as enhancers of the cosmetic properties of hair treated with detergent compositions, namely in particular those described in patent application EP-A-0 337 354 and in French patent applications FR-A-2 270 846, 2 383 660, 2 598 611, 2 470 596 and 2 519 863.
By non-saccharide polymers, we mean polymers that do not contain a glycosidic bond between monosaccharides.
Even more generally, in the sense of the present invention, the term "cationic polymer" designates any polymer that contains cationic groups and / or groups ionizable to cationic groups.
Preferred cationic polymers are selected from those containing motifs comprising primary, secondary, tertiary and / or quaternary amine groups that can form part of the polymer backbone, or be carried by a side substituent directly attached thereto.
ES 2 345 503 T3
The cationic polymers used generally have a number average molecular mass between 500 and 5 x 10<sup>6</sup> approximately, and preferably between 10<sup>3</sup> and 3 x 10<sup>6</sup> about.
Among the cationic polymers, mention may be made more particularly of polyamine, polyaminoamide and polyquaternary ammonium type polymers. These are known products.
Polymers of the polyamine, polyamidoamide, polyquaternary ammonium type, usable according to the present invention, which may be particularly mentioned, are those described in French patents No. 2,505,348 or 2,542,997.
(1) Homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the following formulas:
<img file="ES2345503T3_D0001.tif" />
in which:
R<sub>1</sub> and R<sub>2</sub>, the same or different, represent hydrogen or an alkyl group having 1 to 6 carbon atoms and preferably methyl or ethyl;
R<sub>3</sub>, the same or different, designate a hydrogen atom or a radical CH<sub>3</sub>;
A, the same or different, represent an alkyl group, linear or branched, of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms;
R<sub>4</sub>, R<sub>5</sub>, R<sub>6</sub>, the same or different, represent an alkyl group having 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group having 1 to 6 carbon atoms;
X designates an anion derived from a mineral or organic acid such as a methosulfate anion or a halide such as chloride or bromide.
ES 2 345 503 T3
Family (1) copolymers may further contain one or more motifs derived from comonomers that may be selected from the family of acrylamides, methacrylamides, acrylamide diaketones, acrylamides and nitrogen substituted methacrylamides with lower alkyls (C<sub>1</sub>-C<sub>4</sub>), acrylic or methacrylic acids or their esters, vinylactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.
Thus, among these family (1) copolymers, the following can be mentioned:
- copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as that marketed under the name HERCOFLOC by the company HERCULES,
- the copolymers of acrylamide and methacryloyloxyethyl-trimethylammonium chloride described, for example, in patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY,
- the copolymer of acrylamide and methacryloyloxyethyl-trimethylammonium methosulfate marketed under the name RETEN by the company HERCULES,
- quaternized or unquaternized vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products marketed under the name "GAFQUAT" by the ISP company, such as "GAFQUAT 734" or "GAFQUAT 755" or the products called "COPOLYMER 845, 958 and 937 ". These polymers are described in detail in French patents 2,077,143 and 2,393,573,
- Dimethyl amino ethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers such as the product marketed under the name GAFFIX VC 713 by the company ISP,
- the vinylpyrrolidone / methacrylamidopropyl dimethylamine copolymers marketed in particular under the name STYLEzE CC 10 by ISP.
- and the copolymers of vinylpyrrolidone / quaternized dimethylamino-propyl methacrylamide such as the product marketed under the name "GAFQUAT HS 100" by the company ISP.
(2) polymers made up of piperazinyl motifs and divalent alkylene or hydroxyalkylene radicals with straight or branched chains, optionally interrupted by oxygen, sulfur, nitrogen atoms or by aromatic or heterocyclic rings, as well as oxidation and / or quaternization products of these polymers. Said polymers are particularly described in French patents 2,162,025 and 2,280,361;
(3) the water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; These polyaminoamides can be cross-linked by an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bishaloacyldiamine, a bis-alkyl halide or also by an oligomer resulting from the reaction of a bifunctional compound reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epylhalohydrin, to a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions that vary between 0.025 and 0.35 moles per amine group of the polyaminoamide; These polyaminoamides can be alkylated or, if they comprise one or more tertiary amine functions, quaternized. Said polymers are particularly described in French patents 2,252,840 and 2,368,508;
(4) the derivatives of polyaminoamides that result from the condensation of polyalcoylene polyamines with polycarboxylic acids followed by an alkylation with bifunctional agents. Mention may be made, for example, of adipic acid-diakylaminohydroxyalkyldialoylene triamine polymers in which the alkoyl radical comprises 1 to 4 carbon atoms and preferably designates methyl, ethyl, propyl. Such polymers are particularly described in French patent 1,583,363.
Among these derivatives, mention may be made more particularly of the polymers of adipic acid / dimethylaminohydroxypropyl / diethylene triamine sold under the designation "Cartaretine F, F4 or F8" by the company Sandoz.
(5) polymers obtained by reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids having 3 to 8 carbon atoms. The molar ratio between the polyalkylene polylamine and the dicarboxylic acid being between 0.8: 1 and 1.4: 1; reacting the resulting polyaminoamide with epichlorohydrin in a molar ratio of epichlorohydrin to the secondary amine group of the polyaminoamide comprised between 0.5: 1 and 1.8: 1. Such polymers are particularly described in US Patents 3,227,615 and 2,961,347.
Polymers of this type are marketed in particular under the name "Hercosett 57" by the company Hercules Inc. or under the name "PD 170" or "Delsette 101" by the company Hercules, in the case of adipic acid / epoxypropyl / diethylene triamine.
ES 2 345 503 T3 (6) alkyl diallyl amine or dialkyl diallyl ammonium cyclopolymers such as homopolymers or copolymers that comprise as main constituent of the chain motifs that respond to formulas (VII) or (VIII):
<img file="ES2345503T3_D0002.tif" />
formulas in which k and t are equal to 0 or 1, where the sum k + t is equal to 1; R<sub>12</sub> designates a hydrogen atom or a methyl radical; R<sub>10</sub> and Rn, independently of each other, designate an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amidoalkyl group (C<sub>1</sub>-C<sub>4</sub>) or R<sub>10</sub> and R<sub>11</sub> they can designate, together with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; Y<sup>-</sup> it is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. These polymers are particularly described in French patent 2,080,759 and in its certificate of addition 2,190,406.
R<sub>10</sub> and R<sub>11</sub>, independently of each other, preferably designate an alkyl group having 1 to 4 carbon atoms.
Among the polymers defined above, mention may be made more particularly of the homopolymer of dimethyldiallylammonium chloride sold under the name "Merquat 100" by the company NALCO (and its homologues of reduced weight average molecular masses) and the copolymers of diallyldimethylammonium chloride and acrylamide. marketed under the name "MERQUAT 550".
(7) the quaternary diammonium polymer that contains recurring motifs that respond to the formula:
<img file="ES2345503T3_D0003.tif" />
formula (IX) in which:
R<sub>13</sub>, R<sub>14</sub>, R<sub>15</sub> and R<sub>16</sub>, the same or different, represent aliphatic, alicyclic, or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or R<sub>13</sub>, R<sub>14</sub>, R<sub>15</sub> and R<sub>16</sub>Together or separately, they constitute, with the nitrogen atoms to which they are attached, heterocycles that optionally contain a second heteroatom other than nitrogen or R<sub>13</sub>, R<sub>14</sub>, R<sub>15</sub> and R<sub>16</sub> represent an alkyl radical of C<sub>1</sub>-C<sub>6</sub> linear or branched substituted with a nitrile, ester, acyl, amide, or -CO-OR group<sub>17</sub>-D or -CONH-R<sub>17</sub>-D where R<sub>17</sub> is an alkylene and D is a quaternary ammonium group;
A1 and B1 represent polymethylene groups containing from 2 to 20 carbon atoms that can be straight or branched, saturated or unsaturated, and that can contain, attached to or interspersed in the main chain, one or more aromatic rings, or one or more atoms oxygen, sulfur, or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide, or ester groups, and
X<sup>-</sup> designates an anion derived from a mineral or organic acid;
A1, R<sub>13</sub> and R<sub>15</sub> they can form, with the two nitrogen atoms to which they are attached, a piperazine ring; furthermore, if A1 designates a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1
ES 2 345 503 T3 can also designate a group (CH<sub>2</sub>)<sub>n</sub>-CO-D-OC- (CH<sub>2</sub>)<sub>n</sub>- n is an integer that varies between approximately 2 and 20, where D designates:
a) a glycol residue of the formula: -OZO-, where Z designates a linear or branched hydrocarbon radical or a group that responds to one of the following formulas:
- (CH<sub>2</sub>-CH<sub>2</sub>-OR)<sub>X</sub>-CH<sub>2</sub>-CH<sub>2</sub>Do ch<sub>2</sub>-CH (CH<sub>3</sub>) -O] and -CH<sub>2</sub>-CH (CH<sub>3</sub>) where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization;
b) a bis-secondary diamine residue such as a piperazine derivative;
c) a bis-primary diamine residue of the formula: -NH-Y-NH-, where Y designates a linear or branched hydrocarbon radical, or the bivalent radical
<img file="ES2345503T3_D0004.tif" />
d) a ureylene group of formula: -NH-CO-NH-;
Preferably X<sup>-</sup> it is an anion such as chloride or bromide.
