Patent Application
20250073147
The present invention relates to a process for colouring the hair comprising the application to the hair of at least one composition C comprising one or more (poly)carbodiimide compounds; and the application to the hair of at least one composition D comprising at least one silicone elastomer containing carboxylic acid functions. Composition C and/or composition D comprise at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.
In the field of colouring keratinous hair fibres, in particular human keratinous hair fibres, it is already known practice to colour keratinous hair fibres via various techniques using direct dyes or pigments for non-permanent colouring, or dye precursors for permanent colouring.
There are essentially three types of process for colouring the hair:
For this last type of colouring, it is known practice to use pigments. Specifically, the use of pigment on the surface of keratinous fibres generally makes it possible to obtain colourings that are visible on dark hair, since the surface pigment masks the natural colour of the fibre. However, the colourings obtained via this colouring method have the drawback of having poor resistance to shampoo washing and also to external agents such as sebum, perspiration, brushing and/or rubbing.
There is thus still a need for a process for colouring the hair, which has the advantage of obtaining a uniform-coloured coating on the hair, while at the same time forming a coating that is persistent with respect to shampoo washing and to the various attacking factors to which the hair may be subjected such as brushing and/or friction without degradation of the cosmetic properties of the hair.
Thus, the aim of the present invention is to develop a process for colouring the hair, which has the advantage of obtaining a smooth and uniform coloured coating on the hair, while at the same time forming a coating that is persistent with respect to shampoo washing and to the various attacking factors to which the hair may be subjected such as brushing and/or friction without degradation of the cosmetic properties of the hair.
One subject of the present invention is thus a process for colouring the hair comprising the following steps:
By means of the process for colouring the hair according to the invention, coloured coatings are obtained on the hair that make it possible to obtain a colouring that is visible on all types of hair in a manner that is persistent with respect to shampoo washing, while at the same time preserving the physical qualities of the hair.
Such a coating may be resistant to the external attacking factors to which the hair may be subjected, such as blow-drying and perspiration. It makes it possible in particular to obtain a uniform deposit.
For the purposes of the present invention, the term “colouring that is persistent with respect to shampoo washing” means that the colouring obtained persists after one shampoo wash, preferably after three shampoo washes, more preferentially after five shampoo washes.
The term “keratinous hair fibres” means the hair. In other words, the expressions “keratinous hair fibres” and “hair” are equivalent in the remainder of the description.
For the purposes of the present invention, the term “hair” means the hair on the head. This term does not correspond to body hair, the eyebrows or the eyelashes.
The term “at least one” means one or more.
Unless indicated otherwise, the limits of a range of values are included in this range, in particular in the expressions “between” and “ranging from . . . to . . . ”.
The invention is not limited to the illustrated examples. The characteristics of the various examples may notably be combined within variants which are not illustrated.
For the purposes of the present invention and unless otherwise indicated:
Unless indicated otherwise, when compounds are mentioned in the present application, this is understood to also mean the optical isomers thereof, the geometric isomers thereof, the tautomers thereof and the salts thereof, alone or in a mixture.
Composition C employed within the context of the process according to the invention comprises at least one (poly)carbodiimide compound.
The composition may comprise at least two different (poly)carbodiimide compounds, present as a mixture in the composition.
The term “(poly)carbodiimide compound” means a compound comprising one or more carbodiimide groups, preferably at least two carbodiimide groups, more preferentially at least three carbodiimide groups; in particular, the number of carbodiimide groups does not exceed 200, preferably 150, more preferentially 100.
The term “carbodiimide group” means a divalent linear triatomic fraction of general formula —(N═C═N)—.
The (poly)carbodiimide compound(s) according to the invention may optionally comprise in their structure one or more reactive groups different from carbodiimide groups, chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups.
The reactive group(s) other than the carbodiimide groups may be side or end groups. Preferably, the (poly)carbodiimide compound(s) comprise one or more end groups different from carbodiimide groups, preferably one or more end groups chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups.
According to a particular embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) below:
in which:
According to another embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I′) below:
in which:
Preferably, Z1 and Z2 independently represent a reactive end group; more preferentially, Z1 and Z2 independently represent a group chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups.
Such (poly)carbodiimide compounds are sold, for example, by the company Stahl B.V, under the name Permutex XR, or under the name RelcaLink10. or under the name Picassian XL and by the company Nisshinbo under the name Carbodilite with the series V-02, V-02-L2, SV-02, E-02, V-10, SW-12G, E-03A, E-04DG-T, E-05, V-04, V-02B, V-04PF, V-05.
Preferably, the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) below:
in which:
The term “hydrocarbon-based radical” means a saturated or unsaturated, linear or branched radical containing from 1 to 300 carbon atoms, preferably from 1 to 250 carbon atoms, more preferentially from 1 to 200 carbon atoms. Preferably, the hydrocarbon-based radical is a saturated linear radical.
The hydrocarbon-based radical may comprise one or more cyclic groups.
The hydrocarbon-based radical may be interrupted with one or more heteroatoms, in particular chosen from O, S or N and/or substituted with one or more cations, anions or zwitterions or cationic groups such as ammonium, anionic groups such as carboxylate, or zwitterionic groups, and/or comprising a metal ion which may be incorporated in the form of a salt.
The term “heteroatom(s)” means an oxygen 0, sulfur S or nitrogen N atom, and also halogen atoms such as Cl, F, Br and I. If the heteroatom is included in the chain of the hydrocarbon-based radical, the heteroatom is preferably chosen from oxygen O, sulfur S or nitrogen N atoms.
Preferably, X1 and X2 independently represent an oxygen atom.
Preferably, R1 and R2 are independently chosen from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, and mixtures thereof.
In a preferred embodiment, R1 and R2 are independently chosen from groups (i) to (iv) below:
R7—O—C(O)—C(R8)(H)— (III),
in which R7 represents a C1-C3 alkyl group and R8 represents a hydrogen atom or a C1-C3 alkyl group; preferably, R7 is a methyl and R8 is a hydrogen atom or a methyl.
R9—[O—CH2—C(H)(R10)]p— (IV),
in which R9 represents a C1-C4 alkyl group, R10 represents a hydrogen atom or a C1-C4 alkyl group and p denotes an integer ranging from 1 to 3; preferably, R9 is a methyl, ethyl or butyl, R10 is a hydrogen atom or a methyl and p is equal to 1.
(R11)2N—CH2—C(H)(R12)— (V),
in which R11 represents a C1-C4 alkyl group and R12 represents a hydrogen atom or a C1-C4 alkyl group; preferably, R11 is a methyl, ethyl or butyl and R12 is a hydrogen atom or a methyl.
R13—[O—CH2—C(H)(R14)]q— (VI),
in which R13 represents a C1-C4 alkyl group or a phenyl, R14 represents a hydrogen atom or a C1-C4 alkyl group and q denotes an integer ranging from 4 to 30; preferably, R13 is a methyl, ethyl or butyl and R14 is a hydrogen atom or a methyl.
Preferably, R1 and R2 independently represent a compound of formula (VI) in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.
According to an alternative embodiment, R1 and R2 are different and one of the radicals R1 or R2 represents a compound of formula (IV) as described above and the other radical R1 or R2 represents a compound of formula (VI) as described above.
Preferably, in formula (IV), R9 is a methyl, ethyl or butyl and R10 is a hydrogen atom or a methyl and p is equal to 1.
Preferably, in formula (VI), R13 is a methyl, ethyl or butyl and R14 is a hydrogen atom or a methyl and q denotes an integer ranging from 4 to 30.
According to another alternative embodiment, R1 and R2 are identical and represent a compound of formula (VI) in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.
Preferably, n denotes an integer ranging from 1 to 20, more preferentially from 2 to 20.
Preferably, z denotes an integer ranging from 1 to 20, more preferentially from 2 to 20.
Preferably, w is equal to 1.
Preferably, w is equal to 1, n+z denotes an integer ranging from 4 to 10.
Preferably, L1 is chosen from a C1-C15 divalent aliphatic hydrocarbon-based radical such as methylene, ethylene and propylene, a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene and cyclohexylene, a C3-C12 heterocycloalkylene group such as imidazolene, pyrrolene and furanylene, or a C6-C14 arylene group such as phenylene, and mixtures thereof.
For example, L1 may be chosen from a radical derived from tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis(8-isocyanatooctyl)-1,3-dioctylcyclobutane, 4,4′-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-napththylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate and phenylene diisocyanate, and mixtures thereof.
