HAIR COLORING PROCESS COMPRISING A COLORING STEP WITH HENNE AND / OR INDIGO AND A PROCESSING STEP CO

专利摘要:
The present invention relates to a method for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, wherein said fibers are treated in several distinct stages, comprising: i) at least one staining step i) said fibers setting a coloring cosmetic composition Ci), preferably aqueous, comprising at least a) indigo and / or henna, ii) at least one treatment step ii) said fibers comprising the application to the fibers of a composition aqueous composition (A) which comprises b) at least one direct dye, preferably distinct from henna and indigo, c) at least one thickener, d) preferably at least one organic solvent, and water and a composition B) which comprises at least e) a fatty substance, preferably an oil, the compositions (A) and (B) being applied either separately one after the other, or together in a single composition Cii) , iii) even at least one intermediate rinsing step of said fibers, preferably with water, between step i) and step ii) (or between step ii) and i) (depending on the order of steps i) and ii)).
公开号:FR3075637A1
申请号:FR1763115
申请日:2017-12-22
公开日:2019-06-28
发明作者:Marie GIAFFERI；Julia Puech；Mickael Agach；Hidetoshi Yamada；Boris Lalleman；Leila Hercouet
申请人:LOreal SA；
IPC主号:

专利说明:

Hair coloring process comprising a coloring step with henna and / or indigo and a treatment step comprising the application of an aqueous phase, a fatty phase and a direct dye
The present invention relates to a multi-step process for coloring keratin fibers, in particular human keratin fibers such as the hair, in which said fibers are treated with a composition comprising indigo and / or henna and a step comprising 'application of an aqueous phase, a fatty phase and a direct dye, synthetic or natural.
Two main modes of coloring human keratin fibers, and in particular the hair, are known.
The first, called oxidation or permanent coloring, consists in using one or more oxidation dye precursors, more particularly one or more oxidation bases possibly associated with one or more couplers.
Usually, oxidation bases are chosen from ortho- or paraphenylenediamines, ortho- or para-aminophenols as well as heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, allow access, through an oxidative condensation process, to colored species which remain trapped inside the fiber. Very often, the nuances obtained with these oxidation bases are varied by associating them with one or more couplers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds.
The variety of molecules involved in the oxidation bases and couplers allows obtaining a rich palette of colors.
The second mode of coloring, called direct or semi-permanent coloring, involves the application of direct dyes which are colored and coloring molecules, having an affinity for fibers. Given the nature of the molecules used, they rather remain on the surface of the fiber and penetrate relatively little inside the fiber, compared to the small molecules of oxidation dye precursors. The main advantages of this type of coloring is that it does not require an oxidizing agent which limits the degradation of the fibers and that it does not use dyes with a certain reactivity, hence limiting the risks of intolerance.
The first hair dyes were semi-permanent. One of the most well-known natural dyes is that derived from the henna plant. Henna continues to be used to beautify women by coloring hair, nails, or to color leather, silk and wool, etc. It is also traditionally used for important events, celebrations and various beliefs.
Red henna consists of leaves of shrubs of the genus Lawsonia of the Lythraceae family which is based on the principle of coloring by the active ingredient Lawsone: 2-hydroxy-1,4-naphthoquinone. Lawone [83-72-7] (Cl Natural Orange 6; Cl 75420) also known as isojuglone, can be found in Henna shrubs (Lawsonia alba, Lawsonia inermis) ("Dyes, Natural", Kirk- Othmer Encyclopedia of Chemical Technology, "Henna" Encyclopedia Brittan ica).
This dye provides an orange-red coloration with white hair, and a "warm" color, that is to say coppery to red with brown hair. The process of coloring from henna is complicated to implement. It is first made a kind of "paste", often called "poultice", from ground or henna leaf powder which is then diluted at the time of use with hot water and said paste is then applied to the keratin fibers.
Another very well-known natural dye is indigo (see Ullmann's Encyclopedia of Industrial Chemistry, “hair preparation”, point 5.2.3, 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; 10.1002 / 14356007.a12 571.pub2 ). Indigo continues to be used to beautify women by coloring hair, nails, or to color fabrics (jeans) leather, silk and wool, etc. Indigo [482-89-3] is a natural dye, originating in particular from the indigo tree of raw formula is: C16H10N2O2; its structure:
Indigo comes from the Indian can be prepared from different plants called indigoferes such as Indigofera tinctoria, Indigo suffraticosa, Isatis tinctoria etc (see Kirk-Othmer Encyclopedia of Chemical Technology, updated on 04/17 / 2009, DOI: 10.1002 / 0471238961.0425051903150618.a01.pub2). Indigo plants are usually cut and soaked in hot water, heated, fermented and air oxidized to release indigo purple blue in color (see Chem. Rev. 2011, 111, 2537-2561, p. 2537-2561). Indigo is the result of fermentation and then oxidation of the Indian (glycosylated precursor). Indigo as a molecule is insoluble in water.
The problem is that coloring from indigo leaf is difficult because the rise in color in the keratin fibers is very small. This dye provides a blue color to white hair, and an “ashy” to purple color to the hair
brown. The coloring process from indigo leaves is complicated to implement. It is first made a kind of "paste" (often called poultice) from ground or powdered leaves of indigo (or indigo india or indigo dyers) or pastel dyers (or guède or Isatis tinctoria ) it must have been fermented, which is then diluted at the time of use with hot water and said paste is then applied to the keratin fibers
When we color the hair with these types of dyes, as much the color obtained on brown hair has a natural effect, as much the white hair is colored in an orange color with henna or blue with indigo, unsightly and unnatural . In addition, the colors obtained are not homogeneous between the root and the tip or from one fiber to another.
In particular, coloring from indigo leaf is difficult because the coloring kinetics in keratin fibers are variable and moreover the coloring process is unstable. Indigo theoretically provides a blue coloration with white hair, and a "cold" ash-like color. However, the coloring process from indigo is difficult to control due to the competitive reaction of indirubin formation (also involving an oxidation step with the formation of isatin of intermediate yellow color) bringing yellow reflections to violins complementary to brown hair over time.
The colors resulting from the mixtures of indigo and henna are therefore generally evolutionary over time in terms of color, they exhibit a characteristic yellow / green coloration on the day of application (“raw” color which is not very aesthetic, little appreciated by consumers of coloration) which evolve towards the desired colourations after a few hours (48H to 1 week) and can change color over time (appearance of purplish red reflections after generally 2 to 3 weeks). There is therefore a need to stabilize this coloring in order to obtain aesthetic coloring on the day of the application (example brown free of yellow / green reflections) which changes little over time (without color change).
To remedy this problem of color evolution and widen the range of shades obtained with these dyes, direct dyes, synthetic or natural, can be added, in particular to mask unwanted reflections. One can in particular use anionic synthetic direct dyes (also called acid direct dyes) which make it possible to obtain excellent performance in terms of color fastening on the fiber, but often have the disadvantage of also pigmenting the scalp. Natural dyes can also be staining on the skin and the concentrations generally used to obtain a sufficient level of coloring of the hair amplifies the risk of staining of the scalp. 4
Therefore, there is a need to develop a new direct dyeing process which does not have the above drawbacks.
In particular, there is a need to develop natural coloring processes based on henna and / or indigo which make it possible to obtain powerful, aesthetic and natural colorings at the end of the application and which in particular make it possible to obtain fast coloring, the coloring obtained of which does not present any reflections, in particular yellow / green, judged unsightly, by the user, having a good rise in color, less aggressive for the hair and at the same time which resist external agents (light, bad weather, shampoos), which are tenacious and / or homogeneous while remaining powerful and / or chromatic, which is stable and does not veer over time in particular towards red reflections.
In addition, the coloring process must not stain the scalp, or reduce staining of the scalp as much as possible.
This (s) object (s) is (are) achieved by the present invention which relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, in which said fibers are treated in several distinct stages comprising: i) at least one stage of coloring i) of said fibers using a coloring cosmetic composition Ci), preferably aqueous, comprising at least a) indigo and / or henna, ii) at least a step of treatment ii) of said fibers comprising the application to the fibers of an aqueous composition (A) which comprises b) at least one direct dye, chosen from synthetic direct dyes and natural dyes, preferably distinct from henna and indigo, c) at least one thickener, d) preferably at least one organic solvent, and water and a composition B) which comprises at least e) a fatty substance, preferably an oil, the compositions (A ) and (B) being applied either separately one after the other, or together in a single composition Cii), iii) optionally at least one intermediate rinsing step of said fibers, preferably with water, between step i) and step ii) (or between step ii) and i) (depending on the order of steps i) and ii)).
Preferably, the treatment step with composition Ci) is the first step in the coloring process according to the invention.
Preferably, the method implements in order: step i) of treating said fibers with a coloring composition Ci) then the coloring step ii) with the composition Cii).
The compositions Ci / and Cii) are separate compositions.
Preferably, the method according to the invention comprises a step iii) of intermediate rinsing between step i) and step ii).
Preferably, the method according to the invention comprises a final rinsing step after the implementation of all the steps of the method.
Preferably, the treatment step ii) comprises the application of the compositions (A) and (B) together in a single composition Cii).
The method according to the invention has the advantage of dyeing keratin fibers, in particular human fibers, with results of powerful, chromatic dyes, resistant to washing, perspiration, sebum and light without alteration of the fibers. In addition, the colorings obtained from the process according to the invention are not very selective, that is to say that they have a uniform color between the root and the tip of the fibers. In addition, the coloring process used makes it possible to induce "a rise" and / or very satisfactory coloring power.
Furthermore, the time devoted to coloring, in particular from natural product, according to the process of the invention is faster and easier. Indeed, the implementation of the treatment step with the composition Ci) makes it possible to reduce the pause time of the coloring composition or compositions while obtaining improved colonelle properties.
The process for dyeing keratin fibers according to the invention has the advantage of dyeing said fibers, in particular human keratin fibers, in particular the hair, with natural dye results without yellow / green reflections, and / or powerful dyes, chromatic, resistant to washing, perspiration, sebum and to light and more durable without alteration. In addition, the colors obtained from the process are homogeneous from the root to the tip of a fiber (low color selectivity).
The compositions used according to the invention are cosmetic compositions i.e. they are cosmetically acceptable therefore suitable for use for application to keratin fibers, in particular for application to human keratin fibers, such as the hair.
Preferably, the composition Ci) is obtained by mixing just before use the indigo and / or the henna with an aqueous composition to obtain a coloring composition Ci) ready for use, preferably in the form of a poultice.
Preferably, the composition Ci) is an aqueous composition. ο Other objects, characteristics, aspects and advantages of the present invention will appear even more clearly on reading the description and the examples which follow. STEP i) Step i) of coloring uses a coloring cosmetic composition Ci) comprising at least indigo and / or henna. a) Henna and / or indigo
According to the present invention, by "henna" is meant a powder of henna plant and / or a coloring extract of henna plant, preferably of henna plant such as Lawsonia alba or Lawsonia inermis. The powder and / or coloring extract of henna plant comprises in particular lawsone and / or one of its glucosylated precursors.
Preferably, the henna used according to the present invention is in powder form.
According to the present invention, by “indigo” is meant an indigofere plant powder and / or a coloring extract of indigofere plant, preferably Indigofera Tinctoria or Isatis Tinctoria. The indigofere powder and / or coloring extract of plant includes in particular indigo and / or indirubin and / or one of their glucosylated precursors, such as indican and / or isatan.
Preferably, the indigo used according to the present invention is in powder form
It is understood that "henna powder" and "indigofere plant powder" is different from an extract. Indeed, an extract is a maceration product in generally organic solvents, while the powder according to the invention is a natural product originating from henna plants or indigoferes, reduced by grinding or other mechanical means, into fine particles.
Preferably the henna used in the invention is red henna (Lawsonia inermis, alba). Lawone [83-72-7] (Cl Natural Orange 6; Cl 75420) also known as isojuglone, can be found in Henna shrubs (Lawsonia alba, Lawsonia inermis). Preferably the henna is in powder form. The henna powder can be sieved to obtain particles of upper limit sizes corresponding to the orifices or mesh sizes of the sieve particularly between 35 and 80 mesh (US). According to a particular embodiment of the invention, the particle size of the henna powder is fine. According to the invention, more particularly means a particle size less than or equal to 500 μητ. Preferably, the powder consists of fine particles of size inclusive between 10 and 300 μίτι and more particularly between 50 and 250 μητ It is understood that said particles henna preferably have a moisture content between 0 to 10% by weight, relative to the total weight of the powders.
Preferably, said henna particles come from henna leaves. /
As indigofere plant we can cite many species from the genera: - Indigofera such as Indigofera tinctoria, Indigo suffraticosa, Indigofera articulata Indigofera arrecta, Indigofera gerardiana, Indigofera argenta, Indigofera indica, Indigofera longiracemosa; - Isatis such as Isatis tinctoria; - Polygonum or Persicaria such as Polygonum tinctorium (Persicaria tinctoria); - Wrightia such as Wrightia tinctoria; - Calanthe such as Calanthe veratrifolia; and - Baphicacanthus such as Baphicacanthus cusia.
Preferably the indigofere plant is of the genus Indigofera and more particularly is Indigofera tinctoria.
One can use all or part (in particular the leaves in particular for Indigofera tinctoria) of the indigofere plant.
The indigofere plant powder can be sieved to obtain particles of upper limit sizes corresponding to the orifices or mesh sizes of the sieve, particularly between 35 and 80 mesh (US).
According to a particular embodiment of the invention, the particle size of the indigofere plant powder. is fine. According to the invention, more particularly means a particle size of less than or equal to 500 μητ. Preferably, the powder consists of fine particles of size inclusive between 10 and 300 μΐη and more particularly between 50 and 250 μΐη
It is understood that said particles of indigofere plant (s) preferably have a moisture content of between 0 to 10% by weight, relative to the total weight of the powders.
In one embodiment, indigo is in the form of indigofere plant powder.
In another embodiment, indigo is in the form of a coloring extract of indigofere plant.
Composition Ci) used in the process for dyeing keratin fibers preferably comprises at least 0.1% by weight of henna and / or indigo, relative to the total weight of said composition, more preferably from 0.2 to 50 % by weight, better still from 0.3 to 40% by weight, preferably from 1 to 30% by weight relative to the total weight of the composition Ci).
Preferably, the coloring composition Ci) is an aqueous composition and comprises at least water. Preferably, according to this embodiment, the composition Ci) comprises a water content ranging from 10% to 99% by weight, more particularly from 20% to 90% by weight, better still from 40% to 80% by weight relative to the weight of the composition Ci). δ
According to a particular embodiment of the invention, the composition Ci) is obtained by mixing just before use (that is to say extemporaneously) indigo and / or henna with water or with an aqueous composition to obtain a coloring composition Ci) ready for use, preferably in the form of a poultice.
Additional dyes
According to one embodiment, the composition Ci) used in the coloring process of the invention may also contain one or more additional direct dyes, in particular synthetic or of natural origin, different from indigo and henna, these dyes can be chosen from dyes b) mentioned below.
When it (s) is (are) present, the direct, natural or synthetic dye (s) different from indigo and henna used in the process of the invention, represents in particular, from 0.001% to 10% by weight of the total weight of the composition Ci) and even more preferably from 0.05% to 5% by weight, relative to the total weight of the composition.
Preferably, the compositions of the invention do not contain synthetic direct dyes, i.e. which have no natural occurrence.
According to one embodiment, the composition Ci) does not include any additional dye other than henna and / or indigo. STEP ii) The treatment step ii) comprises the application to the fibers of an aqueous composition (A) which comprises b) a direct dye, synthetic or natural, c) a thickener, preferably d) an organic solvent and water and a composition B) which comprises at least one e) fatty substance, preferably an oil, the compositions (A) and (B) being separate compositions which are applied either separately one after the other, either together in a single composition Cii) b) Direct dyes,
The aqueous composition (A) comprises b) one or more direct dyes chosen from synthetic direct dyes, natural dyes and their mixtures.
The direct dye b) is preferably different from henna and indigo as described above. there
Preferably the dye b) is a synthetic direct dye.
Natural dyes
By “natural dyes” is meant dyes derived from natural materials (vegetable, mineral or animal origin) such as, for example, extracts, shreds, decoctions, and more or less concentrated in dyes.
Among the natural dyes according to the invention, we include the compounds which may be present in nature and which are reproduced by (hemi) chemical synthesis.
The natural dyes can in particular be chosen from spinulosin, orceins, polyphenols or orthodiphenols (also called ODPs in the following description) and all extracts rich in ODPs, curcumin, indole derivatives such as l 'isatin or indole-2,3-dione, indigoids, phthalocyanines and porphyrins in particular complexed with a metal, glycosylated or non-glycosylated iridoids, chromene dyes, anthraquinones and naphthoquinones dyes, juglone, spinulosin, dyes chromenic or chromanic, such as neoflâvanols and néoflavanones, flavanols; and anthocyanidols, orceins, betalains and mixtures thereof.
It is also possible to use the extracts or decoctions containing these natural dyes and in particular the poultices or plant extracts containing the said dyes.
These natural colors can be added as defined compounds, extracts, or parts of plants. Said defined compounds of extracts, or part of plants are preferably in the form of powders, in particular fine powders, the particles of which have sizes identical to that of henna powders and indigofere plant (s) as defined above. .
The ODP (s) can be salified or not. They can also be in the form of aglygone (without bound sugar) or in the form of glycosylated compounds. One can for example use the orthodiphenols such as those described in the application FR 3 029 405. They can be synthetic (s) or natural (s).
More particularly, the ODP (s) which can be used in the process of the invention (is) are in particular: flavanols such as catechin and epichatechin gallate, flavonols such as quercetin, anthocyanidins such as cyanidine, delphinidine, petunidine, anthocyanins or anthocyanins such as myrtillin,
1U orthohydroxybenzoates, for example gallic acid salts, flavones such as luteolin, hydroxystilbenes, for example tetrahydroxy-3,3 ', 4,5'-stilbene, possibly oxylated (for example glucosylated), la 3, 4-dihydroxyphenylalanine and its derivatives, 2,3-dihydroxyphenylalanine and its derivatives, 4,5-dihydroxyphenylalanine and its derivatives, dihydroxycinnamates such as caffeic acid and chlorogenic acid, orthopolyhydroxycoumarines, the orthopolyhydroxyisocoumarines, the orthopolyhydroxycoumarones, orthopolyhydroxyisocoumarones, orthopolyhydroxychalcones, orthopolyhydroxychromones, quinones, hydroxyxanthones, 1,2 dihydroxybenzene and its derivatives, 1,2,4 trihydroxybenzene and its derivatives, 1,2,3 trihydroxybenzene and its derivatives, 2,4 , 5 trihydroxytoluene and its derivatives, proanthocyanidins and in particular proanthocyanidins A1, A2, B1, B2, B3 and C1, chromanic and chromenic compounds proathocyanins, tannic acid, ellagic acid, and mixtures of the foregoing.
Preferably, the ODPs of the invention are chromenic or chromanic and are preferably chosen from hematein, hematoxylin, brasilein, brasilin, santaline A. Mention may be made, for example, hematoxylin (Natural Black 1 according to the INCI name) and braziline (Natural Red 24 according to the INCI name), dyes from the indochroman family, which are commercially available. The latter can exist in an oxidized form and can be obtained by synthesis or by extraction from plants or plants known to be rich in these dyes. ODPs can be used in the form of extracts. The following plant extracts (genus and species) Haematoxylon campechianum, Haematoxylon brasiletto, Ouebracho (schinopsis lorentsii), Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpina Brasiliensis can be used.
According to one embodiment, the natural ODPs are derived from extracts of animals, bacteria, fungi, algae, plants and fruits used in whole or in part. In particular with regard to plants, the extracts come from fruits including citrus fruits, vegetables, trees, shrubs. It is also possible to use mixtures of these extracts, rich in ODPs as defined above.
Preferably, the natural ODP (s) of the invention are derived from plant extracts or parts of plants.
The extracts are obtained by extracting various parts of plants such as for example the root, the wood, the bark, the leaf, the flower, the fruit, the seed, the pod, the peel.
Among the plant extracts, there may be mentioned extracts of tea leaves, of rose.
Among the fruit extracts, mention may be made of apple, grape (in particular grape seed) extracts, or extracts of cocoa beans and / or cocoa pods.
Among vegetable extracts, we can quote potato extracts, onion peels.
Examples of tree wood extracts include pine bark extracts, logwood extracts, pernambuco wood, sappan wood and Brazilian wood, preferably. As extract of logwood one can for example use the one whose name INCI is EXTRACT OF OXID CAMPÈCHE (HAEMATOXYLON CAMPECHIANUM) marketed by SCRD under the reference HEMATINE HCK S 21.
Preferably, the ODP (s) is (are) chosen (s) from catechin, quercetin, hematin, hematoxylin, brasilin, brasilein, gallic acid, tannic acid and the natural extracts container chosen from grape marc, pine bark, green tea, onion, cocoa bean, logwood, red wood and gall nut, and their mixtures.
Mention may also be made of the natural dyes chosen from the compounds of formulas (a) or (b) below, or their mixtures:
Such compounds are for example extracted from molds of the Monascus purpureus species (synonyms: M. albidus, M. anka, M. araneosus, M. major, M. rubiginosus, and M. vini) -
In terms of preferred natural dyes, mention may in particular be made of carmine, carmine ammonium, diosindigo, chlorophyllin, hematein, orceinine, the following extracts: blackcurrant, blueberry, black rice, grape skin, hibiscus, red cabbage, black carrot, elderberry,
12 rhubarb, monascus, purple sweet potato, goji, radish, orcein, gardenia, khaki diospyros, logfish, quebracho and their mixtures.
Synthetic direct dyes
The synthetic direct dye (s) are, for example, chosen from those conventionally used in direct dyeing, and among which mention may be made of all the aromatic and / or non-aromatic dyes in common use such as neutral, benzene, acid or cationic direct dyes, neutral azo direct dyes, acid or cationic, quinone direct dyes and in particular neutral anthraquinone dyes, acid or cationic, azine direct dyes, triarylmethane, indoamines, methines, styriles, porphyrins, metalloporphyrins, phthalocyanines, cyanines methinics, and fluorescent dyes.
According to a preferred embodiment of the invention, the direct dye (s), preferably synthetic, which can be used according to the invention are chosen from anionic dyes, commonly called "acid" direct dyes for their affinity with alkaline substances. The anionic direct dyes according to the invention can be natural or synthetic.
The term “anionic direct dyes” means any direct dye comprising in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes can be chosen from acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and natural acid dyes. As anionic direct dyes (or acids) which can be used according to the invention, mention may in particular be made of dyes of formulas (I), (II), (III), (IV), (V), (VI), ( VII), (VIII), (IX), (X), (XI) and (XII) below: a) the anionic diaryl azo dyes of formula (I) or (II):
IJ
formulas (I) and (II) in which: - R7, Rs, R9, R10, R'7, R's, R'9 and R'10, identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkÿlthio; - hydroxy, mercapto; - nitro, nitroso; - R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X ”- with R ° representing a hydrogen atom, a alkyl or aryl group; X, X and X ”, identical or different, representing an oxygen, sulfur atom or N R with R representing a hydrogen atom or an alkyl group; - (O) 2S (O ') -, M + with M + representing a hydrogen atom or a cationic counterion; - (O) CO'-, M + with M + as defined above; - R ”-S (O) 2-, with R” representing a hydrogen atom, an alkyl group, an aryl group, (di) (alkyl) amino, aryl (alkyl) amino; preferably a phenylamino or phenyl group; - R ’” - S (O) 2-X’- with R ’” representing an optionally substituted alkyl or aryl group, X ’as defined above; - (di) (alkyl) amino; - aryl (alkyl) amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) 2S (O ') -, M + and iv) alkoxy, with M + as defined above; - optionally substituted heteroaryl, preferably a benzothiazolyl group; - cycloalkyl, in particular cyclohexyl; - Ar-N = N- with Ar representing an optionally substituted aryl group, preferably a phenyl optionally substituted by one or more alkyl groups, (O) 2S (O ') -, M + or phenylamino; - or then two contiguous groups R7 with Rs or Rs with Rg or Rg with R10 together form a fused benzo group A ’; and R’7 with R’s or R’s
