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Publication numberUS3917817 A
Publication typeGrant
Publication dateNov 4, 1975
Filing dateNov 28, 1972
Priority dateNov 29, 1971
Also published asCA1026039A1, DE2258222A1, DE2258222B2, DE2258222C3
Publication numberUS 3917817 A, US 3917817A, US-A-3917817, US3917817 A, US3917817A
InventorsGuy Vanlerberghe, Henri Sebag
Original AssigneeOreal
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hair treating cosmetic compositions containing piperazine based cationic polymer
US 3917817 A
Abstract
Piperazine-based low molecular weight film-forming cationic polymer is employed in a cosmetic hair-conditioner composition comprising a solution of the polymer in amounts of about 0.1-5 weight percent of the composition in a solvent such as water, acidified water, or aqueous alcohol solution.
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Description  (OCR text may contain errors)

United States Patent 1 Vanlerberghe et a1.

[45] Nov. 4, 1975 HAIR TREATING COSMETIC COMPOSITIONS CONTAINING PIPERAZINE BASED CATIONIC POLYMER [75] Inventors: Guy Vanlerberghe, Montjay-la-Tour par Claie-Souilly; Henri Sebag, Paris, both of France [73] Assignee: LOreal, Paris, France [22] Filed: Nov. 28, 1972 [21] Appl. No.: 310,088

[30] Foreign Application Priority Data Nov. 29, 1971 Luxembourg 064371 260/29.6 HN; 424/47, 70, 71, DIG. 1, DIG. 2

[56] References Cited UNITED STATES PATENTS 3,069,390 12/1962 Kline et a]. 424/47 X 3,250,682 5/1966 Wilmsmann et a1. 3,267,046 8/1966 Bonvicini 260/2 BP 3,274,312 9/1966 Compostella et al. 264/78 3,280,044 10/1966 Bonvicini et a1. 260/2 BP Primary ExaminerAlbert T. Meyers Assistant Examiner-Vera C. Clarke Attorney, Agent, or FirmCushman, Darby & Cushman [57] ABSTRACT Piperazine-based low molecular weight film-forming cationic polymer is employed in a cosmetic hairconditioner composition comprising a solution of the polymer in amounts of about 0.1-5 weight percent of the composition in a solvent such as water, acidified water, or aqueous alcohol solution.

7 Claims, No Drawings 1. HAIR TREATING COSMETIC COMPOSITIONS CONTAINING PIPERAZINE BAsEn-CATIoNIC POLYMER-- The present invention relates to compositions fo r treatingand conditioning the hair. More particularly, the prese n t invention i'elates to cosmetic compositions for the hair, containing a low m'olecu lar weight, filmforming cationic polymer. l i A Many people's hair because of itsgerieral state orlits sensitivity due tov relatively frequent periodic treatments such asbleaching, dyeingor permanent waving, often is difficultto comb out and to arrange e specially in the case of abundanthair. To varying degrees, such hair often is also dry, dull and rough or lacks vigor and life-Further, such hair is very sensitive to,hurnidity in theair, which explains why hair-sets do not hold for an acceptable length OftimeDC nsequently, the frequency of such treatments, as described above has tobe increased, which, in turn increases the above-mentioned disadvantages. n, j c

The present invention now makesit possible to substantially limit or avoid these, disadyantagesby applying to the hair as a conditioner therefor-a low molecular weight, film-forming cationic polymer that imparts to the .hair an appearance of vigorand radiance.-

This polymer can be used alone-o'r as. the maincomponent in ahair-dressing lotion, cream, gel, hairsetting lotion hair-setting 'reinforcer, or alternatively, as an adjuvant in a composition for shampooing, setting, in permanent waving the hair, in a hair dyeing composition, in a cream for treating-dry or greasy hair, in an antidandruff lotion or in similarcompositi'ons forapplication to the hair.

The application of the hair conditioner cosmetic composition of this invention results in improving the facility and ease of combing out wet hair and imparts thereto brilliancy, softness and manageability of dry hair. Hair treated with the,composition of this invention feels lighten while at the "same 'time appears thickerand more alive. I

The conditioner according to the 'inven'tion, which acts as a softener and emollient, producesafter application of the same to the hair in. a shampoo, for example, a more brilliant, more voluminous and more aerated hair without the appearance of static electricity. Further, the cationic polymer of the present invention, provides the additional advantage of avoiding a powdering phenomenon which is frequently observed with numerous conventionally employed polymers. Moreover, the inclusion of the hair conditioner of thepres- Zen't invention in cosmetic compositions for the hair,

which comositions also include other components or hair treating agents, does not entail any appreciable -re- 'duction of the properties or effectiveness of theseother components.

The cationic polymer of the present invention is i characterized by the fact that the cationic groups are part of the main polymer chain and that they are essentially derivedfrorn. bisecondary heterocyclic amines, preferably, piperazine. Structu rally', the 'low molecular weight, filmforming, cationic polymer of the present invention can be represented by the pattern 2 wherein A represents a radicalderived from a heterocycle containing two secondary amine functions and, preferably, the radical and. Z. -r.eprefsents the,symbol P orB' ,;each of whicl'rindependently represents a bivalentfradical selected from thegroup consistingof (i) hydroxypropylene, (.ii),alkylene having up to 5 carbon atoms inclusive and interrupted by l 2 members selected from the group consisting of -CONl-l and I 4 I -con' NCO and (iii) hydroxy alkyl ene wherein the alkylene moiety has up to 6 carbon atoms inclusive and is interrupted by "a member selected'from the group consisting of 'alkyla- 'rn'i ne wherein the alkyl moiety has 12m 16 carbon atoms, benzylamin'e,' ole'ylam'ine" and oxygen.

Often, polymers of the present invention-are those in which A has the meaning given above and B and B each independently represent a branched or straight chain radical selected from the group consisting of hydroxyalkyl 'ene having and, preferably, 3 carbon atoms, lower" alkyl-carbonamide lower alkyl-carbonamide-lower alkyl having 5 to 8 'and, preferably 6 m7 carbon atoms, hydroxypropyl-Oxyhydroxypropyl,"hydroxypropyl-alkylaminohydroxypropyl wherein the alkyl moiety has 12 to 16 carbon atoms, hydroxypropyl-alkenylamino-hydroxypropyl wherein the alk enyl moiety has 18 carbon atoms,hydroxypropylpiperazinylhydroxypropyl, propiOnyl-piperazinyl-propionyl and hydroxypropyl-benzylamino-hydroxypropyl.

