WO2017165931A1

WO2017165931A1 - Hair care compositions comprising latex polymers and methods for treating hair

Info

Publication number: WO2017165931A1
Application number: PCT/BR2016/050069
Authority: WO
Inventors: Sintia AGUIAR; Bruno Maiko SATO; João GUIMARÃES; Jim Singer
Original assignee: L'oreal
Priority date: 2016-03-31
Filing date: 2016-03-31
Publication date: 2017-10-05
Also published as: BR112018010483A2; BR112018010483A8

Abstract

Hair care compositions comprising latex polymers and methods for treating hair The present disclosure relates hair care compositions comprising at least two latex polymers, an amino silicone, a cationic polymer, and a nonionic surfactant. 5 One latex polymer can have a Young's modulus ranging from about 0.1 MPa to about 10 MPa and a strain, under stress at 0.5 MPa, of at least about 1%; and the other latex polymer can have a Young's modulus ranging from about 10 MPa to about 6 GPa and a strain, under stress at 0.5 MPa, of less than about 5%. The disclosed hair care compositions are useful in methods for imparting durable styling or shaping benefits 10 and/or frizz control to hair by applying the hair care compositions to hair.

Description

HAIR CARE COMPOSITIONS COMPRISING LATEX POLYMERS

AND METHODS FOR TREATING HAIR FIELD OF THE DISCLOSURE

The present disclosure relates hair care compositions comprising at least two latex polymers, an amino silicone, optionally, a cationic polymer, and a nonionic surfactant. The disclosure also relates to methods for imparting durable styling or shaping benefits and/or frizz control to hair by applying the hair care compositions to hair.

BACKGROUND

Consumers desire new multi-functional hair care products that can impart good styling benefits to hair, are durable, even with several washings, and impart certain cosmetic characteristic to the hair. Such products should be pleasing to the senses, have innovative, interesting and/or pleasing textures, without loss in functional performance. Furthermore, many consumers prefer hair care products that provide a light feel, are easy to apply, and add shine and luster to the hair.

Traditional hair care products on the cosmetic market appear in various forms. They range anywhere from solutions, foams, gels, creams, waxes, mousses, sprays, serums, to aerosols and can impart a variety of levels of protection (or damage) to the hair depending on the state of the hair and the components of the product. Generally, products that are designed to impart styling or shaping benefits to hair are in the form of hair styling or hair care/hair treatment products. Such products are often sticky or tacky upon application and once dry, may become stiff and/or "crunchy" {i.e. the film is hard and brittle resulting in a crunching feel or sound when the hair is touched), which is undesirable for many consumers.

Current products for imparting styling or shaping benefits to hair often include water soluble film-forming polymers. Depending on the chemical make-up of these polymers, they may be either soluble in water, or they may be water insoluble polymers which are made water soluble via various chemical modifications, such as neutralization. Solutions comprising these polymers tend to be viscous, i.e. as the concentration of the polymer increases, its viscosity builds up rapidly. Translated to styling applications, as the solvent evaporates, the polymer solution becomes thicker on the hair surface, resulting in a sticky or tacky film. SUMMARY OF THE DISCLOSURE

The instant disclosure relates to hair care compositions that are unique in their ability to impart a variety of desirable properties to hair. For example, the compositions maintain the shape of hair, achieve long-lasting frizz control, provide strong styling hold, and impart a pleasant texture and shine to hair. Furthermore, upon application to the hair, the compositions have a clean, natural, and light-weight feel. The compositions are particularly unique in that hair treated with the compositions continues to exhibit the desirable properties, even after multiple washings.

Many consumers seek hair care products to prevent or minimize the frizziness of hair, particularly under high humidity conditions in which hair tends to absorb moisture causing it to be less manageable, which makes it more difficult to shape and style. Applying a coating, such as a moisture barrier or a film on the hair can help to keep moisture out of the hair, allowing for more efficient hair shaping and maintenance of hair shape. However, many films or moisture barriers on hair deteriorate or are removed with several washings. The instant compositions are resilient to multiple washings. Therefore, the compositions impart longer lasting frizz control, as well as prevent or minimize the reversion of curly hair that has been straightened back to a curly state, especially under very humid conditions.

The hair care compositions of the instant disclosure typically comprise, in a cosmetically acceptable carrier:

(a) a first latex polymer;

(b) a second latex polymer;

(c) an amino silicone;

(d) optionally, a cationic polymer; and

(e) a nonionic surfactant.

The first latex polymer of (a) may be a latex polymer having a Young's modulus ranging from about 0.1 MPa to about 10 MPa and a strain, under stress at 0.5 MPa, of at least about 1 %; and the second latex polymer of (b) may be a latex polymer having a Young's modulus ranging from about 10 MPa to about 6 GPa and a strain, under stress at 0.5 MPa, of less than about 5%.

A high Young's Modulus demonstrates a hard composition, while a lower Young's Modulus represents a more elastic composition. A high Strain demonstrates a stretchy, elastic property, while a lower Strain represents a more brittle property. Thus, the latex polymers of (a) and (b) may be a combination of a harder or more brittle latex polymer with a softer or more elastic latex polymer.

The first latex polymer of (a) and/or the second latex polymer of (b) may be in the form of particles, and the particles may be dispersed in an aqueous medium, in the hair care composition, or in a cosmetically acceptable carrier (which are not mutually exclusive, i.e., they may be one and the same).

In some cases, the first latex polymer of (a) is an acrylate latex polymer. For instance, the acrylate latex polymer may be, for example, acrylates copolymer, a (meth)acrylate copolymer, a butyl acrylate/hydroxypropyl dimethicone acrylate copolymer, an acrylates/Ci 2-C₂2 alkylmethacrylate copolymer, an acrylates copolymer in combination with isododecane, an acrylates/octylacrylamide copolymer, and combinations thereof.

In some cases, the second latex polymer of (b) is a polyurethane latex polymer. For instance, the polyurethane latex polymer may be, for example, polyurethane- 32, polyurethane-34, polyurethane-35, and combinations thereof.

The amino silicone of (c) may be, for example, a polyether amino silicone, amodimethicone, a modified amodimethicone (such as bis-cetearyl amodimethicone and bis-hydroxy/methoxy amodimethicone), an amino gum silicone, and combinations thereof.

The cationic polymer of (d) may, or may not, be present. In some cases, when present, the cationic polymer of (d) may be, for example, a polyquaternium compound.

The nonionic surfactant of (e) may be, for example, a polyol ester, a glycerol ether, an oxyethylenated ether, an oxypropylenated ether, an ethylene glycol polymer, or a combination thereof.

The hair care composition may be in the form of an emulsion, e.g., oil-in- water (O/W), water-in-oil (W/O), and oil-in-alcohol emulsions. The compositions of the instant disclosure may be in the form of a liquid emulsion, such as a liquid-lotion, liquid-gel, Iiquid-cream, or a cream emulsion, such as a thick cream or gel-cream, or a foam or mousse or spray wherein the liquid emulsion form has a thinner consistency than the cream emulsion form. The hair care composition may also be in the form of an aqueous or aqueous-alcoholic composition such as a lotion or a non-aerosol spray or aerosolized spray. The hair care compositions described herein may further comprise: (f) an oil. The oil may be, for example, a hydrocarbon-based oil (e.g., mineral oil). The hair care compositions described herein may have an acidic pH, i.e., a pH less than 7, a pH of 5 to less than 7, or pH of 5 to 6.

The hair care compositions described herein may be used in various methods for treating hair, for example, human hair, including human hair one an individual's head. For example, the compositions are useful for: (i) improving or retaining curl definition of hair; (ii) imparting humidity resistance to hair; (iii) reducing hair frizz; (iv) controlling hair volume; (v) styling hair; (vi) straightening hair; and (vi) improving the appearance of hair; wherein the methods typically comprise applying a hair care composition disclosed herein to the hair. These methods are particularly useful for naturally curly hair. The hair care compositions disclosed herein are useful in methods for imparting durable styling or shaping properties and/or frizz control to hair, the method comprising applying a hair care composition to hair, including naturally curly hair.

The hair care compositions described herein may be provided in the form of any one of the following: a hair styling product, a rinse-off or leave-in hair conditioning product, a rinse-off or leave-in hair masque, or a rinse-off or leave-in hair treatment product.

DETAILED DESCRIPTION OF THE DISCLOSURE

The hair care compositions of the instant disclosure typically comprise, in a cosmetically acceptable carrier, (a) a latex polymer having a Young's modulus ranging from about 0.1 MPa to about 10 MPa and a strain, under stress at 0.5 MPa, of at least about 1 %; (b) a latex polymer having a Young's modulus ranging from about 10 MPa to about 6 GPa and a strain, under stress at 0.5 MPa, of less than about 5%; (c) an amino silicone; (d) optionally, a cationic polymer; and (e) a nonionic surfactant. In some cases, the latex polymer of (a) is an acrylate latex polymer.

Although both polymers (a) and (b) are latex polymers, they differ with respect to the Young's modulus and the strain. A high Young's Modulus demonstrates a hard film, while a lower Young's Modulus represents a more elastic film. A high Strain demonstrates a stretchy, elastic property, while a lower Strain represents a more brittle property.

The latex polymer of (a) may also have a glass transition temperature (Tg) ranging from about -90°C to about 40°C; and/or the latex polymer polymer of (b) may have a glass transition temperature (Tg) ranging from about 40°C to about 200°C.

In some cases, the latex polymer of (b) is a polyurethane latex polymer. The latex polymers may be particles dispersed in an aqueous medium, or when used in hair care compositions, the latex polymers may be particles dispersed in the cosmetically acceptable carrier.

In instances when the latex polymer of (a) is an acrylate latex polymer, the acrylate latex polymer may be selected from the group consisting of an ammonium acrylate copolymer, an acrylates copolymer, a (meth)acrylate copolymer, a butyl acrylate/hydroxypropyl dimethicone acrylate copolymer, an acrylates/C i 2-C₂2 alkylmethacrylate copolymer, an isododecane and acrylates copolymer, an acrylates/octylacrylamide copolymer, and combinations thereof. In some instances, the acrylate latex polymer is acrylates copolymer.

In some cases, the latex polymer of (a) is present in an amount of about 0.01 to about 10 wt.%, about 0.01 to about 8 wt.%, about 0.01 to about 6 wt.%, about 0.01 to about 5 wt.%, about 0.1 to about 5 wt.%, about 0.1 to about 4 wt.% or about 0.1 to about 3 wt.%, based on the total weight of the hair care composition.

In instances when the latex polymer of (b) is a polyurethane latex polymer, the polyurethane latex polymer may be selected from the group consisting of consisting of polyurethane-32, polyurethane-34, polyurethane-35, and combinations thereof. In some instances, the polyurethane latex polymer is polyurethane-34.

In some cases, the latex polymer of (b) is present in an amount of about 0.01 to about 10 wt.%, about 0.01 to about 8 wt.%, about 0.01 to about 6 wt.%, about 0.01 to about 5 wt.%, about 0.1 to about 5 wt.%, about 0.1 to about 4 wt.% or about 0.1 to about 3 wt.%, based on the total weight of the hair care composition.

The weight ratio of the latex polymer of (a) to the latex polymers of (b) may be from 1 :10 to 10:1 , 7:1 to 1 :7, 1 :5 to 5:1 , 1 :3 to 3:1 , 1 :2 to 2:1 , or about 1 :1 .

The hair care composition of claim 1 , wherein the (c) amino silicone is selected from the group consisting of a polyether amino silicone, amodimethicone, a modified amodimethicone (such as bis-cetearyl amodimethicone and bis-hydroxy/methoxy amodimethicone), an amino gum silicone, and combinations thereof. As mentioned previously, the hair care compositions of the instant disclosure includes (c) an amino silicone. The amino silicone may be, for example, amodimethicone, bis-cetearyl amodimethicone, amodimethicone/morpholinomethyl silsesquioxane copolymer, PEG-40/PPG-8 methylaminopropyl/hydroxypropyl dimethicone copolymer, bisamino PEG/PPG-41 /3 aminoethyl PG-propyl dimethicone, and combinations thereof. Furthermore the amino silicone may be amodimethicone {e.g., Dow Corning 2-8566 Amino Fluid), bis-cetearyl amodimethicone (e.g., Silsoft AX), bis-amino PEG/PPG-41/3 aminoethyl PG-propyl dimethicone {e.g., Silsoft A-843), PEG-40/PPG-8 methylaminopropyl hydroxypropyl dimethicone copolymer {e.g., Silsoft A+), bis-isobutyl/PEG/PPG- 20/35/amodimethicone copolymer {e.g., Dow Corning CE 8401 Emulsion), and combinations thereof.

