Patent Grant
7108726
The present invention relates to a composition for the direct dyeing of keratin fibers, in particular human keratin fibers and more particularly the hair, comprising at least one direct dye and at least one cationic associative polyurethane.
It is known practice to dye keratin fibers, and in particular human hair, with dye compositions containing direct dyes, in particular nitrobenzene dyes, acidic azo dyes, cationic azo dyes, anthraquinone dyes and natural dyes.
These colorations may be produced by directly applying to the keratin fibers the composition containing the direct dye(s) or by applying a mixture, prepared extemporaneously, of a composition containing the direct dye(s) with a composition containing an oxidizing bleaching agent, which is preferably aqueous hydrogen peroxide solution. The coloration is then referred to as lightening direct dyeing.
To localize the dye product on application to the hair so that it does not run down the face or beyond the areas which it is proposed to dye, use has been made hitherto of conventional thickeners such as crosslinked polyacrylic acid, hydroxyethylcelluloses, waxes or mixtures of nonionic surfactants with an HLB (Hydrophilic-Lipophilic Balance) value, which, when suitably chosen, give rise to a gelling effect when they are diluted with water and/or surfactants.
However, the Applicant has found that the thickening systems mentioned above do not make it possible to obtain intense and chromatic shades of low selectivity and good staying power, while at the same time leaving the treated hair in a good cosmetic condition. Moreover, the Applicant has also found that ready-to-use dye compositions containing the direct dye(s) and also the thickener systems of the prior art do not allow a sufficiently precise application without running or falls in viscosity over time.
After considerable research conducted in this matter, the Applicant has now discovered that it is possible to obtain direct dye compositions that do not run and thus remain satisfactorily localized at the point of application, and that also make it possible to obtain powerful and chromatic (luminous) shades with low selectivity and good staying power with respect to chemical agents (shampoos, permanent-waving agents, etc.) or natural agents (light, perspiration, etc.) while at the same time giving the hair good cosmetic properties, if an effective amount of a cationic associative polyurethane is introduced either (i) into the composition containing at least one direct dye [or composition A1], or (ii) into the oxidizing composition [or composition B1] used for lightening direct dyeing, or (iii) into both compositions at the same time.
These discoveries form the basis of the present invention.
One subject of the present invention is thus a direct dye composition for keratin fibers, in particular for human keratin fibers and more particularly the hair, comprising, in a medium that is suitable for dyeing, at least one direct dye, which is characterized in that it also comprises at least one cationic associative polyurethane.
Another subject of the invention relates to a ready-to-use composition for dyeing keratin fibers, which comprises at least one direct dye and at least one cationic associative polyurethane and an oxidizing agent.
For the purposes of the invention, the expression “ready-to-use composition” means the composition intended to be applied in unmodified form to the keratin fibers, i.e. it may be stored in unmodified form before use, or may result from the extemporaneous mixing of two or more compositions.
The invention is also directed toward a process for the direct dyeing of keratin fibers, in particular for human keratin fibers and more particularly the hair, which consists in applying to the fibers a composition comprising, in a medium that is suitable for dyeing, at least one direct dye and at least one cationic associative polyurethane.
The invention is also directed toward a process for the lightening direct dyeing of keratin fibers, in particular for human keratin fibers and more particularly the hair, which consists in applying to the fibers an extemporaneous mixture of a composition A1 comprising, in a medium that is suitable for dyeing, at least one direct dye, and of a composition B1 comprising at least one oxidizing agent, composition A1 and/or composition B1 comprising at least one cationic associative polyurethane.
A subject of the invention is also devices for the direct dyeing and the lightening direct dyeing of human keratin fibers, and more particularly the hair, or two-compartment “kits”.
A two-compartment device for direct dyeing according to the invention comprises a first compartment containing, in a medium that is suitable for dyeing, at least one direct dye, and a second compartment containing at least one cationic associative polyurethane.
Other two-compartment devices for lightening direct dyeing according to the invention comprise a compartment that contains a composition A1 comprising, in a medium that is suitable for dyeing, at least one direct dye, and another compartment contains a composition B1 comprising, in a medium that is suitable for dyeing, an oxidizing agent, at least one cationic associative polyurethane being present in composition A1 or composition B1, or in each of the compositions A1 and B1.
However, other characteristics, aspects, subjects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.
Associative polymers are polymers whose molecules are capable, in the formulation medium, of combining with each other or with the molecules of other compounds.
One special case of associative polymers is amphiphilic polymers, i.e. polymers comprising one or more hydrophilic portions which make them water-soluble, and one or more hydrophobic zones (comprising at least one fatty chain) via which the polymers interact and assemble together or with other molecules.
Cationic Associative Polyurethanes
The cationic associative polyurethanes according to the present invention are chosen more particularly from water-soluble or water-dispersible cationic associative amphiphilic polyurethanes.
The term “water-soluble” regarding the associative polyurethanes of the present invention means that these polymers have a solubility in water at room temperature of at least 1% by weight, i.e. up to this concentration, no precipitate is visible to the naked eye, and the solution is totally clear and uniform.
The term “water-dispersible” polyurethanes means polymers which, when suspended in water, spontaneously form globules that have a mean size, measured by light scattering on a Coulter machine, of between 5 nm and 600 nm and in particular between 5 nm and 500 nm.
The family of cationic associative polyurethanes according to the invention was described by the Applicant in French patent application No 00/09609; it may be represented by the general formula (Ia) below:
R-X-(P)n-[L-(Y)m]r-L′-(P′)p-X′-R′ (Ia)
in which:
In one preferred embodiment of the polyurethanes of the present invention, the only hydrophobic groups are the groups R and R′ at the chain ends.