These polymers have a number average molecular mass generally between 1000 and 100000.
Polymers of this type are particularly described in French patents 2,320,330, 2,270,846, 2,316,271,
2,336,434 and 2,413,907 and US patents 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462,
2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020.
It is possible to use, more particularly, polymers that are constituted by recurring motifs that respond to the formula:
<sup>R</sup>1 <sup>R</sup>3
II -N- (CH<sub>2</sub>) -N- (CH<sub>2</sub>)<sub>p</sub> - (a) R<sub>2</sub> X 'R<sub>4</sub><sup>X</sup> in which R<sub>1</sub>, R<sub>2</sub>, R<sub>3</sub> and R<sub>4</sub>, the same or different, designate an alkyl or hydroxyalkyl radical having approximately 1 to 4 carbon atoms, n and p are integers that vary between approximately 2 and 20, and X<sup>-</sup> It is an anion derived from a mineral or organic acid.
A particularly preferred compound of formula (a) is that for which R<sub>1</sub>, R<sub>2</sub>, R<sub>3</sub> and R<sub>4</sub>, represent a methyl radical and n = 3, p = 6 and X = Cl, called Hexadimethrine chloride according to the INCl nomenclature (CTFA).
(8) quaternary polyammonium polymers constituted by reasons of formula (X):
<img file="ES2345503T3_D0005.tif" />
ES 2 345 503 T3 formula in which:
R<sub>18</sub>, R<sub>19</sub>, R<sub>20</sub> and R<sub>21</sub>, the same or different, represent a hydrogen atom or a methyl, ethyl, propyl, j6-hydroxyethyl, β-hydroxypropyl or -CH radical<sub>2</sub>CH<sub>2</sub>(OCH<sub>2</sub>CH<sub>2</sub>)<sub>p</sub>OH, where p is equal to 0 or to an integer between 1 and 6, provided that R<sub>18</sub>, R<sub>19</sub>, R<sub>20</sub> and R<sub>2</sub>i do not simultaneously represent a hydrogen atom, r and s, the same or different, are integers between 1 and 6, q is equal to 0 or an integer between 1 and 34,
X designates an anion such as a halide,
A designates a radical of a dihalogenide or preferably represents -CH<sub>2</sub> -CH<sub>2</sub> -O-CH<sub>2</sub>-CH<sub>2</sub>-.
Said compounds are particularly described in patent application EP-A-122324.
Mention may be made, for example, among these, of the products "Mirapol® A 15", "Mirapol® AD1", "Mirapol® AZ1" and "Mirapol® 175" marketed by the Miranol company.
(9) The quaternary polymers of vinylpyrrolidone and vinylimidazole such as, for example, the products marketed under the names Luviquat® FC 905, FC 550 and FC 370 by the company BASF
(10) Crosslinked polymers of methacryloyloxyalkyl salts (C<sub>1</sub>-C<sub>4</sub>) trialkyl (C<sub>1</sub>-C<sub>4</sub>) ammonium such as polymers obtained by homopolymerization of dimethylaminoethylmethacrylate quaternized by methyl chloride, or by copolymerization of acrylamide with dimethylaminoethylmethacrylate quaternized by methyl chloride, the homopolymerization being followed by crosslinking by a compound with olefinic unsaturation, in particular bis acrylamide. More particularly, a cross-linked copolymer of acrylamide / methacryloyloxyethyl trimethylammonium chloride (20/80 by weight) can be used in the form of a dispersion containing 50% by weight of said copolymer in mineral oil. This dispersion is marketed under the name "SALCARE® SC 92" by the company CIBA. A crosslinked methacryloyloxyethyl trimethylammonium chloride homopolymer containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester can also be used. These dispersions are marketed under the names "SALCARE® SC 95" and "SALCARE® SC 96" by the company CIBA.
Other cationic polymers that can be used within the framework of the invention are cationic proteins or hydrolysates of cationic proteins, polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium motifs, polyamine and epichlorohydrin condensates, quaternary polyureylenes and chitin derivatives.
Among all the cationic polymers that can be used within the framework of the present invention, it is preferred to use cationic cyclopolymers, in particular the homopolymers or copolymers of dimethyldiallylammonium chloride, marketed under the names "MERQUAT 100", "MERQUAT 550" and " MERQUAT S ”by the company NALCO, the quaternary polymers of vinylpyrrolidone and vinylimidazole and their mixtures.
The silicones that can be used according to the invention are, in particular, polyorganosiloxanes that are insoluble in the composition and can be in the form of oils, waxes, resins or gums.
Organopolysiloxanes are further defined in Walter NOLL's "Chemistry and Technology of Silicones" (1968) Academic Press. These can be volatile or non-volatile.
When they are volatile, the silicones are more particularly selected from those having a boiling point comprised between 60 ° C and 260 ° C, and even more particularly between:
(i) cyclic silicones comprising 3 to 7 silicon atoms and preferably 4 to 5. These are, for example, octamethylcyclotetrasiloxane marketed particularly under the name "VOLATILE SILICONE 7207" by UNION CARBIDE or "SILBIONE 70045 V 2 ”By RHODIA CHIMIE, the decamethylcyclopentasiloxane marketed under the name“ VOLATILE SILICONE 7158 ”by UNION CARBIDE,“ SILBIONE 70045 V 5 ”by RHODIA CHIMIE, as well as their mixtures.
ES 2 345 503 T3
Mention may also be made of cyclocopolymers of the dimethylsiloxanes / methylalkylsiloxane type, such as "SILICONE VOLATILE FZ 3109" marketed by the company UNION CARBIDE, with a chemical structure:
with
<img file="ES2345503T3_D0006.tif" />
DD
<img file="ES2345503T3_D0007.tif" />
with D ':
ch<sub>3</sub>
-Si-O— I c<sub>8</sub>h<sub>)7</sub>
Mixtures of cyclic silicones with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1 '(hexa-2,2,2 ', 2', 3,3'-trimethylsilyloxy) bis-neopentane;
(ii) linear volatile silicones having 2 to 9 silicon atoms and having a viscosity less than or equal to 5 x 10<sup>-6</sup> m<sup>2</sup>/ s at 25 ° C. It is, for example, decamethyltetrasiloxane marketed in particular under the name "SH 200" by the company TORAY SILICONE. Silicones that fall into this class are also described in the article published in Cosmetics and toiletries, Vol. 91, January 76, P. 27-32 - TODD & BYERS “Volatile Silicone fluids for Cosmetics”.
Non-volatile silicones are preferably used and more particularly polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, polyorganosiloxanes modified with organofunctional groups as well as mixtures thereof.
These silicones are more particularly selected from polyalkylsiloxanes, among which there may be mentioned mainly polydimethylsiloxanes with terminal trimethylsilyl groups having a viscosity of 5 x 10 <sup>6</sup> at 2.5 m<sup>2</sup>/ s at 25 ° C and preferably 1 x 10 <sup>5</sup> at 1 m<sup>2</sup>/ s. The viscosity of silicones is measured for example at 25 ° C according to ASTM 445 Appendix C.
Among these polyalkylsiloxanes, the following commercial products may be mentioned, but not limited to:
- SILBIONE oils from the 47 and 70 047 series or MIRASIL oils marketed by RHODIA CHIMIE, such as, for example, 70 047 V 500 000 oil;
- the MIRASIL series oils marketed by the RHODIA CHIMIE company;
- the oils of the 200 series from the DOW CORNING company, such as more particularly DC200 with a viscosity of 60000 Cst;
- VISCASIL oils from GENERAL ELECTRIC and some oils from the SF series (SF 96, SF 18) from GENERAL ELECTRIC.
Mention may also be made of the polydimethylsiloxanes with dimethylsilanol end groups (Dimethiconol according to the CTFA designation) such as the 48 series oils from the company RHODIA CHIMIE.
In this class of polyalkylsiloxanes, the products marketed under the names "ABIL WAX 9800 and 9801" by the company GOLDSCHMIDT which are polyalkyl (C<sub>1</sub>-C<sub>20</sub>) siloxanes.