Preferably, L1 is chosen from a C3-C15 cycloalkylene radical or a C6-C14 arylene group, and mixtures thereof, such as the compounds of formula (VII) below:
Preferably, L1 is 4,4-dicyclohexylenemethane corresponding to formula (VIII) below:
According to another embodiment, when L1 is a C6-C14 arylene group, L1 is not the m-tetramethylxylylene radical represented by formula (IX) below:
As indicated previously, E independently represents a group chosen from:
Preferably, R3 and R4 are independently chosen from a C6-C14 arylene radical such as phenylene, a C3-C12 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C1-C18 alkylene radical such as methylene and ethylene, optionally interrupted with one or more heteroatoms, and mixtures thereof.
More preferentially, R3 and R4 are independently chosen from a linear or branched C1-C18 alkylene radical such as methylene, butylene, propylene or ethylene, optionally interrupted with one or more heteroatoms.
Preferably, when R5 is not a covalent bond, R5 is chosen from a C6-C14 arylene radical such as phenylene, a C3-C12 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C1-C18 alkylene radical such as methylene and ethylene, optionally interrupted with one or more heteroatoms, and mixtures thereof.
Preferably, R6 is chosen from a C6-C14 arylene radical such as phenylene, a C3-C12 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C1-C18 alkylene radical such as methylene and ethylene, optionally interrupted with one or more heteroatoms, and mixtures thereof.
Preferably, E represents a group —O—R3—O— in which R3 is chosen from a C6-C14 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched C1-C18 alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.
More preferentially, E represents a group —O—R3—O— in which R3 represents a linear or branched C1-C18 alkylene radical such as methylene, butylene, propylene or ethylene, optionally interrupted with one or more heteroatoms.
According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from α-methylstyryl isocyanates of formula (X) below:
In this embodiment, the term “alkyl group” is as defined previously.
In this embodiment, the term “cycloalkyl group” is as defined previously.
In this embodiment, n may denote an integer ranging from 2 to 50, preferably from 3 to 30 and even more preferentially from 5 to 10.
According to another particular embodiment, the (poly)carbodiimide compound is a compound of formula (XI) below:
The “alkyl group”, the “cycloalkyl group” and the “aryl group” are as defined previously.
According to a preferred embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) or of formula (II) in which:
Preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:
More preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:
Even more preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:
R13—[O—CH2—C(H)(R14)]q— (VI),
Even more preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:
R13—[O—CH2—C(H)(R14)]q— (VI)
in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;
According to a preferred embodiment, the (poly)carbodiimide compound is a compound of formula (XII) below:
Advantageously, the total amount of the (poly)carbodiimide compound(s) ranges from 0.01% to 40% by weight, preferably from 0.5% to 30% by weight, more preferentially from 1% to 20% by weight, even more preferentially from 2% to 15% and better still from 3% to 10% by weight relative to the total weight of composition C.
Composition C may also comprise at least one anionic thickener, preferably a non-carboxylic anionic thickener.
For the purposes of the present invention, the term “non-carboxylic agent” means an agent which does not comprise any carboxylic acid functions (—COOH) or carboxylate functions (—COO—).
For the purposes of the present invention, the term “thickener” means a compound which increases the viscosity of a composition into which it is introduced to a concentration of 0.05% by weight relative to the total weight of the composition, by at least 20 cps, preferably by at least 50 cps, at room temperature (25° C.), at atmospheric pressure and at a shear rate of 1 s−1 (the viscosity may be measured using a cone/plate viscometer, a Haake R600 rheometer or the like).
Preferably, the non-carboxylic anionic thickener(s) are chosen from non-carboxylic anionic polymers, more preferentially from anionic polymers bearing (a) sulfonic group(s).
For the purposes of the invention, the term “anionic polymer” means a polymer comprising one or more anionic or anionizable groups, and not comprising any cationic or cationizable groups.
Advantageously, the non-carboxylic anionic thickener(s) are chosen from anionic polymers including at least one ethylenically unsaturated monomer bearing a sulfonic group, in free form or partially or totally neutralized form.
These polymers may be crosslinked or non-crosslinked. They are preferably crosslinked.
These polymers may be associative or non-associative, preferably non-associative.
It is recalled that “associative polymers” are polymers that are 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.
The term “hydrophobic group” means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.
Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.
The ethylenically unsaturated monomers bearing a sulfonic group are notably chosen from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(C1-C22)alkylsulfonic acids, N—(C1-C22)alkyl(meth)acrylamido(C1-C22)alkylsulfonic acids such as undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.
(Meth)acrylamido(C1-C22)alkylsulfonic acids, for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, will more preferentially be used. 2-Acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially or totally neutralized forms thereof, will more particularly be used.
Among the 2-acrylamido-2-methylpropanesulfonic acid copolymers, mention may be made of partially or totally neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of acrylamide; mention may be made in particular of the product described in Example 1 of EP 503 853, and reference may be made to said document as regards these polymers.
Mention may also be made of copolymers of 2-acrylamido-2-methylpropanesulfonic acid or salts thereof and of hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT 10 by the company SEPPIC (INCI name: hydroxyethylacrylate/sodium acryloyldimethyl taurate copolymer).
The associative AMPS polymers may notably be chosen from statistical associative AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or di-n-alkylamine, 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 ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acid derivatives, such as esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, or mixtures of these compounds.
The preferred polymers of this family are chosen from associative copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer.
These same copolymers may also contain one or more ethylenically unsaturated monomers not including a fatty chain, such as (meth)acrylic acid derivatives, notably esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, or mixtures of these compounds.
These copolymers are described notably in patent application EP-A 750 899, patent U.S. Pat. No. 5,089,578 and in the following publications from Yotaro Morishima:
Among these polymers, mention may be made of:
Mention may also be made of copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.
Preferably, the non-carboxylic anionic thickener(s) are chosen from sodium 2-acrylamido-2-methylpropanesulfonate/hydroxyethyl acrylate copolymer, sold by the company SEPPIC (INCI name hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer).
Advantageously, the total amount of the anionic thickener(s) can range from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, better still from 0.1% to 5% by weight, and even better still from 0.1% to 3% by weight, relative to the total weight of composition C.
Advantageously, the total amount of the non-carboxylic anionic thickener(s) can range from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, better still from 0.1% to 5% by weight, and even better still from 0.1% to 3% by weight, relative to the total weight of composition C.
Composition C employed within the context of the process according to the invention may also comprise at least one amino silicone.
The term “amino silicone” denotes any silicone including at least one primary, secondary or tertiary amine or a quaternary ammonium group.
The weight-average molecular masses of these amino silicones may be measured by gel permeation chromatography (GPC) at room temperature (25° C.), as polystyrene equivalent. The columns used are p styragel columns. The eluent is THF and the flow rate is 1 ml/min. 200 μl of a 0.5% by weight solution of silicone in THF are injected. Detection is performed by refractometry and UV-metry.
Preferably, the amino silicone(s) that may be used in the context of the invention are chosen from:
R′aG3-a-Si(OSiG2)n-(OSiGbR′2-b)m—O-SiG3-a-R′a (B)
Preferably, the amino silicone(s) are chosen from the amino silicones of formula (B).
Preferably, the amino silicones of formula (B) are chosen from the amino silicones corresponding to formulae (C), (D), (E), (F) and/or (G) below.
According to a first embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones known as “trimethylsilyl amodimethicone” corresponding to formula (C):
According to a second embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (D) below:
Preferably, the alkoxy radical is a methoxy radical.
The hydroxy/alkoxy mole ratio preferably ranges from 0.2:1 to 0.4:1 and preferably from 0.25:1 to 0.35:1 and more particularly is equal to 0.3:1.
The weight-average molecular mass (Mw) of these silicones preferably ranges from 2000 to 1 000 000 and more particularly from 3500 to 200 000.
According to a third embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (E) below:
Preferably, the alkoxy radical is a methoxy radical.
The hydroxy/alkoxy mole ratio generally ranges from 1:0.8 to 1:1.1 and preferably from 1:0.9 to 1:1 and more particularly is equal to 1:0.95.
The weight-average molecular mass (Mw) of the silicone preferably ranges from 2000 to 200 000, even more particularly from 5000 to 100 000 and more particularly from 10 000 to 50 000.