Additionally, the amino silicone may be, for example, a quaternized polysiloxane, such as, silicone quaternium 22 {e.g., Abil T Quat 60), silicone quaternium 12 (Pecosil CA-1240), silicone quaternium 16 (and) undeceth-1 1 (and) butyloctanol (and) undeceth-5 {e.g., Dow Corning 5-71 13 Silicone Quat Microemulsion),

In some cases, the amino silicone of (c) is present in an amount of 0.01 to 10 wt.%, about 0.01 to about 8 wt.%, about 0.01 to about 6 wt.%, about 0.01 to about 5 wt.%, about 0.1 to about 5 wt.%, about 0.1 to about 4 wt.% or about 0.1 to about 3 wt.%, based on the total weight of the hair care composition.

The cationic polymer of (d), if present, may be any polymer containing a net positively-charged atom/s or associated group/s of atoms covalently linked to its polymer molecule. Examples are the ammonium, phosphonium and sulfonium cations. The cationic polymer may be, for example, cationic proteins or cationic protein hydrolysates, polyalkyleneimines, such as polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, and chitin derivatives. Additionally, the cationic polymer may be a polyquaternium. A non-limiting list of polyquaterniums include polyquaternium-10, polyquaternium-1 1 , polyquaternium-22, polyquaternium-34, polyquaternium-53, polyquaternium-67, or combinations thereof.

In some cases, the cationic polymer of (d) is present in an amount of about 0.01 to about 10 wt.%, about 0.01 to about 8 wt.%, about 0.01 to about 6 wt.%, about 0.01 to about 5 wt.%, about 0.1 to about 5 wt.%, about 0.1 to about 4 wt.% or about 0.1 to about 3 wt.%, based on the total weight of the hair care composition. The hair care composition includes (e) a nonionic surfactant. The nonionic surfactant may be a single nonionic surfactant or two or more nonionic surfactants in combination. Thus, a single type of nonionic surfactant or a combination of different type of nonionic surfactants may be used. For example, the nonionic surfactant of (e) may be a polyol ester, a glycerol ether, an oxyethylenated, an oxypropylenated ether, an ethylene glycol polymer, or a combinations thereof. In some cases, the nonionic surfactant comprises a combination of a polyol ester and an ethylene glycol polymer. In some cases, the nonionic surfactant comprises a combination of glyceryl stearate, PEG-100 stearate, and steareth-20.

In some cases, the nonionic surfactant of (e) is present in an amount of about 0.01 to about 20 wt.%, about 0.1 to about 18 wt.%, about 1 to about 15 wt.%, about 1 to about 12 wt.%, or about 3 to about 12 wt.%, based on the total weight of the hair care composition.

The hair care composition may be in the form of an emulsion, e.g., oil-in- water (O/W), water-in-oil (W/O), and oil-in-alcohol emulsions. The compositions of the instant disclosure may be in the form of a liquid emulsion, such as a liquid-lotion, liquid-gel, Iiquid-cream, or a cream emulsion, such as a thick cream or gel-cream, or a foam or mousse wherein the liquid emulsion form has a thinner consistency than the cream emulsion form.

The instant disclosure further relates to a hair care composition comprising, in a cosmetically acceptable carrier: (a) about 0.01 to about 10 wt.% of an acrylate latex polymer; (b) about 0.01 to about 10 wt.% of a polyurethane latex polymer; (c) about 0.01 to about 10 wt.% of an amino silicone; (d) optionally, a cationic polymer; and (e) a nonionic surfactant. The acrylate latex polymers and/or the polyurethane latex polymers may be particles dispersed in an aqueous medium, or when used in hair care compositions, the latex polymers may be particles dispersed in the cosmetically acceptable carrier.

The acrylate latex polymer may be selected from the group consisting of an ammonium acrylate copolymer, an acrylates copolymer, a (meth)acrylate copolymer, a butyl acrylate/hydroxypropyl dimethicone acrylate copolymer, an acrylates/C i 2-C₂2 alkylmethacrylate copolymer, an isododecane and acrylates copolymer, an acrylates/octylacrylamide copolymer, and combinations thereof. In some instances, the acrylate latex polymer is acrylates copolymer. The latex polymer of (a) may be present in an amount of about 0.01 to about 10 wt.%, about 0.01 to about 8 wt.%, about 0.01 to about 6 wt.%, about 0.01 to about 5 wt.%, about 0.1 to about 5 wt.%, about 0.1 to about 4 wt.% or about 0.1 to about 3 wt.%, based on the total weight of the hair care composition.

The polyurethane latex polymer may be selected from the group consisting of consisting of polyurethane-32, polyurethane-34, polyurethane-35, and combinations thereof. In some instances, the polyurethane latex polymer is polyurethane-34. The latex polymer of (b) may be present in an amount of about 0.01 to about 10 wt.%, about 0.01 to about 8 wt.%, about 0.01 to about 6 wt.%, about 0.01 to about 5 wt.%, about 0.1 to about 5 wt.%, about 0.1 to about 4 wt.% or about 0.1 to about 3 wt.%, based on the total weight of the hair care composition.

The weight ratio of the acrylate latex polymer of (a) to the polyurethane latex polymers of (b) may be from about 1 :10 to about 10:1 , 7:1 to about 1 :7, about 1 :5 to about 5:1 , about 1 :3 to 3:1 , about 1 :2 to about 2:1 , or about 1 :1 .

The hair care composition of claim 1 , wherein the (c) amino silicone is selected from the group consisting of a polyether amino silicone, amodimethicone, a modified amodimethicone (such as bis-cetearyl amodimethicone and bis-hydroxy/methoxy amodimethicone), an amino gum silicone, and combinations thereof.

As mentioned previously, the hair care compositions of the instant disclosure includes (c) an amino silicone. The amino silicone may be, for example, amodimethicone, bis-cetearyl amodimethicone, amodimethicone/morpholinomethyl silsesquioxane copolymer, PEG-40/PPG-8 methylaminopropyl/hydroxypropyl dimethicone copolymer, bisamino PEG/PPG-41/3 aminoethyl PG-propyl dimethicone, and combinations thereof.

Additionally, the amino silicone may be, for example, a quaternized polysiloxane, such as, silicone quaternium 22 {e.g., Abil T Quat 60), silicone quaternium 12 (Pecosil CA-1240), , silicone quaterium 16 (and) undeceth-1 1 (and) butyloctanol (and) undeceth-5 {e.g., Dow Corning 5-71 13 Silicone Quat Microemulsion), , and combinations thereof.

In some cases, the amino silicone of (c) is present in an amount of about 0.01 to about 10 wt.%, about 0.01 to about 8 wt.%, about 0.01 to about 6 wt.%, about 0.01 to about 5 wt.%, about 0.1 to about 5 wt.%, about 0.1 to about 4 wt.% or about 0.1 to about 3 wt.%, based on the total weight of the hair care composition. The cationic polymer of (d), when present, may be any polymer containing a net positively-charged atom/s or associated group/s of atoms covalently linked to its polymer molecule. Examples are the ammonium, phosphonium and sulfonium cations. The cationic polymer may be, for example, cationic proteins or cationic protein hydrolysates, polyalkyleneimines, such as polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, and chitin derivatives. Additionally, the cationic polymer may be a polyquaternium. A non-limiting list of polyquaterniums include polyquaternium-10, polyquaternium-1 1 , polyquaternium-22, polyquaternium-34, polyquaternium-53, polyquaternium-67, or combinations thereof.

In some cases, the cationic polymer of (d) is present in an amount of about

0.01 to about 10 wt.%, about 0.01 to about 8 wt.%, about 0.01 to about 6 wt.%, about 0.01 to about 5 wt.%, about 0.1 to about 5 wt.%, about 0.1 to about 4 wt.% or about 0.1 to about 3 wt.%, based on the total weight of the hair care composition.

The hair care composition include (e) a nonionic surfactant. The nonionic surfactant may be a single nonionic surfactant or two or more nonionic surfactants in combination. Thus, a single type of nonionic surfactant or a combination of different type of nonionic surfactants may be used. For example, the nonionic surfactant of (e) may be a polyol ester, a glycerol ether, an oxyethylenated ether, an oxypropylenated ether, an ethylene glycol polymer, or a combinations thereof. In some cases, the nonionic surfactant comprises a combination of a polyol ester and an ethylene glycol polymer. In some cases, the nonionic surfactant comprises a combination of glyceryl stearate, PEG-100 stearate, and steareth-20.

The hair care composition may be in the form of an emulsion, e.g., oil-in- water (O/W), water-in-oil (W/O), and oil-in-alcohol emulsions. The compositions of the instant disclosure may be in the form of a liquid emulsion, such as a liquid-lotion, liquid-gel, Iiquid-cream, or a cream emulsion, such as a thick cream or gel-cream, or a foam or mousse wherein the liquid emulsion form has a thinner consistency than the cream emulsion form. The hair care compositions described herein may further comprise: (f) an oil. The oil may be, for example, a hydrocarbon-based oil (e.g., mineral oil). The hair care compositions described herein may have an acidic pH, i.e., a pH less than 7, a pH of 5 to less than 7, or pH of 5 to 6.

More exhaustive but non-limiting lists of components useful in the hair care compositions disclosed herein are presented below.

ACRYLATE LATEX POLYMERS

By way of non-limiting example only, examples of acrylate latex polymers include those resulting from the homopolymerization or copolymerization of monomers chosen from (meth)acrylics, (meth)acrylates, (meth)acrylamides and/or vinyl homopolymers or copolymers. The term "(meth)acryl" and variations thereof, as used herein, means acryl or methacryl.

The (meth)acrylic monomers may be chosen from, for example, acrylic acid, methacrylic acid, citraconic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and maleic anhydride. Additional non-limiting examples of (meth)acrylic monomers include C1 - C8 alkyl (meth)acrylic, such as, for example, methyl (meth)acrylic, ethyl (meth)acrylic, propyl (meth)acrylic, isopropyl (meth)acrylic, butyl (meth)acrylic, tert-butyl (meth)acrylic, pentyl(meth) acrylic, isopentyl (meth)acrylic, neopentyl (meth)acrylic, hexyl (meth)acrylic, isohexyl (meth)acrylic, 2-ethylhexyl (meth)acrylic, cyclohexyl (meth)acrylic, isohexyl (meth)acrylic, heptyl (meth)acrylic, isoheptyl (meth)acrylic, octyl (meth)acrylic, isooctyl (meth)acrylic, as well as combinations of any of the above. The esters of (meth)acrylic monomers may be, by way of non-limiting example, C1 -C8 alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl(meth) acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, isohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, isohexyl (meth)acrylate, heptyl (meth)acrylate, isoheptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, allyl (meth)acrylate, and combinations thereof. Additional and non-limiting examples include C1 -C8 alkoxy (meth)acrylates, such as methoxy (meth)acrylate, ethoxy (meth)acrylate, propyl oxide (meth)acrylate, isopropyl oxide (meth)acrylate, butyl oxide (meth)acrylate, tert-butyl oxide (meth)acrylate, pentyl oxide (meth) acrylate, isopentyl oxide (meth)acrylate, neopentyl oxide (meth)acrylate. The esters may be, by way of non-limiting example, C2-C6 hydroxy alkyl (meth)acrylates, such as hydroxy ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol mono(meth)acrylate, 1 ,4-butane diol di(meth)acrylate, 1 ,6,hexane diol di(meth)acrylate, and any combination thereof. The esters may be, by way of non-limiting example, aryl (meth)acrylates such as benzyl (meth)acrylate, phenyl (meth)acrylate, and any combination thereof. The esters can further contain amino groups such as aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, Ν,Ν-dimethylaminopropyl (meth)acrylate, N,N- dimethylaminodimethylpropyl (meth)acrylate, Ν,Ν-diethyleaminoethyl (meth)acrylate, and Ν,Ν,Ν-trimethylaminoethyl (meth)acrylate; and salts of the ethylenic amines.