Polyalkylarylsiloxanes are particularly selected from polydimethyl methylphenylsiloxanes, linear and / or branched polydimethyl diphenylsiloxanes with a viscosity of 1 x 10 <sup>5</sup> to 5 x 10 <sup>2</sup> m<sup>2</sup>/ s at 25 ° C.
Among these polyalkylarylsiloxanes, mention may be made, by way of example, of the products marketed under the following names:
• SILBIONE oils from the 70 641 series from RHODIA CHIMIE;
• RHODORSIL 70 633 and 763 series oils from RHODIA CHIMIE;
• DOW CORNING 556 COSMETIC GRAD FLUID oil from DOW CORNING;
ES 2 345 503 T3 • silicones of the PK series from BAYER such as the product PK20;
• BAYER's PN, PH series silicones such as PN1000 and PH1000 products;
• some oils from the GENERAL ELECTRIC SF series such as SF 1023, SF 1154, SF 1250, SF 1265.
The silicone gums that can be used according to the invention are particularly polydiorganosiloxanes having high number average molecular masses of between 200,000 and 1,000,000 used alone or as a mixture in a solvent. This solvent can be selected from volatile silicones, polydimethylsiloxane oils (PDMS), polyphenylmethylsiloxane oils (PPMS), isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecanes or their mixtures.
The following products may be mentioned more particularly:
- polydimethylsiloxane
- polydimethylsiloxane / methylvinylsiloxane gums,
- polydimethylsiloxane / diphenylsiloxane,
- polydimethylsiloxane / phenylmethylsiloxane,
- polydimethylsiloxane / diphenylsiloxane / methylvinylsiloxane.
Products more particularly usable according to the invention are mixtures such as:
• mixtures formed from a chain-end hydroxylated polydimethylsiloxane (called dimethiconol according to the CTFA dictionary nomenclature) and a cyclic poly-dimethylsiloxane (called cyclomethicone according to the CTFA dictionary nomenclature) such as product Q2 1401 sold by the DOW CORNING company;
• mixtures formed from a polydimethylsiloxane rubber with a cyclic silicone such as the product SF 1214 Silicone Fluid from GENERAL ELECTRIC, this product is an SF 30 rubber corresponding to a dimethicone, which has a number average molecular weight of 500000 dissolved in SF 1202 Silicone Fluid oil corresponding to decamethylcyclopentasiloxane;
• mixtures of two PDMS of different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from the company GENERAL ELECTRIC. The product Sf 1236 is the mixture of a rubber SE 30 defined above having a viscosity of 20 μm<sup>2</sup>/ s and an SF 96 oil with a viscosity of 5 x 10<sup>-6</sup>m<sup>2</sup>/ s. This product preferably comprises 15% SE 30 gum and 85% SF 96 oil.
The organopolysiloxane resins usable according to the invention are cross-linked siloxane systems containing the units:
R<sub>2</sub>Yes<sub>2/2</sub>, R<sub>3</sub>Yes<sub>1/2</sub>, RSiO<sub>3/2</sub> and SiO<sub>4/2</sub> in which R represents a hydrocarbon group having 1 to 16 carbon atoms or a phenyl group. Among these products, particularly preferred are those in which R designates a lower alkyl radical of C<sub>1</sub>-C<sub>4</sub>, more particularly methyl, or a phenyl radical.
Among these resins, mention may be made of the product marketed under the name "DOW CORNING 593" or those marketed under the names "SILICONE FLUID SS 4230 and SS 4267" by the company GENERAL ELECTRIC and which are silicones with a dimethyl / trimethyl siloxane structure.
Mention may also be made of the trimethylsiloxysilicate type resins marketed particularly under the names X22-4914, X21-5034 and X21-5037 by the company SHIN-ETSU.
The organo modified silicones usable according to the invention are silicones as defined above and which comprise in their structure one or more organofunctional groups fixed by means of a hydrocarbon radical.
Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising:
- polyethyleneoxy and / or polypropylenoxy groups optionally comprising C alkyl groups<sub>6</sub>-C<sub>24</sub> such as the products called dimethicone copolyol marketed by the company DOW CORNING under the name DC 1248 or the oils SILWET L 722, L 7500, L 77, L 711 from the company UNION CARBIDE and the alkyl (C12) methicone copolyol marketed by the company DOW CORNING under the name Q2 5200;
ES 2 345 503 T3
- substituted or unsubstituted amino groups such as the products sold under the names GP 4 Silicone Fluid and GP 7100 by the GENESEE company or the products sold under the names Q2 8220 and DOW CORNiNg 929 or 939 by the DOW CORNING company. Substituted amino groups are, in particular, Ci-C aminoalkyl groups<sub>4</sub>;
- thiol groups such as the products marketed under the names "GP 72 A" and "GP 71" from GENESEE;
- Alkoxylated groups such as the product marketed under the name "SILICONE COPOLYMER F-755" by SWS SILICONES and ABIL WAX 2428, 2434 and 2440 by the company GOLDSCHMIDT;
- hydroxylated groups such as the polyorganosiloxanes with hydroxyalkyl function described in the French patent application FR-A-85 16334 that correspond to the formula (XI):
<img file="ES2345503T3_D0008.tif" />
in which the radicals R<sub>3</sub> the same or different are selected from the methyl and phenyl radicals; designating at least 60% by mole of the radicals R<sub>3</sub> methyl; the radical R '<sub>3</sub> is a hydrocarbon divalent alkylene member of C<sub>2</sub>-C<sub>18</sub>; p is between 1 and 30 inclusive; q is between 1 and 150 inclusive;
- acyloxyalkyl groups such as, for example, the polyorganosiloxanes described in US-A-4957732 and which respond to formula (XII):
<img file="ES2345503T3_D0009.tif" />
in which:
R<sub>4</sub> designates a methyl, phenyl, -OCOR group<sub>5</sub>, hydroxyl, with only one of the radicals R<sub>4</sub>, per silicon atom, be OH;
R '<sub>4</sub> designates methyl, phenyl; designating at least 60% in molar proportion of all the radicals R<sub>4</sub> and R '<sub>4</sub> methyl;
R<sub>5</sub> designates C alkyl or alkenyl<sub>8</sub>-C<sub>20</sub>;
R "designates a divalent, linear or branched hydrocarbon alkylene radical of C<sub>2</sub>-C<sub>18</sub>;
r is between 1 and 120 inclusive;
p is between 1 and 30;
ES 2 345 503 T3 q is equal to 0 or is less than 0.5 p, where p + q is between 1 and 30; the polyorganosiloxanes of formula (XII) may contain groups:
CH, —Yes — OH <sup>3</sup> I
Or in proportions that do not exceed 15% of the sum p + q + r.
- anionic groups of the carboxylic type as, for example, in the products described in patent EP 186 507 of the company CHISSO CORPORATION, or of the alkylcarboxylic type as those present in the product X-22-3701 E of the company SHIN-ETSU; 2-hydroxyalkylsulfonate; 2-hydroxyalkylthiosulfate such as the products marketed by the company GOLDSCHMIDT under the names "ABIL S201" and "ABIL S255".
hydroxyacylamino groups, such as the polyorganosiloxanes described in application EP 342 834. Mention may be made, for example, of the product Q2-8413 from the company DOW CORNING.
According to the invention, silicones can also be used that comprise a polysiloxane portion and a portion constituted by a non-silicone organic chain, one of the two portions constituting the main chain of the polymer, the other being grafted onto said main chain. These polymers are described, for example, in patent applications EP-A-412 704, EP-A-412 707, EP-A-640 105 and WO 95/00578, EP-A-582 152 and WO 93/23009 and US patents US 4,693,935, US 4,728,571 and US 4,972,037. These polymers are preferably anionic or nonionic.
Said polymers are, for example, copolymers capable of being obtained by radical polymerization from the mixture of monomers consisting of:
a) 50 to 90% by weight of tert-butyl acrylate;
b) 0 to 40% by weight of acrylic acid;
c) from 5 to 40% by weight of silicone macromer of formula:
<img file="ES2345503T3_D0010.tif" />
with v being a number that varies between 5 and 700; the percentages by weight being calculated with respect to the total weight of the monomers.
Other examples of grafted silicone polymers are particularly polydimethylsiloxanes (PDMS) onto which are grafted, by means of a thiopropylene-type binding member, mixed polymer motifs of the poly (meth) acrylic acid type and of the poly (meth) acrylate type. alkyl and polydimethylsiloxanes (PDMS) to which are grafted, by means of a thiopropylene-type binding member, isobutyl poly (meth) acrylate-type polymer motifs.