The commercial products comprising silicones of structure (D) or (E) may include in their composition one or more other amino silicones the structure of which is different from formula (D) or (E).
A product containing amino silicones of structure (D) is sold by the company Wacker under the name Belsil® ADM 652.
A product containing amino silicones of structure (E) is sold by Wacker under the name Fluid WR 1300® or under the name Belsil ADM Log 1.
When these amino silicones are used, one particularly advantageous embodiment consists in using them in the form of an oil-in-water emulsion. The oil-in-water emulsion may comprise one or more surfactants. The surfactants may be of any nature but are preferably cationic and/or nonionic. The number-average size of the silicone particles in the emulsion generally ranges from 3 nm to 500 nm. Preferably, notably as amino silicones of formula (E), use is made of microemulsions with a mean particle size ranging from 5 nm to 60 nm (limits included) and more particularly from 10 nm to 50 nm (limits included). Thus, use may be made according to the invention of the amino silicone microemulsions of formula (E) sold under the names Finish CT 96 E® or SLM 28020® by the company Wacker.
According to a fourth embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (F) below:
The weight-average molecular mass (Mw) of these amino silicones preferably ranges from 2000 to 1 000 000 and even more particularly from 3500 to 200 000.
Another silicone corresponding to formula (B) is, for example, the Xiameter MEM 8299 Emulsion from Dow Corning (INCI name: amodimethicone and trideceth-6 and cetrimonium chloride).
According to a fifth embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (G) below:
The weight-average molecular mass (Mw) of these amino silicones preferably ranges from 500 to 1 000 000 and even more particularly from 1000 to 200 000.
A silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from Dow Corning.
Such amino silicones are notably described in patent U.S. Pat. No. 4,185,087.
These silicones are described, for example, in patent application EP-A 0 530 974.
Said silicones are preferably formed from repeating units having the following general formulae:
[—(SiMe2O)xSiMe2-R—N(R″)—R′—O(C2H4O)a(C3H6O)b—R′—N(H)—R—]
or alternatively
[—(SiMe2O)xSiMe2-R—N(R″)—R′—O(C2H4O)a(C3H6O)b—]
The siloxane blocks preferably represent between 50 mol % and 95 mol % of the total weight of the silicone, more particularly from 70 mol % to 85 mol %.
The amine content is preferably between 0.02 and 0.5 meq/g of copolymer in a 30% solution in dipropylene glycol, more particularly between 0.05 and 0.2.
The weight-average molecular mass (Mw) of the silicone is preferably between 5000 and 1 000 000 and more particularly between 10 000 and 200 000.
Mention may notably be made of the silicones sold under the name Silsoft A− 843 or Silsoft A+ by Momentive.
Preferably, the amino silicones of formula (B) are chosen from the amino silicones corresponding to formula (E).
Preferably, composition C employed within the context of the process according to the invention comprises at least one amino silicone having the INCI name amodimethicone, preferably introduced in the form of an emulsion or microemulsion with surfactants.
Preferably, composition C employed within the context of the process according to the invention comprises at least one amino silicone having the INCI name amodimethicone as an emulsion or microemulsion with surfactants, having the INCI name trideceth-5 and trideceth-10.
The amino silicone(s) may be present in a total amount ranging from 0.01% to 20%, preferably from 0.05% to 15%, more preferentially from 0.1% to 10%, even more preferentially from 0.25% to 8% by weight and better still from 0.3% to 5% by weight relative to the total weight of composition C.
Composition C employed within the context of the process according to the invention may comprise one or more organic solvents.
Preferably, the composition comprises ethanol.
The organic solvents may be present in a total amount ranging from 0.01% to 50% by weight, preferably ranging from 0.1% to 45% by weight and preferably ranging from 1% to 40% by weight relative to the total weight of composition C.
Composition C employed within the context of the process according to the invention may be aqueous. The water content may range from 1% to 90% by weight, preferably from 10% to 80% by weight and more preferentially from 20% to 75% by weight relative to the total weight of composition C.
Composition D employed within the context of the process according to the invention comprises at least one silicone elastomer containing carboxylic acid functions.
Composition D according to the invention comprises at least one silicone elastomer bearing carboxylic acid functions.
The term “organopolysiloxane elastomer” means a flexible, deformable organopolysiloxane having viscoelastic properties and notably the consistency of a sponge or a flexible sphere. Its modulus of elasticity is such that this material resists deformation and has a limited capacity for extension and contraction. This material is able to return to its original shape after stretching. In general, it is partially or totally crosslinked and is non-cyclic.
The term “silicone elastomer bearing carboxylic acid functions” means an elastomeric organopolysiloxane comprising in its structure at least one, preferably at least two, carboxylic acid groups with at least one carboxylic acid (—COOH) or carboxylate (—COO—) function.
Preferably, the silicone elastomer bearing carboxylic acid functions is partially or totally crosslinked.
According to this embodiment, the silicone elastomer bearing carboxylic acid functions is advantageously the product of reaction of a first siloxane, a second siloxane and a crosslinking agent.
The composition according to the invention advantageously has a total content of silicone elastomer(s) bearing carboxylic acid functions ranging from 0.1% to 40% by weight relative to the weight of composition D. Preferably, this content ranges from 1% to 35% by weight, more preferentially from 5% to 30% by weight, better still from 10% to 25% by weight relative to the weight of composition D.
The composition according to the invention advantageously has a total content of crosslinked silicone elastomer(s) bearing carboxylic acid functions ranging from 0.1% to 40% by weight relative to the weight of composition D. Preferably, this content ranges from 1% to 35% by weight, more preferentially from 5% to 30% by weight, better still from 10% to 25% by weight relative to the weight of composition D.
The silicone elastomers bearing carboxylic acid functions that may be used in the compositions of the invention may be chosen from those described in the published documents WO 2015/066161 (US 2016/0200876), WO 2015/066165, WO 2015/066199, WO 2015/167963, WO 2018/165434, (U.S. Ser. No. 10/918,587B2), IPCOM000250448D and IPCOM000250657D.
Preferably, the silicone elastomer bearing carboxylic acid functions is chosen from those corresponding to formula (XIII) below:
in which:
or to formula (i′) below:
in which:
The term “substituted” means that one or more hydrogen atoms of the hydrocarbon-based radical are replaced with an atom other than hydrogen (i.e. halogen) or that one or more carbon atoms are replaced with an atom other than carbon, such as a heteroatom, for instance oxygen, sulfur or nitrogen.
In formula (XIII), the lower and upper portions are identical or different siloxanes. According to certain particular modes, each siloxane chain comprises siloxane (Si—O—Si) bonds on their respective backbone.
In various embodiments, each siloxane chain may include siloxane bonds separated by one or more divalent groups, for example a —CH2— bonding group. Other examples of divalent groups may include polyether groups: e.g. —CH2CH2O— bonding groups (i.e., ethylene oxide group), —CH(CH3)CH2O— (i.e., propylene oxide), etc.
Combinations of different divalent groups may be present on their respective backbones. Each of the divalent groups may be unique or repeated i.e.: 2 times, 5 times, 10 times, or even more than 10 times, etc. According to certain embodiments, the siloxanes do not comprise a polyether group.
In various embodiments, one or both siloxanes may comprise at least one [SiR1R2—O—] unit (“D” units or R*2SiO2/2). Typically, each siloxane has a repetition of D units, which generally constitutes the linear portions of the siloxanes. The siloxanes also typically have terminal R*3SiO1/2 units (“M” units).
In certain particular modes, one or both of the siloxanes may optionally be branched, partially branched and/or include a resin portion having a network of three-dimensional structure. In such cases, the corresponding siloxane(s) may also comprise R*SiO3/2 units (“T” units) and/or SiO4/2 units (“Q” units). The branched or resinous nature of the siloxane(s) may be attributed to the presence of T and/or Q units. The branched nature of a siloxane may be attributed to side groups of one or more D units. According to particular modes, one or both siloxanes may be free of T units and/or Q units. The two siloxanes may be identical or different: i.e. one is linear and the other branched, or both siloxanes are linear.
According to certain particular modes, the radicals R1 in the compounds of formula (XIII) independently denote an alkyl, aryl, alkenyl, alkaryl or aralkyl radical.
More particularly, the radicals R1 denote an alkyl radical, preferably containing from 1 to 20, from 1 to 15, from 1 to 10, from 1 to 6, from 1 to 4, or 1 or 2 carbon atoms, for instance methyl, ethyl, propyl, butyl or pentyl.