The polymers of the present invention are more generally strictly alternated, -i.e. of the type wherein A and B have the meanings give n aboveQj These rigorously'alternated polymers, which can be used in the present invention, can be prepared byconventional processes such as by polyaddition or polycon- .densation of (a) piperazine or a derivative thereof such as, for example, N,Nbis(hydroxyethyl)piperazine,,on (b) abifunctional compound such as c I 1.; alkyl or'alkyl-aryl dihalides, such as ethylene chlo- -ride ethylene bromide or his chloromethyl, 1,4-benzene wherein the alkyl moiety has 1-4 carbon atoms, the aryl moiety is phenyl and the halide moiety is chloride or bromide;

2. more complex'dihalogen derivatives, such as bis (chloroacetyl) ethylene diamine;

3. bis halohydrins, such as,bis 3-chloro 2-hydroxy propylether, or otherbis chlorohydrins which can be obtained by'conventional procedures such as by the condensation of epichlorohydrin. on (i) a primary amine, optionally hydroxylated, (ii) on a bisecondary diamine such as'piperazine, 4,4'- dipiperidyl, bis 4,4 (N-methylaminophenyl) methane, N,N 'dimethylethy- 'lene; diamine Orpropylene diamine, (iii) on. a,w-dimercaptoalkane, (iv) on a diol such as ethylene glycol or (v) Ona bis phenol such as hydroquinone or his .phenOlA;' v 1' 4. bis epoxide such as diglycidyl ether or N,Nbis (epoxy-2,3 propyl)piperazine, eventually obtained from the corresponding bis halohydrin;

5. epihalohydrins, such as epichlorohydrin or epibromohydrin;

bisecondary bis unsaturated derivatives, such as divinyl sulfone, bis maleimide derived from ethylene diamine, or bis acrylamide such as methylene bis acrylamide or piperazine bis acrylamide derived from 'biprimary or bissecondary diamines;

, 7. unsaturated acids, such as acrylic or methacrylic acid or their methyl or ethyl esters;

- 8. diacids, such as succinic, adipic, 2,2,4-trimethyl or 2,4,4-trimethyl adipic or terephthalic acids, acid chlorides or the corresponding methyl or ethyl esters; and 9. diisocyanates, such as toluene diisocyanate or 2,2,4- or 2,4,4-trimethyl hexamethylene isocyanate.

The polyaddition or polycondensation reaction can be carried out at ambient pressure and at a temperature ranging fromabout to 100C, the molar ratio of (a) to (b), defined above being 0.85 l to 1.15 1.

1 Of course, the polymers of the present invention can in certain cases advantageously be prepared in essentially the same way by polycondensation or polyaddition of (a N,Nbis(3-chloro 2-hydroxy propyl) piperazine or N,N'bis (2,3-epoxy propyl) piperazine on (b') a bifunctional compound such as a bisecondary diamine, a dimercaptan, a diol, a diphenol, a diacid, and

a primary amine such as an alkylamine, alkenylamine,

aralkylamine, of which the two hydrogen atoms can be substituted and which behaves as a bifunctional compound,'the molar ratio of (a') to(b') ranging from 0.85

Further, the cationic polymers of the present inventi'oncan also, in certain cases, be of the pattern iLe. be made up of polymer chains in which A, representing a bisecondary heterocyclic amine group, for example, the piperazine group, is distributed regularly, the two B and B groups designated by Z in formula (I) beingdistributed statistically. This type of polymer is 1 obtained'when piperazine or one of its derivatives is condensed with a mixture of two bifunctional derivatives.

The polycondensates of type I, II or [II can then, in

accordance with conventional procedures, be oxidized propylene oxide, epichlorohydrin or glycidol.

In those polymers of this invention wherein Z or B and B groups do not comprise base nitrogen or thioether, only the A groups will be modified statistically or almost totally by quaternization or oxidation. Other- I wise, any group can be modified.

The oxidation reaction of the polycondensate of type i I, [1 or [II can be performed with the amount of oxidizing agent being present in amounts from 0 to 100 percent relative to the oxidizable groups, while the quaternization reaction of the polycondensate of type I, II or .111 can be performed with the amount of quaternization 7 agent being present in amounts of 0 to 50 percent.

The cationic polymers of the present invention are also characterized by the fact that they are all filmforming and are generally of relatively low molecular weight, i.e. less than 15,000 and generally about LOCO-15,000. They are water soluble in acid medium and a number of them are also soluble as such in water without addition of acid or in dilute alcohol medium such as ethanol or isopropanol. The alcohol, i.e. lower alkanol, can be present in amounts of about 0 to 50 percent by weight of said composition. Generally, when an aqueous acidic medium is employed as the solvent for the polymers of the present invention, the acid employed can be hydrochloric, acetic, lactic, or tartaric acid in amounts sufficient to solubilize the said poly mer. Generally, the acid will be present in amounts of about 0 to 5 percent by weight of the composition. These polymers are particularly effective for hair which has become sensitives as a result of such treatments as bleaching, permanent waving, or dyeing. They can, however, also advantageously be used for normal hair.

Thus, an object of the present invention is the provision of a cosmetic composition for conditioning the hair comprising a solution in a solvent selected from the group consisting of water and an aqueous solution of a lower alkanol, of a member selected from the group consisting of (l) a low molecular weight, film-forming cationic polymer of the formula in which A represents a radical derived from a heterocycle carrying two secondary amine functions and preferably the radical and Z represents the symbol B or B; B and B each independently representing a bivalent radical selected from the group consisting of (i) hydroxypropylene, (ii) alkylene having up to 5 carbon atoms inclusive and interrupted by l-2member selected from the group consisting of CONH and CON. NCO

and (iii) hydroxy alkylene wherein the alkylene moiety has up to 6 carbon atoms inclusive and interrupted by a member selected from the group consisting of alkylamine wherein the alkyl moiety has 12-16 carbon atoms, benzylamine, oleylamine and oxygen, or (2) quaternary ammonium salt of the cationic polymer in (l) or (3) the oxidation product of the cationic polymer in (1).

Many of the polymers of formula (1) are new compounds.

Among the preferred polymers are those in which A and B and B, each independently represent a branched or straight chain radical selected from the group consisting of hydroxyackylene having l-6 carbon atoms, preferably 3 carbon atoms, lower alkyl-carbonamidelower alkyl-carbonamide-lower alkyl having 5-8 and preferably 6-7 carbon atoms, hydroxypropyl-oxyhydroxypropyl, hydroxypropyl-alkylamino-hydroxypropyl wherein the alkyl moiety has 12-16 carbon atoms, hydroxypropyl-alkenylamino-hydroxypropyl wherein the alkenyl moiety has 18 carbon atoms, hydroxypropyl-piperizinyl-hydroxypropyl, propionylpiperizinylpropionyl and hydroxypropyl-benzylamino-hydroxypropyl.

The polymer can be present in amounts of about 0.1 to 5 percent and preferably 0.2 to 3 percent by weight in the various cosmetic compositions of the present invention. These compositions include hair-dressing lotions, creams or gels as the main constituent, shampoos, hair-setting compositions, permanent wave composition or hair dye compositions, etc. The polymers can also be employed as an adjuvant in the presence of other components such as anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants, oxidizing agents, foam stabilizers or synergists, sequestrants, superfatting agents, thickeners, softeners, antiseptics, preservatives, dyes, perfumes, germicides or other anionic, cationic, amphoteric or non-ionic polymers.

The polymers can be used in different compositions whose pI-l varies from 3 to 11, or in the form of inorganic or organic acid salts, or in the form of free base or, alternatively, the quaternary ammonium salt thereof.

The cosmetic compositions for hair according to the present invention can be in the form of an aqueous solution, a dilute alcohol solution, a cream, a paste, a gel, or a powder. They can also contain a conventional aerosol propellant such as dichlorodifluoromethane, monochlorotrifluoromethane, mixtures thereof or other conventional aerosol propellants, and can be packaged in a conventional aerosol bomb under pressure.