1 + with R’g or R’g with R’w together form a merged benzo group B ’; with A ’and B’ optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) 2S (O ') -, M +; iv) hydroxy; v) mercapto; vi) (di) (alkyl) amino; vii) R ° -C (X) -X’-; viii) R ° -X’-C (X) -; ix) R ° -X’-C (X) -X ”-; x) Ar-N = N- and xi) aryl (alkyl) amino optionally substituted; with M +, R °, X, X ’, X” and Ar as defined above; - W represents a sigma o bond, an oxygen, sulfur atom or a divalent radical i) -NR- with R as defined above, or ii) methylene -C (Ra) (Rb) - with Ra and Rb identical or different, representing a hydrogen atom or an aryl group, or then Ra and Rb together form with the carbon atom which carries them a cycloaikyle spiro, preferably W represents a sulfur atom or Ra and Rb together form a cyclohexyl ; it being understood that formulas (I) and (II) comprise at least one sulfonate radical (O) 2S (O ') -, M + or a carboxylate radical (O) CO'-, M + on one of the rings A, A', B, B 'or C; preferably sodium sulfonate. Mention may in particular be made, as examples of dyes of formula (I): Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2 and Food yellow 3 or sunset yellow. Examples of dyes of formula (II) that may especially be mentioned: Acid Red 111, Acid Red 134 and Acid yellow 38. b) the azo anionic pyrrazolone dyes of formula (III) and (IV):
1
formulas (III) and (IV) in which: - Ru, R12 and Rn, identical or different, represent a hydrogen or halogen atom, an alkyl group or (O) 2S (O ') -, M + with M + as defined above; - R14 represents a hydrogen atom, an alkyl group or a C (O) O'-, M + group with M + as defined above; - R15 represents a hydrogen atom; - Rw represents an oxo group in which case R’w is absent, or then R15 with Rw together form a double bond; - Rn and Rw, identical or different, represent a hydrogen atom, or a group chosen from: - (O) 2S (O ') -, M + with M + as defined above; - Ar-O-S (O) 2- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl groups; - R19 and R20, together form either a double bond or a benzo group D ’, optionally substituted; - R’w, R’w and R’20, identical or different, represent a hydrogen atom or an alkyl or hydroxy group; - R21 represents a hydrogen atom, an alkyl or alkoxy group; - Ra and Rb, identical or different, are as defined above, preferably Ra represents a hydrogen atom and Rb represents an aryl group; - Y represents either a hydroxy group or an oxo group; _ represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group; it being understood that formulas (III) and (IV) comprise at least one sulfonate radical (O) 2S (O ') -, M + or a carboxylate radical C (O) O'-, M + on one of the rings D or E; preferably sodium sulfonate.
As examples of dyes of formula (III), there may be mentioned in particular: Acid Red 195, Acid Yellow 23, Acid Yellow 27 and Acid Yellow 76. By way of example of dye of formula (IV), one can in particular quote: Acid Yellow 17. c) the anthraquinone dyes of formula (V) and (VI):
formulas (V) and (VI) in which: - R22, R23, R24, R25, R26 and R27, identical or different, represent a hydrogen or halogen atom or a group chosen from: - alkyl; - hydroxy, mercapto; - alkoxy, alkÿlthio; - aryloxy or arylthio optionally substituted; preferably substituted by one or more groups chosen from alkyl and (0) 2S (0 ') -, M + with M + as defined above; - aryl (alkyl) amino optionally substituted by one or more groups chosen from alkyl and (O) 2S (0 ') -, M + with M + as defined above; - (di) (alkyl) amino;
1 / - (di) (hydroxyalkyl) amino; - (0) 2S (0 ') -, M + with M + as defined above; - Z 'represents a hydrogen atom or a group NR28R29 with R28 and R29, identical or different, representing a hydrogen atom or a group chosen from: - alkyl; - polyhydroxyalkyl such as hydroxyethyl; - Aryl optionally substituted by one or more groups more particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O) 2S (O ') -, M + with M + as defined above; iii) R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X ”-with R °, X, X 'and X ”As defined above, preferably R ° represents an alkyl group; - cycloaikyle; especially cyclohexyl; - Z represents a group chosen from hydroxy and NR’2sR’29 with R’28 and R’29, identical or different, representing the same atoms or groups as R28 and R29 as defined above; it being understood that formulas (V) and (VI) comprise at least one sulfonate radical (O) 2S (O ') -, M + or a carboxylate radical C (O) O'-, M +; preferably sodium sulfonate. As examples of dyes of formula (V), there may be mentioned in particular: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3 and EXT violet No. 2. By way of example of dye of formula (VI), there may be mentioned in particular: Acid Black 48. d) nitro dyes of formula (VII) and (VIII):
1δ
Vvm; formulas (VII) and (VIII) in which: - R30, R31 and R32, identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - alkoxy optionally substituted by one or more hydroxy groups, alkÿlthio optionally substituted by one or more hydroxy groups> - hydroxy, mercapto; - nitro, nitroso; - polyhaloalkyl; - R ° -C (X) -X’-, R ° -X’-C (X) -, R ° -X’-C (X) -X ”- with R °; X, X ’and X” as defined above; - (O) 2S (O ') -, M + with M + as defined above; - (O) CO'-, M + with M + as defined above; - (di) (alkyl) amino; - (di) (hydroxyalkyl) amino; - heterocycloalkyl such as piperidino, piperazino or morpholino; more particularly R30, R31 and R32 represent a hydrogen atom; - Rc and Rd, identical or different, represent a hydrogen atom or an alkyl group; - W is as defined above, W more particularly represents an —NH- group; - ALK represents a divalent alkylene group, linear or branched, in C1-C6, more particularly ALK represents a group -CH2-CH2-; - n is 1 or 2; - p represents an integer inclusive between 1 and 5; - q represents an integer inclusive between 1 and 4; - u is 0 or 1; - when n is 1, J represents a nitro group, or nitroso; more particularly nitro;
iy - when n is 2, J represents an oxygen or sulfur atom or a divalent radical -S (O) m- with m representing an integer 1 or 2; more preferably J represents a radical -SO2-; - Represents me a hydrogen atom or a cationic counterion; cx · "'present or absent represents a benzo group optionally substituted by one or more R30 groups as defined above; it being understood that the formulas (VII) and (VIII) comprise at least one sulfonate radical (O) 2S (O') -, M + or a carboxylate radical C (O) O'-, M +; more preferably sodium sulfonate, examples of dyes of formula (VII) that may be mentioned include: Acid Brown 13 and Acid Orange 3. A Examples of dyes of formula (VIII) that may be mentioned include: Acid Yellow 1, the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino 5- acid nitro benzene sulfonic, 2 (4'-N, N (2 "-hydroxyethyl) amino-2'-nitro) aniline ethane sulfonic acid, 4-p-hydroxyethylamino-3-nitrobenzene sulfonic acid and EXT D & C yellow 7. d) triarylmethane dyes of formula (IX):
formula (IX) in which: - R33, R34, R35 and R36, identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; more particularly an alkyl and benzyl group optionally substituted by a group (O) mS (O ') -, M + with M + and m as defined above; - R37, R38, R39, R40, R41, R42, R43 and R44, identical or different, represent a hydrogen atom or a group chosen from:
ζυ - alkyl; - alkoxy, alkylthio; - (di) (alkyl) amino; - hydroxy, mercapto; - nitro, nitroso; - R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X ”- with R ° representing a hydrogen atom, a alkyl or aryl group; X, X ’and X”, identical or different, representing an oxygen or sulfur atom or N R with R representing a hydrogen atom or an alkyl group; - (O) 2S (O ') -, M + with M + representing a hydrogen atom or a cationic counterion; - (O) CO'-, M + with M + as defined above; - or then two contiguous groups R41 with R42 or R42 with R43 or R43 with R44 together form a benzo fused group: I ’; with I 'optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) 2S (O ') -, M +; iv) hydroxy; v) mercapto; vi) (di) (alkyl) amino; vii) R ° -C (X) -X’-; viii) R ° -X’-C (X) -; ix) R ° -X’-C (X) -X ”-; with M +, R °, X, X ', X ”as defined above> more particularly R37 to R4o represent a hydrogen atom, and R4i to R44, identical or different, represent a hydroxy group or (O) 2S (O ') -, M +; and when R43 with R44 together form a benzo group; it is preferably substituted by an (O) 2S (O ') - group; it being understood that at least one of the rings G, H, I or I ’comprises at least one sulfonate radical (O) 2S (O ') - or a carboxylate radical C (O) O'-, more preferably sulfonate. Examples of dyes of formula (IX) that may be mentioned include: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5 and Acid Green 50. e) dyes derived from xanthene of formula (X):
ZI
formula (X) in which: - R45, R46, R47 and R48, identical or different, represent a hydrogen atom or a halogen atom; - R49, R50, R51 and R52, identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - alkoxy, alkÿlthio; - hydroxy, mercapto; - nitro, nitroso; - (O) 2S (O ') -, M + with M + representing a hydrogen atom or a cationic counterion; - (O) CO'-, M + with M + as defined above; preferably R49 R50, R51 and R52 represent a hydrogen or halogen atom; - G represents an oxygen, sulfur atom or an NRe group with Re as defined above; more particularly G represents an oxygen atom; - L represents an alcoholate 0; M +; a thioalcoholate S; M + or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M + as defined above; M + is particularly sodium or potassium; - The represents an oxygen, sulfur atom or an ammonium group: N + RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an optionally substituted alkyl, aryl group; L ′ represents more particularly an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (0) mS (0 ') -, M + with m and M + as defined above; - Q and Q ’, identical or different, represent an oxygen or sulfur atom; more particularly Q and Q ’represent an oxygen atom; - M + is as defined above.
k examples of dyes of formula (X) that may be mentioned include: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95 and Acid Violet 9. f) dyes derived from indole of formula (XI):
formula (XI) in which: - R53, R54, R55, Rse, R57, Rsa, R59 and R6o, identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso; - R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X ”- with R ° representing a hydrogen atom, a alkyl or aryl group; X, X ’and X”, identical or different, representing an oxygen or sulfur atom or N R with R representing a hydrogen atom or an alkyl group; - (O) 2S (O ') -, M + with M + representing a hydrogen atom or a cationic counterion; - (O) CO'-, M + with M + as defined above; - G represents an oxygen, sulfur atom or an NRe group with Re as defined above; more particularly G represents an oxygen atom; - R, and Rh, identical or different, represent a hydrogen atom or an alkyl group; it being understood that formula (XI) comprises at least one sulphonate radical (O) 2S (O ') -, M + or a carboxylate radical C (O) O'-, M +, more preferably sodium sulphonate. As an example of a dye of formula (XI), mention may especially be made of: Acid
Blue 74. g) dyes derived from quinoline of formula (XII):
- Rei represents a hydrogen atom, a halogen atom or an alkyl group> - R62, R63, and R64, identical or different, represent a hydrogen atom or a group (O) 2S (O ') -, M + with M + representing a hydrogen atom or a cationic counterion; - or then R6i with R62, or R6i with R64, together form a benzo group optionally substituted by one or more (O) 2S (O ') groups -, M + with M + representing a hydrogen atom or a cationic counterion; it being understood that formula (XII) comprises at least one sülfonate (O) 2S (O ') - radical, more preferably sodium sülfonate. Examples of dyes of formula (XII) that may be mentioned include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
The anionic direct dye (s) which can be used according to the invention are preferably chosen from those of formulas (I), (II), (III), (IV), (V), (VI), (Vil), (VIII), (IX), (X), (XI) and (XII) as defined above.
More particularly, the dyes of formula (I) to (X) which can be used according to the invention are chosen from:
/ α
Most of these dyes are described in particular in the Color Index published by The Society of Dyers and Colorists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN England.
The anionic direct dye (s) particularly preferred according to the invention are chosen from 1,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid
ZO (Cl 58005), the monosodium salt of 2 - [(9,10-dihydro-4-hydroxy-9,10-dioxo-1-anthracenyl) -amino] -5-methyl-benzene sulfonic acid (Cl 60730 ), the monosodium salt of 4 - [(2-hydroxy-1-naphthalenyl) -azo] -benzene sulfonic acid (Cl 15510), the disodium salt of 6-hydroxy-5 - [(4-sulfophenyl acid) ) -azo] -2-naphthalene sulfonic (Cl 15985), the disodium salt of 5-amino-4-hydroxy-3- (phenylazo) -2,7-naphthalene disulfonic (Cl 17200), the disodium salt of 1-amino-2- (4'-nitrophenylazo) -7-phenylazo-8-hydroxy-3,6-naphthalene disulfonic acid (Cl 20470), the disodium salt of N-ethyl-N- [4 - [[ 4- [ethyl [3-sulfophenyl) -methyl] -amino] -phenyl] (2-sulfophenyl) -methylene] -2,5-cyclohexadien-1-ylidene] -3-sulfobenzenemethanaminium hydroxide (Cl 42090), the disodium salt 2,2 '- [(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl) -diimino] -bis- [5-methyl] -benzene sulfonic acid (Cl 61570), salt 5-hydroxy-1- (4-sulfophenyl) -4- (4-sulfophenylazo) py trisodium acid razole-3-carboxylic (C.l. 19140), 4 - [(9,10-dihydro-4-hydroxy-9,10-dioxo-1-anthryl) amino] toluene-3-sodium sulfonate (Cl 60730), the trisodium salt of acid 7 -hydroxy-8 - [(4-sulfo-1-naphthalenyl) azo] -1,3-naphthalenedisulfonic (Cl 16255), and a mixture of these compounds.
It is also possible to use compounds corresponding to the mesomeric, tautomeric forms, of structures (I) to (XII).
In a preferred variant of the invention, the synthetic direct dye (s) are chosen from anionic direct dyes.
The direct or natural dye (s), natural or synthetic, preferably represent a total content of at least 0.05% by weight, preferably at least 0.08% by weight, preferably from 0.1 to 5% by weight. weight, relative to the total weight of the aqueous composition (A)
The direct dye (s) preferably represent a total content of at least 0.01% by weight, preferably at least 0.05% by weight, preferably from 0.1 to 5% by weight, relative to the total weight of the compositions (A) and (B) applied to the fibers during step ii).
As indicated above, the aqueous composition (A) used in the process according to the invention comprises one or more thickeners of aqueous phase e). c) Water thickeners
By “aqueous phase thickener” is meant according to the present invention compounds which increase by their presence at a concentration of 0.05% by weight the viscosity of an aqueous composition in which they are 2 / introduced by at least 20 cps, preferably at least 50 cps, at room temperature (25 ° C), at atmospheric pressure and at a shear rate of 1s_1 (the viscosity can be measured using a cone / plane viscometer, Rheometer Haake R600 or similar).
The aqueous phase thickener (s) are preferably chosen from non-associative thickening polymers with sugar units, non-associative thickening polymers without sugar unit, associative thickening polymers, and mixtures of these compounds.
By sugar unit is meant in the sense of the present invention an oxygenated hydrocarbon compound which has several alcohol functions, with or without aldehyde or ketone function, and which contains at least 4 carbon atoms.
The sugar units can be optionally modified by substitution, and / or by oxidation and / or by dehydration.
The sugar units which can enter into the composition of the thickening polymers of aqueous phase of the invention preferably come from the following sugars: glucose; galactose; arabinose; rhamnose; mannose; xylose; fucose; anhydrogalactose; galacturonic acid; glucuronic acid; mannuronic acid; galactose sulfate; anhydrogalactose sulfate and fructose.
Mention may in particular be made, as non-associative thickening polymers with sugar units, of native gums such as: a) exudates from trees or shrubs including: - gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid); - ghatti gum (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid); - karaya gum (polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid); - tragacanth (or tragacanth) gum (polymer of galacturonic acid, galactose, fucose, xylose and arabinose); b) gums derived from algae, including: - agar (polymer derived from galactose and anhydrogalactose); - alginates (polymers of mannuronic acid and glucuronic acid); - carrageenans and furcelleranes (polymers of galactose sulfate and anhydrogalactose sulfate); c) gums obtained from seeds or tubers including: - guar gum (polymer of mannose and galactose); - carob gum (polymer of mannose and galactose); Ζδ - fenugreek gum (polymer of mannose and galactose); - tamarind gum (polymer of galactose, xylose and glucose); - konjac gum (glucose polymer and mannose); d) microbial gums, including: - xanthan gum (polymer of glucose, mannose acetate, mannose / pyruvic acid and glucuronic acid); - gellan gum (partially acylated glucose polymer, rhamnose and glucuronic acid); - scleroglucan gum (glucose polymer); e) plant extracts including: - cellulose (glucose polymer); - starch (glucose polymer) and - inulin.
These polymers can be modified physically or chemically. By way of physical treatment, mention may especially be made of temperature. As chemical treatments, mention may be made of esterification, etherification, amidation, oxidation reactions. These treatments make it possible to lead to polymers which can be in particular nonionic, anionic or amphoteric.
Preferably, these chemical or physical treatments are applied to guar gums, carob gums, starches and celluloses.
The nonionic guar gums which can be used according to the invention can be modified by C1-C6 (poly) hydroxylakyl groups.
Among the C1-C6 (poly) hydroxyalkyl groups that may be mentioned by way of example, the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.
These guar gums are well known in the state of the art and can for example be prepared by reacting oxides of corresponding alkenes such as for example propylene oxides with guar gum so as to obtain a guar gum modified by hydroxypropyl groups.
The rate of hydroxyalkylation preferably varies from 0.4 to 1.2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on guar gum.
Such nonionic guar gums optionally modified with hydroxyalkyl groups are for example sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120 by the company RHODIA CHIMIE.
The starch molecules which can be used in the present invention may have cereals or tubers as botanical origin. Thus, the starches are for example chosen from starches of corn, rice, cassava, barley, potato, wheat, sorghum, peas.
The starches can be modified chemically or physically: in particular by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, heat treatments.
Diamidon phosphates or compounds rich in diamidon phosphate will preferably be used, such as the product proposed under the references PREJEL VA-70-T AGGL (phosphate of hydroxypropylated cassava gelatinized) or PREJEL TK1 (phosphate of diamidon of cassava gelatinized) or PREJEL 200 (acetylated cassava diamidon phosphate gelatinized) by the company AVEBE or NATIONAL STARCH STRUCTURE ZEA (diamatin phosphate cornified gelatinized).
According to the invention, amphoteric starches can also be used, these amphoteric starches comprise one or more anionic groups and one or more cationic groups. The anionic and cationic groups can be linked to the same reactive site of the starch molecule or to different reactive sites; preferably they are linked to the same reactive site. The anionic groups can be of the carboxylic, phosphate or sulphate type and preferably carboxylic. The cationic groups can be of primary, secondary, tertiary or quaternary amine type.
The starch molecules can come from all vegetable sources of starch such as in particular corn, potato, oats, rice, tapioca, sorghum, barley or wheat. It is also possible to use the hydrolysates of the starches mentioned above. The starch is preferably obtained from the potato.
The non-associative thickening polymers of the invention can be cellulosic polymers that do not contain a C10-C30 fatty chain in their structure.
The term “cellulosic” polymer is understood to mean, according to the invention, any polysaccharide compound having in its structure sequences of glucose residues united by β-1,4 bonds; in addition to unsubstituted celluloses, the cellulose derivatives can be anionic, cationic, amphoteric or nonionic.
Thus, the cellulose polymers which can be used according to the invention can be chosen from unsubstituted celluloses, including in microcrystalline form and cellulose ethers.
Among these cellulose polymers, there are the cellulose ethers, the cellulose esters and the cellulose ether esters.
Among the cellulose esters, there are inorganic cellulose esters (nitrates, sulfates or cellulose phosphates, etc.), organic cellulose esters (monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates or acetate trimellitates, etc.) and mixed organic / inorganic esters of cellulose such as acetate butyratesulfates and cellulose acetate propionatesulfates. Among the cellulose ether esters, mention may be made of hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.
Among the non-ionic cellulose ethers without a C10-C30 fatty chain, ie “non-associative”, mention may be made of (Ci-C4) alkylcelluloses such as methylcelluloses and ethylcelluloses (for example Ethocel standard 100 Premium from DOW CHEMICAL); (poly) hydroxy (Ci-C4) alkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example Natrosol 250 HHR proposed by AQUALON) and hydroxypropylcelluloses (for example Klucel EF from AQUALON); mixed (poly) hydroxy (Ci-C4) alkyl- (Ci-C4) alkylcelluloses such as hydroxypropyl-methylcelluloses (for example Methocel E4M from DOW CHEMICAL), hydroxyethyl-methylcelluloses, hydroxyethyl-ethylcelluloses (for example Bermocoll E 481 FQ from AKZO NOBEL) and hydroxybutyl-methylcelluloses.
Among the anionic cellulose ethers without a fatty chain, mention may be made of (poly) carboxy (Ci-C4) alkylcelluloses and their salts. By way of example, mention may be made of carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company AQUALON) and carboxymethylhydroxyethylcelluloses and their sodium salts.
Among the cationic cellulose ethers without a fatty chain, mention may be made of cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in US Pat. No. 4,131,576, such as (poly) hydroxy (Ci-C4) alkyl celluloses, such as hydroxymethyl-, hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a salt of methacryloylethyl trimethylammonium, of methacrylmidopropyl trimethylammonium, of dimethyl-diallylammonium. The marketed products meeting this definition are more particularly the products sold under the name "Celquat® L 200" and "Celquat® H 100" by the National Starch Company.
Among the non-associative thickening polymers without sugar units which can be used according to the invention, mention may be made of cross-linked acrylic or methacrylic acid homopolymers or copolymers, cross-linked homopolymers of 2-acrylamido-2-methyl-propane sulfonic acid and their cross-linked copolymers d acrylamide, ammonium acrylate homopolymers or copolymers of ammonium acrylate and acrylamide alone or in mixtures.
A first family of suitable non-associative thickening polymers is represented by crosslinked acrylic acid homopolymers.
Among homopolymers of this type, mention may be made of those crosslinked with an allyl alcohol ether of the sugar series, such as for example the products sold under the names CARBOPOLS 980, 981, 954, 2984 and 5984 by the company NOVEON or products sold under the names SYNTHALEN M and SYNTHALEN K by the company 3 VSA. These polymers are called INCI Carbomer.
The non-associative thickening polymers can also be crosslinked (meth) acrylic acid copolymers such as the polymer sold under the name AQUA SF1 by the company NOVEON.
The non-associative thickening polymers can be chosen from homopolymers of 2-acrylamido-2-methylpropane sulfonic acid and their copolymers, crosslinked or not,.
Among the copolymers of 2-acrylamido-2-methylpropane sulfonic acid, mention may be made of crosslinked copolymers of 2-acrylamido-2-methyl-propane sulfonic acid and partially or totally neutralized acrylamide, mention may be made in particular of the product described in Example 1 of document EP 503 853 and reference may be made to this document with regard to these polymers.
Mention may also be made of the copolymers of 2-acrylamido-2-methylpropane sulfonic acid and of hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT 10 by the company SEPPIC.
The aqueous composition (A) can likewise comprise, as non-associative thickening polymers, homopolymers of ammonium acrylate or copolymers of ammonium acrylate and of acrylamide. As examples of ammonium acrylate homopolymers, mention may be made of the product sold under the name MICROSAP PAS 5193 by the company HOECHST. Among the copolymers of ammonium acrylate and of acrylamide, mention may be made of the product sold under the name BOZEPOL C NEW or the product PAS 5193 sold by the company HOECHST. Reference may in particular be made to documents FR 2 416 723, US 2798053 and US 2923692 with regard to the description and preparation of such compounds.
It is also possible to use cationic thickening polymers of acrylic type.
Among the thickening polymers of the aqueous phases, mention may also be made of associative polymers well known to those skilled in the art and in particular of a nonionic, anionic, cationic or amphoteric nature.
It is recalled that the "associative polymers" are polymers capable, in an aqueous medium, of reversibly associating with each other or with other molecules.
Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.
By "hydrophobic group" is meant a radical or polymer with a hydrocarbon chain, saturated or unsaturated, linear or branched, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms. carbon and more preferably from 18 to 30 carbon atoms.
Preferably, the hydrocarbon group comes from a monofunctional compound. For example, the hydrophobic group can be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol. It can also denote a hydrocarbon polymer such as for example polybutadiene.
Among the associative polymers of anionic type, there may be mentioned: - (a) those comprising at least one hydrophilic unit, and at least one allyl ether unit with a fatty chain, more particularly those whose hydrophilic unit consists of an anionic monomer ethylenically unsaturated, more particularly still by a vinyl carboxylic acid and very particularly by an acrylic acid or a methacrylic acid or mixtures thereof.
Among these anionic associative polymers, particularly preferred according to the invention, the polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, from 5 to 60% by weight of (meth) acrylates lower alkyls, from 2 to 50% by weight of fatty chain allyl ether, and from 0 to 1% by weight of a crosslinking agent which is a well known copolymerizable polyethylene unsaturated monomer, such as diallyl phthalate , allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide.
Among the latter, very particularly preferred are crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) stearyl alcohol ether (Steareth 10), in particular those sold by the company CIBA under the names SALCARE SC80® and SALCARE SC90® which are 30% aqueous emulsions of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40/50/10). - (b) those comprising i) at least one hydrophilic unit of olefinic unsaturated carboxylic acid type, and ii) at least one hydrophobic unit of alkyl ester (C10-C30) type of unsaturated carboxylic acid.
(C10-C30) alkyl esters of unsaturated carboxylic acids useful in the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.
Anionic polymers of this type are for example described and prepared, according to US Patents 3,915,921 and 4,509,949.
Among this type of anionic associative polymers, use will be made more particularly of those consisting of 95 to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit) , and 0 to 6% by weight of polymerizable crosslinking monomer, or else those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of C10-C30 alkyl acrylate ( hydrophobic unit), and 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above.
Among said polymers above, very particularly preferred according to the present invention, the products sold by the company GOODRICH under the trade names PEMULEN TR1®, PEMULEN TR2®, CARBOPOL 1382®, and even more preferably PEMULEN TR1®, and product sold by SEPPIC under the name COATEX SX®.
Mention may also be made of the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer sold under the name Acrylidone LM by the company ISP. - (c) terpolymers of maleic anhydride / C30-C38 α-olefin / alkyl maleate such as the product (maleic anhydride / α-olefin C30-Css / isopropyl maleate copolymer) sold under the name PERFORMA V 1608® by NEWPHASE TECHNOLOGIES. - (d) acrylic terpolymers comprising: i) approximately 20 to 70% by weight of an α, β-monoethylenically unsaturated carboxylic acid [A], ii) approximately 20 to 80% by weight of an α unsaturated monomer , non-surfactant β-monoethylenic other than [A], iii) approximately 0.5 to 60% by weight of a nonionic mono-urethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate, such as those described in patent application EP-A-0173109 and more particularly that described in Example 3, namely, a methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl isocyanate alcohol isocyanate terpolymer ethoxylated (40OE) in 25% aqueous dispersion. - (e) copolymers comprising, among their monomers, an α, β-monoethylenically unsaturated carboxylic acid and an ester of α, β-monoethylenically unsaturated carboxylic acid and an oxyalkylenated fatty alcohol.