More particularly, all the radicals R1 denote a methyl group (i.e. —CH3).
Preferably, the radical R3 is a divalent, saturated or unsaturated hydrocarbon-based radical, optionally substituted with at least one heteroatom such as oxygen, sulfur or nitrogen. In particular, R3 is a group (CH2)n where n is an integer ranging from 1 to 30, from 1 to 25, from 1 to 20, from 1 to 15, from 1 to 10, from 1 to 5, or from 1 to 3, and more particularly equal to 3.
According to various particular modes, each of the radicals R4 and R5 may independently denote a substituted or unsubstituted hydrocarbon-based radical, notably chosen from those defined previously for the radicals R1.
According to certain modes, each radical R4 independently denotes an alkyl or aryl (i.e. phenyl) group or a group (R6O)m.
When R4 is a group (R6O)m, R6 is preferably an alkyl or aryl (i.e.: phenyl) radical and m is an integer ranging from 1 to 50, from 1 to 25, from 1 to 10, from 1 to 5, or 1. The group (R6O)m may be a polyether group (i.e.: with ethylene oxide and/or propylene oxide units). According to particular modes, a radical R4 may be a divalent group of a silicone side chain of the siloxane.
According to a particular mode, R4 may denote an anhydride group of formula (A)
in which R3 has the identical definition indicated previously.
According to a particular mode, R4 may denote an alkyl radical, preferably hexyl.
Preferably, the radicals R4 denote an alkyl radical or a polyether group.
Preferably, the radicals R5 independently denote an alkyl, aryl, alkenyl, alkaryl, or aralkyl radical.
More particularly, the radicals R5 denote an alkyl radical, preferably containing from 1 to 20, from 1 to 15, from 1 to 10, from 1 to 6, from 1 to 4, or 1 or 2 carbon atoms, for instance methyl, ethyl, propyl, butyl or pentyl.
More particularly, all the radicals R5 denote a methyl group (i.e. —CH3).
Preferably, w is an integer ranging from 0 to 1000, from 0 to 950, from 0 to 750, from 0 to 500, from 0 to 400, from 1 to 350, from 1 to 300, from 25 to 250, from 50 to 200, from 50 to 150, from 75 to 125, from 90 to 110, from 90 to 100, from 90 to 95, and most particularly is equal to 93.
Preferably, x is an integer from 1 to 100, from 1 to 75, from 1 to 50, from 1 to 25, from 1 to 20, from 1 to 10, or from 1 to 5, and more particularly equal to 3.
Preferably, y is an integer ranging from 0 to 1000, from 0 to 950, from 0 to 750, from 0 to 500, from 0 to 400, from 1 to 350, from 1 to 300, from 1 to 250, from 1 to 200, from 1 to 150, from 1 to 100, from 1 to 75, from 1 to 50, from 1 to 25, from 1 to 20, from 1 to 15, from 1 to 10, or from 1 to 5.
According to various embodiments, w and y are not simultaneously equal to 0. In certain modes, the sum w+x+y ranges from 25 to 1500, from 25 to 1000, from 25 to 900, from 25 to 800, from 25 to 700, from 25 to 600, from 25 to 500, from 25 to 400, from 25 to 300, from 50 to 200, from 75 to 150, from 85 to 125 or from 90 to 110.
In certain modes, x is at least equal to 1, at least equal to 10, at least equal to 25, at least equal to 50, at least equal to 75 or at least equal to 5.
The units of formula (XIII), notably those represented in square brackets indexed by w, ww, x, xx, y or yy, may be present in any order, randomly or in sequential form.
According to certain particular modes, the radicals R11, which may be identical or different, denote a linear, branched or cyclic C1-C20, C1-C15, C1-C10, C1-C6, C1-C4 or C1-C2 alkyl radical such as methyl, ethyl, propyl, butyl, pentyl groups, etc. More preferentially, the radicals R11 are a methyl group.
According to certain particular modes, the radicals R14, which may be identical or different, denote an alkyl, aryl (i.e. phenyl) or (R16O)mm radical. When R14 is a group (R16O)mm, R16 denotes an alkyl or aryl (i.e. phenyl) group and mm is an integer ranging from 1 to 50, 1 to 25, 1 to 10, 1 to 5, or 1. The group (R16O)mm may be a polyether group (i.e. with ethylene oxide and/or propylene oxide units).
According to particular modes, the radicals R14 independently denote an alkyl radical containing 2 to 20, 2 to 15, 2 to 10, 2 to 5, or 2 carbon atoms.
In other particular modes, R14 may be a divalent bonding group of a silicone side chain of the siloxane.
According to a particular mode, R14 may denote an anhydride group of formula (A) as defined previously.
According to a particular mode, R14 may denote an alkyl radical, preferably hexyl.
Preferably, the radicals R14 denote an alkyl radical or a polyether group.
Preferably, the radicals R15 independently denote an alkyl, aryl, alkenyl, alkaryl, or aralkyl radical.
More particularly, the radicals R15 denote an alkyl radical, preferably containing from 1 to 20, from 1 to 15, from 1 to 10, from 1 to 6, from 1 to 4, or 1 or 2 carbon atoms, for instance methyl, ethyl, propyl, butyl or pentyl.
More particularly, all the radicals R15 denote a methyl group (i.e. —CH3).
Preferably, ww is an integer ranging from 0 to 1000, from 0 to 950, from 0 to 750, from 0 to 500, from 0 to 400, from 1 to 350, from 1 to 300, from 25 to 250, from 50 to 200, from 50 to 150, from 75 to 125, from 90 to 110, from 90 to 100, from 90 to 95, and most particularly 93.
Preferably, xx is an integer ranging from 1 to 100, from 1 to 75, from 1 to 50, from 1 to 25, from 1 to 20, from 1 to 10 or from 1 to 5, and more particularly 3.
Preferably, yy is an integer ranging from 0 to 1000, from 0 to 950, from 0 to 750, from 0 to 500, from 0 to 400, from 1 to 350, from 1 to 300, from 1 to 250, from 1 to 200, from 1 to 150, from 1 to 100, from 1 to 75, from 1 to 50, from 1 to 25, from 1 to 20, from 1 to 15, from 1 to 10 or from 1 to 5.
In various embodiments, ww and yy are not simultaneously equal to 0. According to certain particular modes, the sum ww+xx+yy ranges from 25 to 1500, from 25 to 1000, from 25 to 900, from 25 to 800, from 25 to 700, from 25 to 600, from 25 to 500, from 25 to 400, from 25 to 300, from 50 to 200, from 75 to 150, from 85 to 125, or from 90 to 110.
According to certain particular modes, xx is at least equal to 1, at least equal to 10, at least equal to 25, at least equal to 50, at least equal to 75, or at least equal to 85.
The radical X of formula (XIII) corresponds to the general formula (i) below:
or to the general formula (i′) below:
in which:
in which:
The units of formula (ii) represented in square brackets indexed by a, b, or c are present in any order, randomly or in sequential form.
According to a particular form, the siloxane of formula (ii) may be a resin of formula R*sSiO(4-s)/2. Preferably, a silicone resin has along its chain T and/or Q units with M units and optionally D units. The radicals R* may be independently chosen from a substituted (i.e. hydroxyl, amine functions) or unsubstituted hydrocarbon-based radical and s ranges from 0 to 3. The groups R* that may be used may be those described previously for the radicals R8, R9 and R10. Various combinations of such groups may be present. According to these particular cases, the silicone resin comprises a combination of M, D, T and/or Q units. It may notably be an MDT resin, an MT resin, an MDQ resin, an MQ resin or an MDTQ resin. Each of the M, D and T units may contain different groups R*. The resin may have various molecular weights such as a number-average molecular weight ranging from 800 to 500 000.
According to a particular form of the invention, the silicone elastomers bearing carboxylic acid functions have a carboxyl equivalent ranging from 100 to 50 000, from 500 to 10 000 or from 500 to 5000.
The silicone elastomers bearing carboxylic functions of formula (XIII) may be obtained according to one of the synthetic processes described in WO 2015/066161 (US 2016/0200876).
According to a first variant of the synthetic process, certain silicone elastomers bearing carboxylic acid functions may be obtained by reacting 1) a first siloxane bearing anhydride side groups, 2) a second siloxane bearing anhydride side groups and 3) an organic polyol. According to a particular mode, one or more siloxanes different from the first two may be reacted with the three preceding reagents.