The hair shampoo compositions according to the invention are characterized by the fact that they contain, in addition to an anionic, cationic, non-ionic, amphoteric and/or switterionic surfactant, one or more compounds of formula I and optionally foam stabilizers or synergists, sequestrants, superfatting agents, thickeners, one or more other cosmetic resins, softeners, dyes, perfumes, antiseptics, preservatives and any other adjuvant usually used in cosmetic compositions.

The polymers of formula I also make it possible to prepare hair-setting lotions, hair-setting reinforcers,

'treatment creams, hair conditioners, anti-dandruff lotions and other similar compositions characterized by the fact that they contain one or more polymers of formula I having a molecular weight, determined by lowering of the vapor tension, between 1,000 and 15,000, or the quaternary ammonium salt or amine oxide of these polymers, possibly mixed with other cosmetic resins.

EXAMPLES OF PREPARATION OF THE POLYMER Example 1 Polycondensation of piperazine and epichlorohydrin. To a solution of 97 g (0.5 mole) of piperazine hexahydrate in 125 g of water, there are added, drop by 6 drop, over a period of l hour, 46.3 g (0.5 mole) of epichlorohydrin, with stirring, while maintaining the temperature at 20C. Stirring is continued for 1 hour at 20C. The reaction mass is then heated at 95C for 2 hours. Over a period of one hour, 0.5 mole of sodium hydroxide is then added in the form of a 40 percent (50 g) NaOH solution. A cloud then appears in the solution. The temperature is maintained at the 9095C level for 15 minutes more, and the reaction mixture is then cooled with stirring while adding 182 g of water to bring the concentration to 20 percent of dry extract (14.5 percent active material and a 5.5 percent NaCl).

A limpid and almost colorless solution is thus obtained, having a viscosity of 2.5 poises, measured at 25C.

On evaporation of a dilute solution of the polymer thus prepared, there is obtained a wrinkled film, opaque because of the presence of the sodium chloride, but hard and not sticky.

Example 2 Polycondensation of N,N'bis-(2,3-epoxy propyl) piperazine and piperazine.

A polymer similar to that of Example 1, but free of sodium chloride, is prepared by olycondensation of piperazine and N,N' bis(2,3-epoxy propyl) piperazine in an aqueous medium and in stoichiometric proportions. The N,Nbis-(2,3-epoxy propyl) piperazine can be prepared in the following way:

To 86 g (1 mole) of anhydrous piperazine, dissolved in 540 g of isopropanol, there are added, over a 30 minute period at a temperature of l0l5C, 185 g of epichlorohydrin (2 moles). This temperature is maintained at this level while the reaction mixture is stirred for 7 hours.

The resulting dichlorohydrin, derived from piperazine, is filtered and dried. It is a white crystallized product having a melting point of l08l 10C.

50.7 g (0.18 mole) of the dichlorohydrin thus obtained are dispersed in ml of benzene. The suspension is cooled to 10C. There are then added by fractions, over a 30 minute period, 15.5 g (0.37 mole) of ground sodium hydroxide. This temperature is maintained for 2 1% hours. The sodium chloride precipitate is filtered and rinsed with three times 100 ml of benzene.

After elimination of the benzene, under partial vacuum, there are collected 26 g of white solid corresponding, according to functional analyses, to N,N'bis- (2,3-epoxy propyl) piperazine.

25 g (0.125 mole) of product thus prepared are heated with reflux with 10.8 g (0.125 mole) of anhydrous piperazine in 60 g of isopropanol for 3 9% hours. The cationic polymer is then partially precipitated. The solvent is eliminated under partial vacuum and an almost white powder is thus obtained which is soluble in water and which exhibits a melting point of 190C. The molecular weight of this polymer, measured in chloroform by the method of lowering the vapor tension, is 2460.

Example 3 Quaternization of the piperazine and 'epichlorohydrin polycondensate.

To 200 g of solution obtained according to Example 1 which contains 0.4 equivalent of base nitrogen, there are added g of absolute ethyl alcohol and then 25 .3 g (0.2 mole) of benzyl chloride. The reaction mixture is heated at 80C for 1% hours. The ethanol is then elimi- '7 nated under partial vacuum, while re-adding water, to obtain a 10 percent solution of dry extract.

Example 4 mole) of 200 volume hydrogen peroxide. The tempera- 1O ture is maintained at this level for hours.

The polymer solution obtained is perfectly limpid and yields, on evaporation, films comparable to those of Example 1.

Example 5 Polycondensation of piperazine, benzylamine and epichlorohydrin.

To a solution of 97 g (0.5 mole) of hexahydrated piperazine, in 384 g of isopropyl alcohol, there are added, drop by drop at C, 92.5 g (1 mole) of epichlorohydrin. The resulting solution is maintained, with stirring, at 15C for 2 hours. Thereafter it is heated to 70C, and over a 15 minute period, 54 g (0.5 mole) of benzylamine are added. The resulting mixture is heated with reflux for an hour. There are then added, drop by drop, 160 g of methanol solution of sodium methylate (0.98 mole). Heating is continued for 1 hour.

After cooling, the formed sodium chloride is filtered and the isopropanol is eliminated under partial vacuum. After drying under vacuum and in the presence of phosphoric anhydride, a hard, brittle, colorless solid is obtained, having a softening point of 65C and a molecular weight, measured in absolute ethanol of 1600.

The compound thus obtained is soluble in water in an acid medium and in a dilute alcohol medium. It yields beautiful, hard and very brilliant films, after evaporation of its dilute alcohol solvent.

Example 6 Polycondensation of N,N-bis(2,3-epoxy propyl) piperazine and cetylamine.

'24 g (0.1 mole) of cetylamine and g (0.1 mole) of N,N'-bis(2,3-epoxy propyl) piperazine prepared according to Example 2, are heated with reflux in 45 g of isopropanol for 15 hours. The resin obtained is soluble in water in an acid medium, such as hydrochloric acid.

Example 7 Quaternization of the product obtained in Example To 68 g of the above isopropanol solution (0.23 equivalent in base nitrogen) there are added, drop by drop at 30C, 14.6 (0.11 mole) of dimethyl sulfate. Stirring is continued for 2 hours. The solvent is then eliminated under partial vacuum, with water being added to produce a final aqueous solution that is 10 percent by weight.

The film obtained by evaporation of the dilute solution is rather hard and not sticky.

Example 8 Polycondensation of N,N'bis(2,3-epoxy propyl) piperazine and dodecylamine.

18.5 g (0.1 mole) of dodecylamine and 20 g (0.1 mole) of N,N'bis(2,3-epoxy propyl)piperazine, prepared according to Example 2, are dissolved in 90 g of isopropyl alcohol. After 10 hours of heating at reflux,

the solvent is eliminated under partial vacuum. There is thus obtained a soft, colorless, transparent resin, soluble in water in the presence of hydrochloric acid and also in alcohol such as ethanol or isopropanol.

The molecular weight of this resin, measured in absolute ethanol, is 2900.

By evaporation of dilute solutions, soft, slightly sticky films are obtained.

Example 9 Quaternization of the N,N'-bis(2,3-epoxy propyl) piperazine and dodecylamine polycondensate.

To 30 g of resin obtained according to Example 7 (0.21 equivalent in base nitrogen), dissolved in 40 g of isopropanol, there are added, drop by drop at 30C, 13.5 g (0.1 mole) of dimethyl sulfate. Stirring is kept up for 2 hours at the same temperature. Then the solvent is eliminated under partial vacuum, with water being added to obtain the resin in the form ofa 10 weight percent solution in water.