According to the invention, all silicones can also be used in the form of emulsions, nanoemulsions or microemulsions.
Particularly preferred polyorganosiloxanes according to the invention are:
- non-volatile silicones selected from the family of polyalkylsiloxanes with trimethylsilyl end groups such as oils having a viscosity between 0.2 and 2.5 μm<sup>2</sup>/ s at 25 ° C such as the oils of the DOW CORNING DC200 series in particular the 60000 Cst viscosity, the SILBIONE 70047 and 47 series and more particularly the 70 047 V 500000 oil marketed by the company RHODIA CHIMIE, the polyalkylsiloxanes with dimethylsilanol end groups such as dimethiconols or polyalkylarylsiloxanes such as SILBIONE 70641 V 200 oil sold by the company RHODIA CHIMIE;
ES 2 345 503 T3
- the organopolysiloxane resin sold under the name DOW CORNING 593;
- polysiloxanes with amino groups such as amodimethicones or trimethylsilylmodimethicone;
Cationic proteins or protein hydrolysates are in particular chemically modified polypeptides which carry, or grafted onto, quaternary ammonium groups at the end of the chain. Its molecular mass can vary, for example, between 1,500 and 10,000, and in particular between approximately 2,000 and 5,000. Among these compounds, there may be particularly mentioned:
- collagen hydrolysates bearing triethylammonium groups such as the products marketed under the name "Quat-Pro E" by the company MAYBROOK and referred to in the CTFA dictionary as "Triethonium Hydrolyzed Collagen Ethosulfate";
- collagen hydrolysates bearing trimethylammonium and trimethyl stearylammonium chloride groups, marketed under the name "Quat-Pro S" by the MAYBROOOK company and referred to in the CTFA dictionary as "Steartrimonium Hydrolyzed Collagen";
- animal protein hydrolysates bearing trimethylbenzylammonium groups such as the products marketed under the name "Crotein BTA" by the company CRODA and called "Benzyltrimonium hydrolyzed animal protein" in the CTFA dictionary;
- protein hydrolysates bearing quaternary ammonium groups in the polypeptide chain comprising at least one alkyl radical having 1 to 18 carbon atoms.
Among these protein hydrolysates, there may be mentioned among others:
- "Croquat L" whose quaternary ammonium groups comprise an alkyl group of C<sub>12</sub>;
- "Croquat M" whose quaternary ammonium groups comprise C alkyl groups<sub>10</sub>-C<sub>18</sub>;
- "Croquat S" whose quaternary ammonium groups comprise an alkyl group of C<sub>18</sub>;
- "Crotein Q" whose quaternary ammonium groups comprise at least one alkyl group having 1 to 18 carbon atoms.
These different products are marketed by the Croda company.
Other quaternized proteins or hydrolyzates are, for example, those that respond to the formula (XIV):
OHI <sup>R</sup>5 <sup>—</sup> N®-R<sub>6</sub>—NH —A xo (XIV) ch<sub>3</sub> in which X<sup>-</sup> is an anion of an organic or mineral acid, A designates a protein residue derived from collagen protein hydrolysates, R<sub>5</sub> designates a lipophilic group comprising up to 30 carbon atoms, R<sub>6</sub> represents an alkylene group having 1 to 6 carbon atoms. Mention may be made, for example, of the products marketed by the company Inolex, under the name "Lexein QX 3000", referred to in the CTFA dictionary as "Cocotrimonium Collagent Hydrolysate".
Quaternized vegetable proteins such as wheat, corn or soy proteins may also be mentioned: As quaternized wheat proteins, mention may be made of those marketed by the Croda company under the names "Hydrotriticum WQ or QM", called in the CTFA dictionary "Cocodimonium Hydrolysed wheat protein", "Hydrotriticum QL" called in the CTFA dictionary "Laurdimonium hydrolysed wheat protein. ", Or also" Hydrotriticum QS ", called in the CTFA dictionary" Steardimonium hydrolysed wheat protein ".
According to the present invention, the ceramide-type compounds are in particular ceramides and / or glycoceramides and / or pseudoceramides and / or neoceramides, natural or synthetic.
ES 2 345 503 T3
Ceramide-type compounds are described, for example, in patent applications DE4424530, DE4424533, DE4402929, DE4420736, WO95 / 23807, WO94 / 07844, EP-A-0646572, WO95 / 16665, FR-2 673 179, EP-A -0227994 and WO 94/07844, WO94 / 24097, WO94 / 10131 whose teachings are included herein by reference.
Particularly preferred ceramide compounds according to the invention are, for example:
- 2-N-linoleoylamino-octadecane-1,3-diol,
- 2-N-oleoylamino-octadecane-1,3-diol,
- 2-N-palmitoylamino-octadecane-1,3-diol,
- 2-N-stearoylamino-octadecane-1,3-diol,
- 2-N-behenoylamino-octadecane-1,3-diol,
- 2-N- [2-hydroxy-palmitoyl] -amino-octadecane-1,3-diol,
- 2-N-stearoylamino-octadecane-1,3,4 triol and in particular N-stearoyl phytosphingosine,
- 2-N-palmitoylamino-hexadecane-1,3-diol
- (bis- (N-hydroxyethyl N-cetyl) malonamide),
- N- (2-hydroxyethyl) -N- (3-cetyloxy-2-hydroxypropyl) cetyl acid amide
- N-docosanoyl N-methyl-D-glucamine or mixtures of these compounds.
Cationic surfactants can also be used, among which there may be mentioned, in particular: primary, secondary or tertiary fatty amine salts, optionally polyoxyalkylenated; quaternary ammonium salts; imidazoline derivatives; or amine oxides with cationic character.
Quaternary ammonium salts are, for example:
- those with the following general formula (XV):
+
X '(XV) <sup>R</sup>1 \ x <sup>R</sup>3
R ^ in which the radicals R1 to R4, which may be the same or different, represent an aliphatic radical, linear or branched, comprising from 1 to 30 carbon atoms, or an aromatic radical such as aryl or alkylaryl. Aliphatic radicals can comprise heteroatoms such as particularly oxygen, nitrogen, sulfur and halogens. Aliphatic radicals are selected, for example, from alkyl, alkoxy, polyoxyalkylene (C<sub>2</sub>-C<sub>6</sub>), alkylamide, alkyl (C<sub>12</sub>-C<sub>22</sub>) amido alkyl (C<sub>2</sub>-C<sub>6</sub>), alkyl (C<sub>12</sub>-C<sub>22</sub>) acetate, hydroxyalkyl, comprising about 1 to 30 carbon atoms; X is an anion selected from the group of halides, phosphates, acetates, lactates, alkyl (C<sub>2</sub>-C<sub>6</sub>) sulfates, alkyl-o-alkylaryl sulfonates,
- the quaternary ammonium salts of imidazolinium, such as that of the following formula (XVI):
<img file="ES2345503T3_D0011.tif" />
CH<sub>2</sub>-CH<sub>2</sub>-N (Rg) -CO-R<sub>5</sub><sup>R</sup>7
<img file="ES2345503T3_D0012.tif" />
(XVI) in which R<sub>5</sub> represents an alkenyl or alkyl radical containing from 8 to 30 carbon atoms, for example derived from tallow fatty acids, R<sub>6</sub> represents a hydrogen atom, a C alkyl radical<sub>1</sub>-C<sub>4</sub> or a
ES 2 345 503 T3 alkenyl or alkyl radical comprising from 8 to 30 carbon atoms, R<sub>7</sub> represents an alkyl radical of C<sub>1</sub>C<sub>4</sub>, R<sub>8</sub> represents a hydrogen atom, a C alkyl radical<sub>1</sub> -C<sub>4</sub>, X is an anion selected from the group of halides, phosphates, acetates, lactates, alkyl sulfates, alkyl-o-alkylaryl sulfonates. Preferably R<sub>5 </sub>and R<sub>6</sub> designate a mixture of alkenyl or alkyl radicals comprising 12 to 21 carbon atoms, for example derived from tallow fatty acids, R7 designates methyl, R8 designates hydrogen. Said product is, for example, marketed under the name REWOQUAT W 75 by the company DEGUSSA,
- the quaternary diammonium salts of formula (XVII):
++
<img file="ES2345503T3_D0013.tif" />
2X (XVII) in which R<sub>9</sub> designates an aliphatic radical comprising about 16 to 30 carbon atoms, R<sub>10</sub>, R<sub>11</sub>, R<sub>12</sub>, R<sub>13</sub> and R<sub>14</sub>, the same or different, are selected from hydrogen or an alkyl radical comprising 1 to 4 carbon atoms, and X is an anion selected from the group of halides, acetates, phosphates, nitrates and methyl sulfates. Said quaternary diammonium salts comprise particularly propane diammonium dichloride.