Preferably, these compounds also comprise, as monomer, an ester of α, β-monoethylenically unsaturated carboxylic acid and of C1-C4 alcohol. As an example of this type of compound, mention may be made of ACULYN 22® sold by the company ROHM and HAAS, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer as well as ACULYN 88 also sold by the company ROHM and HAAS. - (f) Amphiphilic polymers comprising at least one ethylenically unsaturated monomer containing a sulfonic group, in free or partially or totally neutralized form and comprising at least one hydrophobic part. These polymers can be crosslinked or non-crosslinked. They are preferably crosslinked.
The ethylenically unsaturated monomers containing a sulfonic group are chosen in particular from vinylsulfonic acid, styrenesulfonic acid, (meth) acrylamido (Ci-C22) alkylsulfonic acids, N- (C1-C22) alkyl (meth) acrylamido- acids. (Ci-C22) alkylsulfonic like undecyl-acrylamido-methane-sulfonic acid as well as their partially or totally neutralized forms.
More preferably, use will be made of (meth) acrylamido (Ci-C22) alkylsulfonic acids such as, for example, acrylamido-methane-sulfonic acid, acrylamido-ethane-sulfonic acid, acrylamido-propane-sulfonic acid, 2-acrylamido-2-methylpropane-sulfonic acid, methacrylamido-2-methylpropane-sulfonic acid, 2-acrylamido-n-butane-sulfonic acid, 2-acrylamido-2,4,4-trimethylpentane- acid sulfonic, 2-methacrylamido-dodecyl-sulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptane-sulfonic acid and their partially or fully neutralized forms.
More particularly, 2-acrylamido-2-methylpropane-sulfonic acid (AMPS) will be used as well as its partially or completely neutralized forms.
The polymers of this family can in particular be chosen from random amphiphilic polymers of AMPS modified by reaction with an n-monoalkylamine or a di-n-alkylamine of C6-C22, and such as those described in patent application WO 00 / 31154 (forming an integral part of the content of the description). These polymers may also contain other hydrophilic ethylenically unsaturated monomers chosen, for example, from (meth) acrylic acids, their alkyl derivatives substituted in β or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth) acrylamides , vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.
The preferred polymers of this family are chosen from amphiphilic copolymers of AMPS and of at least one hydrophobic ethylenically unsaturated monomer.
These same copolymers can also contain one or more ethylenically unsaturated monomers not comprising a fatty chain such as (meth) acrylic acids, their alkyl derivatives substituted in β or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.
These copolymers are described in particular in patent application EP-A-750899, US patent 5089578 and in the following publications by Yotaro Morishima - “Self-assembling amphiphilic polyelectrolytes and their nanostructures -Chinese Journal of Polymer Science Vol. 18, No. 40, (2000), 323-336. "; - "Miscelle formation of random copolymers of sodium 2- (acrylamido) -2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, Vol. 33, No. 10 (2000), 3694-3704 "; - "Solution properties of miscelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte: knows effects on rheological behavior - Langmuir, Vol. 16, No. 12, (2000) 5324-5332 ”; - "Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido) -2-methylpropanesulfonate and associative macromonomers - Polym. Preprint, Div. Polym. Chem., 40 (2), (1999), 220-221 ”.
Among these polymers, there may be mentioned: - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (Cs-Ci6) alkyl (meth) units acrylamide or (C8-Ci6) alkyl (meth) acrylate units with respect to the polymer, such as those described in application EP-A 750 899; - Terpolymers comprising from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS units and from 5 to 80 mol% of n- (de6-Ci8) alkylacrylamide units, such as those described in US patent 5,089,578.
Mention may also be made of copolymers of fully neutralized AMPS and of dodecyl methacrylate as well as copolymers of non-crosslinked and crosslinked AMPS and n-dodecylmethacrylamide, such as those described in the articles by Morishima cited above.
Among the cationic associative polymers that may be mentioned: (a) cationic associative polyurethanes; (b) the compound marketed by the company NOVEON under the name AQUA CC and which corresponds to the name INCI POLYACRYLATE-1 CROSSPOLYMER.
POLYACRYLATE-1 CROSSPOLYMER is the product of the polymerization of a mixture of monomers comprising: - a di (C1-C4 alkyl) amino methacrylate (Οι-Οβ alkyl), - one or more C1 alkyl esters -C30 and (meth) acrylic acid, - a polyethoxylated C10-C30 alkyl methacrylate (20-25 moles of ethylene oxide unit), - a polyethylene glycol / polypropylene glycol allyl 30/5, - a hydroxy methacrylate (C2-C6 alkyl), and - an ethylene glycol dimethacrylate. (c) quaternized (poly) hydroxyethylcelluloses modified by groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof. The alkyl radicals carried by the above quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote the phenyl, benzyl, naphthyl or anthryl groups. Examples of quaternized fatty chain C8-C30 alkyl hydroxyethyl celluloses, such as QUATRISOFT LM 200®, QUATRISOFT LM-X 529-18-A®, QUATRISOFT LM-X 529-18-B® may be mentioned C12 alkyl) and QUATRISOFT LM-X 529-8® (Cw alkyl) sold by the company AQUALON, the products CRODACEL QM®, CRODACEL QL® (C12 alkyl) and CRODACEL QS® (Cw alkyl) CRODA and the SOFTCAT SL 100® product sold by AQUALON. (d) cationic polyvinyllactam polymers.
Such polymers are for example described in patent application WO-OO / 68282.
As poly (vinyllactam) polymers according to the invention, particularly using the terpolymers vinylpyrrolidone / dimethylaminopropylmethacrylamide / dodecyldimethylmethacrylamidopropylammonium tosylate, the terpolymers vinylpyrrolidone / dimethylaminopropylmethacrylamide / tosylate cocoyldiméthyl-méthacrylamidopropylammonium, the terpolymers vinylpyrrolidone / dimethylaminopropylmethacrylamide / tosylate or chloride lauryldiméthylméthacrylamido -propylammonium.
The amphoteric associative polymers are preferably chosen from those comprising at least one non-cyclic cationic unit. More particularly still, those prepared from or comprising 1 to 20 mol% of monomer comprising a fatty chain, and preferably 1.5 to 15 mol% and more particularly still 1.5 to 6 mol%, are preferred, relative to the number total moles of monomers.
Amphoteric associative polymers according to the invention are for example described and prepared in patent application WO 9844012.
Among the amphoteric associative polymers according to the invention, the acrylic acid / (meth) acrylamidopropyl trimethyl ammonium chloride / stearyl methacrylate terpolymers are preferred.
The associative polymers of nonionic type which can be used according to the invention are preferably chosen from: (a) copolymers of vinyl pyrrolidone and of hydrophobic monomers with a fatty chain, which may be mentioned, for example: - ANTARON V216® products or GANEX V216® (vinylpyrrolidone / hexadecene copolymer) sold by the company ISP - ANTARON V220® or GANEX V220® products (vinylpyrrolidone / eicosene copolymer) sold by the company I.S.P. (b) copolymers of Οι-Οβ alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain, such as for example the methyl acrylate / oxyethylenated stearate acrylate sold by the company GOLDSCHMIDT under the name ANTIL 208®. (c) copolymers of hydrophilic methacrylates or acrylates and hydrophobic monomers comprising at least one fatty chain, such as for example the polyethylene glycol methacrylate / lauryl methacrylate copolymer. (d) polyether polyurethanes comprising in their chain, both hydrophilic sequences of a nature most often polyoxyethylenated and hydrophobic sequences which can be aliphatic sequences alone and / or cycloaliphatic and / or aromatic sequences. (e) polymers with an aminoplast ether skeleton having at least one fatty chain, such as the PURE THIX® compounds offered by the company SUD-CHEMIE. (f) celluloses or their derivatives, modified by groups comprising at least one fatty chain such as alkyl, arylalkyl, alkylaryl groups or their mixtures in which the alkyl groups are Cs- and in particular:
* nonionic alkylhydroxyethylcelluloses such as the products NATROSOL PLUS GRADE 330 CS and POLYSURF 67 (Cw alkyl) sold by the company AQUALON * nonoxynylhydroxyethylcelluloses nonionics such as the product AMERCELL HM-1500 sold by the company AMERCHOL; * non-ionic alkylcelluloses such as the product BERMOCOLL EHM 100 sold by the company BEROL NOBEL; (g) associative guar derivatives such as hydroxypropylguars modified by a fatty chain such as the product ESAFLOR HM 22 (modified by a C22 alkyl chain) sold by the company LAMBERTI; the product MIRACARE XC 95-3 (modified by a C14 alkyl chain) and the product RE 205-146 (modified by a C20 alkyl chain) sold by RHODIA CHIMIE.
Preferably, the polyether polyurethanes comprise at least two lipophilic hydrocarbon chains, having from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon chains being able to be pendant chains or chains at the end of hydrophilic block. In particular, it is possible that one or more hanging chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block.
The polyether polyurethanes can be multiblock in particular in the form of a triblock. The hydrophobic blocks can be at each end of the chain (for example: triblock copolymer with hydrophilic central block) or distributed both at the ends and in the chain (multiblock copolymer for example). These same polymers can also be in grafts or in a star.
The nonionic fatty chain polyurethane polyethers can be triblock copolymers whose hydrophilic block is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups. Nonionic polyether polyurethanes have a urethane bond between hydrophilic blocks, hence the origin of the name.
By extension, also included among the nonionic fatty-chain polyurethane polyethers are those whose hydrophilic sequences are linked to the lipophilic sequences by other chemical bonds. As examples of non-ionic polyether polyurethanes with a fatty chain which can be used in the invention, it is also possible to use Rheolate 205® with urea function sold by the company RHEOX or also Rhéolates® 208, 204 or 212, as well as Acrysol RM 184®.
Mention may also be made of the product ELFACOS T210® with a C12-14 alkyl chain and the product ELFACOS T212® with a Cw alkyl chain from AKZO.
The product DW 1206B® from ROHM & HAAS with C20 alkyl chain and urethane bond, available at 20% dry matter in water, can also be used.
It is also possible to use solutions or dispersions of these polymers, especially in water or in an alcoholic medium. By way of example, such polymers that may be mentioned are RHEOLATE® 255, RHEOLATE® 278 and RHEOLATE® 244 sold by the company RHEOX. One can also use the product DW 1206F and the DW 1206J offered by the company ROHM & HAAS.
The polyether polyurethanes which can be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 271, 380.389 (1993).
More particularly still, it is preferred to use a polyether polyurethane capable of being obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide, (ii) stearyl alcohol or decyl alcohol and (iii) at least one diisocyanate.
Such polyether polyurethanes are sold in particular by the company ROHM & HAAS under the names ACULYN 46® and ACULYN 44® [ACULYN 46® is a polycondensate of polyethylene glycol containing 150 or 180 moles of ethylene oxide, stearyl alcohol and methylene bis (4-cyclohexyl-isocyanate) ( SMDI), 15% by weight in a matrix of maltodextrin (4%) and water (81%); ACULYN 44® is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, decyl alcohol and methylene bis (4-cyclohexylisocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol ( 39%) and water (26%)].
Preferably, the aqueous phase thickener (s) are chosen from polymers not comprising sugar units.
More preferably, the thickener (s) in the aqueous phase are chosen from thickening polymers with acrylic or methacrylic units, associative or non-associative, polymers with 2-acrylamido-2-methyl-propane sulfonic acid units and / or their salified form.
In a preferred variant of the invention, the aqueous phase thickener (s) are chosen from homopolymers or copolymers of acrylic acid, in particular homopolymers of acrylic acid, homopolymers or copolymers of 2-acrylamido-2- acid methyl-propane sulfonic acid and / or their salified form, in particular copolymers of 2-acrylamido-2-methyl-propane sulfonic acid and / or their salified form, more particularly copolymers of 2-acrylamido-2-methyl- acid propane sulfonic and / or their salified form and acrylamide or the copolymers of 2-acrylamido-2-methyl-propane sulfonic and / or their salified form and hydroxyethylacrylate, said polymers being able to be crosslinked or non-crosslinked.
The aqueous phase thickener (s) generally represent a total content ranging from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, and better still from 1.5 to 10% by weight relative to the weight total of the aqueous composition (A).
The aqueous phase thickener (s) generally represent a total content ranging from 0.05 to 15% by weight, preferably from 0.1 to 10% by weight, and better still from 1 to 5% by weight relative to the total weight of the compositions (A) and (B).
Preferably, the aqueous composition (A) used in the process according to the invention also comprises one or more organic solvents d). d) Organic solvents
Preferably, the organic solvent (s) are chosen from linear or branched monoalcohols having from 1 to 8 carbon atoms, polyols, polyethylene glycol, aromatic alcohols and mixtures of these compounds.
Preferably, the organic solvent (s) are chosen from ethanol, propanol, butanol, isopropanol, isobutanol, propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerol, sorbitol, benzyl alcohol, phenoxyethanol and mixtures of these compounds.
Very particularly preferably, the organic solvent (s) are chosen from ethanol, dipropylene glycol, benzyl alcohol and a mixture of these compounds.
When (s) is (are) present, The organic solvent (s) generally represent a total content ranging from 1 to 30% by weight, preferably from 2 to 25% by weight, and better still from 5 to 20 % by weight relative to the total weight of the aqueous composition (AJ.
When (s) is (are) present, The organic solvent (s) generally represent a total content ranging from 0.5 to 20% by weight, preferably from 1 to 15% by weight, and better still from 5 at 10% by weight relative to the total weight of the compositions (A) and (BJ.
The aqueous composition (A) used in the process according to the invention also comprises water. Water can represent at least 50% by weight, preferably at least 60% by weight, and more preferably at least 70% by weight relative to the total weight of the aqueous composition (A). The water can represent at least 20% by weight, preferably at least 30% by weight, and more preferably at least 40% by weight relative to the total weight of the compositions (A) and (B). Water generally represents from 50 to 95% by weight, preferably from 60 to 93% by weight, and more preferably from 65 to 90% by weight relative to the total weight of the aqueous composition (A). Water generally represents from 20 to 85% by weight, preferably from 30 to 80% by weight, and more preferably from 40 to 70% by weight relative to the total weight of the compositions (A) and (B).
As mentioned previously, the method according to the invention comprises the application of a composition (B) comprising at least g) a fatty substance, preferably an oil. h) Macaw body
By "fatty substance" is meant an organic compound insoluble in water at room temperature (25 ° C) and at atmospheric pressure (1.013.105 Pa) (solubility less than 5% by weight, and preferably less than 1% by weight, even more preferably less than 0.1% by weight). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms and / or a chain of at least two siloxane groups. In addition, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as, for example, chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran ( THF), petrolatum oil or decamethylcyclopentasiloxane.
The fatty substances can be solid, pasty or liquid at room temperature and at atmospheric pressure.
Preferably the composition (B) comprises at least one fatty substance which is liquid at ambient temperature (25 ° C.) and at atmospheric pressure also called oil.
The oil or oils present in composition (B) used in the process according to the invention can be volatile or non-volatile.
The volatile or non-volatile oils can be hydrocarbon oils, in particular of animal or vegetable origin, synthetic oils, silicone oils, fluorinated oils, or mixtures thereof.
For the purposes of the present invention, the term "silicone oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group.
The term “hydrocarbon-based oil” means an oil mainly containing hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur and / or phosphorus atoms. A hydrocarbon oil does not include a silicon atom.
The oil or oils present in composition (B) used in the process according to the invention can be non-volatile.
For the purposes of the present invention, the term "non-volatile oil" means an oil having a vapor pressure of less than 0.13 Pa (0.01 mm Hg).
The non-volatile oils can in particular be chosen from hydrocarbon oils, where appropriate fluorinated oils and / or non-volatile silicone oils.
As non-volatile hydrocarbon oil suitable for the invention, there may be mentioned in particular: - hydrocarbon oils of animal origin, - hydrocarbon oils of plant origin such as phytostearyl esters, such as phytostearyl oleate, l phytostearyl isostearate and lauroyl / octyldodecyl / phytostearyl glutanate, for example sold under the name ELDEW PS203 by AJINOMOTO, the triglycerides consisting of fatty acid esters of glycerol whose fatty acids can have various chain lengths of C4 to C24, the latter may be linear or branched, saturated or unsaturated; these oils are in particular heptanoic or octanoic triglycerides, sweet almond oil, argan oil, avocado oil, peanut oil, camellia oil, safflower oil , calophyllum oil, rapeseed oil, coconut oil, coriander oil, squash oil, wheat germ oil, jojoba oil or liquid jojoba wax, linseed oil, macadamia oil, corn germ oil, hazelnut oil, walnut oil, vernonia oil, apricot kernel oil, oil olive oil, evening primrose oil, palm oil, passionflower oil, grape seed oil, rose oil, castor oil, rye oil, l sesame oil, rice bran oil, camelina oil, soybean oil, sunflower oil, pracaxi oil, babassu oil, mongongo oil, l marula oil, arara oil, shea butter oil, brazil nut oil; or the triglycerides of caprylic / capric acids such as those sold by the company STEARINERIES DUBOIS or those sold under the names MIGLYOL 810®, 812® and 818® by the company DYNAMIT NOBEL, the refined vegetable perhydrosqualene marketed under the name fitoderm by the company Cognis; the vegetable hemisqualane such as for example that marketed by the company Amyris under the reference Neossance hemisqualane, the vegetable squalane marketed for example under the name Squalive by the company Biosynthis; - hydrocarbon oils of mineral or synthetic origin such as for example: (a) synthetic ethers having from 10 to 40 carbon atoms; (b) linear or branched hydrocarbons, of mineral or synthetic origin such as petrolatum, polydecenes, hydrogenated polyisobutene such as parlameam, squalane and their mixtures, and in particular hydrogenated polyisobutene, (c) esters of synthesis such as oils of formula R1COOR2 in which Ri represents the remainder of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R2 represents a notably branched hydrocarbon chain containing from 1 to 40 carbon atoms provided that Ri + R2 or> 10.
The esters can in particular be chosen from esters, in particular of fatty acid, for example: - cetostearyl octanoate, esters of isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, palmitate ethyl, 2-ethyl-hexyl palmitate, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters such as isostearyl lactact, hydroxystearate d octyl, diisopropyl adipate, heptanoates, and in particular isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate , 4-diheptanoate and 2-hexyl ethyl palmitate, alkyl benzoate, polyethylene glycol diheptanoate, propylene glycol diethyl 2-hexanoate and mixtures thereof, benzoates of C12 to C15 alcohols,hexyl laurate, esters of neopentanoic acid such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyldocecyl neopentanoate, isononanoic acid esters such as isononanoate d isononyl, isotridecyl isononanoate, octyl isononanoate, hydroxylated esters such as isostearyl lactate, di-isostearyl malate; - polyol esters, and pentaetrythritol esters, such as dipentaerythritol tetrahydroxystearate / tetraisostearate, - esters of dimer diols and diacid dimers such as Lusplan DD-DA5® and Lusplan DD-DA7®, marketed by the company NIPPON FINE CHEMICAL and described in application FR 03 02809, (d) fatty alcohols liquid at room temperature with branched and / or unsaturated carbon chain having from 12 to 26 carbon atoms such as 2-octyldodecanol, isostearyl alcohol, oleic alcohol , 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol, (e) unsalted higher fatty acids such as oleic acid, linoleic acid, linolenic acid and mixtures thereof, and (f) di-alkyl carbonates, the 2 alkyl chains possibly being identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC®, by Cognis, (g) and their mixtures.
Non-volatile silicone oils are, for example chosen from non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising pendant alkyl or alkoxy groups and / or at the ends of the silicone chain, groups each having 2 to 24 carbon atoms, the phenylated silicones such as the phenyl trimethicones, the phenyl dimethicones, the phenyl trimethylsiloxy diphenylsiloxanes, the diphenyl dimethicones, the diphenyl methyldiphenyl trisiloxanes, and the 2-phenylethyl trimethylsiloxysilicates, dimethicones or phenyltrimethicone mixtures or lower viscosity mixtures or phenyltrimethicone.
The non-volatile oils can be chosen from mixtures of non-volatile hydrocarbon and silicone oils.
The oil or oils present in composition (B) used in the process according to the invention may be volatile.
For the purposes of the present invention, the term "volatile oil" means an oil (or non-aqueous medium) capable of evaporating on contact with the skin in less than an hour, at room temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil, liquid at room temperature, in particular having a non-zero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 to 40,000 Pa (10- 3 to 300 mm Hg), in particular ranging from 1.3 to 13,000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 to 1,300 Pa (0.01 to 10 mm Hg).
The volatile hydrocarbon oils can be chosen from hydrocarbon oils having from 8 to 16 carbon atoms, and in particular branched Cs-Cw alkanes (also called isoparaffins) such as isododecane (also called 2,2,4,4,6 -pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names of Isopars® or Permethyls®.
It is also possible to use volatile fluorinated oils such as nonafluoromethoxybutane or perfluoromethylcyclopentane, and mixtures thereof.
As volatile oils, volatile silicones can also be used, such as, for example, volatile linear or cyclic silicone oils, in particular those having a viscosity <8 centistokes (8 x 10'6 m2 / s), and in particular having from 2 to 10 silicon atoms, and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil which can be used in the invention, mention may be made in particular of dimethicones of viscosity 5 and 6 cSt, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hex disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof.
It is also possible to use a mixture of volatile hydrocarbon and silicone oils.
Preferably, the oil or oils are chosen from C6-C20 alkanes, hydrocarbons, linear or branched, of mineral or synthetic origin of more than 16 carbon atoms, non-silicone oils of animal origin, oils of vegetable origin, fluorinated oils, liquid fatty alcohols, liquid fatty esters, non-salified liquid fatty acids, silicone oils, and mixtures of these compounds.
Mention may in particular be made of the following mixtures of linear or branched alkanes, preferably of plant origin: - a mixture of branched alkanes at C15-C16, for example that which is marketed by the company SEPPIC under the name EMOGREEN L15 ; - A mixture of linear and / or branched C15-C19 alkanes, for example that which is marketed by the company SEPPIC under the name EMOGREEN L19.
By alcohol, ester or fatty acid, is meant for the purposes of the present invention an alcohol, ester or acid comprising an alkyl chain, linear or branched, saturated or unsaturated, comprising at least 8 carbon atoms, preferably from 8 to 30 atoms carbon, more preferably from 12 to 24 carbon atoms.
In a particularly preferred manner, the oil or oils are chosen from Ce-Cw alkanes, hydrocarbons, linear or branched, of mineral or synthetic origin of more than 16 carbon atoms, liquid fatty alcohols, liquid fatty esters, oils of plant origin, in particular hydrocarbon oils of plant origin, and mixtures of these compounds.
Most preferably, the oil or oils are chosen from C 1 -C 6 alkanes, hydrocarbons, linear or branched, of mineral or synthetic origin of more than 16 carbon atoms, liquid fatty alcohols, vegetable origin, especially hydrocarbon oils of vegetable origin, and mixtures of these compounds.
The fatty substance (s), preferably the liquid fatty substance (s) or oil, generally represent a total content ranging from 50 to 99% by weight, preferably from 70 to 98% by weight, and better still from 80 to 95% by weight relative to the total weight of the composition (B).
The fatty substance (s), preferably the liquid fatty substance (s) or oil, generally represent a total content ranging from 8 to 50% by weight, preferably from 10 to 45% by weight, and better still from 15 to 40% by weight relative to the total weight of the compositions (A) and (B).
According to one embodiment, the composition (B) according to the invention is an oily composition comprising at least one oil as defined above. Preferably the oil is present in a content of at least 8% by weight relative to the total weight of the composition (B), preferably of at least 10% by weight, better still of at least 15% by weight , even better at least 20% by weight of the composition (B).
According to one embodiment, the composition (B) used in the process according to the invention also preferably comprises h) one or more fatty phase thickeners, distinct from the fatty substances g).
According to one embodiment, the composition (B) used in the process according to the invention is an oily composition as defined above comprising at least one oil and h) one or more thickeners of fatty phase. h) Fat thickener
By “fatty phase thickener” is meant according to the present invention compounds which increase by their presence at a content of 0.05% by weight the viscosity of a fatty composition into which they are introduced by at least 20 cps, preferably at least 50 cps, at 25 ° C, at atmospheric pressure and at a shear rate of 1s_1 (the viscosity can be measured using a cone / plane viscometer, Haake R600 rheometer or the like).
The concept of fatty phase thickener is analogous to the concept of lipophilic thickener.
The fatty phase thickener (s) used in composition (B) used in the process according to the invention can be chosen from mineral fatty phase thickeners, organic fatty phase thickeners, and mixtures of these compounds.
The fatty phase mineral thickeners which can be used in composition (B) used in the process according to the invention are preferably mineral particles essentially consisting of oxide and / or mineral hydroxides.
These particles are preferably insoluble in water at room temperature (25 ° C). By insoluble is meant a solubility of less than 0.5% by weight.
Preferably, the primary size in number of these mineral particles varies from 0.01 to 500 μm, preferably varies from 0.1 to 200 μm, and even more preferably varies from 1 to 100 μm.
For the purposes of the present invention, the term "primary particle size" means the maximum dimension which it is possible to measure between two diametrically opposite points of an individual particle.
The size of the mineral particles can be determined by transmission electron microscopy or from the measurement of the specific surface by the BET method or from a laser granulometry.