According to at least certain exemplary embodiments, the alkyl group of the esters may be either fluorinated or perfluorinated, e.g. some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. The monomers can also be fluorine- containing monomers, such as, by way of non-limiting example, trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,4,4-hexafluorobutyl methacrylate, perfluorooctyl methacrylate and perfluorooctyl acrylate; and silicone macromonomers.

The amides of (meth)acrylic monomers can, for example, be made of (meth)acrylamides, and especially N-alkyl (meth)acrylamides, in particular N-(C1 -C12) alkyl (meth)acrylates such as N-ethyl (meth)acrylamide, N-t-butyl (meth)acrylamide, N-t- octyl (meth)acrylamide, N-methylol (meth)acrylamide and N-diacetone (meth)acrylamide, and any combination thereof. The vinyl monomers can include, but are not limited to, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate, triallyl cyanurate; vinyl halides such as vinyl chloride and vinylidene chloride; aromatic mono- or divinyl compounds such as styrene, D-methylstyrene, chlorostyrene, alkylstyrene, divinylbenzene and diallyl phthalate, and combination thereof. Other non-limiting ionic monomers can include para-styrensulfonic, vinylsulfonic, 2- (meth)acryloyloxyethylsulfonic, 2-(meth)acrylamido-2-methylpropylsulfonic acids.

The list of monomers given is not limiting, and it should be understood that it is possible to use any monomer known to those skilled in the art which includes acrylic and/or vinyl monomers (including monomers modified with a silicone chain).

Silicone acrylic polymers may also optionally be used as vinyl polymer i. In at least certain, non-limiting exemplary embodiments, a latex polymer may be chosen from aqueous dispersions of Methacrylic Acid/Ethyl Acrylate copolymer (I NCI: Acrylates Copolymer, such as LUVIFLEX® Soft by BASF), PEG/PPG-23/6 Dimethicone Citraconate/C10-30 Alkyl PEG-25 Methacrylate/Acrylic Acid/Methacrylic Acid/Ethyl Acrylate/Trimethylolpropane PEG-15 Triacrylate copolymer (INCI: Polyacrylate-2 Crosspolymer, such as FIXATE SUPERHOLD TM by Lubrizol), Styrene/Acrylic copolymer (such as NEOCRYL® A-1 120, DSM), Ethylhexyl Acrylate/Methyl Methacrylate/Butyl Acrylate/Acrylic Acid/ Methacrylic Acid copolymer (INCI : Acrylates/Ethylhexyl Acrylate Copolymer, such as Daitosol 5000SJ, Daito Kasei Kogyo), Acrylic/Acrylates Copolymer (INCI name: Acrylates Copolymer, such as DAITOSOL 5000AD, Daito Kasei Kogyo), Vinyl Acetate Acrylic Ester Copolymer (INCI name: Acrylates/VA Copolymer, such as VINYSOL 2140, Daido Chemical) and Acrylates Copolymers, such as those known under the tradename ACULYN™ 33 (Dow Chemical), under the tradename LUVIMER® MAE (BASF), or under the tradename BALANCE CR (AKZO NOBEL), Styrene/Acrylates Copolymer, known under the tradename JONCRYL 77 from BASF, Styrene/Acrylates/Ammonium Methacrylate Copolymer, known under the tradename SYNTRAN PC5620 CG from Interpolymer, and mixtures thereof.

POLYURETHANE LATEX POLYMERS

In yet further exemplary and non-limiting embodiments, one of the at least two latex polymers may be chosen from polyurethane latex polymers, such as aqueous polyurethane dispersions comprising the reaction products of (i), (ii), and/or (iii), defined below.

Reaction product (i) may be any prepolymer according to the formula:

H O O H H O O H

I II II I I II II I

OCN— R₂-|-N— C— O— Rj— O— C— N— R₂-f N— C— O— R₃— O— C— N— R₂†- -NCO

wherein R1 is chosen from bivalent radicals of a dihydroxyl functional compound, R2 is chosen from hydrocarbon radicals of an aliphatic or cycloaliphatic polyisocyanate, and R3 is chosen from radicals of a low molecular weight diol, optionally substituted with ionic groups, n ranges from about 0 to about 5, and m is greater than about 1 .

Suitable dihydroxyl compounds for providing the bivalent radical R1 include those having at least two hydroxy groups, and having number average molecular weights ranging from about 700 to about 16,000, such as, for example, from about 750 to about 5000. Non-limiting examples of the high molecular weight compounds include polyester polyols, polyether polyols, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxy polyacrylates, polyhydroxy polyester amides, polyhydroxy polyalkadienes and polyhydroxy polythioethers. In various embodiments, polyester polyols, polyether polyols, and polyhydroxy polycarbonates may be chosen. Mixtures of such compounds are also within the scope of the disclosure.

The polyester diol(s) may optionally be prepared from aliphatic, cycloaliphatic, or aromatic dicarboxylic or polycarboxylic acids, or anhydrides thereof; and dihydric alcohols such as diols chosen from aliphatic, alicyclic, or aromatic diols.

The aliphatic dicarboxylic or polycarboxylic acids may be chosen from, for example: succinic, fumaric, glutaric, 2,2-dimethylglutaric, adipic, itaconic, pimelic, suberic, azelaic, sebacic, maleic, malonic, 2,2-dimethylmalonic, nonanedicarboxylic, decanedicarboxylic, dodecanedioic, 1 ,3-cyclohexanedicarboxylic, 1 ,4-cyclo-ihexane- dicarboxylic, 2,5-norboranedicarboxylic, diglycolic, thiodipropionic, 2,5-naphthalene- dicarboxylic, 2,6-naphthalenedicarboxylic, phthalic, terephthalic, isophthalic, oxanic, 0- phthalic, tetrahydrophthalic, hexahydrophthalic or trimellitic acid. The acid anhydrides may, in further exemplary embodiments, be chosen from o-phthalic, trimellitic or succinic acid anhydride or a mixture thereof. By way of non- limiting example only, the dicarboxylic acid may be adipic acid.

The dihydric alcohols may be chosen from, for example, ethanediol, ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, tetraethylene glycol, 1 ,2- propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,3-butanediol, 2,3-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 2,2- dimethyl-1 ,3-propanediol, 1 ,4-dihydroxycyclohexane, 1 ,4-dimethylolcyclohexane, cyclohexanedimethanol, 1 ,8-octanediol, 1 ,10-decanediol, 1 ,12-dodecanediol, neopentyl glycol, and mixtures thereof. The cycloaliphatic and/or aromatic dihydroxyl compounds may also be suitable as the dihydric alcohol(s) for the preparation of the polyester polyol(s).

The polyester diols may also be chosen from homopolymers or copolymers of lactones, which are, in at least certain embodiments, obtained by addition reactions of lactones or lactone mixtures, such as butyrolactone, ε-caprolactone and/or methyl-ε- caprolactone with the appropriate polyfunctional, e.g. difunctional, starter molecules such as, for example, the dihydric alcohols mentioned above. The corresponding polymers of ε- caprolactone may be chosen in at least some embodiments.

The polyester polyol, e.g. polyester diol, radical R1 , may be obtained by polycondensation of dicarboxylic acids, such as adipic acid, with polyols, e.g. diols, such as hexanediol, neopentyl glycol, and mixtures thereof.

The polycarbonates containing hydroxyl groups comprise those known per se, such as the products obtained by reacting diols, such as (1 ,3)-propanediol, (1 ,4)- butanediol and/or (1 ,6)-hexanediol, diethylene glycol, triethylene glycol, or tetraethylene glycol with diaryl carbonates, for example diphenyl carbonate or phosgene.

Optional polyether polyols may be obtained in any known manner by reacting starting compounds which contain reactive hydrogen atoms with alkylene oxides, such as, for example, ethylene oxide; propylene oxide; butylene oxide; styrene oxide; tetrahydrofuran; or epichlorohydrin, or with mixtures of these alkylene oxides. In at least certain embodiments, the polyethers do not contain more than about 10% by weight of ethylene oxide units. For example, polyethers obtained without addition of ethylene oxide may be chosen. Polyethers modified with vinyl polymers are also suitable according to various embodiments of the disclosure. Products of this type can be obtained by polymerization, for example, of styrene and acrylonitrile in the presence of polyethers, for example as described in U.S. Patent Nos. 3,383,351 ; 3,304,273; 3,523,095; 3,1 10,695; and German patent 1 152 536.

Among the polythioethers which may be chosen include the condensation products obtained from thiodiglycol per se and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids, and/or amino alcohols. The products obtained are either mixed polythioethers, polythioether esters, or polythio-iether ester amides, depending on the co-components.

Optional polyacetals include but are not limited to the compounds which can be prepared from aldehydes, for example formaldehyde, and from glycols, such as diethylene glycol, triethylene glycol, ethoxylated 4,4'-(dihydroxy)diphenyl-dimethylmethane, and (1 ,6)-hexane-idiol. Polyacetals useful according to various non-limiting embodiments of the disclosure can also be prepared by polymerization of cyclic acetals.

Optional polyhydroxy polyesteramides and polyamines include, for example, the mainly linear condensation products obtained from saturated or unsaturated, polybasic carboxylic acids or anhydrides thereof, and from saturated or unsaturated, polyvalent amino alcohols, from diamines, or from polyamines, as well as mixtures thereof.

Optional monomers for the production of polyacrylates having hydroxyl functionality comprise acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, 2- hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate.

Mixtures of dihydroxy compounds can also be chosen.

Optional polyisocyanates for providing the hydrocarbon-based radical R2 include, for example, organic diisocyanates having a molecular weight ranging from about 100 to about 1500, such as about 1 12 to about 1000, or about 140 to about 400.

Optional diisocyanates are those chosen from the general formula R2(NCO)2, in which R2 represents a divalent aliphatic hydrocarbon group comprising from about 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group comprising from about 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group comprising from about 7 to 15 carbon atoms, or a divalent aromatic hydrocarbon group comprising from about 6 to 15 carbon atoms. Examples of the organic diisocyanates which may be chosen include, but are not limited to, tetramethylene diisocyanate, 1 ,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane-1 ,3-diisocyanate and cyclohexane-1 ,4- diisocyanate, 1 -isocyanato-3-isocyanato-imethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI), bis(4-isocyanatocyclohexyl)-methane, 1 ,3- bis(isocyanatomethyl)cyclohexane and 1 ,4-bis(isocyanatomethyl)cyclohexane and bis(4- isocyanato-3-methylcyclohexyl)methane. Mixtures of diisocyanates can also be used.

In at least certain embodiments, diisocyanates are chosen from aliphatic and cycloaliphatic diisocyanates. For example, 1 ,6-hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate, as well as mixtures thereof may be chosen.

The use of diols, for example low molecular weight diols, R3, may in at least certain embodiments allow a stiffening of the polymer chain. The expression "low molecular weight diols" means diols having a molecular weight ranging from about 50 to about 800, such as about 60 to 700, or about 62 to 200. They may, in various embodiments, contain aliphatic, alicyclic, or aromatic groups. In certain exemplary embodiments, the compounds contain only aliphatic groups. The diols that may be chosen may optionally have up to about 20 carbon atoms, and may be chosen, for example, from ethylene glycol, diethylene glycol, propane-1 ,2-diol, propane-1 ,3-diol, butane-1 ,4-diol, 1 ,3- butylene glycol, neopentyl glycol, butylethylpropanediol, cyclohexanediol, 1 ,4- cyclohexanedimethanol, hexane-1 ,6-diol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxy-icyclo-ihexyl)-propane), and mixtures thereof. For example, R3 may be derived from neopentyl glycol.