One preferred family of cationic associative polyurethanes is the one corresponding to formula (Ia) described above and in which:
Another preferred family of cationic associative polyurethanes is the one corresponding to formula (Ia) above in which:
The fact that n and p are 0 means that these polymers do not comprise units derived from a monomer containing an amine function, incorporated into the polymer during the polycondensation. The protonated amine functions of these polyurethanes result from the hydrolysis of excess isocyanate functions, at the chain end, followed by alkylation of the primary amine functions formed with alkylating agents containing a hydrophobic group, i.e. compounds of the type RQ or R′Q, in which R and R′ are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
Yet another preferred family of cationic associative polyurethanes is the one corresponding to formula (Ia) above in which:
The number-average molecular mass of the cationic associative polyurethanes is preferably between 400 and 500 000, in particular between 1000 and 400 000 and ideally between 1000 and 300 000.
The expression “hydrophobic group” means a radical or polymer containing a saturated or unsaturated, linear or branched hydrocarbon-based chain, which may contain one or more hetero atoms such as P, O, N or S, or a radical containing a perfluoro or silicone chain. When the hydrophobic group denotes a hydrocarbon-based radical, it comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably 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 such as, for example, polybutadiene.
When X and/or X′ denote(s) a group comprising a tertiary or quaternary amine, X and/or X′ may represent one of the following formulae:
in which:
The groups L, L′ and L″ represent a group of formula:
in which:
The groups P and P′ comprising an amine function may represent at least one of the following formulae:
in which:
As regards the meaning of Y, the term “hydrophilic group” means a polymeric or nonpolymeric water-soluble group.
By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol.
When it is a hydrophilic polymer, in accordance with one preferred embodiment, mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides or a mixture of these polymers. The hydrophilic compound is preferentially a polyether and in particular a poly(ethylene oxide) or poly(propylene oxide).
The cationic associative polyurethanes of formula (Ia) according to the invention are formed from diisocyanates and from various compounds with functions containing a labile hydrogen. The functions containing a labile hydrogen may be alcohol, primary or secondary amine or thiol functions, giving, after reaction with the diisocyanate functions, polyurethanes, polyureas and polythioureas, respectively. The term “polyurethanes” in the present invention encompasses these three types of polymer, namely polyurethanes per se, polyureas and polythioureas, and also copolymers thereof.
A first type of compound involved in the preparation of the polyurethane of formula (Ia) is a compound comprising at least one unit containing an amine function. This compound may be multifunctional, but the compound is preferentially difunctional, that is to say that, according to one preferential embodiment, this compound comprises two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, secondary amine or thiol function. A mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low may also be used.
As mentioned above, this compound may comprise more than one unit containing an amine function. In this case, it is a polymer bearing a repetition of the unit containing an amine function.
Compounds of this type may be represented by one of the following formulae:
HZ-(P)n-ZH
or
HZ-(P′)p-ZH
in which Z, P, P′, n and p are as defined above.
Examples of compounds containing an amine function that may be mentioned include N-methyldiethanolamine, N-tert-butyldiethanolamine and N-sulfoethyldiethanolamine.
The second compound involved in the preparation of the polyurethane of formula (Ia) is a diisocyanate corresponding to the formula:
O═C═N—R4—N═C═O
in which R4 is as defined above.
By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.
A third compound involved in the preparation of the polyurethane of formula (Ia) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (Ia).
This compound consists of a hydrophobic group and of a function containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.
By way of example, this compound may be a fatty alcohol such as, in particular, stearyl alcohol, dodecyl alcohol or decyl alcohol. When this compound comprises a polymeric chain, it may be, for example, [lacuna]-hydroxylated hydrogenated polybutadiene.
The hydrophobic group of the polyurethane of formula (Ia) may also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit. Thus, the hydrophobic group is introduced via the quaternizing agent. This quaternizing agent is a compound of the type RQ or R′Q, in which R and R′ are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
The cationic associative polyurethane may also comprise a hydrophilic block. This block is provided by a fourth type of compound involved in the preparation of the polymer. This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture in which the percentage of multifunctional compound is low.
The functions containing a labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends with one of these functions containing a labile hydrogen.
By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol.
When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these polymers. The hydrophilic compound is preferentially a polyether and especially a poly(ethylene oxide) or poly(propylene oxide).
The hydrophilic group termed Y in formula (Ia) is optional. Specifically, the units containing a quaternary amine or protonated function may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solution.
Although the presence of a hydrophilic group Y is optional, cationic associative polyurethanes comprising such a group are, however, preferred.
Said cationic associative polyurethanes are water-soluble or water-dispersible.
In the dye composition according to the invention, the cationic associative polyurethane(s) is (are) preferably used in an amount that may range from about 0.01% to 10% by weight relative to the total weight of the composition. More preferably, this amount ranges from about 0.1% to 5% by weight.
The direct dyes that may be used according to the invention are preferably chosen from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo dyes, neutral, acidic or cationic quinone, and in particular anthraquinone, direct dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
Among the benzene-based direct dyes that may be used according to the invention, mention may be made, in a nonlimiting manner, of the following compounds:
Among the azo direct dyes that may be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714 954, the content of which forms an integral part of the invention.
Among the azo direct dyes, mention may also be made of the following dyes, described in the Color Index International 3rd edition:
Mention may also be made of 1-(4′-aminodiphenylazo)-2-methyl-4-bis(β-hydroxyethyl)aminobenzene and 4-hydroxy-3-(2-methoxyphenylazo)-1-naphthalenesulfonic acid.