- quaternary ammonium salts containing at least one ester function
Quaternary ammonium salts containing at least one ester function usable according to the invention are, for example, those of the following formula (XVIII)
<img file="ES2345503T3_D0014.tif" />
in which:
- R<sub>15</sub> is selected from the alkyl radicals of C<sub>1</sub>-C<sub>6</sub> and the hydroxyalkyl or dihydroxyalkyl radicals of C<sub>1</sub>EC;
- R<sub>16</sub> is selected from:
- the radical
OR
II R<sub>1V</sub>C-
- the radicals R<sub>20</sub> C hydrocarbons<sub>1</sub>-C<sub>22</sub> linear or branched, saturated or unsaturated,
- the hydrogen atom,
- R18 is selected from:
- the radical
OR
II r<sub>2T</sub>c19
ES 2 345 503 T3
- the radicals R<sub>22</sub> C hydrocarbons<sub>1</sub>-C<sub>6</sub> linear or branched, saturated or unsaturated,
- the hydrogen atom,
- R<sub>17</sub>, R<sub>19</sub> and R<sub>21</sub>, the same or different, are selected from the hydrocarbon radicals of C<sub>7</sub>-C<sub>21</sub>, linear or branched, saturated or unsaturated;
- n, p and r, the same or different, are integers that have a value from 2 to 6;
- y is an integer that is worth 1 to 10;
- x and z, the same or different, are integers that have a value from 0 to 10;
- X is a simple or complex anion, organic or inorganic; provided that the sum x + y + z is 1 to 15, that when x is 0 then R<sub>16</sub> designate R<sub>20</sub> and that when z is 0 then R<sub>18</sub> designate R<sub>22</sub>.
The alkyl radicals R<sub>15</sub> they can be linear or branched and more particularly linear.
Preferably R<sub>15</sub> designates a methyl, ethyl, hydroxyethyl or dihydroxypropyl radical and, more particularly, a methyl or ethyl radical.
Advantageously, the sum x + y + z is 1 to 10.
When R<sub>16</sub> is a radical R<sub>20</sub> hydrocarbon, it can be long and have 12 to 22 carbon atoms or short and have 1 to 3 carbon atoms.
When R<sub>18</sub> is a radical R<sub>22</sub> hydrocarbon, preferably has 1 to 3 carbon atoms.
Advantageously, R<sub>17</sub>, R<sub>19</sub> and R<sub>21</sub>, the same or different, are selected from the hydrocarbon radicals of C<sub>11</sub>-C<sub>21</sub>, linear or branched, saturated or unsaturated and, more particularly, between the C11C alkyl and alkenyl radicals<sub>21</sub>, linear or branched, saturated or unsaturated.
Preferably x and z, the same or different, are equal to 0 or 1.
Advantageously, y is equal to 1.
Preferably, n, p, and r, the same or different, are equal to 2 or 3 and even more particularly equal to 2.
The anion is preferably a halide (chloride, bromide or iodide) or an alkyl sulfate, more particularly methylsulfate. However, methanesulfonate, phosphate, nitrate, tosylate, an anion derived from organic acid such as acetate or lactate or any other ester functional ammonium compatible anion can be used.
The anion X is, even more particularly, chloride or methylsulfate.
More particularly, the ammonium salts of formula (XVIII) are used in which:
- R<sub>15</sub> designates a methyl or ethyl radical,
- x and y are equal to 1;
- z is equal to 0 or 1;
- n, p and r are equal to 2;
- R<sub>16</sub> is selected from:
- the radical
OR
II R19-C-
- C14-C22 methyl, ethyl or hydrocarbon radicals
- the hydrogen atom;
ES 2 345 503 T3
- R18 is selected from:
- the radical or ιι r<sub>2T</sub>c-
- the hydrogen atom;
R<sub>17</sub>, R<sub>19</sub> and R<sub>21</sub>, the same or different, are selected from the hydrocarbon radicals of C<sub>13</sub>-C<sub>17</sub>, linear or branched, saturated or unsaturated and preferably between the alkyl and alkenyl radicals of C<sub>13</sub>-C<sub>17</sub>, linear or branched, saturated or unsaturated.
Advantageously, the hydrocarbon radicals are linear.
Mention may be made, for example, of compounds of formula (XVI) such as the salts (particularly chloride or methylsulfate) of diacyloxyethyl dimethyl ammonium, of diacyloxyethyl hydroxyethyl methyl ammonium, of monoacyloxyethyl dihydroxyethyl methyl ammonium, of triacyloxyethyl methyl ammonium, of monoacyloxyethyl dimethyl hydroxyethyl ammonium and its mixtures. The acyl radicals preferably have 14 to 18 carbon atoms and come more particularly from a vegetable oil such as palm or sunflower oil. When the compound contains several acyl radicals, the latter may be the same or different.
These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine, optionally oxyalkylenated in fatty acids or in fatty acid mixtures of vegetable or animal origin or by transesterification of their methyl esters. This esterification is followed by a quaternization with the aid of an alkylating agent such as an alkyl halide (preferably methyl or ethyl), a dialkyl sulfate (preferably methyl or ethyl), methyl methanesulfonate, methyl paratoluenesulfonate, glycol chlorohydrin. or glycerol.
Said compounds are, for example, marketed under the names DEHYQUART by the company COGNIS, STEPANQUAT by the company STEPAN, NOXAMIUM by the company CECA, REWOQUAT WE 18 by the company DEGUSSA.
The ammonium salts containing at least one ester function described in US-A-4874554 and US-A-4137180 can also be used.
Among the quaternary ammonium salts of formula (XV), preferred are, on the one hand, tetraalkylammonium chlorides such as, for example, dialkyldimethylammonium or alkyltrimethylammonium chlorides, in which the alkyl radical comprises about 12 to 22 carbon atoms. , in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium, benzyl dimethyl stearyl ammonium chlorides or also, on the other hand, stearamidopropyldimethyl (myristyl acetate) ammonium chloride marketed under the name CERAPHYL 70 by the company VAN DYK.
The fatty acids are more particularly selected from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid.
The fatty acid derivatives are particularly the carboxylic acid esters, in particular the mono, di, tri or tetracarboxylic esters.
The esters of monocarboxylic acids are, in particular, the monoesters of saturated or unsaturated, linear or branched aliphatic acids of C<sub>1</sub>-C<sub>26</sub> and of saturated or unsaturated, linear or branched aliphatic alcohols of C<sub>1</sub>-C<sub>26</sub>, the total carbon number of the esters being greater than or equal to 10.
Among the monoesters, there may be mentioned dihydroabiethyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; C alkyl lactate<sub>12</sub>-C<sub>15</sub>; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso) stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; Isodecyl Oleate; isononyl isononanoate; isostearyl palmitate; methyl acetyl ricinoleate; Myristyl Stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate, hexyl stearate, butyl stearate, stearate isobutyl; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isostearyl neopentanoate, and isodecyl neopentanoate.
The di- or tricarboxylic acid esters of C<sub>4</sub>-C<sub>22</sub> and C alcohols<sub>1</sub> -C<sub>22</sub> and the esters of mono di or tricarboxylic acids and of di, tri, tetra or pentahydroxy alcohols of C<sub>2</sub>-C<sub>26</sub>.
ES 2 345 503 T3
Particular mention may be made of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; Octyldodecyl Stearoyl Stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; Propylene glycol dicaprylate dicaprate; tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate.
Among the esters mentioned above, it is preferred to use ethyl and isopropyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate. , hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate, cetyl octanoate, isostearyl neopentanoate, isodecyl neopentanoate.
Fluoro oils are, for example, perfluoropolyethers described in particular in the patent application EPA-486135 and the fluorohydrocarbon compounds described in particular in the patent application WO 93/11103. The teaching of these two applications is incorporated in their entirety into the present application by reference.
The term fluorohydrocarbon compounds designates compounds whose chemical structure comprises a carbon skeleton of which some hydrogen atoms have been replaced with fluorine atoms.
Fluorinated oils can also be fluorocarbons such as fluoroamines, for example perfluorotributylamine, fluorinated hydrocarbons, for example perfluorodecahydronaphthalene, fluoroesters and fluoroethers;
Perfluoropolyethers are, for example, marketed under the trade names FOMBLIN by the company MONTEFLUOS and KRYTOX by the company DU PONT.
Among the fluorohydrocarbon compounds, mention may also be made of the fluorinated fatty acid esters such as the product sold under the name NOFABLE FO by the company NIPPON OIL.
Of course, it is possible to use mixtures of conditioning agents.