According to a second variant of the synthetic process, certain silicone elastomers bearing carboxylic acid functions may be obtained by reacting 1) a first siloxane bearing anhydride side groups, 2) a second siloxane bearing anhydride side groups and 3) an organic polyamine. According to a particular mode, one or more additional siloxanes different from the first two may be reacted with the three preceding reagents.
According to a third variant of the synthetic process, certain silicone elastomers bearing carboxylic acid functions may be obtained by reacting 1) a first siloxane bearing anhydride side groups, 2) a second siloxane bearing anhydride side groups and 3) a third siloxane containing at least two hydroxyl groups. According to a particular mode, one or more additional siloxanes different from the first two may be reacted with the three preceding reagents.
According to a fourth variant of the synthetic process, certain silicone elastomers bearing carboxylic acid functions may be obtained by reacting 1) a first siloxane bearing anhydride side groups, 2) a second siloxane bearing anhydride side groups and 3) a third siloxane containing amine side groups and/or amine end groups. According to a particular mode, one or more additional siloxanes different from the first two may be reacted with the three preceding reagents.
According to a fifth variant of the synthetic process, certain silicone elastomers bearing carboxylic acid functions may be obtained by reacting 1) a first siloxane bearing hydroxyl side groups, 2) a second siloxane bearing hydroxyl side groups and 3) a third siloxane containing at least two anhydride end groups. According to a particular mode, one or more additional siloxanes different from the first two may be reacted with the three preceding reagents.
According to a sixth variant of the synthetic process, certain silicone elastomers bearing carboxylic acid functions may be obtained by reacting 1) a first siloxane bearing amine side groups, 2) a second siloxane bearing amine side groups and 3) a third siloxane containing at least two anhydride end groups. According to a particular mode, one or more additional siloxanes different from the first two may be reacted with the three preceding reagents.
According to a seventh variant of the synthetic process, certain silicone elastomers bearing carboxylic acid functions may be obtained by reacting 1) a first organic alcohol, 2) a second organic alcohol and 3) a siloxane containing anhydride end groups. According to a particular mode, one or more additional organic alcohols different from the first two may be reacted with the three preceding reagents.
Among the silicone elastomers bearing carboxylic acid functions of formula (XIII), mention may be made of compounds 1 to 12 below as described, respectively, in Examples 4, 5 and 7 to 16 of patent application WO 2015/066161 or in the examples of patent application US 2020/0323765:
According to a particular form, the composition of the invention contains at least compound 11 as defined previously.
Among the silicone elastomers bearing carboxylic acid functions that may be used in the compositions of the invention, mention may also be made of the silicone elastomer having the INCI name: Hexyl/Succinyl Dimethicone Crosspolymer.
According to a particular form, the silicone elastomers bearing carboxylic acid functions are in solid form. They may notably be chosen from compounds 2 and 3 as defined previously.
According to another particular form, the silicone elastomers bearing carboxylic acid functions are in dispersion in at least one oil and are preferably in gel form.
The term “oil” means a fatty substance which is liquid at room temperature (25° C.) and atmospheric pressure (760 mmHg or 105 Pa).
The oil may be chosen from volatile oils and/or non-volatile oils.
The term “non-volatile oil” means an oil which remains on the keratin material at room temperature (25° C.) and atmospheric pressure (760 mmHg) for at least several hours and which notably has a vapour pressure of less than 10 mmHg (0.13 Pa).
The oil may be chosen from hydrocarbon-based oils.
The term “hydrocarbon-based oil” means an oil mainly including carbon and hydrogen atoms and optionally one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.
As examples of volatile hydrocarbon-based oils that may be used in the oily dispersion of a silicone elastomer bearing carboxylic functions, mention may be made of hydrocarbon-based oils containing from 8 to 16 carbon atoms, and notably C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example oils sold under the trade names Isopars or Permethyls, branched C8-C16 esters, isohexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon-based oils such as petroleum distillates, notably those sold under the name Shell Solt by the company Shell, may also be used; volatile linear alkanes such as those described in the patent application of the company Cognis DE10 2008 012 457.
As examples of linear non-volatile hydrocarbon-based oils, mention may be made of:
Preferably, the hydrocarbon-based oil used is isododecane.
Preferably, the oily dispersion of silicone elastomer bearing carboxylic acid functions comprises from 10% to 40% by weight of silicone elastomer active material, and more preferentially from 20% to 35% by weight of silicone elastomer active material relative to the total weight of the oily dispersion.
Preferably, the composition according to the invention comprises at least one silicone elastomer bearing carboxylic acid functions in dispersion in isododecane and preferably in gel form. In particular, said silicone elastomer is chosen from compounds 1 and 4 to 11 as defined previously.
More preferably, the composition according to the invention comprises compound 11 in dispersion in isododecane and in gel form, and more particularly in an active material content equal to 30% by weight relative to the total weight of the dispersion.
According to another particularly preferred form, the composition of the invention comprises a silicone elastomer bearing carboxylic acid functions in dispersion in isododecane and in gel form, having the INCI name: Isododecane (and) Hexyl/Succinyl Dimethicone Crosspolymer and more particularly in an active material content equal to 30% by weight relative to the total weight of the dispersion.
Mention may be made of the commercial product Dowsil EL-7314 Silicone Elastomer Blend® sold by the company Dow Corning, comprising 30% by weight of active material of said silicone elastomer.
Composition C and/or composition D employed within the context of the process according to the invention comprise(s) one or more colouring agent(s) chosen from pigments, direct dyes and mixtures thereof.
Preferably, composition C and/or composition D employed within the context of the process according to the invention comprise(s) one or more pigments.
The term “pigment” refers to any pigment that gives colour to keratinous materials. Their solubility in water at 25° C. and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.
The pigments that may be used are notably chosen from the organic and/or mineral pigments known in the art, notably those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.
They may be natural, of natural origin, or non-natural.
These pigments may be in pigment powder or paste form. They may be coated or uncoated.
The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof.
The pigment may be a mineral pigment. The term “mineral pigment” refers to any pigment that satisfies the definition in Ullmann's encyclopaedia in the chapter on inorganic pigments. Mention may be made, among the inorganic pigments of use in the present invention, of iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.
The pigment may be an organic pigment. The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann's encyclopaedia in the chapter on organic pigments.
The organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal-complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.
In particular, the white or coloured organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.
Examples that may also be mentioned include pigment pastes of organic pigments, such as the products sold by the company Hoechst under the names:
The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may be composed notably of particles including an inorganic core, at least one binder for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core.
The organic pigment may also be a lake. The term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.
The mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.
Among the dyes, mention may be made of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green 5 (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).
An example of a lake that may be mentioned is the product known under the following name: D&C Red 7 (CI 15 850:1).
The pigment may also be a pigment with special effects. The term “pigments with special effects” means pigments that generally create a coloured appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from coloured pigments, which afford a standard uniform opaque, semi-transparent or transparent shade.
Several types of pigments with special effects exist: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.
Examples of pigments with special effects that may be mentioned include nacreous pigments such as mica covered with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and notably with ferric blue or with chromium oxide, mica covered with titanium and with an organic pigment as defined previously, and also nacreous pigments based on bismuth oxychloride. Nacreous pigments that may be mentioned include the nacres Cellini sold by BASF (mica-TiO2-lake), Prestige sold by Eckart (mica-TiO2), Prestige Bronze sold by Eckart (mica-Fe2O3) and Colorona sold by Merck (mica-TiO2—Fe2O3).
Mention may also be made of the gold-coloured nacres sold notably by the company BASF under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold notably by the company Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company BASF under the name Super bronze (Cloisonne); the orange nacres sold notably by the company BASF under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown nacres sold notably by the company BASF under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper tint sold notably by the company BASF under the name Copper 340A (Timica); the nacres with a red tint sold notably by the company Merck under the name Sienna fine (17386) (Colorona); the nacres with a yellow tint sold notably by the company BASF under the name Yellow (4502) (Chromalite); the red nacres with a gold tint sold notably by the company BASF under the name Sunstone G012 (Gemtone); the pink nacres sold notably by the company BASF under the name Tan opale G005 (Gemtone); the black nacres with a gold tint sold notably by the company BASF under the name Nu antique bronze 240 AB (Timica), the blue nacres sold notably by the company Merck under the name Matte blue (17433) (Microna), the white nacres with a silvery tint sold notably by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold notably by the company Merck under the name Indian summer (Xirona), and mixtures thereof.