The mineral particles which can be used in accordance with the invention can be in different forms, for example in the form of a sphere, needle, glitter or wafer.
In a preferred variant of the invention, the fatty phase mineral thickener (s) are platelet particles.
The fatty phase mineral thickener (s) that can be used in composition (B) used in the process according to the invention may preferably be chosen from silicas and silicates.
The silicates of the invention can be natural or chemically modified (or synthetic).
Silicates correspond to possibly hydrated silica, part of the silicon atoms of which are replaced by metal cations such as Al3 +, B3 +, Fe3 +, Ga3 +, Be2 +, Zn2 +, Mg2 +, Co3 +, Ni3 +, Na +, Li +, Ca2 +, Cu2 +.
More particularly, the silicates which can be used in the context of the invention are chosen from clays from the smectite family such as montmorillonites, hectorites, bentonites, beidellites, saponites, as well as from the vermiculites family, from the stevensite, chlorites.
These clays can be of natural or synthetic origin. Preferably, clays are used which are cosmetically compatible and acceptable with keratin materials.
The silicate can be chosen from montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and their mixtures.
Mention may thus be made of the compounds marketed by the company LAPORTE under the name LAPONITE XLG and LAPONITE XLS.
The silicate (s) are preferably chosen from bentonites or hectorites.
The silicate (s) can be modified with a compound chosen from quaternary amines, tertiary amines, amino acetates, imidazolines, amino soaps, fatty sulfates, alkyl aryl sulfonates, amine oxides, and their mixtures.
As suitable silicates, mention may be made of quaternium-18 bentonites such as those sold under the names Bentone 3, Bentone 38, Bentone 38V by the company Rhéox, Tixogel VP by the company United catalyst, Claytone 34, Claytone 40, Claytone XL by Southern Clay company; stearalkonium bentonites such as those sold under the names Bentone 27 by the company Rheox, Tixogel LG by the company United Catalyst, Claytone AF, Claytone APA by the company Southern Clay; quaternium-18 / benzalkonium bentonites such as those sold under the names Claytone HT, Claytone PS by the company Southern Clay, Ouaternium-18 Hectorites such as those sold under the names Bentone Gel DOA, Bentone Gel ECO5, Bentone Gel EUG, Bentone IPP Gel, Bentone Gel ISD, Bentone Gel SS71, Bentone Gel VS8, Bentone Gel VS38 by Rhéox and Simagel M, Simagel SI 345 by Biophil.
The silicates which can be used in composition (B) used in the process according to the invention can be chosen, in particular from modified hectorites such as hectorite modified with ammonium chloride of C10-C12 fatty acid, in particular distearyl dimethylammonium chloride and benzyldimethylammonium steary chloride.
As explained above, the mineral thickener or thickeners which can be used in composition (B) used in the process according to the invention can be silicas.
The silicas which can be used in composition (B) used in the process according to the invention are preferably pyrogenic.
Pyrogenic silicas can be obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process makes it possible in particular to obtain hydrophilic silicas which have a large number of silanol groups on their surface. Such hydrophilic silicas are for example sold under the names "AEROSIL 130®", "AEROSIL 200®", "AEROSIL 255®", "AEROSIL 300®", "AEROSIL 380®" by the company Degussa, "CAB-O- SIL HS-5® ”,“ CAB-O-SIL EH-5® ”,“ CAB-O-SIL LM-130® ”,“ CAB-O-SIL MS-55® ”,“ CAB-O-SIL M -5® ”by Cabot.
It is possible to chemically modify the surface of said silicas, by chemical reaction generating a reduction in the number of silanol groups. Silanol groups can in particular be substituted by hydrophobic groups: a hydrophobic silica is then obtained.
The hydrophobic groups can be: (a) trimethylsiloxyl groups, which are in particular obtained by treatment of fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are called "Silica silylate" according to the CTFA (6th edition, 1995). They are for example marketed under the references "AEROSIL R812®" by the company Degussa, "CAB-O-SIL TS-530®" by the company Cabot; (b) dimethylsilyloxyl or polydimethylsiloxane groups, which are in particular obtained by treatment of fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called "Silica dimethyl silylate" according to the CTFA (6th edition, 1995). They are for example marketed under the references "AEROSIL R972®", "AEROSIL R974®" by the company Degussa, "CAB-O-SIL TS-610®", "CAB-O-SIL TS-720®" by the company Pooch.
Preferably, the fumed silicas which can be used in composition (B) used in the process according to the invention are hydrophilic, such as that sold under the name "AEROSIL 200®".
Preferably, the fatty phase mineral thickener (s) are chosen from organophilic clays, hydrophilic fumed silicas and their mixtures.
More preferably, the mineral fatty phase thickener (s) are chosen from hectorites modified with ammonium chloride of C10-C12 fatty acid, in particular distearyl dimethylammonium chloride and benzyldimethylammonium stearyl chloride, and fumed silicas hydrophilic such as hydrophilic silicas sold under the name "AEROSIL 200®".
Even more preferably, the mineral thickener (s) in the fatty phase are chosen from hectorites modified with an ammonium chloride of C10-C12 fatty acid, in particular hectorite modified with distearyl dimethylammonium chloride, such as that sold under the name of Bentone 38VCG by the company Elementis, and the hectorite modified by stearyl chloride of benzyldimethylammonium, such as that sold under the name of Bentone 27V by the company Elementis.
As explained above, the fatty phase thickener (s) which can be used in the composition (B) used in the process according to the invention can also be chosen from organic fatty phase thickeners.
Preferably, the organic fatty phase thickener (s) are chosen from semi-crystalline polymers, non-silicone polyamides, silicone polyamides, mono- or polyalkylester of saccharide or polysaccharide such as dextrin palmitate, derivatives N-acylated amino acid amides, polymers comprising an alkylene and / or styrene block such as stearyl polyacrylates, elastomeric organopolysiloxanes, solid fatty esters, in particular esters of C8-C30, preferably C18, fatty acids -C24, and mixtures of these compounds. These copolymers can be di-block, tri-block, multi-block, radial-block polymers also called star copolymers, or also comb polymers.
Among the fatty acid esters of C8-C30, preferably of C18-C24, there may be mentioned the mono-, di- or triesters of fatty acids of C8-C30, preferably of C18-C24 and of polyols, more particularly the mono-, di- or triesters of C8-C30, preferably C18-C24 fatty acids of glycerol. One can in particular use a mixture of these compounds such as a mixture of mono-, di- and tri-esters of behenic acid and glycerol.
Very particularly, the organic thickener (s) of fatty phase are chosen semi-crystalline polymers, non-silicone polyamides, silicone polyamides, mono or polyalkyl ester of saccharide or polysaccharide such as dextrin palmitate, polymers comprising an alkylene and / or styrene block such as stearyl polyacrylates, solid fatty esters, in particular esters of C8-C30, preferably C18-C24 fatty acids, and mixtures of these compounds.
Even more preferably, the organic fatty phase thickener (s) are chosen from mono- or polyalkyl esters of saccharide or polysaccharide such as dextrin palmitate, esters of fatty acids of C8-C30, preferably of C18-C24 and their mixtures, better still the mono-, di- or triesters of C8-C30 fatty acids, preferably of C18-C24 and of polyols, more particularly the mono-, di- or triesters of C8-C30 fatty acids, preferably C18-C24, and glycerol.
Preferably, the fatty phase thickener (s) are chosen from organic thickeners.
The fatty phase thickener (s) generally represent a total content ranging from 1 to 40% by weight, preferably from 2 to 30% by weight, and better still from 5 to 20% by weight, relative to the total weight of the composition ( B).
The fatty phase thickener (s) h) generally represent a total content ranging from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, and better still from 1 to 8% by weight, relative to the total weight of the compositions (A) and (B).
Preferably, the weight ratio of the quantity of composition (B) to the quantity of aqueous composition (A) is greater than 0.1.
Preferably, this ratio is greater than 0.10 and less than or equal to 1, preferably ranges from 0.15 to 0.7 and more preferably from 0.25 to 0.5.
Preferably, the aqueous composition (A) and the composition (B) used in the process according to the invention do not comprise a surfactant. When they include them, the content of surfactants is less than 2% by weight, relative to the total weight of each composition containing them.
Preferably, the aqueous composition (A) and the composition (B) are in the form of gels.
Preferably, each of the two compositions (A) and (B) has a viscosity greater than or equal to 0.1 Pa.s, preferably ranging from 0.1 to 500 Pa.s, more preferably ranging from 0.5 to 300 Pa.s, and even more preferably ranging from 1 to 200 Pa.s, at a temperature of 25 ° C, at atmospheric pressure and at a shear rate of 1 s-1 (measurable for example with a Haake RS600 rheometer).
Preferably, each of the two compositions (A) and (B) has a threshold stress at 25 ° C ranging from 0.1 to 300 Pa, preferably from 1 to 250 Pa, and more preferably from 10 to 200 Pa.
The threshold stress is determined by stress sweeping at 25 ° C. We use a Thermo Haake RS600 rheometer with imposed stress in sandblasted cone-plane geometry. The temperature is regulated by a Peltier effect plan and an anti-evaporation device (solvent trap filled with water for measurements at 25 ° C).
A stress logarithmic rise of 0.5 to 500 Pa is carried out over a period of 3 minutes. Two adjustment lines corresponding to the stationary regimes (solid and liquid behaviors) are plotted on the curve representing the deformation as a function of the stress (logarithmic coordinates). The intersection of these two lines provides the value of the threshold stress.
The pH of the aqueous composition (A) used in the process according to the invention generally varies from 1.5 to 10 and preferably from 2 to 7. Even more preferably, the pH of the aqueous composition (A) used work in the process according to the invention is less than or equal to 5, better going from 2 to 4.
It can be adjusted using pH agents, in particular acidifying agents as described above for composition Ci).
According to a particular embodiment of the invention, the composition (A) comprises at least one acid, preferably chosen from mineral acids which are preferably chosen from hydrochloric, phosphoric and sulfuric acids and their conjugated salts, in particular l phosphoric acid and its salts.
Preferably, composition (A) comprises an inorganic buffer system comprising a mixture of at least one mineral (inorganic) acid and its conjugate base, namely the inorganic salt of said inorganic acid. Preferably, composition (A) comprises an inorganic buffer system comprising a mixture of at least phosphoric acid (H3PO4) and at least one inorganic phosphate salt, in particular chosen from potassium dihydrogen phosphate KH2PO4, sodium dihydrogen phosphate NaHLPCL , dipotassium hydrogen phosphate K2HPO4, disodium hydrogen phosphate Na2HPC> 4, potassium hydrogen phosphate K3PO4, sodium phosphate Na3PC> 4 and their mixtures.
As described above, the compositions (A) and (B) used in step iii) of the method according to the invention are applied either separately one after the other, or together in a single composition.
In a first variant of the invention, the compositions (A) and (B) are applied separately one after the other.
Preferably in this variant, these two compositions are applied without intermediate rinsing.
Preferably in this variant, the composition (B) is applied before the aqueous composition (A).
In a second variant of the invention, the compositions (A) and (B) are applied together in a single composition Cii).
Preferably in this second variant, the compositions (A) and (B) are applied together in a single composition prepared beforehand or obtained by an extemporaneous mixture before application, and preferably prepared beforehand.
In this variant, the composition resulting from the mixture of the compositions (A) and (B) as defined above can be prepared beforehand in the following manner: a) a step of preparation, separately from one another, of the compositions ( A) and (B) as described above by mixing the constituents of each composition, then b) a step of bringing the compositions (A) and (B) into contact. The step of bringing the different compositions into contact can be carried out by means of one or more static or non-static mixers.
Thus, to carry out the mixing of the compositions (A) and (B), the ingredients of the composition (A) are mixed separately from the ingredients of the composition (B). Each of the compositions is produced in a tank of its own. Each composition is then introduced separately into a static mixer or not.
According to a preferred embodiment, the compositions (A) and (B) are applied together in one and the same composition Cii), prepared beforehand or obtained by an extemporaneous mixture before the application.
In step iii) of the process according to the invention, the compositions (A) and (B) can be applied to dry or wet keratin fibers, which may have been washed with a shampoo.
The additives :
The compositions used in the coloring process according to the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic or surface active agents. their mixtures, anionic, cationic, nonionic, amphoteric, zwitterionic polymers or their mixtures, mineral or organic thickening agents, distinct from the fatty phase and aqueous phase thickeners present in compositions A and B, and in particular thickeners associative anionic, cationic, nonionic and amphoteric polymers, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, d preservatives, clouding agents.
The above additives can generally be present in an amount for each of them between 0.01 and 20% by weight, relative to the total weight of each composition containing them.
Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition or to the composition (s) useful in the coloring process according to the invention are not not, or not substantially, altered by the planned addition (s).
The cosmetic composition (s) used according to the process according to the invention can be in various dosage forms, such as a powder, a lotion, a foam, a cream, a gel or under any another suitable form for dyeing keratin fibers. They can also be packaged in a pump bottle without propellant or under pressure in an aerosol bottle in the presence of a propellant and form a foam.
Multi-step coloring process
The process for dyeing keratin fibers of the invention uses several distinct steps, comprising: i) at least one step for dyeing i) said fibers using a coloring cosmetic composition Ci), preferably aqueous, comprising at least a) indigo and / or henna, ii) at least one step of treatment ii) of said fibers comprising the application to the fibers of an aqueous composition (A) which comprises b) at least one direct dye, of preferably distinct from henna and indigo, c) at least one thickener, d) preferably at least one organic solvent, and water and a composition B) which comprises at least e) a fatty substance, preferably an oil, the compositions (A) and (B) being applied either separately one after the other, or together in a single composition Cii), iii) optionally at least one intermediate rinsing step of said fibers, preferably with water, between step i) and step ii) (or between step ii) and i) (depending on the order of steps i) and ii)).
According to a preferred embodiment of the invention, the treatment step with the composition Ci) is carried out prior to the coloring step with the composition Cii)), it is then a step of pre -treatment with the composition Ci).
Preferably, the method according to the invention comprises a step iii) of intermediate rinsing between step i) and step ii).
Preferably, the method implements in order: step i) of treatment of said fibers with the cosmetic composition Ci) then the coloring step ii) with the composition Cii).
Preferably, in this embodiment, the method according to the invention comprises a step iii) of intermediate rinsing between step i) and step ii).
Preferably, the method according to the invention comprises a final rinsing step after the implementation of all the steps of the method.
Preferably, the intermediate rinsing step or steps for keratin fibers is / are preferably carried out with a composition comprising water.
In particular, according to a preferred embodiment of the invention, said intermediate rinsing step (s) is / are carried out exclusively with water, without the addition of an additional compound. According to another embodiment, the composition used to carry out the said rinsing step or steps may / may also comprise one or more additional compounds.
Preferably, the treatment step ii) comprises the application of the compositions (A) and (B) together in a single composition Cii).
Particularly in the coloring process of the invention, the pause time on the keratin fibers of the composition Ci) as defined above is between 1 minutes and 2 hours, more particularly between 5 minutes and 1 hour, preferably between 10 to 45 minutes. Preferably, the pause of the composition Ci) on the keratin fibers is carried out at a temperature between 20 ° C. and 50 ° C., more preferably between room temperature (25 ° C.) and 40 ° C.
The compositions (A) and (B) used in step iii), whether they are applied one after the other or in a single composition, are preferably left to stand for 1 to 30 minutes, preferably 2 to 20 minutes. At the end of the coloring process, the keratin fibers are generally rinsed with water, optionally undergoes washing with a shampoo followed by rinsing with water, before being left to dry or being dried by heat treatment by heating at a temperature between 30 and 60 ° C. In practice, this operation can be carried out using a hairdressing helmet, a hair dryer, an infrared ray dispenser and other conventional heating devices.
It is also possible to use, both as a means of heating and smoothing the hair, a heating iron at a temperature between 60 and 220 ° C. and preferably between 120 and 200 ° C.
According to a preferred embodiment, the method according to the invention does not use a chemical oxidizing agent.
According to a particular embodiment of the invention, the method according to the invention does not use hydrogen peroxide. Preferably, according to this embodiment, the method according to the invention does not use a chemical oxidizing agent. A particular embodiment of the invention relates to a coloring process which is carried out at room temperature (25 ° C).
In all the particular modes and variants of the processes described above, the compositions mentioned are ready-to-use compositions which can result from the extemporaneous mixture of two or more of two compositions and in particular of compositions present in dye kits. The evaluation of the coloration obtained from keratin fibers can be carried out visually or with a spectrocolorimeter in the CIE L * a * b * system, for example by means of a Minolta CM 3600 spectrocolorimeter (illuminant D65, angle 10 °, specular component included).
In this system L * a * b *; L * represents the clarity of the color, a * indicates the green / red color axis and b * the blue / yellow color axis. The lower the value of L *, the darker, more powerful the coloration.
The lower the value of a * and the greener the color, the higher the value of a * the more the color is red.
The lower the value of b * and the more blue the color, the higher the value of b * the more yellow the color.
The rise in color corresponds to the variation in coloring between the locks of hair, before and after treatment or coloring is defined by (ΔΕ *) according to the following equation: ΔΕ * = * -Lo *) 2 + (a * - a0 *) 2 + (b * - b0 *) 2
In this equation, L *, a * and b * represent the values measured on locks of hair after coloring and Lo *, ao * and bo * represent the values measured on locks of uncolored hair. The larger the value of ΔΕ *, the better the rise in color.
The stability of the coloration of the keratin fibers is also evaluated over time, in particular after 9 days by measuring the colon coordinates of the keratin fibers and by comparing them to the colon coordinates immediately after implementation of the coloring process according to the invention. The color difference ΔΕ * between the color at TO and the color after 9 days represents the stability of the hair color and is calculated by the following equation:
In this equation, Lo *, ao * and bo * represent the colorimetric coordinates measured on locks of hair at TO immediately after the implementation of the method and L3S *, a3S * and b * 3S represent the colorimetric coordinates 9 days after the implementation of the process. The lower the value of AE * stab, the more stable the coloration.
In particular, within the framework of the invention, a coloration for which the ΔΕ * 9 days after coloration is less than 2 is considered to be stable over time.
Note, we can in the same way evaluate the evolution of the coloration after 3 weeks, from the colorimetric coordinates 3 weeks after the coloration of the keratin fibers.
In the context of the present invention, it is therefore preferably sought to obtain immediately after the coloring process a value of b * as low as possible and / or a value of a * as high as possible. We seek to obtain these results while having an effective color rise (large color rise value) and stable coloring over time.
The following examples serve to illustrate the invention without, however, being limiting in nature.
EXAMPLES
Example 1
The following compositions were prepared from the following ingredients in the proportions indicated in grams.
Composition Ci)
Coloring composition Cii)
Application process
According to the invention:
Composition Ci) is applied to locks of 90% natural white hair, at a rate of 20 g of composition for 1 gram of hair left to stand for 30 minutes at 33 ° C. in plastic film and then rinsed.
Then applying a composition Cii) obtained after mixing at the time of the use of phases A and B and applied at the rate of 4 grams of mixture per gram of hair and left to stand for 15 minutes at 40 ° C. in plastic film.
Comparatives: 1 / Composition Ci) is applied to locks of 90% natural white hair, at a rate of 20 g of composition for 1 gram of hair left to stand for 30 minutes at 33 ° C. in plastic film and then rinsed. 2 / A composition Cii) _ obtained after mixing at the time of the use of phases A and B and applied at the rate of 4 grams of mixture per gram of hair and left to stand for 15 minutes at 40 ° C. in plastic film. At the end of the coloring pause time, the locks are rinsed and then shampooed with the Optimizer Anti Residue shampoo. Results
The colorimetric measurements were carried out using a Minolta CM3600D spectrocolorimeter (illuminant D65, angle 10 °, specular component included) in the CIELab system.
In this system, L * represents clarity. The lower the value of L *, the darker and more powerful the coloration obtained. Chromaticity is represented by the values a * and b *, a * representing the red / green axis and b * the yellow / blue axis.
The rise in color is represented by the difference in color ΔΕ between the non-colored lock and the colored lock: the higher the value of ΔΕ, the greater the rise in color. This value is calculated from the following equation (i):
In equation (i), L *, a * and b * represent the values measured on locks of uncolored hair, and Lo *, ao * and bo * represent the values measured on locks of colored hair.
The results are listed in the table below:
It is observed visually on the locks that the method of the invention makes it possible to very clearly intensify the color obtained on the hair compared to the methods using only one of the coloring compositions Ci) or Cii).
This is confirmed by the colorimetric measurements showing significantly higher ΔΕ values in the case of the method of the invention, that is to say a greater increase in coloring.
The colorimetric measurements also show significantly lower L * values in the case of the process of the invention, that is to say a more intense coloring.
Example 2
The following compositions were prepared from the following ingredients in the proportions indicated in grams:
Composition Ci)
Coloring composition Cii)
Application process
According to the invention:
Composition Ci), prepared at the time of use by mixing dyes and water, is applied to locks of 90% natural white hair, at a rate of 10 g of
composition for 1 gram of hair left for 60 minutes at 33 ° C in plastic film then rinsed and washed with a standard shampoo then the locks are dried.
Then applying a composition Cii) obtained after mixing at the time of the use of phases A and B (pH of the mixture = 2.5) and applied at the rate of 4 grams of mixture per gram of hair and left to stand for 15 minutes at 40 ° C. in plastic film.
Comparative:
Composition Ci), prepared at the time of use by mixing dyes and water, is applied to locks of 90% natural white hair, at a rate of 10 g of composition per 1 gram of hair left for 60 minutes. 33 ° C in plastic film then rinsed and washed with a standard shampoo then the locks are dried.
In both cases, at the end of the coloring pause time, the locks are rinsed and then shampooed with a standard shampoo. Results
The colorimetric measurements were carried out on the day of coloring (OJ) and 7 days after (D7), according to the protocol described above in Example 1.
The results are listed in the table below:
It is observed visually on the locks that the process of the invention makes it possible to very markedly intensify the color obtained on the hair compared to the process using only the composition Ci).
This is confirmed by the colorimetric measurements showing significantly higher values of Δ dans in the case of the method of the invention, that is to say a
greater increase in coloring, as well as significantly lower L * values in the case of the process of the invention, that is to say more intense coloring.
In addition, the method according to the invention makes it possible to reduce the change in color and in particular the shift towards yellow / green.
In addition, it is visually observed that the scalp is not or only slightly stained with the coloring process according to the invention.
Example 3
The following compositions were prepared from the following ingredients in the proportions indicated in grams:
Composition Ci)
Coloring composition Cii)
Application process
According to the invention:
Composition Ci), prepared at the time of use by mixing dyes and water, is applied to locks of 90% natural white hair, at a rate of 10 g of composition per 1 gram of hair left for 60 minutes. 33 ° C in plastic film then rinsed and washed with a standard shampoo then the locks are dried.
Then applying a composition Cii) obtained after mixing at the time of the use of phases A and B (pH of the mixture = 3) and applied at the rate of 4 grams of mixture per gram of hair and left to stand for 15 minutes at 40 ° C. in plastic film.
Comparative:
Composition Ci), prepared at the time of use by mixing dyes and water, is applied to locks of 90% natural white hair, at a rate of 10 g of composition per 1 gram of hair left for 60 minutes. 33 ° C in plastic film then rinsed and washed with a standard shampoo then the locks are dried.
In both cases, at the end of the coloring pause time, the locks are rinsed and then shampooed with a standard shampoo.
Results
The colorimetric measurements were carried out on the day of coloring (OJ) and 7 days after (D7), according to the protocol described above in Example 1.
The results are listed in the table below:
It is observed visually on the locks that the process of the invention makes it possible to very markedly intensify the color obtained on the hair compared to the process using only the composition Ci).
This is confirmed by the colorimetric measurements showing significantly higher values of ΔΕ in the case of the method of the invention, that is to say a greater increase in coloring, as well as significantly lower values of L * in the case of the process of the invention, that is to say a more intense coloring.
In addition, the method according to the invention makes it possible to reduce the change in color and in particular the shift towards yellow / green.
In addition, it is visually observed that the scalp is not or only slightly stained with the coloring process according to the invention.