On evaporation of the dilute aqueous solutions, films are obtained which are always soft but which are no longer sticky.

Example 10 Polycondensation of piperazine and N,N-bis(- chloroacetyl)ethylene diamine.

To a solution of 10.6 g (0.05 mole) of N,N'-bis chloroacetyl ethylene diamine in 125 g of water, there are added 9.7 g (0.05 mole) of hexahydrated piperazine. The mixture is heated for 3 hours at C. While the heating is continued, the acid formed is neutralized by addition, in several fractions, of 0.1 mole of sodium hydroxide in the form of a 40 percent (10 g) NaOI-l solution.

A colloidal solution having good film-forming properties is thus obtained.

Example 1 1 Polycondensation of N,N-bis(2,3-epoxy propyl) piperazine, oleyamine and piperazine.

To a solution of 20 g (0.1 mole) of N,N-bis(2,3- epoxy propyl) piperazine in 47 g of isopropanol, there are added 10.7 g (0.04 mole) of oleylamine and 5.16 g (0.06 mole) of anhydrous piperazine. After 4 hours of heating at reflux, the solvent is eliminated under reduced pressure. There is then obtained a white solid having a softening point of around 100C, the product being insoluble in neutral water, but soluble in ethanol and in water in an acid medium such as HCl.

Films obtained by evaporation of the dilute solution are transparent, not sticky and slightly hard.

Example 12 Polycondensation of piperazine and diglycidyl ether.

To 6.63 g (0.077 mole) of anhydrous piperazine in 11 g of isopropanol there are added over a 15 minute period at 30C, 10 g (0.077 mole) of diglycidyl ether. The mixture is heated at reflux for 4% hours. Then the solvent is eliminated, at reduced pressure, while water is added to obtain a colloidal solution of 5 weight percent active material, i.e. polymer.

Films obtained by evaporation of the dilute solution are opalescent, hard and not sticky.

The diglycidyl ether is prepared by reacting at 1520C a stoichiometric amount of sodium hydroxide on bis(3-chloro 2-hydroxy propyl) ether. The diglycidyl ether is isolated by distillation under reduced pres- 9 sure. The boiling point is 8085C/0.05 mm Hg,

Example 13 Polycondensation of piperazine and methylene bisacrylamide.

To 15.4 g (0.1 mole) of methylene bisacrylamide provided in paste form with 18.6 g of water, there are By evaporating the dilute aqueous solution, there is obtained very hard transparent and non-sticky films.

Example 14 Polycondensation of piperazine and piperazine bisacrylamide.

To a solution of 19.4 g (0.l mole) of piperazine bi- To 688 g (8 moles) of anhydrous piperazine dissolved in 1500 g of isopropanol, there are added 92.5 g (1 mole) of epichlorohydrin over a period of 1 hour at a temperature of C. The resulting reaction mixture is then heated for a period of 1.5 hours at 80C throughout said period. There are then added over a period of one-half hour 250 g of sodium methylate. The reaction mixture is then cooled and filtered to remove sodium chloride formed during the reaction. The remaining reaction mixture is then concentrated under a partial vacuum thereby eliminating the greatest part of the excess piperazine. The desired compound is isolated bydistillation. It is awhite solid having a melting point of 78C and a boiling point of 147l52C/0.07 mm Hg. Method 2 To a solution of 116.4 g (0.6 mole) of piperazine hexahydrate in 353 g of water, there are added in small sacrylamide in 35 g of water, there are added with agi- Example 15 Polycondensation of 1,3-bis piperazine-Z-propanol and methylene bisacrylamide. Method 1 To 15.4 g (0.1 mole) of. methylene bisacrylamide provided in paste form with-23.1 g of water there are added with agitation at a temperature between 0 and 5C under a nitrogen atmosphere, 152.5 g of a standardized aqueous solution containing 22.8 g (0.1 mole) of 1,3-bis piperazine-2-propanol. The mixture is left standing for 30 hours at C.

The polymer is precipitated in accordance with the procedure outlined in Example 14.

There is thus obtained a white solid exhibiting a softening point of 176C and a melting point of 200-2l0C.

By evaporating the dilute aqueous solution, there is obtained very hard, transparent and non-sticky films.

The l,3-bis-piperazine-2-propanol, utilized above, can be prepared as follows:

Structural Pattern Example No.

portions a total of 46 .2 g (0.3 mole) of solid methylene bisacrylamide, with agitation at a temperature between 0 to 5C and under a nitrogen atmosphere. The resulting reaction mixture is left to stand for 24 hours at 25C. There are then added, little by little, 27.75 g (0.3 mole) of epichlorohydrin over a period of 1 hour while maintaining the temperature of the reaction mixture at 20C.

The reaction mixture is stirred again for a period of 1 hour at a temperature of 20C. Then there are added at this temperature over a 1 hour period, 30 g (0.3 mole) of a 40 percent NaOH solution.

After an additional 1 hour period of stirring the reaction mixture at 20C, the reaction mixture is heated for 1 hour at C. There is thus obtained a 20 percent solution of the polymer exhibiting a very light opalescence and being nearly'colorless. By evaporating the dilute aqueous solution there is obtained a very hard, transparent and non-sticky film.

Example 16 Polycondensation of 1,3-bis piperazine-2-propanol and piperazine bisacrylamide.

To a solution of. 19.4 g (0.1 mole) of piperazine bisacrylamide in 39.1 g of water there are added with stirring at a temperature between 0 to 5C and under a nitrogen atmosphere 152.5 g of a standardized aqueous solution containing 22.8 g (0.1 mole) of 1,3-bis piperazine 2-propanol. The resulting reaction mixture is left to stand for 30 hours at 25C. The polymer is precipitated from the reaction mixture in accordance with the procedure outlined in Example 14 thereby yielding a white solid having a melting point of about 205210C. By evaporating the dilute aqueous solution there is obtained a hard, transparent and nonsticky film.

The following Table summarizes the reactions of Examples 1-16.

TAB"

- A B J- A B' A B A B Reaction Formula of RepeatingUnits l 1 1 Condensation of v 1 N N- CH CH.-CH piperazine and epil I chlor'ohydrin OH Citric acid, q.s.p. pH 6 Water, q.s.p.