Optionally, the low molecular weight diols may contain ionic or potentially ionic groups. Suitable low molecular weight diols containing ionic or potentially ionic groups may be chosen from those disclosed in U.S. Patent No. 3,412,054. In various embodiments, compounds may be chosen from dimethylohbutanoic acid (DMBA), dimethylolpropionic acid (DMPA), and carboxyl-containing caprolactone polyester diol. If low molecular weight diols containing ionic or potentially ionic groups are chosen, they may, for example, be used in an amount such that less than about 0.30 meq of -COOH is present per gram of polyurethane in the polyurethane dispersion. In at least certain exemplary and non-limiting embodiments, the low molecular weight diols containing ionic or potentially ionic groups are not used.

Reaction product (ii) may be chosen from at least one chain extender according to the formula:

H₂N - R4 - NH₂

wherein R4 is chosen from alkylene or alkylene oxide radicals, said radicals not being substituted with ionic or potentially ionic groups.

Reaction product (ii) may optionally be chosen from alkylene diamines, such as hydrazine, ethylenediamine, propylenediamine, 1 ,4-butylenediamine and piperazine; and alkylene oxide diamines such as dipropylamine diethylene glycol (DPA-DEG available from Tomah Products, Milton, Wl), 2-methyl-1 ,5-pentanediamine (Dytec A from DuPont), hexanediamine, isophorone-idiamine, and 4,4-methylenedi(cyclohexylamine), and the DPA-series of ether amines available from Tomah Products, Milton, Wl, including dipropylamine propylene glycol, dipropylamine dipropylene glycol, dipropylamine tripropylene glycol, dipropylamine polypropylene glycol), dipropylamine ethylene glycol, dipropylamine poly(ethylene glycol), dipropylamine 1 ,3-propanediol, dipropylamine 2- methyl-1 ,3-propanediol, dipropylamine 1 ,4-butanediol, dipropylamine 1 ,3-butanediol, dipropylamine 1 ,6-hexanediol and dipropylamine cyclohexane-1 ,4-dimethanol, and mixtures thereof.

Reaction product (iii) may be chosen from at least one chain extender according to the formula:

H₂N - R5 - NH₂

wherein R5 is chosen from alkylene radicals substituted with ionic or potentially ionic groups. In at least certain exemplary embodiments, the compounds may have an ionic or potentially ionic group and two isocyanate-reactive groups.

As used herein, ionic or potentially ionic groups may include groups comprising ternary or quaternary ammonium groups, groups convertible into such groups, carboxyl groups, carboxylate groups, sulphonic acid groups, and sulphonate groups. At least partial conversion of the groups convertible into salt groups of the type mentioned may take place before or during the mixing with water. Specific compounds include diaminosulphonates, such as for example the sodium salt of N-(2-aminoethyl)-2- aminoethanesulphonic acid (AAS) or the sodium salt of N-(2-aminoethyl)-2- aminopropionic acid.

In at least certain embodiments, R5 represents an alkylene radical substituted with sulphonic acid or sulphonate groups. By way of example only, the compound is chosen from sodium salts of N-(2-aminoethyl)-2-aminoethanesulphonic acid.

By way of non-limiting example, such latexes include, but are not limited to, aqueous polyurethane dispersions comprising a reaction product of a prepolymer such as, for example, those sold under the BAYCUSAN® name by Bayer such as, for example, BAYCUSAN® C1000 (INCI name: Polyurethane-34), BAYCUSAN® C1001 (INCI name: Polyurethane-34), BAYCUSAN® C1003 (INCI name: Polyurethane-32), BAYCUSAN® C1004 (INCI name: Polyurethane-35) and BAYCUSAN® C1008 (INCI name: Polyurethane-48). In various exemplary embodiments, polyurethane latexes may be chosen from, but are not limited to, aqueous polyurethane dispersion of Isophthalic Acid/Adipic Acid/Hexylene Glycol/Neopentyl glycol/Dimethylolpropanoic Acid/lsophorone Diisocyanate copolymer (INCI name: Polyurethane-1 , such as LUVISET® P.U.R, BASF), polycarbonate polyurethane, aliphatic polyurethane and aliphatic polyester polyurethane (such as the NEOREZ® series, DSM, such as NEOREZ® R989, and NEOREZ® R-2202).

AMINO SILICONES

The term "amino silicone" is intended to mean any silicone comprising at least one primary, secondary or tertiary amine or a quaternary ammonium group.

As amino silicone that may be used in the scope of the instant disclosure, the following can be cited:

a) polysiloxanes corresponding to formula (A):

in which x' and y' are integers such that the weight-average molecular weight

(Mw) is comprised between about 5000 and 500 000 b) amino silicones corresponding to formula (B):

R'aG3-a-Si(OSiG₂)n-(OSiGbR'2-b)m-0-SiG3-a-R'a (B) in which:

G, which may be identical or different, designate a hydrogen atom, or a phenyl, OH or CrC₈ alkyl group, for example methyl, or CrC₈ alkoxy, for example methoxy,

a, which may be identical or different, denote the number 0 or an integer from 1 to 3, in particular 0;

b denotes 0 or 1 , and in particular 1 ;

- m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, it being possible for n to denote a number from 0 to 1999 and in particular from 49 to 149, and for m to denote a number from 1 to 2000 and in particular from 1 to 10;

R', which may be identical or different, denote a monovalent radical having formula -CqH₂qL in which q is a number ranging from 2 to 8 and L is an optionally quaternized amino group chosen from the following groups:

-NR"-Q-N(R")₂

-N(R")₂

-N+(R")₃ A- -N+H(R")₂ A-

-N+H₂(R") A-

-N(R")-Q-N+R"H₂ A-

-NR"-Q-N+ (R")₂H A-

-NR"-Q-N+ (R")₃ A-,

in which R", which may be identical or different, denote hydrogen, phenyl, benzyl, or a saturated monovalent hydrocarbon-based radical, for example a CrC₂₀ alkyl radical; Q denotes a linear or branched CrH_2r group, r being an integer ranging from 2 to 6, or from 2 to 4; and A- represents a cosmetically acceptable ion, in particular a halide such as fluoride, chloride, bromide or iodide.

A group of amino silicones corresponding to this definition (B) is represented by the silicones called "trimethylsilylamodimethicone" having formula (C):

in which n and m have the meanings given above, in formula B.

Another group of amino silicones corresponding to this definition is represented by silicones having the following formulae (D) or (E):

CH, CH,

R; -Si- O— Si " O— Si - -O— Si— R, (D)

(CH 2^3

CH, CH, I CH,

NH

(CH₂)₂

NH, m

in which:

m and n are numbers such that the sum (n + m) can range from 1 to 1000, in particular from 50 to 250 and more particularly from 100 to 200, it being possible for n to denote a number from 0 to 999 and in particular from 49 to 249, and more particularly from 125 to 175, and for m to denote a number from 1 to 1000 and in particular from 1 to 10, and more particularly from 1 to 5;

Ri , R₂, R3, which may be identical or different, represent a hydroxy or Ci-C₄ alkoxy radical, where at least one of the radicals Ri to R₃ denotes an alkoxy radical.

The alkoxy radical is sometimes a methoxy radical.

The hydroxy/alkoxy mole ratio ranges preferably from 0.2:1 to 0.4:1 and preferably from 0.25:1 to 0.35:1 and more particularly equals 0.3:1.

The weight-average molecular weight (Mw) of the silicone ranges preferably from 2000 to 1 000 000, more particularly from 3500 to 200 000. -

in which:

p and q are numbers such that the sum (p + q) ranges from 1 to 1000, particularly from 50 to 350, and more particularly from 150 to 250; it being possible for p to denote a number from 0 to 999 and in particular from 49 to 349, and more particularly from 159 to 239 and for q to denote a number from 1 to 1000, in particular from 1 to 10, and more particularly from 1 to 5;

Ri , R₂, which are different, represent a hydroxy or Ci-C₄ alkoxy radical, where at least one of the radicals or R₂ denotes an alkoxy radical.

The alkoxy radical is preferably a methoxy radical.

The hydroxy/alkoxy mole ratio ranges generally from 1 :0.8 to 1 :1 .1 and preferably from 1 :0.9 to 1 :1 and more particularly equals 1 :0.95.

The weight-average molecular weight (Mw) of the silicone ranges preferably from 2000 to 200 000, even more particularly 5000 to 100 000 and more particularly from 10 000 to 50 000.

Commercial products corresponding to these silicones having structure (D) or (E) may include in their composition one or more other amino silicones whose structure is different than formulae (D) or (E).

A product containing amino silicones having structure (D) is sold by Wacker under the name Belsil® ADM 652.

A product containing amino silicones having structure (E) is sold by Wacker under the name Fluid WR 1300®.

When these amino silicones are used, one particularly advantageous embodiment consists in using them in the form of an oil-in-water emulsion. The oil-in-water emulsion may comprise one or more surfactants. The surfactants may be of any nature but are preferably cationic and/or nonionic. The number-average size of the silicone particles in the emulsion generally ranges from 3 nm to 500 nanometres. Preferably, in particular as amino silicones having formula (E), microemulsions are used whose average particle size ranges from 5 nm to 60 nanometres (limits included) and more preferably from 10 nm to 50 nanometres (limits included). Accordingly, according to the disclosure the microemulsions of amino silicone having formula (E) sold as Finish CT 96 E® or SLM 28020® by Wacker can be used.

Another group of amino silicones corresponding to this definition is represented by the following formula (F):

†H₃ ChL ChL CH₃

HO Si— o- ^■Si - O— Si - Si— OH

i

A

ChL ChL I CH,

NH

(F)

(CH₂)₂

NH, m

in which:

m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, it being possible for n to denote a number from 0 to 1999 and in particular from 49 to 149, and for m to denote a number from 1 to 2000 and in particular from 1 to 10;

- A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably linear.

The weight-average molecular weight (Mw) of these amino silicones ranges preferably from 2000 to 1 000 000 and even more particularly from 3500 to 200 000.

A preferred silicone of formula (F) is amodimethicone (INCI name) sold under the tradename XIAMETER® MEM-8299 Cationic Emulsion by Dow Corning.

Another group of amino silicones corresponding to this definition is represented by the following formula (G): †^H3 CH H, 3 CH, CH,

H₃C- -Si- o- - Si - O— Si - -O— Si— CH,

I

A

CH, CH, I CH, (G)

Π NH

(CH₂)₂

NH m

in which:

A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably branched.

The weight-average molecular weight (Mw) of these amino silicones ranges preferably from 500 to 1 000 000 and even more particularly from 1000 to 200 000.

A silicone having this formula is for example DC2-8566 Amino Fluid by Dow

Corning,

c) amino silicones corresponding to formula (H):

R_c— CH— CHOH— CH₂— N (R₅)₃ Q

(R₅)₃— Si— O- -Si— O Si- -Si-(R 5 3 (H)

R_c in which:

R₅ represents a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a CrC₁₈ alkyl or C₂-C₁₈ alkenyl radical, for example methyl;

R₆ represents a divalent hydrocarbon-based radical, in particular a C Ci₈ alkylene radical or a divalent C_rC₁₈, for example CrC₈, alkylenoxy radical linked to the Si via an SiC bond;

Q- is an anion such as a halide ion, in particular chloride, or an organic acid salt (for example acetate);

r represents a mean statistical value from 2 to 20 and in particular from 2 to

8;

s represents a mean statistical value from 20 to 200 and in particular from 20 to 50.