权利要求:
Claims (27)
[1" id="c-fr-0001]
1. A process for dyeing keratin fibers, in particular human keratin fibers such as the hair, in which said fibers are treated in several distinct steps, comprising: i) at least one dyeing step i) of said fibers using a composition coloring cosmetic Ci), preferably aqueous, comprising at least a) indigo and / or henna, ii) at least one step of treatment ii) of said fibers comprising the application to the fibers of an aqueous composition (A ) which comprises b) at least one direct dye chosen from synthetic direct dyes and natural dyes, preferably distinct from henna and indigo, c) at least one thickener, d) preferably at least one organic solvent, and water and a composition B) which comprises at least e) a fatty substance, preferably an oil, the compositions (A) and (B) being applied either separately one after the other, or e n together in a single composition Cii), iii) optionally at least one intermediate rinsing step of said fibers, preferably with water, between step i) and step ii) (or between step ii ) and i) (depending on the order of steps i) and ii)).
[2" id="c-fr-0002]
2. Method according to the preceding claim wherein the composition Ci) comprises water, preferably comprises a water content ranging from 10% to 99% by weight, more particularly from 20% to 90% by weight, better still from 40 % to 80% by weight relative to the weight of the composition Ci).
[3" id="c-fr-0003]
3. Method according to any one of the preceding claims wherein the henna and / or indigo are in powder form.
[4" id="c-fr-0004]
4. Method according to any one of the preceding claims wherein the indigo is derived from indigofere plant (s), preferably of the genus Indigofera and more particularly Indigofera tinctoria.
[5" id="c-fr-0005]
5. Method according to any one of the preceding claims, characterized in that the henna is red henna.
[6" id="c-fr-0006]
6. Method according to any one of the preceding claims, characterized in that the composition Ci) comprises at least 0.1% by weight of henna and / or indigo, relative to the total weight of the said composition, more preferably 0.2 at 50% by weight, better still from 0.3 to 40% by weight, preferably from 1 to 30% by weight relative to the total weight of the composition Ci).
[7" id="c-fr-0007]
7. Dyeing method according to the preceding claim, characterized in that the composition (A) comprises at least one natural dye, preferably chosen from spinulosin, orceins, polyphenols or orthodiphenols (also called ODPs in the following description) ) and all extracts rich in ODPs, curcumin, indole derivatives such as isatin or indole-2,3-dione, phthalocyanines and porphyrins in particular metal complexed, glycosylated or non-glycosylated iridoids , chromene dyes, anthraquinone and naphthoquinone dyes, juglone, spinulosin, chromenic or chromanic dyes, such as neoflavanols and neoflavanones, flavanols; and anthocyanidols, orceins, betalains and mixtures thereof.
[8" id="c-fr-0008]
8. Method according to any one of the preceding claims, characterized in that the composition (A) comprises at least one natural dye chosen from carmine, carmine ammonium, diosindigo, chlorophyllin, hematin, orcein, the following extracts: blackcurrant, blueberry, black rice, grape skin, hibiscus, red cabbage, black carrot, elderberry, rhubarb, monascus, purple sweet potato, goji, radish, orcein, gardenia, persimmon diospyros, logwood, quebracho and their mixtures.
[9" id="c-fr-0009]
9. Method according to any one of the preceding claims, characterized in that the composition (A) comprises at least one synthetic direct dye, preferably from anionic direct dyes, better from anionic direct dyes chosen from those of formulas (I), ( II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI) and (XII) below, and their mesomeric, tautomeric forms :