Still as examples of nacreous agents, mention may also be made of particles including a borosilicate substrate coated with titanium oxide.
Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC108ORY by the company Toyal.
Finally, examples of nacres that may also be mentioned include polyethylene terephthalate glitter flakes, notably those sold by the company Meadowbrook Inventions under the name Silver 1P 0.004×0.004 (silver glitter flakes). It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.
The pigments with special effects may also be chosen from reflective particles, i.e. notably from particles whose size, structure, notably the thickness of the layer(s) of which they are made and their physical and chemical nature, and surface state, allow them to reflect incident light. This reflection may, where appropriate, have an intensity sufficient to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, highlight points that are visible to the naked eye, i.e. brighter points that contrast with their environment, making them appear to sparkle.
The reflective particles may be selected so as not to significantly alter the colouring effect generated by the colouring agents with which they are combined, and more particularly so as to optimize this effect in terms of colour rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or tint.
These particles may have varied forms and may notably be in platelet or globular form, in particular in spherical form.
The reflective particles, whatever their form, may or may not have a multilayer structure and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, notably of a reflective material.
When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, notably titanium or iron oxides obtained synthetically.
When the reflective particles have a multilayer structure, they may include, for example, a natural or synthetic substrate, notably a synthetic substrate at least partially coated with at least one layer of a reflective material, notably of at least one metal or metallic material. The substrate may be made of one or more organic and/or inorganic materials.
More particularly, it may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, notably aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.
The reflective material may include a layer of metal or of a metallic material.
Reflective particles are notably described in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.
Again as an example of reflective particles including a mineral substrate coated with a layer of metal, mention may also be made of particles including a silver-coated borosilicate substrate.
Particles with a silver-coated glass substrate, in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by the company Toyal.
Particles with a glass substrate coated with nickel/chromium/molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by this same company.
Use may also be made of particles comprising a metal substrate, such as silver, aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.
Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with SiO2 sold under the name Visionaire by the company Eckart.
Mention may also be made of pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f/x from Spectratek). Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.
The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic effects or interference effects.
The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm and more preferentially between 30 nm and 50 μm.
The pigments may be dispersed in the composition by means of a dispersant.
The dispersant serves to protect the dispersed particles against their agglomeration or flocculation. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid in particular and of C8 to C20 fatty acid and of polyols such as glycerol or diglycerol are used, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the company Uniqema, and mixtures thereof.
As other dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C.
The pigments used in the composition may be surface-treated with an organic agent.
Thus, the pigments surface-treated beforehand that are useful in the context of the invention are pigments which have been completely or partially subjected to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as those described notably in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition in accordance with the invention. These organic agents may be chosen, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof, anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, notably polydimethylsiloxanes; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.
The surface-treated pigments that are useful in the composition may also have been treated with a mixture of these compounds and/or may have undergone several surface treatments.
The surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is.
Preferably, the surface-treated pigments are coated with an organic layer.
The organic agent with which the pigments are treated may be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.
The surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in patent U.S. Pat. No. 4,578,266.
An organic agent covalently bonded to the pigments will preferably be used.
The agent for the surface treatment may represent from 0.1% to 50% by weight relative to the total weight of the surface-treated pigment, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 20% by weight relative to the total weight of the surface-treated pigment.
Preferably, the surface treatments of the pigments are chosen from the following treatments:
According to a particular embodiment of the invention, the dispersant is present with organic or mineral pigments in submicron-sized particulate form in composition B.
The term “submicron” or “submicronic” refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometre (μm), in particular between 0.1 and 0.9 μm, and preferably between 0.2 and 0.6 μm.
According to one embodiment, the dispersant and the pigment(s) are present in an amount (dispersant:pigment), according to a weight ratio, of between 1:4 and 4:1, particularly between 1.5:3.5 and 3.5:1 or better still between 1.75:3 and 3:1.
The dispersant(s) may therefore have a silicone backbone, such as silicone polyether and dispersants of amino silicone type different from the amino silicones mentioned previously. Among the suitable dispersants that may be mentioned are:
According to a particular embodiment, the dispersant(s) are of amino silicone type different from the amino silicones mentioned previously and are cationic.
Preferably, the pigment(s) are chosen from mineral, mixed mineral-organic or organic pigments.
In one variant of the invention, the pigment(s) are organic pigments, preferentially organic pigments surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment(s) are mineral pigments.
Preferably, the pigment(s) are chosen from iron oxides, notably red, brown or black iron oxides. By way of example of iron oxide, mention may be made of the iron oxide sold by the company Sun Chemical under the name SunPuro® Red Iron Oxide.
Composition C and/or composition D employed within the context of the process according to the invention may comprise one or more direct dyes.
The term “direct dye” means natural and/or synthetic dyes, other than oxidation dyes. These are dyes that will spread superficially on the fibre.
They may be ionic or nonionic, preferably cationic or nonionic.
Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.
The direct dyes are preferably cationic direct dyes. Mention may be made of the hydrazono cationic dyes of formulae (XIV) and (XV) and the azo cationic dyes (XVI) and (XVII) below:
in which formulae (XIV) to (XVII):
In particular, mention may be made of the azo and hydrazono direct dyes bearing an endocyclic cationic charge of formulae (XIV) to (XVII) as defined previously, more particularly, the cationic direct dyes bearing an endocyclic cationic charge described in patent applications WO 95/15144, WO 95/01772 and EP 714 954, preferentially the following direct dyes:
In particular, the dyes of formulae (XVIII) and (XIX) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof with Q′ being an anionic counterion as defined previously, particularly a halide such as chloride, or an alkyl sulfate such as methyl sulfate or mesyl.
The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes owing to their affinity for alkaline substances. The term “anionic direct dye” means any direct dye including 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 may be chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes.
As acid dyes that are useful for the invention, mention may be made of the dyes of formulae (XX), (XX′), (XXI), (XXI′), (XXII), (XXII′), (XXIII), (XXIII′), (XXIV), (XXV), (XXVI) and (XXVII) below:
As examples of dyes of formula (XX), mention may be made of: 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 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, Food Yellow 3 or Sunset Yellow;
As examples of dyes of formula (XXI), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula (XXI′), mention may be made of: Acid Yellow 17;
As examples of dyes of formula (XXII), mention may be made of: 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; EXT Violet No. 2; and, as an example of a dye of formula (XXII′), mention may be made of: Acid Black 48.
As examples of dyes of formula (XXIII), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (XXIII′), mention may be made of: Acid Yellow 1, the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4′-N,N-(2″-hydroxyethyl)amino-2′-nitro)anilineethanesulfonic acid, 4-p-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7;
As examples of dyes of formula (XXIV), mention may be made of: 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.
As examples of dyes of formula (XXV), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9.
As examples of dyes of formula (XXVI), mention may be made of: Acid Blue 74;
As examples of dyes of formula (XXVII), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Use may also be made of extracts or decoctions containing these natural dyes and notably henna-based poultices or extracts.
Preferably, the direct dyes are chosen from anionic direct dyes.
The colouring agent(s) may be present in a total amount ranging from 0.001% to 20% by weight and preferably from 0.005% to 15% by weight relative to the total weight of composition C and/or of composition D; preferably, the colouring agents are chosen from pigments.
The pigment(s) may be present in a total amount ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight and better still from 0.5% to 12% by weight, relative to the total weight of composition C and/or of composition D.
The direct dye(s) may be present in a total amount ranging from 0.001% to 10% by weight relative to the total weight of the composition, preferably from 0.005% to 5% by weight relative to the total weight of composition C and/or of composition D.
Preferably, composition D comprises at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.
Preferably, composition C does not comprise at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.
Composition C and/or composition D employed within the context of the process according to the invention may contain any adjuvant or additive usually used.
Among the additives that may be contained in composition C, mention may be made of reducing agents, softeners, antifoams, moisturizers, UV-screening agents, peptizers, solubilizers, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers described previously, thickeners other than the polymers described previously, preserving agents, oils, waxes and mixtures thereof.
Composition C and/or composition D employed within the context of the process according to the invention may notably be in the form of a suspension, a dispersion, a gel, an emulsion, notably an oil-in-water (O/W) or water-in-oil (W/O) emulsion, or a multiple emulsion (W/O/W or polyol/O/W or O/W/O), in the form of a cream, a mousse, a stick, a dispersion of vesicles, notably of ionic or nonionic lipids, or a two-phase or multi-phase lotion.