Such amino silicones are described more particularly in patent US 4 185 087. d) uaternary ammonium silicones having formula (I):

in which:

- R₇, which may be identical or different, represent a monovalent hydrocarbon- based radical containing from 1 to 18 carbon atoms, and in particular a CrC₁₈ alkyl radical, a C₂-Ci8 alkenyl radical or a ring containing 5 or 6 carbon atoms, for example methyl;

R₆ represents a divalent hydrocarbon-based radical, in particular a C Ci₈ alkylene radical or a divalent C Ci₈, for example CrC₈, alkylenoxy radical linked to the Si via an SiC bond;

R₈, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C Ci₈ alkyl radical, a C₂-Ci₈ alkenyl radical or a -R₆-NHCOR₇ radical;

X- is an anion such as a halide ion, in particular chloride, or an organic acid salt (for example acetate);

r represents a mean statistical value from 2 to 200 and in particular from 5 to

100;

These silicones are described, for example, in patent application EP-A 0 530

974.

e) amino silicones having formula (J):

H₂N - (C_mH_2m) - NH - (C_nH_2n) - Si -†- O†- Si— O^■ Si - (J)

I

x R,

J 3 in which:

Ri , R₂, R3 and R₄, which may be identical or different, denote a CrC₄ alkyl radical or a phenyl group;

R₅ denotes a CrC₄ alkyl radical or a hydroxyl group;

- n is an integer ranging from 1 to 5;

m is an integer ranging from 1 to 5;

and in which x is chosen such that the amine number is between 0.01 and 1 meq/g; f) multiblockpolyoxyalkylenated amino silicones, of type (AB)n, A being a polysiloxane block and B being a polyoxyalkylenated block containing at least one amine group.

Said silicones are preferably constituted of repeating units having the following general formulae:

[-(SiMe₂0)xSiMe₂ - R -N(R")- R'-0(C2H40)a(C₃H60)b -R'-N(H)-R-] or alternatively

[-(SiMe₂0)xSiMe₂ - R -N(R")- R' - 0(C2H₄0)a(C₃H60)b -] in which:

a is an integer greater than or equal to 1 , preferably ranging from 5 to 200, more particularly ranging from 10 to 100;

b is an integer comprised between 0 and 200, preferably ranging from 4 to 100, more particularly between from 5 and 30;

x is an integer ranging from 1 to 10 000, more particularly from 10 to 5000; R" is a hydrogen atom or a methyl;

R, which may be identical or different, represent a divalent linear or branched

C₂-C₁₂ hydrocarbon-based radical, optionally including one or more heteroatoms such as oxygen; preferably, R denotes an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical, or a -CH2CH2CH₂OCH (OH)CH2- radical; preferentially R denotes a -CH2CH₂CH₂OCH (OH)CH2- radical;

R', which may be identical or different, represent a divalent linear or branched C2-C12 hydrocarbon-based radical, optionally including one or more heteroatoms such as oxygen; preferably, R' denotes an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical, or a -CH2CH₂CH₂OCH (OH)CH2- radical; preferentially R' denotes -CH(CH₃)-CH₂-. The siloxane blocks preferably represent between about 50 and about 95 mol% of the total weight of the silicone, more particularly from 70 to 85 mol%.

The amine content is preferably between about 0.02 and about 0.5 meq/g of copolymer in a 30% solution in dipropylene glycol, more particularly between about 0.05 and about 0.2.

The weight-average molecular weight (Mw) of the silicone is preferably comprised between 5000 and 1 000 000, more particularly between 10 000 and 200 000.

Mention may be made especially of the silicones sold under the names Silsoft™ A-843 or Silsoft™ A+ by Momentive.

g) the alkylamino silicones corresponding to formula (K) below:

in which:

x and y are numbers ranging from 1 to 5000; preferably, x ranges from 10 to 2000 and especially from 100 to 1000; preferably, y ranges from 1 to 100;

Ri and R₂, which may be identical or different, preferably identical, are linear or branched, saturated or unsaturated alkyl radicals, comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms and especially 12 to 20 carbon atoms;

A denotes a linear or branched alkylene radical containing from 2 to 8 carbon atoms,

Preferably, A comprises 3 to 6 carbon atoms, especially 4 carbon atoms; preferably, A is branched. Mention may be made especially of the following divalent radicals: -CH₂CH₂CH₂ and -CH₂CH(CH₃)CH₂-.

Preferably, Ri and R₂, which may be identical or different, are saturated linear alkyl radicals comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms and especially 12 to 20 carbon atoms; mention may be made in particular of dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals; and preferentially, Ri and R₂, which may be identical or different, are chosen from hexadecyl (cetyl) and octadecyl (stearyl) radicals.

Preferentially, the silicone is of formula (K) with:

x ranging from 10 to 2000 and especially from 100 to 1000;

y ranging from 1 to 100;

- A comprising 3 to 6 carbon atoms and especially 4 carbon atoms; preferably,

A is branched; and more particularly A is chosen from the following divalent radicals: CH2CH2CH2 and -CH₂CH(CH₃)CH₂-; and

R-i and R₂, which may be identical or different, being linear, saturated alkyl radicals comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms and especially 12 to 20 carbon atoms; chosen in particular from dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals; preferentially, Ri and R₂, which may be identical or different, being chosen from hexadecyl (cetyl) and octadecyl (stearyl) radicals.

Preferably, the amino silicones according to the disclosure are chosen from a silicone of formula (K). A preferred silicone of formula (K) is bis-cetearylamodimethicone (INCI name).

Mention may also be made especially of the silicone sold under the name Silsoft™ AX by Momentive.

Other preferred amino silicones according to the disclosure are chosen from the amino silicones of formula (F). A preferred silicone of formula (F) is amodimethicone (INCI name) sold under the tradename XIAMETER® MEM-8299 Cationic Emulsion by Dow Corning.

CATIONIC POLYMERS

The term "cationic polymer" means any polymer comprising at least one cationic group and/or at least one group that may be ionized into a cationic group. Cationic polymers useful in the hair care compositions disclosed herein include, for example:

(1 ) homopolymers and copolymers derived from acrylic or methacrylic esters or amides and comprising at least one unit chosen from units of formulae (V), (VI), (VII) and (VI II):

(V) (VI)

(VII) (VI II) wherein:

R₃, which may be identical or different, denotes a hydrogen atom or a CH₃ radical; A, which may be identical or different, represents a linear or branched C.sub.1 - C.sub.6 and, for example, C₂-C₃ alkyl group or a CrC₄ hydroxyalkyl group;

R₄, R₅ and R₆, which may be identical or different, represent a CrC₁₈ alkyl group or a benzyl radical, such as a CrC₆ alkyl group;

R-i and R₂, which may be identical or different, represent hydrogen or a CrC₆ alkyl group, for example methyl or ethyl;

X^" denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.

The polymers of this family can also contain at least one unit derived from at least one comonomer which may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (Ci-C₄)alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.

Thus, among the polymers of this family, exemplary mention may be made of:

copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as the product sold under the name HERCOFLOC by the company Hercules,

the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described, for example, in EP 80 976 and sold under the name BINA QUAT P 100 by the company Ciba Geigy,

the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate sold under the name RETEN by the company Hercules,

quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name GAFQUAT by the company ISP, for instance GAFQUAT 734 or GAFQUAT 755, or alternatively the products known as COPOLYMER 845, 958 and 937,

dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name GAFFIX VC 713 by the company ISP,

vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers sold, for example, under the name STYLEZE CC 1 0 by ISP,

quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name GAFQUAT HS100 by the company ISP, and crosslinked polymers of methacryloyloxyiCrC^alkyltri^ C^alkylammonium salts 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, such as methylenebisacrylamide. In at least one embodiment, a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing about 50% by weight of the copolymer in mineral oil can be used. This dispersion is sold under the name SALCARE.RTM. SC 92 by the company Ciba. In some embodiments, a crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester can be used. These dispersions are sold under the names SALCARE.RTM. SC 95 and SALCARE.RTM. SC 96 by the company Ciba.

Other examples are cellulose ether derivatives comprising quaternary ammonium groups, such as the polymers sold under the names JR (JR 400, JR 125, JR 30M) or LR (LR 400, LR 30M) by the company Union Carbide Corporation.

(2) copolymers of cellulose or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, such as hydroxymethyl-, hydroxyethyl- or hydroxy- propylcelluloses grafted, for instance, with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. These are sold under the name CELQUAT L 200 and CELQUAT H 100 by the company National Starch.

(3) non-cellulose cationic polysaccharides, such as guar gums containing trialkylammonium cationic groups. Such products are sold, for example, under the trade names JAGUAR C13S, JAGUAR C15, JAGUAR C17 and JAGUAR C162 by the company Meyhall.

(4) polymers of piperazinyl units and of divalent alkylene or hydroxyalkylene radicals.

(5) water-soluble polyamino amides prepared, for example, 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-unsatu rated 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 an amount 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 at least one tertiary amine function, they can be quaternized. Exemplary mention may be made of the adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the name CARTARETINE F, F4 or F8 by the company Sandoz.

(6) the polymers obtained by reaction of at least one polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated C.sub.3-C.sub.8 aliphatic dicarboxylic acids. The molar ratio between the polyalkylene polyamine and the dicarboxylic acid ranges from 0.8:1 to 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 ranging from 0.5:1 to 1 .8:1 . Polymers of this type are sold, for example, under the name HERCOSETT 57, PD 170 or DELSETTE 101 by the company Hercules.

(7) cyclopolymers of alkyldiallylamine and of dialkyldiallylammonium, such as the homopolymers or copolymers containing, as main constituent of the chain, at least one unit corresponding to formula (IX) or (X):

(IX)

(X)

wherein formulae k and t are equal to 0 or 1 , the sum k+t being equal to 1 ; R.sub.9 denotes a hydrogen atom or a methyl radical; R₇ and R₈, independently of each other, denote a CrC₈ alkyl group, a hydroxyalkyl group in which the alkyl group is CrC₈, an amidoalkyl group in which the alkyl is CrC₄; or R₇ and R₈ denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidyl or morpholinyl; in at least one embodiment R₇ and R₈, independently of each other, denote a Ci-C₄ alkyl group; Y^" is an organic or mineral anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.

Among the polymers defined above, exemplary mention may be made of the dimethyldiallylammonium chloride homopolymer sold under the name MERQUAT 100 and MERQUAT 280 by the company Nalco (and its homologues of low weight-average molecular mass) and the copolymers of diallyldimethylammonium chloride and of acrylamide, sold under the name MERQUAT 550.

(8) quaternary diammonium polymers containing repeating units of formula (XI):

(XI)

wherein:

Rio, Rn , Ri2 and Ri₃, which may be identical or different, represent CrC₆ aliphatic, alicyclic or arylaliphatic radicals or hydroxyalkylaliphatic radicals wherein the alkyl radical is C C₄, or alternatively R₁₀, Rn , R₁₂ and R₁₃, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second heteroatom other than nitrogen, or alternatively R₁0, Rn , R₁₂ and R13 represent a linear or branched CrC₆ alkyl radical substituted with a nitrile, ester, acyl or amide group or a group -CO-0-Ri₄-D or -CO-NH-Ri₄-D wherein Ri₄ is an alkylene and D is a quaternary ammonium group;

i and Bi represent C₂-C₆ polymethylene groups which are linear or branched, saturated or unsaturated, and which optionally contain, linked to or intercalated in the main chain, at least one aromatic ring or at least one atom chosen from oxygen and sulfur atom or at least one group chosen from sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide and ester groups, and

X^" denotes an anion derived from a mineral or organic acid;

Ai , R₁0 and R₁₂ can form, with the two nitrogen atoms to which they are attached, a piperazine ring;

and wherein, if Ai denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, i can also denote a group -(CH₂), -CO-D-OC-(CH₂)_n- wherein n is a number ranging from 1 to 6, and D is chosen from:

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-CH2-0)x-CH2-CH₂-; or -[CH₂-CH(CH3)-0]_y-CH2-CH(CH₃)-, where x and y denote an integer ranging from 1 to 4, representing a defined and unique degree of polymerization or any number ranging 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-, wherein Y denotes a linear or branched hydrocarbon-based radical, or alternatively the radical -CH₂-CH₂-S-S-

CHz-CH-; and

d) an ureylene group of formula: -NH-CO-NH-.

In at least one embodiment, X^" is an anion such as chloride or bromide.

These polymers, for example, have a number-average molecular mass ranging from 1000 to 100,000.