formulas (I) and (II) in which: - R7, Rs, R9, R10, R'7, R's, R'9 and R'10, identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso; - R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X ”- with R ° representing a hydrogen atom, a alkyl or aryl group; X, X ’and X”, identical or different, representing an oxygen or sulfur atom or N R with R representing a hydrogen atom or an alkyl group; - (O) 2S (O ') -, M + with M + representing a hydrogen atom or a cationic counterion; - (O) CO'-, M + with M + as defined above; - R ”-S (O) 2-, with R” representing a hydrogen atom, an alkyl group, an aryl group, (di) (alkyl) amino, aryl (alkyl) amino; preferably a phenylamino or phenyl group; - R ’” - S (O) 2-X’- with R ’” representing an optionally substituted alkyl or aryl group, X ’as defined above; - (di) (alkyl) amino; - aryl (alkyl) amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) 2S (O ') -, M + and iv) alkoxy, with M + as defined above; - optionally substituted heteroaryl; - cycloalkyl; - Ar-N = N- with Ar representing an optionally substituted aryl group; - or then two contiguous groups R7 with Rs or Rs with Rg or Rg with R10 together form a fused benzo group A ’; and R’7 with R’s or R’s with R’g or R’g with R’10 together form a merged group benzo B ’; with A ’and B’ optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) 2S (O ') -, M +; iv) hydroxy; v) mercapto; vi) (di) (alkyl) amino; vii) R ° -C (X) -X’-; viii) R ° -X’-C (X) -; ix) R ° -X’-C (X) -X ”-; x) Ar-N = N- and xi) aryl (alkyl) amino optionally substituted; with M +, R °, X, X ’, X” and Ar as defined above; - W represents a sigma o bond, an oxygen or sulfur atom, or a divalent radical i) -NR- with R as defined above, or ii) methylene - C (Ra) (Rb) - with Ra and Rb identical or different, representing a hydrogen atom or an aryl group, or then Ra and Rb together form with the carbon atom which carries them a cycloalkyl spiro; it being understood that formulas (I) and (II) comprise at least one sulphonate (O) 2S (O ') -, M + radical or a carboxylate (O) CO'-, M + radical on one of the rings A, A', B, B 'or C; preferably sodium sulfonate;