A person skilled in the art may select the appropriate presentation form, and also the method for preparing it, on the basis of his general knowledge, taking into account firstly the nature of the constituents used, notably their solubility in the support, and secondly the intended application of the composition.
Composition C and composition D described above may be used on wet or dry hair, and also on any type of fair or dark, natural or coloured, permanent-waved, bleached or relaxed hair.
According to a preferred embodiment, composition C and composition D are applied simultaneously to the keratinous fibres.
According to another preferred embodiment, composition D is applied to the hair after applying composition C to the hair.
According to another preferred embodiment, composition D is applied to the hair before applying composition C to the hair.
More preferentially, composition D is applied to the hair after applying composition C to the hair.
According to a particular embodiment of the invention, the hair is washed before applying composition C and composition D.
Preferably, a washing, rinsing, draining or drying step is performed after applying composition C to the hair and before applying composition D to the hair.
More preferentially, a drying step is performed after applying composition C to the hair and before applying composition D to the hair, preferably, the drying step is carried out with the aid of a hairdryer, for example at a temperature of greater than or equal to 30° C.
The application to the hair may be performed via any standard means, in particular using a comb, a fine brush, a coarse brush, a sponge or with the fingers.
The application of composition C and of composition D to the hair is generally performed at room temperature (between 15 and 25° C.).
After applying composition C to the hair, it is possible to wait for between 1 minute and 6 hours, in particular between 1 minute and 2 hours, more particularly between 1 minute and 1 hour, more preferentially between 1 minute and 30 minutes, before, for example, applying composition D to the hair or, for example, a washing, rinsing, draining or drying step.
Preferably, there is no leave-on time after applying composition C to the hair and before applying composition D to the hair.
After applying composition C and composition D, the hair may be left to dry or may be dried, for example at a temperature of greater than or equal to 30° C.
The process according to the invention may thus comprise a step of applying heat to the keratinous fibres using a heating tool.
The heat application step of the process of the invention may be performed using a hood, a hairdryer, a straightening iron, a curling iron, a Climazon, etc.
Preferably, the heat application step of the process of the invention is performed using a hairdryer.
When the process of the invention involves a step of applying heat to the hair, the step of applying heat to the hair takes place after applying composition C and composition D to the hair.
During the step of applying heat to the hair, a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through.
When the step of applying heat to the hair is performed using a hood or a hairdryer, the temperature is preferably between 30° C. and 110° C., preferentially between 50° C. and 90° C.
When the step of applying heat to the hair is performed using a straightening iron, the temperature is preferably between 110° C. and 220° C., preferably between 140° C. and 200° C.
In a particular variant, the process of the invention involves a step (c1) of applying heat using a hood, a hairdryer or a Climazon, preferably a hairdryer, and a step (c2) of applying heat using a straightening or curling iron, preferably a straightening iron.
Step (c1) may be performed before step (c2).
During step (c1), also referred to as the drying step, the hair may be dried, for example at a temperature above or equal to 30° C. According to a particular embodiment, this temperature is above 40° C. According to a particular embodiment, this temperature is above 45° C. and below 110° C.
Preferably, if the hair is dried, it is dried, in addition to a supply of heat, with a flow of air. This flow of air during drying makes it possible to improve the strand separation of the coating.
During drying, a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through.
During step (c2), the passage of the straightening or curling iron, preferably the straightening iron, may be performed at a temperature ranging from 110° C. to 220° C., preferably between 140° C. and 200° C.
After the drying step, a shaping step may be performed, for example with a straightening iron; the temperature for the shaping step is between 11° and 220° C., preferably between 14° and 200° C.
Preferably, the invention is a process for colouring the hair comprising the following steps:
Preferably, the step of applying composition C and/or composition D to the hair is repeated several times.
According to a preferred embodiment, the colouring process according to the invention is a process for colouring the hair which consists in extemporaneously mixing, at the time of use, at least two compositions C and D to obtain a composition E and in applying composition E to the hair, with:
Preferably, composition D comprises at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.
Preferably, composition C does not comprise at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.
According to this embodiment, compositions C and D are mixed preferably less than 15 minutes before application to the hair, more preferentially less than 10 minutes before application, better still less than 5 minutes before application.
The weight ratio between composition C and composition D preferably ranges from 0.1 to 10, preferentially from 0.2 to 5 and better still from 0.5 to 2, or even from 0.6 to 1.5. In a particular embodiment, the weight ratio between composition C and composition D is equal to 1.
The process according to the invention may comprise a step of applying a makeup-removing composition to coloured keratin fibres such as the hair.
Preferably, the process according to the invention comprises a step of applying a makeup-removing composition to the keratin fibres after the application of composition C and composition D.
The makeup-removing composition may correspond to a makeup-removing composition conventionally used in cosmetics.
Preferably, the makeup-removing composition comprises at least one compound chosen from surfactants, solvents, fatty substances, acids, bases and mixtures thereof.
According to a preferred embodiment, the makeup-removing composition comprises at least one hydrocarbon-based oil.
Preferably, the hydrocarbon-based oil or oils are chosen from synthetic esters of formula R1COOR2 in which R1 represents the residue of a fatty acid including from 8 to 29 carbon atoms, and R2 represents a branched or unbranched hydrocarbon-based chain containing from 3 to 30 carbon atoms, and mixtures thereof, more preferentially from isopropyl myristate, isononyl isononanoate and/or mixtures thereof.
The application of composition C and composition D to keratin fibres such as the hair is performed before the application of a makeup-removing composition.
The step of applying heat to the keratin fibres may be performed after the application of composition C and composition D and before the application of the makeup-removing composition to the keratin fibres.
The application of the makeup-removing composition may be performed on dry coloured keratin fibres or wet coloured keratin fibres and also on all types of fibres.
The makeup removal process is generally performed at room temperature (between 15 and 25° C.).
The application of the makeup-removing composition may be performed immediately after the application of composition C and composition D (i.e. a few minutes to a few hours after the application of the colouring composition), or in the days or weeks following the application of the colouring composition.
The makeup-removing composition may be applied using any suitable medium, notably one that is capable of absorbing it, for example a fibrous makeup-removing disc, e.g. a woven or non-woven, wadding, flocked film, sponge, wipe, or a twisted or injection-moulded mascara application brush.
The makeup-removing composition may be contained in a container and removed as required for each makeup removal operation. As a variant, the makeup-removing composition impregnates the support used for the makeup removal, in which case the carrier may be packaged, for example, in leaktight packaging.
After using the makeup-removing composition, the keratin fibres may be left unrinsed. Alternatively, they may be rinsed. Rinsing may be performed, for example, with running water, without the addition of soap.
The present invention also relates to a device for colouring the hair comprising at least two compartments containing:
According to a preferred variant of the invention, the device for colouring the hair comprises at least two compartments containing:
The present invention will now be described more specifically by means of examples, which are in no way limiting of the scope of the invention. However, the examples make it possible to support specific features, variants and preferred embodiments of the invention.
The (poly)carbodiimide(s) of the invention are accessible via synthetic methods known to those skilled in the art starting from commercial products or reagents that can be synthesized according to chemical reactions that are also known to those skilled in the art. Mention may be made, for example, of the book Sciences of Synthesis—Houben—Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D-70469 Stuttgart, or the American patent U.S. Pat. No. 4,284,730 or the Canadian patent application CA 2 509 861.
More particularly, the process for preparing the (poly)carbodiimides of the invention involves, in a first step, a diisocyanate reagent (1):
To obtain “symmetrical” (poly)carbodiimides, during the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq.) of nucleophilic reagent R1—X1—H and then 0.5 eq. of reagent H-E-H with R1, X1 and E as defined previously, to give the “symmetrical” compound (4) according to the invention:
To obtain “dissymmetrical” (poly)carbodiimides, during the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq.) of nucleophilic reagent R1—X1—H and then 1 eq. of reagent H-E-H with R1, X1 and E as defined previously, to give compound (5):
According to one variant to obtain compound (5) from (3), it is possible first to add 1 eq. of reagent R1—X1—H and then 0.5 eq. of reagent H-E-H.
During a third step, compound (5) reacts with 1 eq. of compound (6)
R2—X2—C(O)—NH-L1-(N═C═N-L1)z-N═C═O (6),
in which formula (3′) L1 and z are as defined previously, which reacts with 1 eq. of nucleophilic reagent R2—X2—H with L1, R2, X2 and z as defined previously, to give the dissymmetrical compound (7):
in which formula (7) R1, X1, L1, R2, X2, n, z and E are as defined previously.