Among the quinone direct dyes that may be mentioned are the following dyes:
Among the azine dyes that may be mentioned are the following compounds:
Among the triarylmethane dyes that may be used according to the invention, mention may be made of the following compounds:
Among the indoamine dyes that may be used according to the invention, mention may be made of the following compounds:
Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurine, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosoin and apigenidin. Extracts or decoctions containing these natural dyes, and especially henna-based poultices or extracts, may also be used.
The direct dye(s) preferably represent(s) from 0.001% to 20% by weight approximately relative to the total weight of the ready-to-use composition, and even more preferably from 0.005% to 10% by weight approximately.
More particularly, the compositions according to the invention may also comprise at least one amphoteric or cationic substantive polymer other than the cationic associative polyurethanes of the invention.
Cationic Polymers
For the purposes of the present invention, the term “cationic polymer” denotes any polymer containing cationic groups and/or groups that may be ionized into cationic groups.
The cationic polymers that may be used in accordance with the present invention may be chosen from all those already known per se as improving the cosmetic properties of the hair, i.e. especially those described in patent application EP-A-337 354 and in French patents FR-2 270 846, 2 383 660, 2 598 611, 2 470 596 and 2 519 863.
The cationic polymers that are preferred are chosen from those containing units comprising primary, secondary, tertiary and/or quaternary amine groups, which may either form part of the main polymer chain or may be borne by a side substituent directly attached thereto.
The cationic polymers used generally have a number-average molecular mass of between 500 and 5×106 approximately and preferably between 103 and 3×106 approximately.
Among the cationic polymers that may be mentioned more particularly are polymers of the polyamine, polyamino amide and polyquaternary ammonium type.
These are known products. They are described in particular in French patents Nos 2 505 348 and 2 542 997. Among said polymers, mention may be made of:
(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of formula (I), (II), (III) or (IV) below:
in which:
The polymers of family (1) can also contain one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C1–C4)alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
Thus, among these polymers of family (1), mention may be made of:
The commercial products corresponding to this definition are more particularly the products sold under the names “Celquat L 200” and “Celquat H 100” by the company National Starch.
(4) The cationic polysaccharides described more particularly in U.S. Pat. Nos. 3,589,578 and 4,031,307, such as guar gums containing cationic trialkylammonium groups. Guar gums modified with a salt (e.g. chloride) of 2,3-epoxypropyltrimethylammonium are used, for example.
Such products are sold in particular under the trade names Jaguar C13 S, Jaguar C 15, Jaguar C 17 or Jaguar C162 by the company Meyhall.
(5) Polymers consisting of piperazinyl units and of divalent alkylene or hydroxyalkylene radicals containing straight or branched chains, optionally interrupted by oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings, as well as the oxidation and/or quaternization products of these polymers. Such polymers are described, in particular, in French patents 2 162 025 and 2 280 361.
(6) Water-soluble polyamino amides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyamino amides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyamino amide; these polyamino amides can be alkylated or, if they contain one or more tertiary amine functions, they can be quaternized. Such polymers are described, in particular, in French patents 2 252 840 and 2 368 508.
(7) The polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents. Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Such polymers are described in particular in French patent 1 583 363.
Among these derivatives, mention may be made more particularly of the adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the name “Cartaretine F, F4 or F8” by the company Sandoz.
(8) The polymers obtained by reaction of a polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio between the polyalkylene polyamine and the dicarboxylic acid is between 0.8:1 and 1.4:1; the polyamino amide resulting therefrom is reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyamino amide of between 0.5:1 and 1.8:1. Such polymers are described in particular in U.S. Pat. Nos. 3,227,615 and 2,961,347.
Polymers of this type are sold in particular under the name “Hercosett 57” by the company Hercules Inc. or alternatively under the name “PD 170” or “Delsette 101” by the company Hercules in the case of the adipic acid/epoxypropyl/diethylenetriamine copolymer.
(9) Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers containing, as main constituent of the chain, units corresponding to formula (V) or (VI):
in which formulae k and t are equal to 0 or 1, the sum k+t being equal to 1; R9 denotes a hydrogen atom or a methyl radical; R7 and R8, independently of each other, denote an alkyl group having from 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower C1–C4 amidoalkyl group, or R7 and R8 can denote, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidyl or morpholinyl; R7 and R8, independently of each other, preferably denote an alkyl group having from 1 to 4 carbon atoms; Y− is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. These polymers are described in particular in French patent 2 080 759 and in its Certificate of Addition 2 190 406.
Among the polymers defined above, mention may be made more particularly of the dimethyldiallylammonium chloride homopolymer sold under the name “Merquat 100” by the company Calgon (and its homologs of low weight-average molecular mass) and the copolymers of diallyldimethylammonium chloride and of acrylamide, sold under the name “Merquat 550”.
(10) The quaternary diammonium polymer containing repeating units corresponding to the formula:
in which formula (VII):
a) a glycol residue of formula: —O-Z-O—, where Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the following formulae:
—(CH2—CH2—O)x—CH2—CH2—
—[CH2—CH(CH3)—O]y—CH2—CH(CH3)—
where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization;
b) a bis-secondary diamine residue such as a piperazine derivative;
c) a bis-primary diamine residue of formula: —NH—Y—NH—, where Y denotes a linear or branched hydrocarbon-based radical, or alternatively the divalent radical
—CH2—CH2—S—S—CH2—CH2—;
d) a ureylene group of formula: —NH—CO—NH—.
Preferably, X− is an anion such as chloride or bromide.
These polymers generally have a number-average molecular mass of between 1000 and 100 000.
Polymers of this type are described in particular in French patents 2 320 330, 2 270 846, 2 316 271, 2 336 434 and 2 413 907 and U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020.