formulas (III) and (IV) in which: - Ri i, R12 and Rw, identical or different, represent a hydrogen atom, halogen, an alkyl group or (O) 2S (O ') -, M + with M + as defined above; - R14 represents a hydrogen atom, an alkyl group or a C (O) O'-, M + group with M + as defined above; - R15 represents a hydrogen atom; - Rw represents an oxo group in which case R’w is absent, or else Rw with Rw together form a double bond; - Rn and Rw, identical or different, represent a hydrogen atom, or a group chosen from: - (O) 2S (O ') -, M + with M + as defined above;

- Ar-0-S (0) 2- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl groups; - R19 and R20, together form either a double bond or a benzo group D ’, optionally substituted; - R’w, R’19 and R’20, identical or different, represent a hydrogen atom or an alkyl or hydroxy group; - R21 represents a hydrogen atom, an alkyl or alkoxy group; - Ra and Rb, identical or different, are as defined above; - Y represents either a hydroxy group or an oxo group; _------ represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group; it being understood that formulas (III) and (IV) comprise at least one sulfonate radical (O) 2S (O ') -, M + or a carboxylate radical C (O) O'-, M + on one of the rings D or E; preferably sodium sulfonate;

formulas (V) and (VI) in which:

- R22, R23, R24, R25, R26 and R27, identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - hydroxy, mercapto; - alkoxy, alkylthio; - aryloxy or arylthio optionally substituted; - aryl (alkyl) amino optionally substituted by one or more groups chosen from alkyl and (O) 2S (O ') -, M + with M + as defined above; - (di) (alkyl) amino; - (di) (hydroxyalkyl) amino; - (O) 2S (O ') -, M + with M + as defined above; - Z 'represents a hydrogen atom or a group NR28R29 with R28 and R29, identical or different, representing a hydrogen atom or a group chosen from: - alkyl; - polyhydroxyalkyl such as hydroxyethyl; - Aryl optionally substituted by one or more groups more particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O) 2S (O ') -, M + with M + as defined above; iii) R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X ”-with R °, X, X 'and X” as defined above; - cycloaikyle; - Z represents a group chosen from hydroxy and NR’28R’29 with R’2s and R’29, identical or different, representing the same atoms or groups as R28 and R29 as defined above; it being understood that formulas (V) and (VI) comprise at least one sulfonate radical (O) 2S (O ') -, M + or a carboxylate radical C (O) O'-, M +; preferably sodium sulfonate;