-continued 15 Condensation of 1,3-

bis-piperazine-2- propanol and methylene bisacrylamide I y I I I N N' CH -CHOH-CH N ir cH -cri -corm-cfl -NHco-c1i,,--cH

k L- I 1 i J I I I l l A B i B 16 Condensation of 1,3-

bis-piperazine-E- propanol and piperazine bisacrylamide I I I I II I 1 N N CH CHOH-CH N N CH -CH CN NC-CH -CH l l I I l 4 I I I I EXAMPLES OF APPLICATION Example l7 Setting lotion for very dry hair Compound prepared according to Example 1 l g Propyl para-hydroxybenzoate 0.4 g Neolane pink dye, C.l. 18810 0.005 g Perfume 0.2 g Water, q.s.p. 100 g Example 18 Setting reinforcer for damaged hair Compound prepared according to Example l l g Polyvinyl pyrrolidone/vinyl acetate 60/40 copolymer (m.W. 50,000 to 70,000) 05 g Trimethyl cetyl ammonium bromide 0.2 g Perfume 0.1 g Methyl para-hydroxybenzoate 0.l g Water, q.s.p. 100 g Example 19 Setting reinforcer for normal hair Compound prepared according to Example 1 l g Vinyl acetate/crotonic acid copolymer (M.W. 20.000) 1 8 Trimethyl cetyl ammonium bromide 0.1 g Methyl violet dye, CI. 42535 0.002 g Perfume 0.1 g Ethyl alcohol, q.s.p. 50 Water, q.s.p. 100 g Example 20 Anionic shampoo R(OCH,CH,),OSO;Na wherein R alkyl C -C in proportions of 70/30 10 g Diethanolamide of copra fatty acids 3 g Water, q.s.p. I00 g pH 7 Example 21 Anionic shampoo Compound prepared according to Example 1 0.75 g Triethanolamine alkyl sulfate wherein alkyl C /C 70/30 15 g Monoethanolamide of copra fatty acid 4 g Sodium N-lauryl sarcosinate 3 g Acetylated lanolin 3 g Water, q.slp. 100 g pH 7.5 Example 22 Non-ionic shampoo Compound prepared according to Example I 2.5 g

R- OCH,iH OH wherein R alkyl C I-[, 15 g H OH Alkoxylated anhydrous lanolin sold under the trademark Lantrol AWS" by Malstrom Chemical Corporation, New Jersey 1.5 Hydroxypropyl methyl cellulose 0.3

-continued EXAMPLES OF APPLICATION Example 17 Setting lotion for very dry hair Compound prepared according to Example I Example 23 Cationic shampoo Compound prepared according to Example 8 Bromide of dodecyl, tetradecyl and hexadecyl trimethylammonium sold under the tradename Cetavlon" Lauryl alcohol oxyethylenated with 12 moles of ethylene oxide Lauryl diethanolamide Ethyl cellulose Lactic acid, q.s.p. pH 4 Water, q.s.p.

Example 24 Amphoteric shampoo Compound prepared according to Example I CH sold under the name Miranol "CZM" by Miranol Chemical Corporation, lrvington. New Jersey Dimethyl alkylamine oxide prepared from copra fatty acids Lauryl diethanolamide Lauryl alcohol, oxyethylenated with 12 moles of ethylene oxide Lactic acid, q.s.p. pH 6 Water, q.s.p. Example 25 Amphoteric shampoo Compound prepared according to Example l Sodium salt of N,N(diethylamino propyl)N'- dodecyl asparagin R OCH,il-l OH wherein R alkyl, C I-l H OH 4 Lactic acid, q.s.p. pH 5 Water, q.s.p. Example 26 Anionic shampoo Compound prepared according to Example 9 Sodium alkyl sulfate (alkyl C C Sodium N-lauryl sarcosinate Lauryl monoethanolamide Glycol distearate Water, q.s.p. pH 7 Example 27 Anionic shampoo Compound prepared according to Example 9 RO(CHCH2)2OSO3N3 wherein R C ll Sodium salt of N,N(diethylamino propyl)-N- dodecyl asparagin Diethylanolamide of copra fatty acids Hydroxypropyl cellulose Water, q.s.p. pH 6.5 Example 28 Cream for treating dry hair Compound prepared according to Example 1, q.s.p. Cetyl alcohol Stearyl alcohol Cetyl-stearyl alcohol oxyethylenated with 15 moles of ethylene oxide Hydroxyethylcellulose Perfume Water, q.s.p.

Application of this cream is followed by rinsing of the hair. Example 29 Conditioner for dry hair Compound prepared according to Example I, q.s.p. Polyvinylpyrrolidone/vinyl acetate copolymer 70/30 (M.W. 40,000) Perfume Water, q.s.p.

This conditioner is to be used after shampooing and before setting, without intermediate rinsing. Example 30 Anti-dandruff lotion for daily use -continued EXAMPLES OF APPLICATION Example 17 Setting lotion for very dry hair Anionic shampoo in the form of a clear solution Ammonium alkylsulfate (alkyl derived from copra) Sodium alkyl ether sulfate'iavherein the alkyl moiety is derived from copra fatty acids and oxyethylenated with 2 moles of ethylene oxide i Compound prepared according -to Example 4' Lauryl diethanolamide Mixture of monoand di-gly'cerides of fatty acids, sold under the tradename "ARLACEL 186" by Atlas Lactic acid, q.s.p. pH 7.5

Water, q.s.p.

Example 32 Anionic shampoo Sodium alkyl ether sulfate wherein the alkyl moiety is derived from copra fatty acids and oxyethylenated with 2 moles of ethylene oxide Copra diethanolamide Compound prepared according to Example 13 Sodium monolauryl sulfosuccinate Lactic acid, q.s.p. pH 7.5

Water, q.s.p.

ts -q mourn Hair treated with the above composition is easy to comb, exhibits good volume, is shiny and lively.

Example 33 Anionic shampoo The composition of Example 32 is repeated except that the compound prepared according to Example 13 is replaced with an essentially equivalent amount of the compound prepared according to Example 14. Essentially similar effective and advantageous results are achieved with this composition.

This solution imparts to hair a lively and shiny appearance.

Further in Examples 17-22, 24, and 28-30, the compound prepared in accordance with Example 1 is replaced with the compound prepared in accordance with Example 15 and 16 in essentially equivalent amounts to provide equally effective hair treating compositions.

In all of the Examples of Application given above, the weight of the polymer is expressed as the active material therein.

What is claimed is:

1. Cosmetic composition for conditioning the hair comprising a solution in a solvent selected from the group consisting of water and water-lower alkanol, of a member selected from the group consisting of l. a film-forming cationic polymer having a molecular weight of about 1,000 to 15,000 and having the formula wherein A represents and Z represents B andIB' wherein B and B each independently represent a bivalent radical selected from the group consisting of (i) hydroxypropylene, (ii) alkylene having up to 5 carbon atoms inclusive and interrupted by l-2 members selected from the group consisting of -CONH and (iii) hydroxy alkylene wherein the alkylene moiety has up to 6 carbon atoms inclusive and interrupted by a member selected from the group consisting of alkylamine wherein the alkyl moiety has 12-16 carbon atoms, benzylamine, oleylamine and oxygen, and (iv) hydroxy propyl-piperazinyl-hydroxypropyl,

2. quaternary ammonium salt of the cationic polymer in l) and 3. the oxidation product of the cationic polymer in said member being present in an amount of about 0.1 to 5 percent by weight of said composition. 2. The composition according to claim 1, characterized by the fact that it is in the form of a cream.

wherein A represents and Z represents B and B wherein B and B each independently represent a bivalent radical selected from the group consisting of (i) hydroxypropylene, (ii) alkylene having up to carbon atoms inclusive and interrupted by 1-2 members selected from the group consisting of -CONH and -CON NCO- (iii) hydroxy alkylene wherein the alkylene moiety has up to 6 carbon atoms inclusive and interrupted by a member selected from the group consisting of alkylamine wherein the alkyl moiety has 12-16 carbon atoms, benzylamine, oleylamine and oxygen and (iv) hydroxy propyl-piperazinyl-hydroxypropyl,

2. quaternary ammonium salt of the cationic polymer in (l) and v 3. the oxidation product of the cationic polymer in said member being present in an amount of about 0.1 to 5 percent by weight of said composition. 5. The composition of claim 4 which also includes an anionic, cationic, non-ionic or amphoteric surfactant.