It is more particularly possible to use polymers that consist of repeating units corresponding to formula (VIII) below:
in which R10, R11, R12 and R13, which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms approximately, n and p are integers ranging from 2 to 20 approximately, and X− is an anion derived from a mineral or organic acid.
(11) Polyquaternary ammonium polymers consisting of repeating units of formula (IX):
in which p denotes an integer ranging from 1 to 6 approximately, D may be nothing or may represent a group —(CH2)r—CO— in which r denotes a number equal to 4 or 7, X− is an anion.
Such polymers may be prepared according to the processes described in U.S. Pat. Nos. 4,157,388, 4,702,906 and 4,719,282. They are described in particular in patent application EP-A-122 324.
Among these products, mention may be made, for example, of “Mirapol A 15”, “Mirapol AD1”, “Mirapol AZ1” and “Mirapol 175” sold by the company Miranol.
(12) Quaternary polymers of vinylpyrrolidone and of vinylimidazole, such as, for example, the products sold under the names Luviquat FC 905, FC 550 and FC 370 by the company BASF.
(13) Polyamines such as Polyquart H sold by Henkel, which is given under the reference name “Polyethylene glycol (15) tallow polyamine” in the CTFA dictionary.
(14) Crosslinked methacryloyloxy(C1–C4)alkyltri(C1–C4)alkylammonium salt polymers such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with a compound containing olefinic unsaturation, in particular methylenebisacrylamide. A crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of said copolymer in mineral oil can be used more particularly. This dispersion is sold under the name “Salcare® SC 92” by the company Allied Colloids. A crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester can also be used. These dispersions are sold under the names “Salcare® SC 95” and “Salcare® SC 96” by the company Allied Colloids.
Other cationic polymers which can be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives.
Among all the cationic polymers which may be used in the context of the present invention, it is preferred to use the polymers of families (1), (9), (10), (11) and (14) and even more preferably the polymers consisting of repeating units of formulae (W) and (U) below:
and in particular those whose molecular weight, determined by gel permeation chromatography, is between 9500 and 9900;
and in particular those whose molecular weight, determined by gel permeation chromatography, is about 1200.
The concentration of cationic polymer in the composition according to the present invention may range from 0.01% to 10% by weight relative to the total weight of the composition, preferably from 0.05% to 5% and even more preferably from 0.1% to 3%.
Amphoteric Polymers
The amphoteric polymers that may be used in accordance with the present invention may be chosen from polymers comprising units K and M randomly distributed in the polymer chain, in which K denotes a unit derived from a monomer comprising at least one basic nitrogen atom and M denotes a unit derived from an acidic monomer comprising one or more carboxylic or sulfonic groups, or alternatively K and M may denote groups derived from zwitterionic carboxybetaine or sulfobetaine monomers;
The amphoteric polymers corresponding to the above definition that are more particularly preferred are chosen from the following polymers:
(1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, α-chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds are described in U.S. Pat. No. 3,836,537. Mention may also be made of the sodium acrylate/acrylamidopropyltrimethylammonium chloride copolymer sold under the name Polyquart KE 3033 by the company Henkel.
The vinyl compound may also be a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride. The copolymers of acrylic acid and of the latter monomer are sold under the names Merquat 280, Merquat 295 and Merquat Plus 3330 by the company Calgon.
(2) Polymers containing units derived from:
The N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are groups in which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.
The acidic comonomers are chosen more particularly from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid and alkyl monoesters, having 1 to 4 carbon atoms, of maleic or fumaric acids or anhydrides.
The preferred basic comonomers are aminoethyl, butylaminoethyl, N,N′-dimethylaminoethyl and N-tert-butylaminoethyl methacrylates.
The copolymers whose CTFA (4th edition, 1991) name is Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer such as the products sold under the name Amphomer or Lovocryl 47 by the company National Starch are particularly used.
(3) Polyamino amides that are crosslinked and alkylated partially or totally derived from polyamino amides of general formula:
in which R19 represents a divalent radical derived from a saturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acid containing an ethylenic double bond, an ester of a lower alkanol, having 1 to 6 carbon atoms, of these acids or a radical derived from the addition of any one of said acids to a bis(primary) or bis(secondary) amine, and Z denotes a bis(primary), mono- or bis(secondary) polyalkylene-polyamine radical and preferably represents:
where x=2 and p=2 or 3, or alternatively x=3 and p=2
this radical being derived from diethylenetriamine, from triethylenetetraamine or from dipropylenetriamine;
The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid, terephthalic acid and acids containing an ethylenic double bond such as, for example, acrylic acid, methacrylic acid and itaconic acid.
The alkane sultones used in the alkylation are preferably propane sultone or butane sultone, and the salts of the alkylating agents are preferably the sodium or potassium salts.
(4) Polymers containing zwitterionic units of formula:
in which R20 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, R21 and R22 represent a hydrogen atom, methyl, ethyl or propyl, R23 and R24 represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R23 and R24 does not exceed 10.
The polymers comprising such units can also contain units derived from nonzwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.
By way of example, mention may be made of the copolymer of butyl methacrylate/dimethyl carboxymethylammonio ethyl methacrylate such as the product sold under the name Diaformer Z301 by the company Sandoz.