ÇVIIIj formulas (VII) and (VIII) in which: - R30, R31 and R32, identical or different, represent a hydrogen or halogen atom or a group chosen from: - alkyl; - alkoxy optionally substituted by one or more hydroxy groups, alkÿlthio optionally substituted by one or more hydroxy groups> - hydroxy, mercapto; - nitro, nitroso; - polyhaloalkyl; - R ° -C (X) -X’-, R ° -X’-C (X) -, R ° -X’-C (X) -X ”- with R °; X, X ’and X” as defined above; - (O) 2S (O ') -, M + with M + as defined above; - (O) CO'-, M + with M + as defined above; - (di) (alkyl) amino; - (di) (hydroxyalkyl) amino; - heterocycloalkyl; - Rc and Rd, identical or different, represent a hydrogen atom or an alkyl group; - W is as defined above; - ALK represents a divalent alkylene group, linear or branched, in C1-Cs; - n is 1 or 2; - p represents an integer inclusive between 1 and 5; - q represents an integer inclusive between 1 and 4; - u is 0 or 1; - when n is 1, J represents a nitro group, or nitroso; - when n is 2, J represents an oxygen, sulfur atom or a divalent radical -S (O) m- with m representing an integer 1 or 2; - Represents me a hydrogen atom or a cationic counterion;

cx present or absent represents a benzo group optionally substituted by one or more R30 groups as defined above; it being understood that formulas (VII) and (VIII) comprise at least one sulfonate radical (O) 2S (O ') -, M + or a carboxylate radical 0 (0) 0 "-, M +;

formula (IX) in which: - R33, R34, R35 and R36, identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; - R37, R38, R39, R40, R41, R42, R43 and R44, identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - (di) (alkyl) amino; - hydroxy, mercapto; - nitro, nitroso; - R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X ”- with R ° representing a hydrogen atom, a alkyl or aryl group; X, X ’and X”, identical or different, representing an oxygen or sulfur atom or N R with R representing a hydrogen atom or an alkyl group; - (O) 2S (O ') -, M + with M + representing a hydrogen atom or a cationic counterion; - (O) CO'-, M + with M + as defined above;

- or then two contiguous groups R41 with R42 or R42 with R43 or R43 with R44 together form a benzo fused group: I ’; with I 'optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) 2S (O ') -, M +; iv) hydroxy; v) mercapto; vi) (di) (alkyl) amino; vii) R ° -C (X) -X’-; viii) R ° -X’-C (X) -; ix) R ° -X’-C (X) -X ”-; with M +, R °, X, X ’, X” as defined above; more particularly R37 to R4o represent a hydrogen atom, and R4i to R44, identical or different, represent a hydroxy group or (O) 2S (O ') -, M +; and when R43 with R44 together form a benzo group; it is preferably substituted by an (O) 2S (O ') - group; it being understood that at least one of the rings G, H, I or I ’comprises at least one sulfonate radical (O) 2S (O ') - or a carboxylate radical C (O) O'-;

formula (X) in which: - R45, R46, R47 and R48, identical or different, represent a hydrogen atom or a halogen atom; - R49, R50, R51 and R52, identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso; - (O) 2S (O ') -, M + with M + representing a hydrogen atom or a cationic counterion; - (O) CO'-, M + with M + as defined above; preferably R49 R50, R51 and R52 represent a hydrogen or halogen atom;

- G represents an oxygen, sulfur atom or an NRe group with Re as defined above; - L represents an alcoholate 0; M +; a thioalcoholate S; M + or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M + as defined above; - The represents an oxygen, sulfur atom or an ammonium group: N + RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an optionally substituted alkyl, aryl group; - Q and Q ’, identical or different, represent an oxygen or sulfur atom; - M + is as defined above;

formula (XI) in which: - R53, R54, R55, Rse, R57, Rsa, R59 and R6o, identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkÿlthio; - hydroxy, mercapto; - nitro, nitroso; - R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X ”- with R ° representing a hydrogen atom, a alkyl or aryl group; X, X and X ”, identical or different, representing an oxygen, sulfur atom or N R with R representing a hydrogen atom or an alkyl group; - (0) 2S (0 ') -, M + with M + representing a hydrogen atom or a cationic counterion; - (O) CO'-, M + with M + as defined above; - G represents an oxygen, sulfur atom or an NRe group with Re as defined above; - R, and Rh, identical or different, represent a hydrogen atom or an alkyl group;

it being understood that formula (XI) comprises at least one sulfonate radical (O) 2S (O ') -, M + or a carboxylate radical C (O) O'-, M +;

- Rei represents a hydrogen atom, a halogen atom or an alkyl group> - R62, R63, and R64, identical or different, represent a hydrogen atom or a group (O) 2S (O ') -, M + with M + representing a hydrogen atom or a cationic counterion; - or then R6i with R62, or R6i with R64, together form a benzo group optionally substituted by one or more (O) 2S (O ') groups -, M + with M + representing a hydrogen atom or a cationic counterion; it being understood that formula (XII) comprises at least one sulphonate radical (O) 2S (O -) -.
[10" id="c-fr-0010]
10. Method according to any one of the preceding claims, characterized in that the direct dye (s) are chosen from 1,2-dihydroxy-9.10-anthraquinone-3-sulfonic acid, the monosodium salt of 2- acid [(9,10-dihydro-4-hydroxy-9,10-dioxo-1-anthracenyl) -amino] -5-methyl-benzene sulfonic, the monosodium salt of acid 4 - [(2-hydroxy-1- naphthalenyl) -azo] -benzene sulfonic, the disodium salt of 5-hydroxy-5 acid - [(4-sulfophenyl) -azo] -2-naphthalene sulfonic, the disodium salt of 5-amino-4- acid hydroxy-3- (phenylazo) -2,7-naphthalene disulfonic acid, the disodium salt of 1-amino-2- (4'-nitrophenylazo) -7-phenylazo-8-hydroxy-3,6-naphthalene disulfonic acid, the disodium salt of N-ethyl-N- [4 - [[4- [ethyl [3-sulfophenyl) -methyl] -amino] -phenyl] (2-sulfophenyl) -methylene] -2,5-cyclohexadien-1- ylidene] -3-sulfobenzenemethanaminium hydroxide, the disodium salt of the acid 2,2 '- [(9,10-dihydro- 9.10- dioxo-1,4-anthracenediyl) -diimino] -bis- [5-methyl] - benzen e sulfonic, the trisodium salt of 5-hydroxy-1- (4-sulfophenyl) -4- (4-sulfophenylazo) pyrazole-3-carboxylic acid, 4 - [(9,10-dihydro-4-hydroxy- 9,10-dioxo-1 -anthryl) amino] sodium toluene-3-sulfonate, the trisodium salt of 7-hydroxy-8 acid - [(4-sulfo-1-naphthalenyl) azo] -1,3- naphthalenedisulfonic and a mixture of these compounds.


[11" id="c-fr-0011]
11. Method according to any one of the preceding claims, characterized in that the direct dye (s) represent a total content of at least 0.01% by weight, preferably at least 0.05% by weight, preferably from 0.1 to 5% by weight, relative to the total weight of the compositions (A) and (B) applied to the fibers.
[12" id="c-fr-0012]
12. Method according to any one of the preceding claims, characterized in that the aqueous phase thickener (s) are chosen from non-associative thickening polymers with sugar units, non-associative thickening polymers without sugar unit, associative thickening polymers, and mixtures of these compounds, preferably are chosen from polymers not comprising sugar units, and more particularly are chosen from thickening polymers with associative or non-associative acrylic or methacrylic units, polymers with 2-acrylamido-2- acid units sulfonic methyl propane and / or their salified form.
[13" id="c-fr-0013]
13. Method according to any one of the preceding claims, characterized in that the aqueous phase thickener (s) are chosen from homopolymers or copolymers of acrylic acid, in particular homopolymers of acrylic acid, homopolymers or copolymers of 2-acrylamido-2-methyl-propane sulfonic acid and / or their salified form, in particular copolymers of 2-acrylamido-2-methyl-propane sulfonic acid and / or their salified form, more particularly copolymers of acid 2 -acrylamido-2-methyl-propane sulfonic acid and / or their salified form and acrylamide or the copolymers of 2-acrylamido-2-methyl-propane sulfonic acid and / or their salified form and hydroxyethylacrylate, said polymers being crosslinked or uncrosslinked.
[14" id="c-fr-0014]
14. Method according to any one of the preceding claims, characterized in that the organic solvent (s) are chosen from linear or branched monoalcohols having from 1 to 8 carbon atoms, polyols, polyethylene glycol, aromatic alcohols and mixture of these compounds, more preferably are chosen from ethanol, propanol, butanol, isopropanol, isobutanol, propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerol, sorbitol , benzyl alcohol, phenoxyethanol, and mixtures of these compounds, and in particular are chosen from ethanol, dipropylene glycol, benzyl alcohol and a mixture of these compounds.
[15" id="c-fr-0015]
15. Method according to any one of the preceding claims, characterized in that the water represents from 20 to 85% by weight, preferably from 30 to 80% by weight, and more preferably from 40 to 70% by weight relative to the total weight of the compositions (A) and (B)) applied to the fibers.
[16" id="c-fr-0016]
16. Method according to any one of the preceding claims, characterized in that the water represents from 50 to 95% by weight, preferably from 60 to 93% by weight, and more preferably from 65 to 90% by weight relative to the total weight of the aqueous composition (A)
[17" id="c-fr-0017]
17. Method according to any one of the preceding claims, characterized in that the composition (B) comprises at least one oil.
[18" id="c-fr-0018]
18. Method according to the preceding claim, characterized in that the oil or oils are chosen from C 1 -C 6 alkanes, hydrocarbons, linear or branched, of mineral or synthetic origin of more than 16 carbon atoms, oils not silicone of animal origin, oils of vegetable origin, fluorinated oils, liquid fatty alcohols, liquid fatty esters, non-salified liquid fatty acids, silicone oils, and mixtures of these compounds, preferably are chosen among the Ce-Cw alkanes, hydrocarbons, linear or branched, of mineral or synthetic origin of more than 16 carbon atoms, liquid fatty alcohols, liquid fatty esters, oils of vegetable origin, in particular hydrocarbon oils of plant origin, and mixtures of these compounds, and more preferably are chosen from C 1 -C 6 alkanes, hydrocarbons, linear or branched, of mineral origin or synthetic with more than 16 carbon atoms, liquid fatty alcohols, oils of vegetable origin, in particular hydrocarbon oils of vegetable origin, and mixtures of these compounds.
[19" id="c-fr-0019]
19. Method according to any one of the preceding claims, characterized in that the fatty substance (s), preferably the liquid fatty substance (s) or oils, represent a total content ranging from 8 to 50% by weight, preferably from 10 to 45% by weight, and better still from 15 to 40% by weight relative to the total weight of the compositions (A) and (B) applied to the fibers.
[20" id="c-fr-0020]
20. Method according to any one of the preceding claims, characterized in that the fatty substance (s), preferably the liquid fatty substance (s) or oils, represent a total content ranging from 50 to 99% by weight, preferably from 70 98% by weight, and better still 80 to 95% by weight relative to the total weight of the composition (B).
[21" id="c-fr-0021]
21. Method according to any one of the preceding claims, characterized in that the composition (B) comprises at least h) a fatty phase thickener, distinct from the fatty substances g), preferably chosen from mineral fatty phase thickeners, organic fatty phase thickeners, and mixtures of these compounds, are preferably chosen from semi-crystalline polymers, non-silicone polyamides, silicone polyamides, mono- or polyalkyl esters of saccharide or polysaccharide such as palmitate dextrin, N-acylated amino acid amide derivatives, polymers comprising one or more alkylene and / or styrene blocks, such as stearyl polyacrylates, elastomeric organopolysiloxanes, solid fatty esters, in particular fatty acid esters of C8 -C30, preferably C18-C24, and mixtures of these compounds, and more preferably are chosen from semi-cr istallins, non-silicone polyamides, silicone polyamides, saccharide or polysaccharide mono- or polyalkyl esters such as dextrin palmitate, polymers comprising an alkylene and / or styrene block such as stearyl polyacrylates, solid fatty esters, in particular the fatty acid esters of C8-C30, preferably of C18-C24, and mixtures of these compounds.
[22" id="c-fr-0022]
22. Method according to the preceding claims, characterized in that the fatty phase thickener (s) are chosen from mono- or polyalkyl esters of saccharide or polysaccharide such as dextrin palmitate, esters of C8-C30 fatty acids, preferably C18-C24 and mixtures thereof, better still the mono-, di- or triesters of C8-C30 fatty acids, preferably C18-C24 and polyols, more particularly the mono-, di- or triesters of C8-C30 fatty acids, preferably C18-C24, and glycerol.
[23" id="c-fr-0023]
23. Method according to any one of the preceding claims, characterized in that the weight ratio of the quantity of composition (B) to the quantity of aqueous composition (A) is greater than 0.10 and preferably greater than 0 , 10 and less than or equal to 1, preferably ranges from 0.15 to 0.7 and more preferably from 0.25 to 0.5.
[24" id="c-fr-0024]
24. Method according to any one of the preceding claims, characterized in that the compositions (A) and (B) are applied together in one and the same composition Cii) prepared beforehand or obtained by an extemporaneous mixture before application, and preferably prepared beforehand.
[25" id="c-fr-0025]
25. Dyeing method according to any one of the preceding claims, characterized in that it implements: i) the step of treatment i) of said fibers using the cosmetic composition Ci) as defined according to any one of preceding claims then ii) the treatment step ii) with the composition Cii) as defined according to any one of the preceding claims.
[26" id="c-fr-0026]
26.. Coloring method according to any one of the preceding claims, characterized in that the treatment step ii) comprises the application of the compositions (A) and (B) together in a single composition.
[27" id="c-fr-0027]
27. A coloring method according to any one of the preceding claims, characterized in that it implements a rinsing step iii), preferably with water, between steps i) and ii).

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同族专利:

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公开号 | 公开日

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FR3075637B1|2019-11-22|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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FR3004942A1|2013-04-26|2014-10-31|Oreal|CAPILLARY COLORING PROCESS USING HENNE THEN INDIGO AND OIL AND / OR BUTTER|FR3098116A1|2019-07-05|2021-01-08|L'oreal|A composition comprising a natural dye, a triarylmethane direct dye and an aromatic compound|

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FR3098118A1|2019-07-05|2021-01-08|L'oreal|Composition comprising a natural dye, an anthraquinone cationic direct dye and an aromatic compound|

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WO2021123061A1|2019-12-20|2021-06-24|L'oreal|Process for preparing a composition for dyeing the hair starting from a composition in powder form and an aqueous composition|

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法律状态:
2018-11-20| PLFP| Fee payment|Year of fee payment: 2 |

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2019-06-28| PLSC| Publication of the preliminary search report|Effective date: 20190628 |

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2019-11-15| PLFP| Fee payment|Year of fee payment: 3 |

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2020-11-12| PLFP| Fee payment|Year of fee payment: 4 |

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2021-11-15| PLFP| Fee payment|Year of fee payment: 5 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1763115A|FR3075637B1|2017-12-22|2017-12-22|HAIR COLORING PROCESS COMPRISING A COLORING STEP WITH HENNE AND / OR INDIGO AND A PROCESSING STEP COMPRISING THE APPLICATION OF AQUEOUS PHASE, A FATTY PHASE AND A DIRECT COLOR|

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FR1763115|2017-12-22|FR1763115A| FR3075637B1|2017-12-22|2017-12-22|HAIR COLORING PROCESS COMPRISING A COLORING STEP WITH HENNE AND / OR INDIGO AND A PROCESSING STEP COMPRISING THE APPLICATION OF AQUEOUS PHASE, A FATTY PHASE AND A DIRECT COLOR|