6. The composition according toclaim 4 having a pH between 3 and 11.

7. The composition according to claim 4 wherein said cationic polymer has a molecular weight less than 15,000. i

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3069390 *Jul 17, 1959Dec 18, 1962Borden CoPolymeric amides from polymeric acrylic acid esters and n-aminoalkyl alkanol amines and reaction products therefrom
US3250682 *Feb 15, 1962May 10, 1966Wella AgMethod of setting hair with epoxy resin compositions
US3267046 *Dec 17, 1962Aug 16, 1966Montedison SpaProcess for regulating the molecular weight of basic nitrogen polycondensates
US3274312 *Dec 17, 1962Sep 20, 1966Montedison SpaProcess for preparing dye-receptive shaped articles
US3280044 *Jan 30, 1963Oct 18, 1966Montedison SpaMetal salts of epichlorohydrin-piperazine-amine polycondensates
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4018721 *Feb 4, 1976Apr 19, 1977Union Carbide CorporationCross-linked, water insoluble poly(N-glycidyl-piperazine)
US4061602 *Aug 3, 1976Dec 6, 1977American Cyanamid CompanyConditioning shampoo composition containing a cationic derivative of a natural gum (such as guar) as the active conditioning ingredient
US4080310 *Jun 11, 1976Mar 21, 1978Beecham Group LimitedN-alkyl-b-aminopropionate or n-alkyl-b-iminodipropionate, cationic polyamide resin
US4101456 *Apr 8, 1976Jul 18, 1978Colgate-Palmolive CompanyLight duty liquid detergent
US4201766 *Feb 27, 1978May 6, 1980L'orealCrosslinked polyaminoamide, quaternized cationic polymer
US4240450 *Mar 14, 1978Dec 23, 1980L'orealHair conditioner of anionic polymers and cationic polymers
US4271053 *Jun 29, 1979Jun 2, 1981Union Carbide CorporationQuaternary ammonium graft copolymers for use as flocculants and method of preparing same
US4305829 *Jun 5, 1980Dec 15, 1981Union Carbide CorporationProcess for flocculating an aqueous suspension of particles with quaternary ammonium graft copolymers
US4314807 *Nov 15, 1976Feb 9, 1982L'orealHair dye composition containing a hair dye formulation packaged in two parts
US4349532 *Sep 14, 1978Sep 14, 1982Guy VanlerbergheCosmetic compositions based on poly-(quaternary ammonium) polymers
US4362528 *Jun 13, 1980Dec 7, 1982Societe Anonyme Dite: L'orealCosmetic composition for dyeing hair and process for using the same
US4465802 *Oct 26, 1982Aug 14, 1984Union Carbide CorporationWith water soluble cationic polymer and cationic surfactant
US4470982 *Apr 12, 1982Sep 11, 1984The Procter & Gamble CompanyShampoo compositions
US4488879 *Jul 5, 1983Dec 18, 1984Basf AktiengesellschaftProcess for dyeing textile materials of polyacrylonitrile: quaternized piperazine copolymer as basic dye retarder
US4647379 *Nov 13, 1985Mar 3, 1987The Dow Chemical CompanyNitrogen-containing water-soluble polymer flocculants
US4656245 *Mar 7, 1986Apr 7, 1987Sumitomo Electric Industries, Ltd.Functional elastomer
US4719099 *Jun 27, 1985Jan 12, 1988L'orealAnionic and cationic
US4761273 *Jul 24, 1985Aug 2, 1988L'orealComposition in the form of an aerosol foam, based on a cationic polymer and an anionic polymer
US4806345 *Nov 21, 1985Feb 21, 1989Nalco Chemical CompanyWater, cosmetically-active agent, and thickeners
US4851532 *Nov 13, 1986Jul 25, 1989Buckman Laboratories, Inc.Ionene polymeric compositions, their preparation and use
US4867966 *Sep 17, 1987Sep 19, 1989L'orealCosmetic compositions based on cationic polymers and alkyloxazoline polymers
US5130056 *Jan 22, 1990Jul 14, 1992Deutsche Solvay-Werke GmbhWashing agents containing nonionic and anionic surfactants
US5236996 *Jul 24, 1991Aug 17, 1993Union Camp CorporationStable polyamide resin dispersions containing piperasine and methods for the manufacture thereof
US6228828Sep 15, 1998May 8, 2001The Procter & Gamble CompanyMaterials which impart appearance and integrity benefits to fabrics and textiles laundered in washing solutions containing them
US6251846 *Sep 15, 1998Jun 26, 2001The Procter & Gamble CompanyAnionically modified, oxidized cyclic amine based polymers, oligomers or copolymer materials, such as imidazole-epichlorohydrin adduct; pill/fuzz reduction, antifading, improved abrasion resistance, softness
US6260556Jan 28, 2000Jul 17, 2001L'orealAnhydrous composition for bleaching keratin fibers
US6262011 *Dec 20, 1999Jul 17, 2001Basf AktiengesellschaftObtained by condensing imidazole or c1-25 alkylimidazoles with alkylene dihalides, epihalohydrins, or bisepoxides or by heating triethanolamine or triisopropanolamine in the presence of an acidic catalyst and quaternizing
US6379401Jan 28, 2000Apr 30, 2002L'oreal, S.A.Alkaline agent, peroxygen salt and polymer thickeners and nonionic surfactant
US6436151Jan 2, 2001Aug 20, 2002L'oreal S.A.Compositions for oxidation dyeing keratin fibers comprising at least one oxidation dye, at least one thickening polymer comprising at least one fatty chain, and at least one fatty alcohol comprising more than twenty carbon atoms and uses thereof
US6444197Dec 13, 2000Sep 3, 2002L'oreal S.A.Bleaching composition for keratin fibers, comprising a combination of two polyurethane polyethers
US6451298Oct 20, 2000Sep 17, 2002L'oreal, S.A.One cationic polymer this combination can give cosmetic properties, such as at least one of smoothness, lightness, and softness, for hair
US6471953Jun 28, 2000Oct 29, 2002L'oreal S.A.Permanent-waving process comprising the preliminary application of a composition comprising at least one anionic polymer
US6472364Oct 6, 1999Oct 29, 2002The Procter & Gamble CompanyDetergent compositions or components
US6482400Jun 29, 2000Nov 19, 2002L'Oréal S.R.Mascara containing film-forming polymers
US6482787Sep 15, 1998Nov 19, 2002The Procter & Gamble CompanyLaundry detergent and fabric conditioning compositions with oxidized cyclic amine based polymers
US6506372Jun 23, 2000Jan 14, 2003L'oreal S.A.Cosmetic compositions containing an amphoteric polymer and a fixing/conditioner polymer, and their uses
US6534047Jun 29, 2000Mar 18, 2003L'oreal S.A.Cosmetic for coating keratin fibers comprising cationic polymer, anionic polymer and aqueous dispersion of a polyalkyl methacrylate; coating, lengthening and curling eyelashes; durable
US6589519Aug 24, 1998Jul 8, 2003L'oreal S.A.Cosmetic compositions containing a polyoxyalkylenated aminosilicone block copolymer and a conditioner, and uses thereof
US6602303Aug 13, 2001Aug 5, 2003L'oreal S.A.And a combination of an alkoxylated or glycerolated fatty alcohol and a hydroxylated