(5) Polymers derived from chitosan, described especially in French patent No 2 137 684 or U.S. Pat. No. 3,879,376, containing monomer units corresponding to formulae (XIII), (XIV) and (XV) below connected in their chain:
the unit (XIII) being present in proportions of between 0 and 30%, the unit (XIV) in proportions of between 5 and 50% and the unit (XV) in proportions of between 30 and 90%, it being understood that, in this unit (XV), R25 represents a radical of formula:
in which q denotes zero or 1;
in which R29 represents a hydrogen atom, a CH3O, CH3CH2O or phenyl radical, R30 denotes hydrogen or a lower alkyl radical such as methyl or ethyl, R31 denotes hydrogen or a lower alkyl radical such as methyl or ethyl, R32 denotes a lower alkyl radical such as methyl or ethyl or a radical corresponding to the formula: -R33—N(R31)2, R33 representing a —CH2—CH2—, —CH2—CH2—CH2— or —CH2—CH(CH3)— group, R31 having the meanings mentioned above,
X denotes the symbol E or E′, E or E′, which may be identical or different, denotes a divalent radical which is an alkylene radical with a straight or branched chain containing up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with hydroxyl groups and which can contain, in addition to the oxygen, nitrogen and sulfur atoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine or alkenylamine groups, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane groups;
and X denotes the symbol E or E′ and at least once E′; E having the meaning given above and E′ being a divalent radical which is an alkylene radical with a straight or branched chain having up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with one or more hydroxyl radicals and containing one or more nitrogen atoms, the nitrogen atom being substituted with an alkyl chain which is optionally interrupted by an oxygen atom and necessarily containing one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloroacetic acid or sodium chloroacetate.
(9) (C1–C5)alkyl vinyl ether/maleic anhydride copolymers partially modified by semiamidation with an N,N-dialkylaminoalkylamine such as N,N-dimethylaminopropylamine or by semiesterification with an N,N-dialkanolamine. These copolymers can also contain other vinyl comonomers such as vinylcaprolactam.
The amphoteric polymers that are particularly preferred according to the invention are those of family (1).
According to the invention, the amphoteric polymer(s) may represent from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight and even more preferably from 0.1% to 3% by weight relative to the total weight of the composition.
The compositions of the invention preferably comprise one or more surfactants.
The surfactant(s) can be chosen without preference, alone or as mixtures, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants.
The surfactants that are suitable for carrying out the present invention are, in particular, the following:
(i) Anionic Surfactant(s):
As examples of anionic surfactants which can be used, alone or as mixtures, in the context of the present invention, mention may be made in particular (nonlimiting list) of salts (in particular alkaline salts, especially sodium salts, ammonium salts, amine salts, amino alcohol salts or magnesium salts) of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylarylpolyether sulfates, monoglyceride sulfates; alkyl sulfonates, alkyl phosphates, alkylamide sulfonates, alkylaryl sulfonates, α-olefin sulfonates, paraffin sulfonates; (C6–C24)alkyl sulfosuccinates, (C6–C24)alkyl ether sulfosuccinates, (C6–C24)alkylamide sulfosuccinates; (C6–C24)alkyl sulfoacetates; (C6–C24)acyl sarcosinates and (C6–C24)acyl glutamates. It is also possible to use the carboxylic esters of (C6–C24)alkylpolyglycosides, such as alkylglucoside citrates, alkylpolyglycoside tartrates and alkylpolyglycoside sulfosuccinates, alkylsulfosuccinamates; acyl isethionates and N-acyltaurates, the alkyl or acyl radical of all of these various compounds preferably containing from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group. Among the anionic surfactants which can also be used, mention may also be made of fatty acid salts such as the salts of oleic, ricinoleic, palmitic and stearic acids, coconut oil acid or hydrogenated coconut oil acid; acyl lactylates in which the acyl radical contains 8 to 20 carbon atoms. Alkyl-D-galactosideuronic acids and their salts, polyoxyalkylenated (C6–C24)alkyl ether carboxylic acids, polyoxyalkylenated (C6–C24)alkylaryl ether carboxylic acids, polyoxyalkylenated (C6–C24)alkylamido ether carboxylic acids and their salts, in particular those containing from 2 to 50 alkylene oxide, in particular ethylene oxide, groups, and mixtures thereof can also be used.
(ii) Nonionic Surfactant(s):
The nonionic surfactants are also compounds that are well known per se (see in particular in this respect “Handbook of Surfactants” by M. R. Porter, published by Blackie & Son (Glasgow and London), 1991, pp. 116–178) and, in the context of the present invention, their nature is not a critical feature. Thus, they can be chosen in particular from (nonlimiting list) polyethoxylated or polypropoxylated alkylphenols, α-diols or alcohols having a fatty chain containing, for example, 8 to 18 carbon atoms, it being possible for the number of ethylene oxide or propylene oxide groups to range in particular from 2 to 50. Mention may also be made of copolymers of ethylene oxide and of propylene oxide, condensates of ethylene oxide and of propylene oxide with fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 mol of ethylene oxide, polyglycerolated fatty amides containing on average 1 to 5, and in particular 1.5 to 4, glycerol groups; polyethoxylated fatty amines preferably having from 2 to 30 mol of ethylene oxide; oxyethylenated fatty acid esters of sorbitan having from 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, alkylpolyglycosides, N-alkylglucamine derivatives, amine oxides such as (C10–C14)alkylamine oxides or N-acylaminopropylmorpholine oxides. It will be noted that the alkylpolyglycosides constitute nonionic surfactants that are particularly suitable in the context of the present invention.
(iii) Amphoteric or Zwitterionic Surfactant(s):
The amphoteric or zwitterionic surfactants, whose nature is not a critical feature in the context of the present invention, can be, in particular (nonlimiting list), aliphatic secondary or tertiary amine derivatives in which the aliphatic radical is a linear or branched chain containing 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxylate, sulfonate, sulfate, phosphate or phosphonate); mention may also be made of (C8–C20)alkylbetaines, sulfobetaines, (C8–C20)alkylamido(C1–C6)alkylbetaines or (C8–C20)alkylamido(C1–C6)alkylsulfobetaines.