According to the invention, the conditioning agent (s) may represent from 0.001% to 20% by weight, preferably from 0.01% to 10% by weight and, more particularly, from 0.1 to 3% by weight with respect to the total weight of the final composition.
The compositions according to the invention may be in the form of aqueous or hydroalcoholic hair care lotions. The cosmetic compositions according to the invention can also be in the form of a gel, a milk, a cream, an emulsion or a foam and used on the hair.
The compositions can be packaged in various forms particularly in vaporizers, dispenser bottles or in aerosol containers to ensure application of the composition in vaporized or foam form. Said packaging forms are indicated, for example, when it is desired to obtain a spray, a lacquer or a mousse for treating the hair.
The pH of the composition applied on the keratin fibers generally varies between 1 and 11. This is preferably 2 to 6, and can be adjusted to the desired value by means of acidifying or alkalizing agents well known in the state of the art of the compositions. applied on keratin fibers.
Among the alkalizing agents there may be mentioned, for example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, oxyethylenated and / or oxypropylene hydroxyalkylamines and ethylenediamines, sodium or potassium hydroxides and the compounds of the following formula:
N - R - N ζ
R<sub>39</sub>^ ^<sup>R</sup>41 in which R is a propylene radical optionally substituted by a hydroxyl group or an alkyl radical of C<sub>1</sub> -C<sub>4</sub>; R3<sub>8</sub>, R<sub>39</sub>, R<sub>40</sub> and R<sub>41</sub>, the same or different, represent a hydrogen atom, a C alkyl radical<sub>1</sub>-C<sub>4</sub> or C1-C4 hydroxyalkyl.
Acidifying agents are conventionally, for example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid or sulfonic acids.
According to a particular embodiment, the treatment method is applied to keratin fibers, in particular hair dyed by direct coloring or by oxidation coloring.
ES 2 345 503 T3
Another object of the invention consists in the use of said process for the protection of keratin fibers against the action of atmospheric agents and particularly against the action of light.
An object of the invention consists in the use of said method after the treatment of an oxidation coloration or a direct coloration of the keratin fibers and, more particularly, of the hair.
Another object of the invention relates to a process for coloring keratin fibers, in particular human hair, comprising at least the following steps a), b) and c):
a) A direct or oxidative coloring of said fibers is carried out
b) A composition comprising, in a physiologically acceptable medium, and in particular cosmetically acceptable, is applied to said fibers at least one protective agent selected from the water-soluble or fat-soluble organic UV filters whose log P is less than or equal to 6
c) A liquid water / steam mixture whose temperature is between 40 and 75 ° C is applied to said fibers, said filters being selected from the cinnamic derivatives and benzophenone derivatives.
A particular process for coloring the fibers comprises the following steps:
1) a) a direct dye or oxidation composition (A) is applied to said fibers for a sufficient time to develop the color,
2) optionally, a rinsing and / or shampooing and / or partial or total drying of said fibers is then carried out,
3) a composition (B) is applied which comprises at least one protective agent as defined above and which does not contain an oxidation coloring agent or an oxidizing agent;
4) optionally, a rinsing and / or shampooing and / or partial or total drying of said fibers is then carried out,
5) a liquid water / water vapor mixture whose temperature is between 40 and 75 ° C is applied to the fibers;
6) optionally, a rinsing and / or shampooing and / or partial or total drying of said fibers is then carried out,
A second particular procedure for coloring the fibers comprises the following steps:
1) a composition (B) is applied which comprises at least one protective agent as defined above and which does not contain oxidation coloring agent or oxidizing agent;
2) optionally a rinsing and / or washing with shampoo and / or partial or total drying of said fibers is carried out,
3) a liquid water / steam mixture whose temperature is between 40 and 75 ° C is applied to the fibers;
4) a direct dye or oxidation composition (A) is applied to said fibers for a sufficient time to develop the color,
5) optionally a rinsing and / or shampooing and / or partial or total drying of said fibers is carried out.
6) optionally, a rinsing and / or shampooing and / or partial or total drying of said fibers is then carried out.
In the different coloring procedures, the composition (B) comprising the protective agent (s) can be applied immediately after coloring or delayed. By delayed, we mean an application that is made several hours, a day or several days (from 1 to 60 days) after coloring. Preferably, the composition (B) will be applied immediately after coloring the keratin fibers.
ES 2 345 503 T3
The nature and concentration of the colorants present in the colorant composition (A) are not critical.
In the case of direct lightening dyes, the coloring compositions (A) result from the mixture, at the time of use, of a coloring composition (A1) that contains at least one direct coloring and of a composition (A2) that contains a oxidizing agent.
In the case of oxidation dyes, the coloring compositions (A) result from the mixture, at the time of use, of a coloring composition (A1) containing at least one oxidation base and optionally at least one coupler and / or a direct dye and a composition (A2) containing an antioxidant agent.
Direct dyes are, more particularly, compounds that absorb light radiation in the visible range (400-750 nm). These can be nonionic, anionic or cationic in nature.
Generally, direct dyes are selected from nitrated benzene dyes, azo, anthraquinone, naphthoquinone, benzoquinone, phenothiazine, indigoid, xanthenic, phenanthridine, phthalocyanine, triarylmethane derivatives, alone or in mixtures.
Among the nitrated benzene dyes, the following red or orange compounds may be mentioned: 1-hydroxy-3-nitro-4-N- (y-hydroxypropyl) amino benzene, N- (d-hydroxy ethyl) amino-3-nitro-4 -amino benzene, 1-amino-3-methyl-4-N- (d-hydroxyethyl) amino-6-nitro benzene, 1-hydroxy-3-nitro-4-N- (d-hydroxyethyl) -amino benzene, 1 , 4-diamino-2-nitrobenzene, 1-amino-2-nitro-4-methylamino benzene, N- (d-hydroxyethyl) -2-nitro-paraphenylenediamine, 1-amino-2-nitro-
4- (d-hydroxy ethyl) amino-5-chloro benzene, 2-nitro-4-amino-diphenylamine, 1-amino-3-nitro-6-hydroxybenzene, 1- (d-amino ethyl) amino-2-nitro -4- (d-hydroxy ethyloxy) benzene, 1- (β, y-dihydroxypropyl) oxy-3-nitro-4- (e-hydroxyethyl) amino benzene, 1-hydroxy-3-nitro-4-aminobenzene, 1 - hydroxy-2-amino-4,6-dinitrobenzene, 1-methoxy-3-nitro-4- (d-hydroxyethyl) amino benzene, 2-nitro-4'-hydroxydiphenylamine, 1-amino-2-nitro-4-hydroxy -5-methylbenzene, alone or in mixtures.
As regards nitrated benzene direct dyes, yellow and yellow-green dyes of this type can be used, such as 1-d-hydroxyethyloxy-3-methylamino-4-nitrobenzene, 1-methylamino-2-nitro-
5- (e, y-dihydroxypropyl) oxybenzene, 1- (d-hydroxyethyl) amino-2-methoxy-4-nitrobenzene, 1- (d-amino ethyl) amino-2-nitro5-methoxy-benzene, 1,3 -di (e-hydroxyethyl) amino-4-nitro-6-chloro benzene, 1-amino-2-nitro-6-methyl-benzene, 1- (d-hydroxyethyl) amino-2-hydroxy-4-nitrobenzene, N - (e-hydroxyethyl) -2-nitro-4-trifluoromethylaniline, 4- (d-hydroxy ethyl) amino-3-nitro-benzenesulfonic acid, 4-ethylamino-3-nitro-benzoic acid, 4- (d-hydroxyethyl) amino-3-nitro-chlorobenzene, 4- (β-hydroxyethyl) amino-3-nitromethyl benzene, 4- (e, y-dihydroxypropyl) amino-3-nitro-trifluoromethylbenzene, 1- (d-ureido ethyl) amino-4-nitrobenzene, 1,3-diamino-4-nitrobenzene, 1-hydroxy-2-amino-5 -nitrobenzene, 1-amino-2- [tris (hydroxymethyl) methyl] amino-5-nitro-benzene, 1- (d-hydroxyethyl) amino-2-nitrobenzene and 4- (d-hydroxyethyl) amino-3-nitrobenzamide.