In some embodiments, polymers are used that consist of repeating units corresponding to formula (XII):

! !

— >r-(C¾)„—†^-(CH₂)^—

Ri i - Ri3 X-

(XII)

wherein R₁₀, Rn , R₁₂ and R13, which may be identical or different, denote a CrC₄ alkyl or hydroxyalkyi radical, n and p are integers ranging from 2 to 6, and X is an anion derived from a mineral or organic acid.

In at least one embodiment, the at least one cationic polymer corresponding to this family comprise repeating units of formulae (W) and (U):

(W)

for example those whose molecular weight, determined by gel permeation chromatography, ranges from 9,500 to 9,900; I Br^" J Br^"

C¾ C¾

(U)

for instance those whose molecular weight, determined by gel permeation chromatography, is 1200.

(9) polyquaternary ammonium polymers consisting of repeating units of formula (XIII): χ- c¾

(CH^— H— CO— D— H— (C¾¾,—N*-(C¾)₂-- 0— (C¾)₂

CH,

(XIII) wherein p denotes an integer ranging from 1 to 6, D may be zero or may represent a group -(CH₂)_r-00- wherein r denotes a number ranging from 1 to 6, and X^" is an anion.

Among these polymers, examples that may be mentioned include the products MIRAPOL A 15, MIRAPOL AD1 , MIRAPOL AZ1 and MIRAPOL 175 sold by the company Miranol.

(10) quaternary polymers of vinylpyrrolidone and of vinylimidazole, for instance the products sold under the names LUVIQUAT FC 905, FC 550 and FC 370 by the company

BASF.

(11) vinylamide homopolymers or copolymers, such as partially hydrolysed vinylamide homopolymers such as poly(vinylamine/vinylamide)s.

(12) cationic polyurethane derivatives, for example those of elastic nature formed from the reaction:

(a1 ) of at least one cationic unit resulting from at least one tertiary or quaternary amine bearing at least two reactive functions containing labile hydrogen,

(a2) of at least one mixture of at least two different nonionic units bearing at least two reactive functions containing labile hydrogen, for instance chosen from hydroxyl groups, primary or secondary amine groups, and thiol groups, and (b) of at least one compound comprising at least two isocyanate functions.

(13) Other cationic polymers that may be used in the context of the disclosure include, for example, cationic proteins or cationic protein hydrolysates, polyalkyleneimines, such as polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, and chitin derivatives.

Particularly useful cationic polymers in the present disclosure include, but are not limited to, polyquaternium 4, polyquaternium 6, polyquaternium 7, polyquaternium 10, polyquaternium 1 1 , polyquaternium 16, polyquaternium 22, polyquaternium 28, polyquaternium 32, polyquaternium-46, polyquaternium-51 , polyquaternium-52, polyquaternium-53, polyquaternium-54, polyquaternium-55, polyquaternium-56, polyquaternium-57, polyquaternium-58, polyquaternium-59, polyquaternium-60, polyquaternium-63, polyquaternium-64, polyquaternium-65, polyquaternium-66, polyquaternium-67, polyquaternium-70, polyquaternium-73, polyquaternium-74, polyquaternium-75, polyquaternium-76, polyquaternium-77, polyquaternium-78, polyquaternium-79, polyquaternium-80, polyquaternium-81 , polyquaternium-82, polyquaternium-84, polyquaternium-85, polyquaternium-86, polyquaternium-87, polyquaternium-90, polyquaternium-91 , polyquaternium-92, polyquaternium-94, and guar hydroxypropyltrimonium chloride.

Particularly preferred cationic polymers of the present disclosure include POLYMER JR-125, POLYMER JR-400, Polymer JR-30M hydroxyethyl cellulosic polymers (polyquaternium 10) available from AMERCHOL; JAGUAR C.RTM. 13-S, guar hydroxypropyltrimonium chloride, available from Rhodia; and MERQUAT.RTM. 100 and 280, a dimethyl dialkyl ammonium chloride (polyquaternium 6) available from Nalco.

Cationic polymers include polyquaternium 4, polyquaternium 6, polyquaternium 7, polyquaternium 10, polyquaternium 1 1 , polyquaternium 16, polyquaternium 22, polyquaternium 32, polyquaternium-53, polyquaternium-67, and guar hydroxypropyltrimonium chloride. Preferred cationic polymers include polyquaternium-10 (Sensomer™ 10M (Lubrizol Co.)), polyquaternium-1 1 (Luviquat® PQ 1 1 (BASF)), polyquaternium-22 (Merquat™ 280 Series (Lubrizol Co.)), polyquaternium-34, polyquaternium-53 (Merquat™ 2003PR Polymer (Lubrizol Co.)), polyquaternium-67 (SoftCAT™ (Dow Corning)), and mixtures thereof.

NONIONIC SURFACTANTS Nonionic surfactants are compounds well known in themselves {see, e.g., in this regard, "Handbook of Surfactants" by M. R. Porter, Blackie & Son publishers (Glasgow and London), 1991 , pp. 1 16-178), which is incorporated herein by reference in its entirety.

The nonionic surfactant can be, for example, selected from alcohols, alpha- diols, alkylphenols and esters of fatty acids, these compounds being ethoxylated, propoxylated or glycerolated and having at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, it being possible for the number of ethylene oxide or propylene oxide groups to range from 2 to 50, and for the number of glycerol groups to range from 1 to 30. Maltose derivatives may also be mentioned. Non-limiting mention may also be made of copolymers of ethylene oxide and/or of propylene oxide; condensates of ethylene oxide and/or of propylene oxide with fatty alcohols; polyethoxylated fatty amides comprising, for example, from 2 to 30 mol of ethylene oxide; polyglycerolated fatty amides comprising, for example, from 1 .5 to 5 glycerol groups, such as from 1 .5 to 4; ethoxylated fatty acid esters of sorbitan comprising from 2 to 30 mol of ethylene oxide; ethoxylated oils from plant origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; polyethoxylated fatty acid mono or diesters of glycerol (C₆-C₂4)alkylpolyglycosides; N-(C₆- C₂₄)alkylglucamine derivatives, amine oxides such as (C₁₀-C₁₄)alkylamine oxides or N- (Cio-Ci₄)acylaminopropylmorpholine oxides; and mixtures thereof.

The nonionic surfactants may preferably be chosen from polyoxyalkylenated or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, and are preferably oxyethylene units.

Examples of oxyalkylenated nonionic surfactants that may be mentioned include: [01 15] oxyalkylenated (C₈-C₂₄)alkylphenols, saturated or unsaturated, linear or branched, oxyalkylenated C₈-C₃₀ alcohols, saturated or unsaturated, linear or branched, oxyalkylenated C₈-C₃o amides, esters of saturated or unsaturated, linear or branched, C₈- C₃₀ acids and of polyethylene glycols, polyoxyalkylenated esters of saturated or unsaturated, linear or branched, C₈-C₃o acids and of sorbitol, saturated or unsaturated, oxyalkylenated plant oils, condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures. The surfactants preferably contain a number of moles of ethylene oxide and/or of propylene oxide of between 2 and 100 and most preferably between 2 and 50. Advantageously, the nonionic surfactants do not comprise any oxypropylene units.

In accordance with one preferred embodiment of the disclosure, the oxyalkylenated nonionic surfactants are chosen from oxyethylenated C.sub.8-C.sub.30 alcohols.

Examples of ethoxylated fatty alcohols (or C₈-C₃o alcohols) that may be mentioned include the adducts of ethylene oxide with lauryl alcohol, especially those containing from 9 to 50 oxyethylene groups and more particularly those containing from 10 to 12 oxyethylene groups (Laureth-10 to Laureth-12, as the CTFA names); the adducts of ethylene oxide with behenyl alcohol, especially those containing from 9 to 50 oxyethylene groups (Beheneth-9 to Beheneth-50, as the CTFA names); the adducts of ethylene oxide with cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol), especially those containing from 10 to 30 oxyethylene groups (Ceteareth-10 to Ceteareth-30, as the CTFA names); the adducts of ethylene oxide with cetyl alcohol, especially those containing from 10 to 30 oxyethylene groups (Ceteth-10 to Ceteth-30, as the CTFA names); the adducts of ethylene oxide with stearyl alcohol, especially those containing from 10 to 30 oxyethylene groups (Steareth-10 to Steareth-30, as the CTFA names); the adducts of ethylene oxide with isostearyl alcohol, especially those containing from 10 to 50 oxyethylene groups (lsosteareth-10 to lsosteareth-50, as the CTFA names); and mixtures thereof.

As examples of polyglycerolated nonionic surfactants, polyglycerolated C₈- C₄₀ alcohols are preferably used.

In particular, the polyglycerolated C.sub.8-C.sub.40 alcohols correspond to the following formula:

RO-[CH₂-CH(CH₂OH)-0]_m-H or RO-[CH(CH₂OH)-CH₂0]_m-H in which R represents a linear or branched C₈-C₄₀ and preferably C₈-C₃o alkyl or alkenyl radical, and m represents a number ranging from 1 to 30 and preferably from 1 .5 to 10.

As examples of compounds that are suitable in the context of the disclosure, mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1 .5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.

The alcohol may represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohol may coexist in the form of a mixture.

According to one of the embodiments according to the present disclosure, the nonionic surfactant may be selected from esters of polyols with fatty acids with a saturated or unsaturated chain containing for example from 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms, and alkoxylated derivatives thereof, preferably with a number of alkyleneoxide of from 10 to 200, and more preferably from 10 to 100, such as glyceryl esters of a C₈-C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and alkoxylated derivatives thereof, preferably with a number of alkyleneoxide of from 10 to 200, and more preferably from 10 to 100; polyethylene glycol esters of a C₈-C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and alkoxylated derivatives thereof, preferably with a number of alkyleneoxide of from 10 to 200, and more preferably from 10 to 100; sorbitol esters of a C₈-C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and alkoxylated derivatives thereof, preferably with a number of alkyleneoxide of from 10 to 200, and more preferably from 10 to 100; sugar (sucrose, glucose, alkylglycose) esters of a C₈-C₂₄, preferably Ci₂-C₂₂, fatty acid or acids and alkoxylated derivatives thereof, preferably with a number of alkyleneoxide of from 10 to 200, and more preferably from 10 to 100; ethers of fatty alcohols; ethers of sugar and a C₈-C₂₄, preferably C₁₂-C₂₂, fatty alcohol or alcohols; and mixtures thereof.

Examples of ethoxylated fatty esters that may be mentioned include the adducts of ethylene oxide with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, especially those containing from 9 to 100 oxyethylene groups, such as PEG-9 to PEG-50 laurate (as the CTFA names: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (as the CTFA names: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (as the CTFA names: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate (as the CTFA names: PEG-9 behenate to PEG-50 behenate); polyethylene glycol 100 EO monostearate (CTFA name: PEG-100 stearate); and mixtures thereof. As glyceryl esters of fatty acids, glyceryl stearate (glyceryl mono-, di- and/or tristearate) (CTFA name: glyceryl stearate) or glyceryl ricinoleate and mixtures thereof can in particular be cited.

As glyceryl esters of C₈-C₂₄ alkoxylated fatty acids, polyethoxylated glyceryl stearate (glyceryl mono-, di- and/or tristearate) such as PEG-20 glyceryl stearate can for example be cited.

Mixtures of these surfactants, such as for example the product containing glyceryl stearate and PEG-100 stearate, marketed under the name ARLACEL 165 by Uniqema, and the product containing glyceryl stearate (glyceryl mono- and distearate) and potassium stearate marketed under the name TEG1 N by Goldschmidt (CTFA name: glyceryl stearate SE), can also be used.

The sorbitol esters of C₈-C₂₄ fatty acids and alkoxylated derivatives thereof can be selected from sorbitan palmitate, sorbitan trioleate and esters of fatty acids and alkoxylated sorbitan containing for example from 20 to 100 EO, such as for example polyethylene sorbitan trioleate (polysorbate 85) or the compounds marketed under the trade names Tween 20 or Tween 60 by Ubiqema.