Among the amine derivatives, mention may be made of the products sold under the name Miranol, as described in U.S. Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names amphocarboxyglycinates and amphocarboxypropionates of respective structures:
R2—CONHCH2CH2—N(R3)(R4)(CH2COO−)
in which: R2 denotes an alkyl radical of an acid R2—COOH present in hydrolyzed coconut oil, a heptyl, nonyl or undecyl radical, R3 denotes a β-hydroxyethyl group and R4 denotes a carboxymethyl group;
and
R2′—CONHCH2CH2—N(B)(C)
in which:
These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.
By way of example, mention may be made of the cocoamphodiacetate sold under the trade name Miranol® C2M Concentrate by the company Rhodia Chimie.
(iv) Cationic Surfactants:
Among the cationic surfactants that may be mentioned in particular (nonlimiting list) are: primary, secondary or tertiary fatty amine salts, optionally polyoxyalkylenated; quaternary ammonium salts such as tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium chlorides or bromides; imidazoline derivatives; or amine oxides of cationic nature.
The amounts of surfactants present in the composition according to the invention can range from 0.01% to 40% and preferably from 0.5% to 30% relative to the total weight of the composition.
The compositions according to the invention can also contain other agents for adjusting the rheology, such as cellulose-based thickeners (hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, etc.), guar gum and its derivatives (hydroxypropyl guar, etc.), gums of microbial origin (xanthan gum, scleroglucan gum, etc.), synthetic thickeners such as crosslinked acrylic acid or acrylamidopropanesulfonic acid homopolymers and ionic or nonionic associative polymers such as the polymers sold under the names Pemulen TR1 or TR2 by the company Goodrich, Salcare SC90 by the company Allied Colloids, Aculyn 22, 28, 33, 44 or 46 by the company Rohm & Haas, and Elfacos T210 and T212 by the company Akzo.
These additional thickeners can represent from 0.01% to 10% by weight relative to the total weight of the composition.
The medium of the composition that is suitable for dyeing is preferably an aqueous medium consisting of water and may advantageously contain cosmetically acceptable organic solvents including, more particularly, alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol, or glycols or glycol ethers such as, for example, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol and diethylene glycol alkyl ethers such as, for example, diethylene glycol monoethyl ether or monobutyl ether. The solvents may then be present in concentrations of between about 0.5% and 20% and preferably between about 2% and 10% by weight relative to the total weight of the composition.
Composition A may also comprise an effective amount of other agents, which are previously known elsewhere for direct dyeing, such as various common adjuvants, for instance sequestering agents such as EDTA and etidronic acid, UV screening agents, waxes, volatile or nonvolatile, cyclic or linear or branched silicones, which are possibly organomodified (especially with amine groups), preserving agents, ceramides, pseudoceramides, plant, mineral or synthetic oils, vitamins or provitamins, for instance panthenol, opacifiers, associative polymers other than those of the invention, and in particular nonionic associative polyurethane polyethers.
Needless to say, a person skilled in the art will take care to select the optional additional compound(s) mentioned above such that the advantageous properties intrinsically associated with the dye composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
In the ready-to-use composition with oxidizing agent, the oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, and persalts such as perborates and persulfates. It is particularly preferred to use hydrogen peroxide. This oxidizing agent advantageously consists of an aqueous hydrogen peroxide solution whose titer may range, more particularly, from about 1 to 40 volumes and even more preferably from about 5 to 40 volumes.
Oxidizing agents that may also be used are one or more redox enzymes such as laccases, peroxidases and 2-electron oxidoreductases (such as uricase), where appropriate in the presence of their respective donor or cofactor.
The pH of the ready-to-use composition [oxidant-free ready-to-use composition or composition resulting from mixing the dye composition A1 and the oxidizing composition B1] is generally between the values 2 and 12. It is preferably between 3 and 11, and may be adjusted to the desired value by means of acidifying or basifying agents that are well known in the prior art in the dyeing of keratin fibers.
More preferentially, when the composition contains an oxidizing agent to lighten the fibers, the pH of the ready-to-use mixture is greater than 7 and even more preferentially greater than 8.
Among the basifying agents that may be mentioned, for example, are aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine and also derivatives thereof, oxyethylenated and/or oxypropylenated hydroxyalkylamines and ethylenediamines, sodium hydroxide, potassium hydroxide and the compounds of formula (XIX) below:
in which R is a propylene residue optionally substituted with a hydroxyl group or a C1–C4 alkyl radical; R38, R39, R40 and R41, which may be identical or different, represent a hydrogen atom, a C1–C4 alkyl radical or a C1–C4 hydroxyalkyl radical.
The acidifying agents are conventionally, for example, mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, carboxylic acids, for instance tartaric acid, citric acid or lactic acid, or sulfonic acids.
The dyeing process according to the invention preferably consists in applying the oxidant-free ready-to-use composition A or the composition prepared extemporaneously at the time of use from compositions A1 and B1 described above, to wet or dry keratin fibers, and leaving the composition to act for an action time preferably ranging from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately, rinsing the fibers and then optionally washing them with shampoo, followed by rinsing them again and drying them.
One variant of this process consists in taking a composition A′ comprising at least one direct dye but without cationic associative polyurethane, and a composition A″ comprising at least one cationic associative polyurethane polymer, and mixing, at the time of use, these compositions A′ and A″ with oxidizing composition B, followed by applying the mixture obtained and leaving it to act as previously.
Concrete examples illustrating the invention are given below, without, however, having any limiting nature.