It is also possible to react 1 molar equivalent of compound O═C═N-L1-(N═C═N-L1)z-N═C═O (3′) with 1/w molar equivalent of H-E-H, followed by 1 eq. of nucleophilic reagent R2—X2—H to give compound (8):
in which formula (8) L1, R2, X2, z and E are as defined previously, and w is an integer between 1 and 3; more preferentially, w=1.
This last compound (8) can then react with 1 eq. of compound (4′):
R1—X1—C(O)—NH-L1-(N═C═N-L1)n-N═C═O (4′),
The (poly)carbodiimide compounds, and similarly all the reaction intermediates and reagents, may be purified via conventional methods known to those skilled in the art, such as extraction with water and water-immiscible organic solvent, precipitation, centrifugation, filtration and/or chromatography.
50 g of 4,4′-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phosphole 1-oxide were placed with stirring in a 500 mL three-necked round-bottomed flask equipped with a thermometer, a stirrer and a reflux tube.
The reaction medium was heated at 140° C. under nitrogen for 4 hours, the reaction being monitored by infrared spectroscopy by means of the absorption of the isocyanate functions between 2200 and 2300 cm−1, and then cooled to 120° C.
A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4-butanediol are introduced with stirring into the reaction medium. The temperature of 120° C. is maintained until the isocyanate functions have totally disappeared, monitored by infrared spectroscopy at 2200-2300 cm−1, and is then cooled to room temperature.
After cooling to room temperature, the reaction medium is poured dropwise with vigorous stirring into a 500 mL glass beaker containing 85 g of distilled water, to give the desired product in the form of a translucent yellow liquid.
Composition C as described below was prepared: the amounts are expressed as g of starting material as obtained/100 g, unless otherwise mentioned. In the table 1 below, “a.m.” means “active material”.
Compositions D1 and D2 as described below were prepared: the amounts are expressed as g of starting material as obtained/100 g.
Composition C is applied to locks of natural hair containing 90% white hairs, in a proportion of 0.4 g of composition per gram of lock. The locks of hair are then combed and dried with a hairdryer.
Composition D1 or composition D2 is then applied to the locks of hair treated beforehand with composition C, in a proportion of 0.4 g of composition per gram of lock.
The locks of hair are then combed and dried with a hairdryer.
In another comparative process, only composition D is applied to locks of natural hair containing 90% white hairs, in a proportion of 0.4 g of composition per gram of lock. The locks of hair are then combed and dried with a hairdryer.
The locks of hair are then left at room temperature and humidity for 24 hours.
The different processes are summarized in the table below:
Thus, the locks of hair treated with compositions C then D1 are treated using process 1 according to the invention.
The locks of hair treated with compositions C then D2 or just D1 are treated using comparative processes 2 and 3.
The locks of hair thus coloured are then subjected to a test of several repeated shampoo washes so as to evaluate the fastness (persistence) of the colouring obtained with respect to shampoo washes, according to the shampoo washing protocol described below.
The coloured locks of hair are combed, moistened with water at 35° C. and then passed between the fingers five times for 5 seconds. The locks of hair are then squeezed dry between two fingers.
A standard shampoo (Gamier Ultra Doux) is applied uniformly to the coloured locks, in a proportion of 0.4 g of standard shampoo per gram of locks, the locks of hair being massaged gently along the length (6 passes) for 15 seconds, from the root to the end.
The locks of hair are then placed on a watch glass and left to stand for 1 minute.
Next, the locks of hair are rinsed with water while passing the lock between the fingers (15 passes). The locks of hair are then squeezed dry between two fingers before the next shampoo wash.
Once the tests of several shampoo washes have been performed, the locks of hair are combed and dried with a hairdryer.
The persistence of the colour of the locks was evaluated in the CIE L* a* b* system, using a Minolta Spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, specular component included).
In this L*a*b* system, L* represents the intensity of the colour, a* indicates the green/red colour axis and b* the blue/yellow colour axis.
The persistence of the colouring is evaluated by the colour difference ΔE between the coloured locks before shampooing, then after having undergone five shampoo washes according to the protocol described above. The lower the ΔE value, the more persistent the colour with respect to shampoo washing.
The ΔE value is calculated according to the following equation:
In this equation, L*a*b* represent the values measured after colouring the hair and after performing the shampoo washes, and L0*a0*b0* represent the values measured after colouring the hair but before shampoo washing.
The locks of hair treated with process 1 according to the invention and washed with five shampoo washes have lower ΔE values than those of the locks of hair treated with comparative processes 2 and 3 respectively.
Thus, the coloured coating obtained with the processes according to the invention shows improved persistence with respect to shampoo washing.
Composition C1 as described below was prepared: the amounts are expressed as g of starting material as obtained/100 g, unless otherwise mentioned. In the table 5 below, “a.m.” means “active material”.
Compositions D3 and D4 as described below were prepared: the amounts are expressed as g of unmodified starting material/100 g.
Composition C2 is applied to locks of natural hair containing 90% white hair strands, at a rate of 0.4 g of composition per gram of lock. The locks of hair are then combed and dried with a hairdryer.
Composition D3 or composition D4 is then applied to the locks of hair treated beforehand with composition C1, in a proportion of 0.4 g of composition per gram of lock.
The locks of hair are then combed and dried with a hairdryer.
The locks of hair thus coloured are then subjected to a test of several repeated shampoo washes so as to evaluate the fastness (persistence) of the colouring obtained with respect to shampoo washes, according to the shampoo washing protocol described below.
The locks of dyed hair are combed, moistened with water at 35° C. and then passed between the fingers five times for 5 seconds. The locks of hair are then squeezed dry between two fingers.
A standard shampoo (Garnier Ultra Doux) is applied uniformly to the coloured locks, in a proportion of 0.4 g of standard shampoo per gram of locks, the locks of hair being massaged gently along the length (6 passes) for 15 seconds, from the root to the end. The locks of hair are then placed on a watch glass and left to stand for 1 minute.
Next, the locks of hair are rinsed with water while passing the locks between the fingers (15 passes). The locks of hair are then squeezed dry between two fingers before the next shampoo wash.
Once the tests of several shampoo washes have been performed, the locks of hair are combed and dried with a hairdryer.
The persistence of the color of the locks was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, specular component included).
In this L*a*b* system, L* represents the intensity of the color, a* indicates the green/red color axis and b* indicates the blue/yellow color axis.
The persistence of the coloring is evaluated by the color difference ΔE between the dyed locks before shampooing, then after having undergone five shampooing operations according to the protocol described above. The lower the ΔE value, the more persistent the colour with respect to shampoo washing.
The ΔE value is calculated according to the following equation:
In this equation, L*a*b* represent the values measured after colouring the hair and after performing the shampoo washes, and L0*a0*b0* represent the values measured after colouring the hair but before shampoo washing.
The locks of hair treated by means of process 1 according to the invention and washed with five shampoo washes have lower ΔE values than those of the locks of hair treated by means of the comparative processes 2 and 3, respectively.
Thus, the coloured coating that is obtained by means of the processes according to the invention shows improved shampoo-fastness.
Composition C3 as described below was prepared: the amounts are expressed as g of starting material as obtained/100 g, unless otherwise mentioned. In the table 5 below, “a.m.” means “active material”.
Composition C′ is prepared by mixing composition C3 and composition C4 in a 1+1 ratio before application.
Composition C′ is then applied to locks of natural hair containing 90% white hair strands, at a rate of 0.8 g of composition per gram of lock. The locks of hair are then combed and dried with a hairdryer.
Composition D5 or composition D6 is then applied to the locks of hair treated beforehand with composition C′, in a proportion of 0.5 g of composition per gram of lock.
The locks of hair are then combed and dried with a hairdryer.
The locks of hair thus dyed are then subjected to a test of several repeated shampoo washes so as to evaluate the fastness (persistence) of the colouring obtained with respect to shampoo washes, according to the shampoo washing protocol described above.
The locks of hair treated by means of process 1 according to the invention and washed with five shampoo washes have lower ΔE values than those of the locks of hair treated by means of comparative process 2.
Thus, the coloured coating that is obtained by means of the processes according to the invention shows improved shampoo-fastness.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2113386 | Dec 2021 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/085399 | 12/12/2022 | WO |