It may also be envisaged to use blue or violet nitrated benzene dyes such as, among others, 1- (d-hydroxyethyl) amino-4-N, N-bis- (e-hydroxyethyl) amino 2-nitrobenzene, 1- (y-hydroxypropyl) amino 4-N, N-bis- (d-hydroxyethyl) amino 2-nitrobenzene, 1- (d-hydroxyethyl) amino 4- (N-methyl, Nd-hydroxyethyl) amino 2-nitrobenzene, 1- (d-hydroxyethyl) amino 4- (N-ethyl, Nd-hydroxyethyl) amino 2-nitrobenzene, 1- (d, Y-dihydroxypropyl) amino 4- (N-ethyl, Nd-hydroxyethyl) amino 2-nitrobenzene, 2-nitroparaphenylenediamines of the following formula:
nhr<sub>5</sub> nr<sub>6</sub>r<sub>7</sub> in which:
R<sub>6</sub> represents an alkyl radical of C<sub>1</sub>-C<sub>4</sub>, a p'-hydroxelyl or β-hydroxypropyl or γ-hydroxypropyl radical;
R<sub>5</sub> and R<sub>7</sub>, the same or different, represent a radical β-hydroxyethyl, β-hydroxypropyl, γ-hydroxypropyl, or / t, vdihydroxypropyl, representing at least one of the radicals R<sub>6</sub>, R<sub>7</sub> or R<sub>5</sub> a γ-hydroxypropyl radical and R cannot<sub>6</sub> and R<sub>7</sub> simultaneously designate a β-hydroxyethyl radical when R<sub>6</sub> it is a γ-hydroxypropyl radical, such as those described in French patent FR 2 692 572.
It is recalled that azo dyes are compounds that comprise, in their structure, at least one N = N- bond not included in a ring; methine dyes are compounds that comprise, in their structure, at least one -C = C- bond not included in a ring; azometin dyes are compounds that comprise, in their structure, at least one -C = N- bond not included in a ring.
ES 2 345 503 T3
The dyes derived from triarylmethane comprise, in their structure, at least one following bond:
<img file="ES2345503T3_D0015.tif" />
<img file="ES2345503T3_D0016.tif" />
Designating A an oxygen or nitrogen atom
Xanthenic dyes comprise in their structure at least one bond of the formula:
<img file="ES2345503T3_D0017.tif" />
Phenanthridine dyes comprise in their structure at least one bond of the formula
<img file="ES2345503T3_D0018.tif" />
Phthalocyanine dyes comprise in their structure at least one bond of the formula:
<img file="ES2345503T3_D0019.tif" />
Phenothiazine dyes comprise in their structure at least one following bond:
<img file="ES2345503T3_D0020.tif" />
ES 2 345 503 T3
Direct dyes can also be selected from basic dyes such as those listed in the Color Index, 3<sup>to</sup> edition, particularly with the names "Basic Brown 16", "Basic Brown 17", "Basic Yellow 57", "Basic Red 76", "Basic Violet 10", "Basic Blue 26" and "Basic Blue 99"; or among the acid direct dyes, listed in the Color Index, 3rd edition, with the names "Acid Orange 7", "Acid Orange 24", "Acid Yellow 36", "Acid Red 33", "Acid Red 184", " Acid Black 2 "," Acid Violet 43 ", and" Acid Blue 62 ", or also cationic direct dyes such as those described in patent applications WO 95/01772, WO 95/15144 and EP 714954 and in particular" Basic Red 51 "," Basic Orange 31 ", "Basic Yellow 87" whose content is an integral part of the present invention.
When present, the direct dye (s) preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight.
The oxidation bases can be selected from the oxidation bases conventionally used in oxidation dyeing and among which may be particularly mentioned paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Among the paraphenylenediamines, paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- (e-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (e-hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- (e-hydroxyethyl) amino 2-chloro aniline, 2-j6-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (e-hydroxypropyl) paraphenylenediamine,
2- hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylenediamine, N, N- (ethyl, j6-hydroxyethyl) paraphenylenediamine, N- (e, Y-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N -phenyl paraphenylenediamine, 2j6-hydroxyethyloxy paraphenylenediamine, 2-e-acetylaminoethyloxy paraphenylenediamine, N- (e-methoxyethyl) paraphenylenediamine, and their addition salts with an acid.
Among the paraphenylenediamines mentioned above, more particularly preferred are paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2- / 7-hydroxyethyl paraphenylenediamine, 2-e-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2 3-dimethyl paraphenylenediamine, N, N-bis (e-hydroxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, 2-e-acetylaminoethyloxy paraphenylenediamine, and their acid addition salts.
Among the bis-phenylalkylenediamines, N, N'-bis- (e-hydroxyethyl) N, N '-bis- (4'-aminophenyl) 1,3-diamino propanol, N, N' - may be mentioned more particularly as an example bis- (e-hydroxyethyl) N, N '-bis- (4'-aminophenyl) ethylenediamine, N, N' -bis- (4-aminophenyl) tetramethylenediamine, N, N '-bis- (e-hydroxyethyl) N, N '-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl-aminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N'-bis- (4'-amino , 3'-methylphenyl) ethylenediamine, 1,8-bis- (2,5-diamino phenoxy) -3,5-dioxaoctane, and its addition salts with an acid.
Among the para-aminophenols, para-aminophenol, 4-amino
3- methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2- aminomethyl phenol, 4-amino 2- (6-hydroxyethyl aminomethyl) phenol, 4-amino 2-fluoro phenol, and their addition salts with an acid.
Among the ortho-aminophenols, 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their acid addition salts may be mentioned more particularly as an example.
Among the heterocyclic bases, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives may more particularly be mentioned, as an example.
Among the pyridine derivatives, mention may be made more particularly of the compounds described for example in GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2, 3-diamino 6-methoxy pyridine, 2- (6-methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.
Among the pyrimidine derivatives, mention may be made, more particularly, of the compounds described, for example, in DE 2 359 399; JP 88-169 571; JP 05 163 124; EP 0 770 375 or patent application WO 96/15765 as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4 -dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazole-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which pyrazol- [1,5 -a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazol- [1,5-a] -pyrimidine-3,7-diamine; pyrazol- [1,5-a] -pyrimidine-3,5-diamine; 2,7-dimethyl pyrazol- [1,5-a] -pyrimidine-3,5-diamine; 3-amino pyrazol- [1,5-a] -pyrimidin-7-ol; 3-amino pyrazol- [1,5-a] -pyrimidin-5ol; 2- (3-amino pyrazol- [1,5-a] -pyrimidin-7-ylamino) -ethanol, 2- (7-amino pyrazol- [1,5-a] -pyrimidin-3-ylamino) -ethanol, 2 [(3-amino-pyrazolo [1,5-a] -pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol, 2 - [(7-amino-pyrazole [1,5- a] -pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol, 5,6-dimethyl pyrazol- [1,5-a] -pyrimidine-3,7-diamine, 2,6-dimethyl pyrazole - [1,5-a] -pyrimidine3,7-diamine, 2,5, n7, N7-tetramethyl pyrazol- [1,5-a] -pyrimidine-3,7-diamine, 3-amino-5-methyl- 7-imidazolylpropylamino
ES 2 345 503 T3 pyrazol- [1,5-a] -pyrimidine and its addition salts with an acid and its tautomeric forms, when a tautomeric equilibrium exists.
Among the pyrazole derivatives, mention may be made, more particularly, of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as 4,5-diamino 1-methyl pyrazole, 4,5-diamino 1- (e-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4'-chlorobenzyl) pyrazole, 4, 5-diamino 1,3-dimethyl pyrazole, 4,5-diamino 3-methyl 1-phenyl pyrazole, 4,5-diamino 1-methyl 3-phenyl pyrazole, 4-amino 1,3-dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1-methyl pyrazole, 4,5-diamino 1-tert. butyl 3-methyl pyrazole, 4,5-diamino 1- (0-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino 1-ethyl 3-methyl pyrazole, 4,5-diamino 1-ethyl 3- (4'-methoxyphenyl) pyrazole, 4,5-diamino 1-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-isopropyl pyrazole, 4,5-diamino 3-methyl 1-isopropyl pyrazole,
4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1-methyl 4- methylamino pyrazole, 3,5-diamino 4- (e-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with an acid.
When used, these oxidation bases preferably represent 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably 0.005 to 6% by weight approximately of this weight.
The oxidation dye compositions according to the invention may also contain at least one coupler and / or at least one direct dye, particularly to modify the hues or enrich them in reflections.
The couplers usable in the oxidation dye compositions according to the invention can be selected from the couplers conventionally used in oxidation dye and among which the metaphenylenediamines, meta-aminophenols, metdiphenols, naphthols and heterocyclic couplers such as , for example, indole derivatives, indolin derivatives, pyridine derivatives, indazole derivatives, pyrazole [1,5-b] -1,2,4-triazole derivatives, pyrazole [3,2-c] -1,2,4-triazole derivatives, benzimidazole derivatives, benzothiazole derivatives, benzoxazole derivatives, 1,3-benzodioxole derivatives and pyrazolones, and their addition salts with an acid.