The following compositions were prepared:
(amounts expressed in grams)
Polymer 1 is the following polymer:
C18H37—O—CONHR4NHCO—O—(CH2)2—N+(CH3)(CH3)—(CH2)2—O—CONHR2NHCO—O(POE)O—CONHR2NHCO—O—(CH2)2—N+(CH3)(CH3)—(CH2)2—O—CONHR4NHCO—OC18H37
with:
It is synthesized from the following reagents:
Polymer 2 is the following polymer:
C18H37N+(CH3)(CH3)—(CH2)2—O—CONHR4NHCO—O(POE)O—CONHR4NHCO—O—(CH2)2—N+(CH3)(CH3)C18H37
with:
It is synthesized from the following reagents:
The dye compositions were mixed, at the time of use, in a plastic bowl for 2 minutes, with the oxidizing composition given above, in a proportion of 1 part of dye composition per 1.5 parts of oxidizing composition.
The mixtures obtained were applied to locks of natural hair containing 90% white hairs, and were left to act on the locks for 30 minutes.
The locks were then rinsed with water, washed with standard shampoo, rinsed again with water and then dried and disentangled.
The hair was dyed in both cases in a strong red shade.
The composition below was prepared:
(expressed in grams)
This composition was applied for 30 minutes to gray hair containing 90% white hairs. After rinsing and drying, the hair was dyed a strong red.
| Number | Date | Country | Kind |
|---|---|---|---|
| 00 14322 | Nov 2000 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/FR01/03427 | 11/6/2001 | WO | 00 | 5/7/2003 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO02/38115 | 5/16/2002 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 2261002 | Moore | Oct 1941 | A |
| 2271378 | Searle | Jan 1942 | A |
| 2273780 | Dittmar | Feb 1942 | A |
| 2375853 | Kirby et al. | May 1945 | A |
| 2388614 | Kirby et al. | Nov 1945 | A |
| 2454547 | Bock et al. | Nov 1948 | A |
| 2528378 | Mannheimer | Oct 1950 | A |
| 2781354 | Mannheimer | Feb 1957 | A |
| 2961347 | Floyd | Nov 1960 | A |
| 3206462 | McCarty | Sep 1965 | A |
| 3227615 | Korden | Jan 1966 | A |
| 3472840 | Stone et al. | Oct 1969 | A |
| 3589578 | Kamphausen | Jun 1971 | A |
| 3632559 | Matter | Jan 1972 | A |
| 3836537 | Boerwinkle et al. | Sep 1974 | A |
| 3874870 | Green et al. | Apr 1975 | A |
| 3879376 | Vanlerberghe et al. | Apr 1975 | A |
| 3910862 | Barabas et al. | Oct 1975 | A |
| 3912808 | Sokol | Oct 1975 | A |
| 3917817 | Vanlerberghe et al. | Nov 1975 | A |
| 3929990 | Green et al. | Dec 1975 | A |
| 3966904 | Green et al. | Jun 1976 | A |
| 4001432 | Green et al. | Jan 1977 | A |
| 4003699 | Rose et al. | Jan 1977 | A |
| 4005193 | Green et al. | Jan 1977 | A |
| 4013787 | Varlerberghe et al. | Mar 1977 | A |
| 4025617 | Green et al. | May 1977 | A |
| 4025627 | Green et al. | May 1977 | A |
| 4025653 | Green et al. | May 1977 | A |
| 4026945 | Green et al. | May 1977 | A |
| 4027008 | Sokol | May 1977 | A |
| 4027020 | Green et al. | May 1977 | A |
| 4031025 | Vanlerberghe et al. | Jun 1977 | A |
| 4031307 | DeMartino et al. | Jun 1977 | A |
| 4131576 | Iovine et al. | Dec 1978 | A |
| 4157388 | Christiansen | Jun 1979 | A |
| 4165367 | Chakrabarti | Aug 1979 | A |
| 4172887 | Vanlerberghe et al. | Oct 1979 | A |
| 4189468 | Vanlerberghe et al. | Feb 1980 | A |
| 4197865 | Jacquet et al. | Apr 1980 | A |
| 4217914 | Jacquet et al. | Aug 1980 | A |
| 4223009 | Chakrabarti | Sep 1980 | A |
| 4240450 | Grollier et al. | Dec 1980 | A |
| 4277581 | Vanlerberghe et al. | Jul 1981 | A |
| 4348202 | Grollier et al. | Sep 1982 | A |
| 4349532 | Vanlerberghe et al. | Sep 1982 | A |
| 4381919 | Jacquet et al. | May 1983 | A |
| 4422853 | Jacquet et al. | Dec 1983 | A |
| 4445521 | Grollier et al. | May 1984 | A |
| 4579732 | Grollier et al. | Apr 1986 | A |
| 4591610 | Grollier | May 1986 | A |
| 4608250 | Jacquet et al. | Aug 1986 | A |
| 4702906 | Jacquet et al. | Oct 1987 | A |
| 4719099 | Grollier et al. | Jan 1988 | A |
| 4719282 | Nadolsky et al. | Jan 1988 | A |
| 4761273 | Grollier et al. | Aug 1988 | A |