As esters of fatty acids and glucose or alkylglucose, in particular glucose palmitate, alkylglucose sesquistearates such as methylglucose sesquistearate, alkylglucose palmitates such as methylglucose or ethylglucose palmitate, methylglucoside fatty esters and more specifically the diester of methylglucoside and oleic acid (CTFA name: Methyl glucose dioleate), the mixed ester of methylglucoside and the mixture oleic acid/hydroxystearic acid (CTFA name: Methyl glucose dioleate/hydroxystearate), the ester of methylglucoside and isostearic acid (CTFA name: Methyl glucose isostearate), the ester of methylglucoside and lauric acid (CTFA name: Methyl glucose laurate), the mixture of monoester and diester of methylglucoside and isostearic acid (CTFA name: Methyl glucose sesqui-isostearate), the mixture of monoester and diester of methylglucoside and stearic acid (CTFA name: Methyl glucose sesquistearate) and in particular the product marketed under the name Glucate SS by AMERCHOL, and mixtures thereof can be cited.

As ethoxylated ethers of fatty acids and glucose or alkylglucose, ethoxylated ethers of fatty acids and methylglucose, and in particular the polyethylene glycol ether of the diester of methylglucose and stearic acid with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose distearate) such as the product marketed under the name Glucam E-20 distearate by AMERCHOL, the polyethylene glycol ether of the mixture of monoester and diester of methyl-glucose and stearic acid with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose sesquistearate) and in particular the product marketed under the name Glucamate SSE-20 by AMERCHOL and that marketed under the name Grillocose PSE-20 by GOLDSCHMIDT, and mixtures thereof, can for example be cited.

As sucrose esters, saccharose palmito-stearate, saccharose stearate and saccharose monolaurate can for example be cited.

As sugar ethers, alkylpolyglucosides can be used, and for example decylglucoside such as the product marketed under the name MYDOL 10 by Kao Chemicals, the product marketed under the name PLANTAREN 2000 by Henkel, and the product marketed under the name ORAMIX NS 10 by Seppic, caprylyl/capryl glucoside such as the product marketed under the name ORAMIX CG 1 10 by Seppic or under the name LUTENSOL GD 70 by BASF, laurylglucoside such as the products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucoside such as the product marketed under the name PLANTACARE 818/UP by Henkel, cetostearyl glucoside possibly mixed with cetostearyl alcohol, marketed for example under the name MONTANOV 68 by Seppic, under the name TEGO-CARE CG90 by Goldschmidt and under the name EMULGADE KE3302 by Henkel, arachidyl glucoside, for example in the form of the mixture of arachidyl and behenyl alcohols and arachidyl glucoside marketed under the name MONTANOV 202 by Seppic, cocoylethylglucoside, for example in the form of the mixture (35/65) with cetyl and stearyl alcohols, marketed under the name MONTANOV 82 by Seppic, and mixtures thereof can in particular be cited.

Mixtures of glycerides of alkoxylated plant oils such as mixtures of ethoxylated (200 EO) palm and copra (7 EO) glycerides can also be cited.

It is preferable that the nonionic surfactant be selected from the group consisting of PEG-7 glyceryl cocoate, PEG-20 methylglucoside sesquistearate, PEG-20 glyceryl tri-isostearate, PG-5 dioleate, PG-4 diisostearate, PG-10 isostearate, PEG-8 isostearate, and PEG-60 hydrogenated castor oil.

Mixtures of these oxyethylenated derivatives of fatty alcohols and of fatty esters may also be used. Preferably, the nonionic surfactant may be a nonionic surfactant with an HLB of 18.0 or less, such as from 4.0 to 18.0, more preferably from 6.0 to 15.0 and furthermore preferably from 9.0 to 13.0. The HLB is the ratio between the hydrophilic part and the lipophilic part in the molecule. This term HLB is well known to those skilled in the art and is described in "The HLB system. A time-saving guide to emulsifier selection" (published by ICI Americas Inc., 1984).

OILS

The hair care composition may include one or more oils, for example, silicone oils, fluoro oils, hydrocarbon-based oils, etc. The term "oil" means any fatty substance which is in liquid form at room temperature (20-25°C.) and at atmospheric pressure (760 mmHg). Often, at least one of the oils in the cosmetic composition is part of an oily phase. An "oily phase" is a phase comprising at least one oil that may include additional liposoluble and lipophilic ingredients and the fatty substances. The oily phase can be combined with an aqueous phase in an emulsion. Oil that is suitable for use herein may be volatile or non-volatile. The term "volatile oil" relates to oil that is capable of evaporating on contact with the skin or a keratin fiber in less than one hour, at room temperature and atmospheric pressure. The volatile oil(s) are liquid at room temperature and have a non-zero vapor pressure, at room temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40 000 Pa (10^~3 to 300 mmHg). The term "non- volatile oil" relates to oil which remains on the skin or the keratin fiber, at room temperature and atmospheric pressure, for at least several hours and which in particular has a vapor pressure of less than 10^"3 mmHg (0.13 Pa).

The term "silicone oil" relates to oil comprising at least one silicon atom, and especially at least one Si-O group. The term "fluoro oil" relates to oil comprising at least one fluorine atom. The term "hydrocarbon-based oil" relates to oil comprising mainly hydrogen and carbon atoms. Hydrocarbon-based oil may be animal hydrocarbon-based oil, plant hydrocarbon-based oil, mineral hydrocarbon-based oil or a synthetic hydrocarbon- based oil. Further, suitable oil may be a mineral hydrocarbon-based oil, a plant hydrocarbon-based oil, or a synthetic hydrocarbon-based oil.

SILICONE OILS

The cosmetic compositions described herein may comprise one or more silicone oils. Non-limiting examples of silicone oils include dimethicone, cyclomethicone, polysilicone-1 1 , phenyl trimethicone, trimethylsilylamodimethicone, and stearoxytrimethylsilane. In some cases, the cosmetic composition includes dimethicone, and optionally additional oils, including additional silicone oils. Typically, the one or more silicone oils is a non-volatile silicon oil. In some embodiments, the silicone oil is polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups which are pendent and/or at the end of the silicone chain, which groups each contain from 2 to 24 carbon atoms, or phenyl silicones, such as phenyl trimethicones, phenyl dimethicones, phenyl(trimethylsiloxy)diphenylsiloxanes, diphenyl dimethicones, diphenyl(methyldiphenyl)trisiloxanes or (2-phenylethyl)trimethylsiloxysilicates.

Other examples of silicone oils that may be mentioned include volatile linear or cyclic silicone oils, especially those with a viscosity 8 centistokes (8x10⁶ m²/s) and especially containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the disclosure, mention may be made especially of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.

FLUORO OILS

The cosmetic compositions described herein may comprise one or more fluoro oils. For example, the onee or more fluoro oil may be selected from the group consisting of perfluoromethylcyclopentane, perfluoro-1 ,3-dimethylcyclohexane, dodecafluoropentane, tetradecafluorohexane, bromoperfluorooctyl, nonafluoromethoxybutane, nonafluoroethoxyisobutane and 4- trifluoromethylperfluoromorpholine. Volatile fluoro oils, such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, may also be used.

HYDROCARBON-BASED OILS

The cosmetic compositions described herein may comprise one or more hydrocarbon-based oils. For example, the hydrocarbon-based oil may be a saturated hydrocarbon, an unsaturated hydrocarbon, lipids, triglycerides, a natural oil, and/or a synthetic oil. In some embodiments, the compositions include a synthetic oil selected from the group consisting of hydrogenated polyisobutene and hydrogenated polydecene. The hydrocarbon-based oil may be a non-volatile hydrocarbon-based, such as:

(i) hydrocarbon-based oils of plant origin, such as glyceride triesters, which are generally triesters of fatty acids and of glycerol, the fatty acids of which can have varied chain lengths from C₄ to C₂₄, it being possible for these chains to be saturated or unsaturated and linear or branched; these oils are in particular wheat germ oil, sunflower oil, grape seed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin seed oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil, and musk rose oil.

(ii) synthetic ethers containing from 10 to 40 carbon atoms;

(iii) linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam, and 4 0 squalane;

(iv) synthetic esters, for instance oils of formula RCOOR' in which R represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R' represents a hydrocarbon-based chain that is especially branched, containing from 1 to 40 carbon atoms on condition that R+R' is ^ 10, for instance Purcellin oil (cetearyl octanoate), isopropyl myristate, isopropyl palmitate, C₁₂-C₁₅ alkyl benzoate, such as the product sold under the trade name Finsolv TN® or Witconol TN® by Witco or Tegosoft TN® by Evonik Goldschmidt, 2-ethylphenyl benzoate, such as the commercial product sold under the name X-Tend 226 by ISP, isopropyl lanolate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethylhexyl palmitate, isostearyl isostearate, diisopropyl sebacate, such as the product sold under the name of "Dub Dis" by Stearinerie Dubois, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, such as propylene glycol dioctanoate; hydroxylated esters, such as isostearyl lactate or diisostearyl malate; and pentaerythritol esters; citrates or tartrates, such as di(linear C₁₂-C₁₃ alkyl) tartrates, such as those sold under the name Cosmacol ETI® by Enichem Augusta Industriale, and also di(linear Ci₄-Ci₅ alkyl) tartrates, such as those sold under the name Cosmacol ETL® by the same company; or acetates; (v) fatty alcohols that are liquid at room temperature, containing a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol or 2-undecylpentadecanol;

(vi) higher fatty acids, such as oleic acid, linoleic acid or linolenic acid;

(vii) carbonates, such as dicaprylyl carbonate, such as the product sold under the name Cetiol CC® by Cognis;

(viii) fatty amides, such as isopropyl N-lauroyl sarcosinate, such as the product sold under the trade name Eldew SL 205® from Ajinomoto; and

(ix) essential oils selected from the group consisting of sunflower oil, sesame oil, peppermint oil, macadamia nut oil, tea tree oil, evening primrose oil, sage oil, rosemary oil, coriander oil, thyme oil, pimento berries oil, rose oil, anise oil, balsam oil, bergamot oil, rosewood oil, cedar oil, chamomile oil, sage oil, clary sage oil, clove oil, cypress oil, eucalyptus oil, fennel oil, sea fennel oil, frankincense oil, geranium oil, ginger oil, grapefruit oil, jasmine oil, juniper oil, lavender oil, lemon oil, lemongrass oil, lime oil, mandarin oil, marjoram oil, myrrh oil, neroli oil, orange oil, patchouli oil, pepper oil, black pepper oil, petitgrain oil, pine oil, rose otto oil, rosemary oil, sandalwood oil, spearmint oil, spikenard oil, vetiver oil, wintergreen oil, and ylang ylang .

In certain instances, the non-volatile hydrocarbon-based oils are glyceride triesters and in particular to caprylic/capric acid triglycerides, synthetic esters and in particular isononyl isononanoate, oleyl erucate, C12-C15 alkyl benzoate, 2-ethylphenyl benzoate and fatty alcohols, such as octyldodecanol.

As volatile hydrocarbon-based oils, mention is made of hydrocarbon-based oils containing from 8 to 16 carbon atoms and in particular of branched C₈-C₁₆ alkanes, such as C₈-C₁₆ isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane or isohexadecane, the oils sold under the Isopar or Permethyl trade names, branched C C₈-Ci₆ esters, and isohexyl neopentanoate.

Implementation of the present disclosure is provided by way of the following examples. The examples serve to illustrate the technology without being limiting in nature.

Example 1

(Procedure for Determination of Physical Properties of Latex Films) The latex film is obtained by allowing a 30 gram water solution containing 4 grams of the latex polymer(s) to dry slowly in a 100 mL PFA Petri dish (100 mm diameter x 15 mm height) at room temperature for at least 3 days. The latex film, with known dimensions (length, width, thickness), was mounted on the Q800 Dynamic Mechanical Analysis from TA Instrument, and tested in a DMA Control Force mode. The stress/strain test was obtained using the following procedure:

Preload force: 0.001 N

Isothermal: 25°C

Soak time: 0.5 minutes

Force ramp rate: 0.5N/min to 18 N

The test ended when the sample broke, 18 N force was reached, or maximum displacement was achieved (25.5 mm).