US6635262Mar 14, 2001Oct 21, 2003L'oreal S.A.Roll-on applicator comprising a hair composition
US6695887Jan 2, 2001Feb 24, 2004L'oreal S.A.Ready-to-use
US6800096Nov 10, 2000Oct 5, 2004L'oreal S.A.Viscosity; hair; amino resin-polyether copolymer as thickener
US6800098Nov 10, 2000Oct 5, 2004L'oreal, S.A.Oxidation dye composition for keratinic fibres containing a thickening polymer with an ether plastic skeleton
US6846333Nov 8, 2002Jan 25, 2005L'oreal, S.A.Mixture containing direct or oxidation dye
US6916344Nov 10, 2000Jul 12, 2005L'oreal S.A.A hair color mixtures comprising a thickener of amino resins-polyether copolymer, or an addition-condensation copolymer; two-compartment kits, in situ mixing
US6919073May 16, 2002Jul 19, 2005L'oreal S.A.Pulverulent composition for bleaching human keratin fibers
US6956017Oct 13, 2000Oct 18, 2005The Procter & Gamble CompanyComprising a semi-polar nonionic surfactant and certain cyclic amine based polymer, oligomer or copolymer materials; pilling and fuzz resistance, improved dye transfer inhibition, antifading agents, improved wear resistance, softness
US7066965Nov 6, 2001Jun 27, 2006L'oreal S.A.Hair dyes
US7077869Nov 6, 2001Jul 18, 2006L'oreal S.A.Composition for bleaching or permanent waving of keratinous fibers comprising a cationic associative polyurethane
US7101405Nov 6, 2001Sep 5, 2006L'oreal S.A.Oxidation dyeing composition for karatinous fibers comprising a cationic associative polyurethane
US7108726Nov 6, 2001Sep 19, 2006L'oreal S.A.Direct dyeing composition for keratinous fibres comprising a cationic associative polyurethane
US7128902Nov 8, 2002Oct 31, 2006L'oreal, SaA dimethylsilanediol or alkoxydimethylsilanol end capped aminoethylamino/propylsilanetriol or alkoxysilanediol monomer containing polysiloxane and a reducing agent for the treatment of human hair
US7135167Nov 8, 2002Nov 14, 2006L'oreal, SaOxidizing composition for treating keratin fibers, comprising a particular aminosilicone
US7138109Nov 8, 2002Nov 21, 2006L'oreal, SaUsing a polysiloxanes
US7147672Oct 21, 2003Dec 12, 2006L'oreal S.A.Dyeing human hair
US7147673Apr 1, 2004Dec 12, 2006L'oreal S.A.Composition for dyeing human keratin materials, comprising at least one fluorescent dye and at least one insoluble polyorganosiloxane conditioning polymer, process therefor and use thereof
US7150764Apr 1, 2004Dec 19, 2006L'oreal S.A.compositions for dyeing with a lightening effect a human keratin material
US7153331Dec 20, 2002Dec 26, 2006L'oreal S.A.Dyeing composition for keratinous fibers comprising an oxyethylene rapeseed fatty acid amide
US7157413Jul 8, 2003Jan 2, 2007L'orealDetergent cosmetic compositions comprising an anionic surfactant, an amphoteric, cationic, and/or nonionic surfactant, and a polysacchardie, and use thereof
US7186278Apr 1, 2004Mar 6, 2007L'oreal S.A.Composition for dyeing human keratin materials, comprising at least one fluorescent dye and at least one compound comprising an acid functional group and processes therefor
US7192454Apr 1, 2004Mar 20, 2007L'oreal S.A.Composition for dyeing human keratin materials, comprising a fluorescent dye and a particular sequestering agent, process therefor and use thereof
US7195650Apr 1, 2004Mar 27, 2007L'oreal S.A.Process for dyeing, with a lightening effect, human keratin fibers that have been permanently reshaped, using at least one composition comprising at least one fluorescent dye
US7195651Apr 1, 2004Mar 27, 2007L'oreal S.A.Reducing skin and/or hair color; lighter, uniform, homogeneous tones of natural appearance; kits
US7198650Apr 1, 2004Apr 3, 2007L'oreal S.A.Applying mixture to hair; development; rinsing
US7204860Apr 1, 2004Apr 17, 2007L'orealUsing aliphatic diol; dyeing hair
US7208018Apr 1, 2004Apr 24, 2007L'orealComposition for dyeing human keratin materials, comprising at least one fluorescent dye and at least one associative polymer, process therefor and use thereof
US7211268Nov 15, 2002May 1, 2007L'oreal S.A.Preparation of polysaccharide betainate type compounds, compounds obtained, their use and compositions comprising them
US7217296Sep 24, 2002May 15, 2007L'oreal S.A.Dyeing composition with a lightening effect for human keratin materials comprising at least one fluorescent dye
US7220285Apr 27, 2006May 22, 2007L'oreal S.A.Pulverulent composition for bleaching human keratin fibers
US7220408Nov 8, 2002May 22, 2007L'oreal, S.A.Mixture of aminosilicone and thickener
US7223385Nov 8, 2002May 29, 2007L'oreal S.A.Cosmetic compositions containing a particular aminosilicone and a conditioner, and uses thereof
US7226486Jan 15, 2004Jun 5, 2007L'oreal S.AReady-to-use bleaching compositions, preparation process and bleaching process
US7232561Jun 2, 2003Jun 19, 2007L'oreal S.A.Washing compositions comprising at least one amphiphilic block copolymer and at least one cationic or amphoteric polymer
US7250064Apr 1, 2004Jul 31, 2007L'oreal S.A.Using crosslinked acrylic polymer
US7258852Sep 10, 2002Aug 21, 2007L'oreal S.A.Cosmetic compositions containing a methacrylic acid copolymer and an oil, and uses thereof
US7261744Dec 23, 2003Aug 28, 2007L'oreal S.A.Method for dyeing or coloring human keratin materials with lightening effect using a composition comprising at least one fluorescent compound and at least one optical brightener
US7267696Mar 25, 2004Sep 11, 2007L'oreal S.A.Composition for dyeing keratinous fibers, comprising a hydroxycarboxylic acid or a salt, ready-to-use composition comprising it, implementation process and device
US7294152Jan 7, 2005Nov 13, 2007L'oreal S.A.Dyeing composition comprising at least one fluorindine compound for the dyeing of keratinic fibers, dyeing process comprising the composition and compound
US7303588Mar 25, 2004Dec 4, 2007L'oreal S.A.Composition for dyeing keratinous fibers, comprising at least one polycarboxylic acid or a salt, ready-to-use composition comprising it, implementation process and device
US7303589Apr 1, 2004Dec 4, 2007L'oreal S.A.Process for dyeing human keratin fibers, having a lightening effect, comprising at least one fluorescent compound and compositions of the same
US7323015Oct 21, 2003Jan 29, 2008L'oreal S.A.Dyeing human hair
US7326256Dec 8, 2003Feb 5, 2008L'ORéAL S.A.dyeing human hair; aqueous solution
US7329287Dec 8, 2003Feb 12, 2008L'oreal S.A.Oxidation dye composition for keratin fibers, comprising at least one oxidation dye, at least one associative polymer, at least one nonionic cellulose-based compound not comprising a C8-C30 fatty chain, and at least one cationic polymer with a charge density of greater than 1 meq/g and not comprising a C8-C30 fatty chain