These couplers are more particularly selected from 2-methyl 5-amino phenol, 5-N- (e-hydroxyethyl) amino 2-methyl phenol, 3-amino phenol, 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4-diamino 1- (0-hydroxyethyloxy) benzene, 2-amino 4- (e-hydroxyethylamino) 1-methoxy benzene, 1,3-diamino benzene, 1,3bis- (2 , 4-diaminophenoxy) propane, sesamol, α-naphthol, 2-methyl-1-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 6-hydroxy indoline, 6-hydroxybenzomorpholine, 3,5 diamino 2,6-dimethoxy pyridine, 1-N- (ehydroxyethyl) amino 3,4 methylenedioxy benzene, 2,6 bis (0hydroxyethylamino) toluene, 2,6-dihydroxy 4-methyl pyridine, 1- H 3-methyl pyrazol-5one, 1-phenyl 3-methyl pyrazol-5-one, and their addition salts with an acid.
When present, the coupler (s) preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dyeing composition and even more preferably from 0.005 to 5% by weight approximately of this weight.
The dyeing composition according to the invention may also contain various adjuvants conventionally used in compositions for hair dyeing, such as anionic, cationic, non-ionic, amphoteric, zwitterionic surfactants or their mixtures, anionic, cationic, non-ionic polymers, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, antioxidant agents, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example silicones, film-forming agents, preserving agents and opacifying agents. Of course, the person skilled in the art will be in charge of selecting this or these possible complementary compounds in such a way that the advantageous properties intrinsically linked to the oxidation dye composition according to the invention are not altered, or are not substantially altered by the or planned additions.
The dyeing composition according to the invention can be presented in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and particularly human hair.
The nature of the oxidizing agent used in direct bleaching coloring (direct coloring with an oxidizing agent) or oxidation coloring is not critical.
The oxidizing agent is preferably selected from the group consisting of hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, persalts such as perborates and persulfates. One or more oxidoreduction enzymes such as laccases, peroxidases and 2-electron oxidoreductases (such as uricase) can also be used as oxidizing agent, if necessary in the presence of their respective donor or cofactor.
According to a particular embodiment of the invention, the process of the invention can be used on hair sensitized by hair treatments other than those of the invention, mentioned above.
ES 2 345 503 T3
The invention will now be more fully illustrated with the aid of the following examples which should not be construed as limiting it to the described embodiments. In all the following or the foregoing, the percentages expressed are by weight. In the examples, MA stands for active matter.
Examples
Example 1
Coloring stage
At the time of use, composition 1 defined below is mixed with hydrogen peroxide (l'Oréal professional hydrogen peroxide 20 volumes at 6%) weight by weight.
The mixture is then applied to locks of hair with 90% gray hair that have been permed at a rate of 10 g of coloring mixture / g of lock. The resting time is 15 minutes on each side of the lock. The coloring is then interrupted by rinsing with water.
<td>Composition 1 colorant</td><td>Amounts in grams</td>
<td>Polyglycerolated oleic alcohol with 2 moles of glycerol</td><td> 4</td>
<td>Polyglycerolated oleic alcohol with 4 moles of glycerol (78% MA)</td><td> 5,69</td>
<td>Oleic acid</td><td> 3</td>
<td>Oleic amine 2 OE marketed under the name ETHOMEEN 012 by the company AKZO</td><td> 7</td>
<td>Diethylaminopropyl laurylamino succinamate, 55% MA sodium salt</td><td> 3</td>
<td>Oleic alcohol</td><td> 5</td>
<td>Oleic acid diethanolamide</td><td> 12</td>
<td>Propylene glycol</td><td> 3,5</td>
<td>Ethyl alcohol</td><td> 7</td>
<td>Dipropylene glycol</td><td> 0,5</td>
<td>Propylene Glycol Monomethyl Ether</td><td> 9</td>
<td>p-phenylenediamine</td><td>6 x 10 '<sup>4</sup> moles</td>
<td>2,4-diaminophenoxyethanol HCl</td><td>6 x 10 '<sup>4</sup> moles</td>
<td>Sodium metabisulfite in 35% aqueous solution of MA</td><td> 0,455</td>
<td>Ammonium acetate</td><td> 0,8</td>
<td>Antioxidant, sequestrant</td><td>cs</td>
<td>Perfume, preservative</td><td>cs</td>
<td>Ammonia 20% NH<sub>3</sub></td><td> 10</td>
<td>Demineralized water</td><td>csp 100</td>
ES 2 345 503 T3
Stages of protective treatment
A protective treatment is carried out on the dyed strands by applying composition 2 indicated below at a rate of 2 g / g of hair. A liquid water / steam mixture is then applied for 10 minutes, maintained at 45 ° C with the MICROMIST apparatus marketed by the TAKARA BELMONT company.
<td>Composition 2</td><td>Amounts in grams</td>
<td>Benzyl alcohol</td><td>4.0 g</td>
<td>Benzoic acid</td><td>0.2 g</td>
<td>Benzophenone-4</td><td>5.0 g</td>
<td>Citric acid / trisodium citrate / triethanolamine buffer</td><td>csp pH = 4</td>
<td>Hydroxyethylcellulose</td><td>1.2 g</td>
<td>Xanthan gum</td><td>0.4 g</td>
<td>Preservatives</td><td>csp</td>
<td>Water</td><td>qs 100 g</td>
The locks are then washed with the chamomile DOP shampoo and dried.
A jury of 10 people evaluates the effects of treatment on colored hair with respect to colored hair that has not undergone the treatment:
1) color toughness after shampooing,
2) color toughness after exposure to UV / visible light,
3) Color toughness after shampooing and light exposure.
Stages of color tenacity after shampooing
A part of the treated locks are subjected to a test 6 successive washes with chamomile DOP shampoo, compared to the untreated dyed locks.
Stages of color toughness after exposure to UV / visible light
Another part of the treated locks is exposed to UV / Visible light compared to untreated dyed locks.
To do this, the strands are exposed to UV light in half their length for a period of 18 h with a Xenon lamp solar simulator that reproduces a reproducible light spectrum close to that of the sun (Suntest XLS marketed by the company Atlas ). The other half of the strand is covered with cardboard.
Stages of color toughness after shampooing followed by exposure to UV / visible light
Another part of the treated locks is subjected to a test 6 successive washes with chamomile DOP shampoo and then exposure to UV / Visible light under the conditions described above in comparison with the untreated dyed locks.
Results
The 10 people of the jury unanimously showed that the dyed locks that have undergone the protective treatment of the invention present with respect to the untreated dyed locks
1) better resistance of the original color against shampooing
2) better lightfastness of the original color
3) Better color toughness after shampooing and light exposure.
Contents27
20 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20
14 members in 9 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 0552956 | France | A | |
| 0552956 | France | A | |
| 061204430552956 | – | – | – |
| FR20050052956 | – | – | – |
Members14
| Document | Office | Kind | |
|---|---|---|---|
| FR2891140A1 | France | A1 | |
| KR20070036724A | Republic of Korea | A | |
| EP1769788A1 | European Patent Office (EPO) | A1 | |
| US2007074356A1 | United States of America | A1 | |
| JP2007091744A | Japan | A | |
| BRPI0604400A | Brazil | A | |
| US2007238146A1 | United States of America | A1 | |
| FR2891140B1 | France | B1 | |
| EP1769788B1 | European Patent Office (EPO) | B1 | |
| AT470426T | Austria | T | |
| ATE470426T1 | Austria | T1 | |
| DE602006014777D1 | Germany | D1 | |
| ES2345503T3This record | Spain | T3 | |
| US7998464B2 | United States of America | B2 |
Numbers
- Publication, DOCDB
- 2345503
- Publication, EPODOC
- ES2345503T
- Application
- 6120443
- Application, DOCDB
- 06120443
- Application, EPODOC
- ES20060120443T
Titles2
- Spanish
- PROCEDIMIENTO DE TRATAMIENTO FOTOPROTECTOR DE LAS FIBRAS DE QUERATINA TEÑIDAS ARTIFICIALMENTE MEDIANTE APLICACION DE UNA MEZCLA DE AGUA LIQUIDA/VAPOR DE AGUA.
- English
- PHOTOPROTECTOR TREATMENT PROCEDURE OF ARTIFICIALLY DYED QUERATINE FIBERS THROUGH APPLICATION OF A LIQUID WATER / VAPOR WATER MIXTURE.
Classification
- CPC, 9
- A61K8/02
- A61K8/36
- A61K8/35
- A61K8/37
- A61Q5/00
- A61Q5/004
- A61Q17/04
- A61Q5/12
- A61K8/49
- IPC, 5
- A61K8 35
- A61K8 34
- A61K8 368
- A61Q5 00
- A61Q17 04