| 4777040 | Grollier et al. | Oct 1988 | A |
| 4803221 | Bair | Feb 1989 | A |
| 4839166 | Grollier et al. | Jun 1989 | A |
| 4948579 | Jacquet et al. | Aug 1990 | A |
| 4970066 | Grollier et al. | Nov 1990 | A |
| 4996059 | Grollier et al. | Feb 1991 | A |
| 5009880 | Grollier et al. | Apr 1991 | A |
| 5057311 | Kamegai et al. | Oct 1991 | A |
| 5061289 | Clausen et al. | Oct 1991 | A |
| 5089252 | Grollier et al. | Feb 1992 | A |
| 5139037 | Grollier et al. | Aug 1992 | A |
| 5196189 | Jacquet et al. | Mar 1993 | A |
| 5380340 | Neunhoeffer et al. | Jan 1995 | A |
| 5478562 | Cauwet et al. | Dec 1995 | A |
| 5534267 | Neunhoeffer et al. | Jul 1996 | A |
| 5643581 | Mougin et al. | Jul 1997 | A |
| 5650159 | Lion et al. | Jul 1997 | A |
| 5663366 | Neunhoeffer et al. | Sep 1997 | A |
| 5708151 | Möckli | Jan 1998 | A |
| 5735908 | Cotteret et al. | Apr 1998 | A |
| 5766576 | Löwe et al. | Jun 1998 | A |
| 5807957 | Samour et al. | Sep 1998 | A |
| 5876463 | Garcia et al. | Mar 1999 | A |
| 5888252 | Möckli | Mar 1999 | A |
| 5958392 | Grollier et al. | Sep 1999 | A |
| 6068835 | Franzke et al. | May 2000 | A |
| 6099592 | Vidal et al. | Aug 2000 | A |
| 6099593 | Terranova et al. | Aug 2000 | A |
| 6260556 | Legrand et al. | Jul 2001 | B1 |
| 6284003 | Rose et al. | Sep 2001 | B1 |
| 6335003 | Kim et al. | Jan 2002 | B1 |
| 6379401 | Legrand et al. | Apr 2002 | B1 |
| 6395265 | Mougin et al. | May 2002 | B1 |
| 6410004 | Kim et al. | Jun 2002 | B1 |
| 6416770 | Leduc et al. | Jul 2002 | B1 |
| 6524564 | Kim et al. | Feb 2003 | B1 |
| 6602303 | Laurent et al. | Aug 2003 | B1 |
| 6641804 | Ohta et al. | Nov 2003 | B1 |
| 6800276 | Kim et al. | Oct 2004 | B1 |
| 20020046431 | Laurent et al. | Apr 2002 | A1 |
| 20030124079 | Mougin et al. | Jul 2003 | A1 |
| 20040141943 | Mougin et al. | Jul 2004 | A1 |
| Number | Date | Country |
|---|---|---|
| 23 59 399 | Jun 1975 | DE |
| 38 43 892 | Jun 1990 | DE |
| 41 33 957 | Apr 1993 | DE |
| 195 43 988 | May 1997 | DE |
| 195 43 989 | May 1997 | DE |
| 0 080 976 | Jun 1983 | EP |
| 0 122 324 | Oct 1984 | EP |
| 0 337 354 | Oct 1989 | EP |
| 0 714 954 | Jun 1996 | EP |
| 0 875 237 | Nov 1998 | EP |
| 1 035 144 | Sep 2000 | EP |
| 1 036 558 | Sep 2000 | EP |
| 1 400 366 | May 1963 | FR |
| 1 492 597 | Sep 1965 | FR |
| 1 583 363 | Oct 1969 | FR |
| 2 077 143 | Oct 1971 | FR |
| 2 080 759 | Nov 1971 | FR |
| 2 137 684 | Dec 1972 | FR |
| 2 162 025 | Jul 1973 | FR |
| 2 190 406 | Feb 1974 | FR |
| 2 252 840 | Jun 1975 | FR |
| 2 270 846 | Dec 1975 | FR |
| 2 280 361 | Feb 1976 | FR |
| 2 316 271 | Jan 1977 | FR |
| 2 320 330 | Mar 1977 | FR |
| 2 336 434 | Jul 1977 | FR |
| 2 368 508 | May 1978 | FR |
| 2 383 660 | Oct 1978 | FR |
| 2 393 573 | Jan 1979 | FR |
| 2 413 907 | Aug 1979 | FR |
| 2 470 596 | Jun 1981 | FR |
| 2 505 348 | Nov 1982 | FR |
| 2 519 863 | Jul 1983 | FR |
| 2 542 997 | Sep 1984 | FR |
| 2 598 611 | Nov 1987 | FR |
| 2 733 749 | Nov 1996 | FR |
| 2 750 048 | Dec 1997 | FR |
| 2 773 991 | Jul 1999 | FR |
| 2 811 993 | Jan 2002 | FR |
| 1021400 | Mar 1966 | GB |
| 1026978 | Apr 1966 | GB |
| 1153196 | May 1969 | GB |
| 1331819 | Sep 1973 | GB |
| 1347051 | Feb 1974 | GB |
| 1479786 | Jul 1977 | GB |
| 1546809 | May 1979 | GB |
| 2-19576 | Jul 1988 | JP |
| 55-4384 | Nov 1988 | JP |
| 7-89822 | Apr 1995 | JP |
| 8-504454 | May 1996 | JP |
| 9-110659 | Apr 1997 | JP |
| 10-259115 | Sep 1998 | JP |
| 10-509742 | Sep 1998 | JP |
| 10-316546 | Dec 1998 | JP |
| 2000-239134 | Sep 2000 | JP |
| 2000-256141 | Sep 2000 | JP |
| 2000-309518 | Nov 2000 | JP |
| WO 9408969 | Apr 1994 | WO |
| WO 9408970 | Apr 1994 | WO |
| WO 9501772 | Jan 1995 | WO |
| WO 9515144 | Jun 1995 | WO |
| WO 9615765 | May 1996 | WO |
| WO 9828355 | Jul 1998 | WO |
| WO 9936047 | Jul 1999 | WO |
| WO 0009609 | Feb 2000 | WO |
| WO 0012588 | Mar 2000 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20040019981 A1 | Feb 2004 | US |