US7364594Nov 22, 2001Apr 29, 2008L'oreal S.A.E.g., a quaternized polyetherurethane copolymer and an acrylamide/ dimethyldiallylammonium chloride/acrylic acid terpolymer.
US7402180Jul 11, 2006Jul 22, 2008L'ORéAL S.A.Composition for the oxidation dyeing of keratin fibres, comprising at least one fatty alcohol chosen from mono- and polyglycerolated fatty alcohols and a particular polyol
US7431740Nov 22, 2001Oct 7, 2008L'oreal, S.A.Oxidation dyeing composition for keratinous fibers comprising an associative polymer and a pearling agent
US7442214Mar 31, 2006Oct 28, 2008L'oreal S.A.Dye composition comprising at least one non-ionic associative polymer and process for dyeing keratin fibers using same
US7485289Feb 15, 2007Feb 3, 2009L'oreal, S.A.Cosmetic compositions containing a particular aminosilicone and a conditioner, and uses thereof
US7498022Mar 28, 2003Mar 3, 2009L'oreal S.A.One amphiphilic polymer chosen from branched block copolymers comprising at least one nonionic unit derived from at least one monomer chosen from C1-20 alkyl (meth)acrylates, N-mono-(C2-12 alkyl)- meth)acrylamides and N,N-di-(C2-12
US7504094Feb 15, 2007Mar 17, 2009L'oreal, S.A.Hair conditioners; alkoxy-capped copolymer with dimethylsiloxy units and 3-(2-aminoethyl)aminopropyl)methyl- (or alkoxy-)siloxy units; for improving the lightness, softness, sheen and/or disentangling, and/or facilitating styling of hair
US7510705Sep 21, 2006Mar 31, 2009L'oreal, S.A.Process for permanently reshaping the hair using particular aminosilicones
US7550015Mar 31, 2006Jun 23, 2009L'oreal S.A.hair dyes comprising oxidation dye precursors and direct dyes, nonionic surfactants or anionic surfactants, hydroxyethylcellulose, cationic polymer; and one fatty substance; fatty acid esters of polyethylene glycol; multi-compartment kit for store the dyes
US7569078Mar 31, 2006Aug 4, 2009L'oreal S.A.Dye composition comprising at least one cellulose and process for dyeing keratin fibers using the dye composition
US7575605Mar 31, 2006Aug 18, 2009L'oreal S.A.Dye composition comprising at least one glycerol ester and a process for dyeing keratin fibers using the composition
US7578854Mar 31, 2006Aug 25, 2009L'oreal S.A.Applying to wet or dry keratin fibers a formulation containing oxidation dye precursor such as phenolamines, a direct dye ( azo dye, methine dye etc.), a fatty alchol, a fatty alcohol ester of polyglycerol, a oxyalkylenated or glycerolated nonionic surfactant, a cationic polymer
US7608115Apr 30, 2004Oct 27, 2009L'oreal S.A.Via applying direct dye, oxidation base, coupler, and oxidizing agent, then heating; oxidation color dyes; hair conditioners; cosmetics
US7651533Mar 31, 2006Jan 26, 2010OrealDye composition with a reduced content of starting materials, process for dyeing keratin fibers using the same and device therefor
US7708981Mar 10, 2004May 4, 2010L'oreal S.A.Cosmetic compositions comprising at least one crosslinked copolymer, at least one insoluble mineral particle and at least one polymer, and uses thereof
US7736631Apr 1, 2004Jun 15, 2010L'oreal S.A.Organic pigment colors and a modified polydimethylsiloxane homopolymer or copolymers for lightening hair or skin; multi-compartment kit for dyeing
US7771491Dec 21, 2007Aug 10, 2010L'oreal S.A.Hair dye; environmentally friendly, due to use of nonionic cellulose; good shampoo fastness
US7771492Feb 23, 2009Aug 10, 2010L'oreal S.A.Hair dyes; anionic thickener has hydrophilic olefinic unsaturated carboxylic acid and a C10-C30 alkyl unsaturated carboxylate; nonionic thickeners are celluloses modified by fatty chain or polyoxyethylenated polyurethanes; cationic thickener is quaternized cellulose with fatty acid chain; resists running
US7799093Oct 25, 2007Sep 21, 2010L'ORéAL S.A.Coloring composition of keratinous fibers comprising at least one polysiloxane/polyurea block copolymer
US7867969Oct 30, 2006Jan 11, 2011L'oreal S.A.Composition for washing keratin materials comprising a magnesium salt anionic surfactant
US7914775Nov 6, 2001Mar 29, 2011L'oreal S.A.Treating keratinous fibres, in particular human keratinous fibres such as hair, comprising in a physiologically acceptable medium, at least a protecting or conditioning agent, and further at least a cationic associative
US7976831Apr 4, 2005Jul 12, 2011L'oreal S.A.Method for treating hair fibers
US7998464Sep 28, 2006Aug 16, 2011L'oreal S.A.Process for the photoprotective treatment of artificially dyed keratin fibers by application of a liquid water/steam mixture
US8586014Oct 30, 2006Nov 19, 2013L'orealComposition for the care of keratin material and cosmetic treatment process using said composition
US8703109Mar 28, 2008Apr 22, 2014L'orealProtection of keratinous fibers using ceramides and/or glycoceramides
US8784506Oct 28, 2011Jul 22, 2014L'orealDye composition having a low content of ammonia
US20090068124 *Feb 23, 2007Mar 12, 2009Raphael BeumerNovel heterocyclic substituted condensation polymers
EP0168719A2 *Jul 4, 1985Jan 22, 1986Revlon, Inc.Low pH hair conditioner compositions containing amine oxides
WO1999014299A1 *Sep 15, 1998Mar 25, 1999Dieter BoeckhLaundry detergent compositions with anionically modified, cyclic amine based polymers
WO1999014300A1 *Sep 15, 1998Mar 25, 1999Dieter BoeckhLaundry detergent compositions with cyclic amine based polymers to provide appearance and integrity benefits to fabrics laundered therewith
WO1999014301A1 *Sep 15, 1998Mar 25, 1999Dieter BoeckhLaundry detergent and fabric conditioning compositions with oxidized cyclic amine based polymers
WO2001032815A1 *Oct 29, 1999May 10, 2001Kemal Vatansever CatalanLaundry detergent compositions with fabric care
WO2001032816A1 *Oct 13, 2000May 10, 2001Kemal Vatansever CatalanLaundry detergent compositions with fabric care
Classifications
U.S. Classification424/70.17, 424/DIG.100, 528/407, 528/392, 424/47, 510/119, 510/475, 510/125, 528/405, 524/608, 524/612, 510/121, 514/252.11, 424/DIG.400, 544/357, 524/389, 510/123, 510/126, 424/DIG.200
International ClassificationA61Q5/00, A61K8/00, A61Q7/00, A61Q5/06, A61Q5/02, C08G73/06, C08G73/02, A61K8/88, A61Q5/12
Cooperative ClassificationC08G73/0633, Y10S424/04, A61K8/88, C08G73/0273, Y10S424/02, A61Q5/12, A61Q5/02, Y10S424/01
European ClassificationA61Q5/12, C08G73/02Q, A61K8/88, A61Q5/02, C08G73/06E2