From the stress/strain curve, the Young's Modulus was calculated as the slope of the linear portion at about 0.01 % Strain to about 1 % Strain. From the stress/strain curve, the % Strain at the stress of 0.5 MPa was also reported.

A high Young's Modulus demonstrates a hard film, while a lower Young's Modulus represents a more elastic film. A high Strain demonstrates a stretchy, elastic film, while a lower Strain represents a more brittle film.

Acrylates copolymer, commercially available from BASF in an aqueous dispersion under the trade name of LUVIFLEX SOFT = Young's Modulus of 2758 MPa and strain, under stress at 0.5 MPa, of <0.01 %.

Polyurethane-34, commercially available from BAYER in an aqueous dispersion under the trade name of BAYCUSAN C1001 = Young's Modulus of 3 MPa and strain, under stress at 0.5 MPa, of 18.82%.

Example 2

(Formulations)

Formulations

Formulation (INCI US) A B C D E

(a) Acrylates Copolymer 0.5 0.5 0.5 0.5 0.5

(b) Polyurethane-34 0.5 0.5 0.5 0.5 0.5

(c) Bis-Cetearyl Ainodimethicone 0.5 0.5 0.5 0.5 0.5 Formulations

Formulation (INCI US) A B C D E

(d) Polyquaternium-67 - 0.2 - - -

(d) Polyquaternium -53 - - 0.3 - -

(d) Polyquaternium -7 - - - - 0.1

(d) Polyquaternium -1 1 - - - 0.1 -

(d) Polyquaternium -22 0.4 - - - -

(d) Polyquaternium -1 0 - - - - 0.1

<e) Glyceryl Stearate 0.2 0.2 0.2 0.2 0.2

(e) PEG- 1 00 Stearate 0.2 0.2 0.2 0.2 0.2

(e) Steareth-20 1 1 1 1 1

(e) Cetearyl Alcohol 5 5 5 5 5

(e) Polysorbate 80 0.04 0.04 0.04 0.04 0.04

(f) Mineral Oil 1 1 1 1 1

Preservative, pH Adjusters, and Moisturizers ~ 1 ~1 ~1 ~1 ~1

Water QS QS QS QS QS

1 00 1 00 1 00 1 00 1 00

provided as a raw material in combination with dimethicone and commercially available under tradename KF-8020 from Shin Etsu (20% active material "AM" of amodimethicone)

provided as a raw material in combination with Trideceth-5 (and Trideceth-10 and commercially available under the tradename BELSIL ADM LOG 1 from Wacker

provided as a raw material in combination with Trideceth-10 under the tradename BELSIL ADM 6300E from Wacker

provided as a raw material in combination with Trideceth-5 and glycerin under the tradename BELSIL ADM 8301 E (SLM 28122), from Wacker

Comparative Comparative

Commercial/Traditional Formulation #1 Commercial/Traditional Formulation #2

Water Glycerin

Cetearyl Alcohol Cetrimonium Chloride

Stearamidopropyl Dimethylamine Cetearyl Alcohol

Dimethicone Perfume

Glycerin Petroleum

Lactic Acid Citric Acid

Perfume Methylparaben

Methylpareben Propylparaben

Petroleum Hexyl Cinnamal

DMDM Hydantoin Limonene

Disodium EDTA Benzyl Salicylate

Cyclopentasiloxane Butylphenyl methylpropional

Trimethylxiloxysilicate Citronellol

Ethylhexyl Methoxycinnamate Alpha-lsomethyl lonone

Methoxypolyoxymethylene Melamine Amyl Cinnamal

Arginine Coumarin

Hydroxyisohexl 3-3 Cyclohexene

Hydrolyzed Elastin

Carboxyaldelyde

Butylphenylmethylpropional Water

Citronellol

Hexyl Cinnamal

Limonene

Linalool

Example 3

(Curl Retention Test)

Hair swatches were treated with a cleansing shampoo and then combed with a wide-tooth comb in the direction of hair root to hair end to remove any knots that may be present. The hair swatches were then combed with a fine-tooth in the same direction. After combing, the damp hair swatches were placed on a dry surface and a test composition (0.15g/g of hair) was homogeneously applied with a brush. An elastic band was used to fasten the swatches on one end of a hair roller and the hair was wound in contiguous spirals without overlap and then fastened to the other end of the hair roller. The rolled swatches were then dried under a dryer at 60°C for 20 minutes. Once dried, the hair swatches were removed from the rollers and suspended on a hook contained on a structural support (a retention framework). The length of the hair swatches were then ascertained using graph paper, which was positioned behind the hair swatches on the support stand. A timer was immediately started and the length of the hair swatches were subsequently measured at predetermined time points. The percentage of curl retention was calculated as follows:

Percent (%) curl retention = (L - Lt) / (L- Lt=0)^*100

or

Percent (%) curl retention = (Lt - Lt=0)/ (Lt=0)^* 100

L: the total hair length;

Lt: the length (in inch or cm) of the swatch at time t; and

Lt=0: the initial curl length (in inch or cm).

Example 4

(Frizz and Volume Control Test)

The frizz and volume control test is used to evaluate a product's ability to control frizz and hair volume over time when exposed to external humidity. After finishing the Curl Retention Test outlined above (Example 3), two fingers were passed through the hair from root to tip to separate the hairs. A timer was immediately started. After a predetermined amount of time, the degree of frizz and volume was measured using standardized grading systems. Frizz reduction was graded from 1 to 4, with 4 being the least frizzy or smallest amount of frizz. Volume reduction was graded from 1 to 4, with 4 being the least area of space occupied by a wavy swatch of hair and corresponding to greatest volume reduction.

Example 5

(Experimental Results)

A Curl Retention Test and a Frizz and Volume Control Test, as outlined above in Examples 3 and 4, were carried out on hair swatches subjected to shampooing using a conventional shampoo (untreated), on hair swatches treated with three different commercial/traditional compositions, on hair swatches treated with formulations comprising components (a) and (b) (Formulation M), and on hair swatches treated with formulations comprising components (a), (b), and (c) (Formulations F-L). The results are provided in the table below (on the following page).

significantly improves the curl retention, resistance to humidity, and frizz control. The addition of a silicone amine (component (c)) contributed to improvement in frizz (less frizz) and more volume control without interfering with the improved curl retention properties.

Example 6

(Experimental Results) A Curl Retention Test and a Frizz and Volume Control Test, as outlined above in Examples 3 and 4, were carried out on hair swatches subjected to shampooing with a conventional shampoo (untreated), on hair swatches treated with a composition comprising component (a), (b), and (c) (Formulation H), and on hair swatches treated with the formulation comprising components (a), (b), (c), and (d) (Formulations A-E). The results are provided in the table below.

The data shows that the addition of a cationic polymer improves the frizz

(less frizz) and volume control in comparison to the negative control (shampoo) and Formula H, which does not contain a cationic polymer (component (d)) but includes the latex polymers of (a) and (b) and an amino silicone of (c).

In summary, the data presented in the tables above illustrates that the latex polymers (component (a) and (b)) significantly improve curl retention and the amino silicones (component (c)) and cationic polymers (component (d)) significantly improve frizz and volume control. Thus, the combination of these components results in inventive compositions that exhibit surprising curl retention, frizz control, and volume control and are therefore useful for maintaining the shape and/or curl of hair, for achieving long-lasting frizz control, and for providing durable styling and volume hold to hair.

As used herein, the terms "comprising," "having," and "including" are used in their open, non-limiting sense.

The terms "a," "an," and "the" are understood to encompass the plural as well as the singular.

The expression "at least one" means one or more and thus includes individual components as well as mixtures/combinations.

All ranges and values disclosed herein are inclusive and combinable. For examples, any value or point described herein that falls within a range described herein can serve as a minimum or maximum value to derive a sub-range, etc.

All publications and patent applications cited in this specification are herein incorporated by reference, and for any and all purposes, as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. In the event of an inconsistency between the present disclosure and any publications or patent application incorporated herein by reference, the present disclosure controls.

Claims

SET OF CLAIMS

1 . A hair care composition comprising, in a cosmetically acceptable carrier:

(a) a latex polymer having a Young's modulus ranging from about 0.1 MPa to about 10 MPa and a strain, under stress at 0.5 MPa, of at least about 1 %;

(b) a latex polymer having a Young's modulus ranging from about 10 MPa to about 6 GPa and a strain, under stress at 0.5 MPa, of less than about 5%;

(c) an amino silicone;

(d) optionally, a cationic polymer; and

(e) a nonionic surfactant.

2. The hair care composition of claim 1 , wherein the weight ratio of the latex polymer of (a) to the latex polymers of (b) is 1 :5 to 5:1 .

3. The hair care composition of claims 1 or 2, wherein the latex polymer of (a) and/or the latex polymer of (b) are particles dispersed in the hair care compositions.

4. The hair care composition of any one of the above claims, wherein the latex polymer of (a) is an acrylate latex polymer.

5. The hair care composition of claim 4, wherein the acrylate latex polymer is selected from the group consisting of an ammonium acrylate copolymer, an acrylates copolymer, a (meth)acrylate copolymer, a butyl acrylate/hydroxypropyl dimethicone acrylate copolymer, an acrylates/Ci 2-C₂2 alkylmethacrylate copolymer, acrylates copolymer in combination or dispersed in isododecane, an acrylates/octylacrylamide copolymer, and combinations thereof.

6. The hair care composition of claim 5, wherein the acrylate latex polymer is acrylates copolymer.

7. The hair care composition of any one of the above claims, wherein the latex polymer of (a) is present in an amount of about 0.01 to about 10 wt.%, based on the total weight of the hair care composition.

8. The hair care composition of any one of the above claims, wherein the latex polymer of (b) is a polyurethane latex polymer.

9. The hair care composition of claim 8, wherein the polyurethane latex polymer is selected from the group consisting of polyurethane-32, polyurethane-34, polyurethane-35, and combinations thereof.

10. The hair care composition of claim 9, wherein the polyurethane latex polymer is polyurethane-34.

1 1 . The hair care composition of any one of the above claims, wherein the latex polymer of (b) is present in an amount of about 0.01 to about 10 wt.%, based on the total weight of the hair care composition.

12. The hair care composition of any one of the above claims, wherein the (c) amino silicone is selected from the group consisting of a polyether amino silicone, amodimethicone, a modified amodimethicone bis-cetearyl amodimethicone and bis-hydroxy/methoxy amodimethicone), an amino gum silicone, and combinations thereof.

13. The hair care composition of claim 12, wherein the amino silicone of (c) is selected from the group consisting of amodimethicone, bis-cetearyl amodimethicone, amodimethicone/morpholinomethyl silsesquioxane copolymer, PEG- 40/PPG-8 methylaminopropyl/hydroxypropyl dimethicone copolymer, bisamino PEG/PPG-41/3 aminoethyl PG-propyl dimethicone, and combinations thereof.

14. The hair care composition of any one of the above claims, wherein the amino silicone of (c) is a quaternized polysiloxane selected from the group consisting of silicone quaternium 22, silicone quaternium 12, amodimethicone, bis- cetearyl amodimethicone, bis-amino PEG/PPG-41/3 aminoethyl PG-propyl dimethicone, PEG-40/PPG-8 methylaminopropyl hydroxypropyl dimethicone copolymer, silicone quaternium 16 (and) undeceth-1 1 (and) butyloctanol (and) undeceth-5, bis- isobutyl/PEG/PPG-20/35/amodimethicone copolymer, and combinations thereof.

15. The hair care composition of any one of the above claims 1 , wherein the amino silicone of (c) is present in an amount of about 0.01 to about 10 wt.%, based on the total weight of the hair care composition.

16. The hair care composition of any one of the above claims comprising the cationic polymer of (d), wherein the cationic polymer of (d) is a polyquaternium.

17. The hair care composition of claim 16, wherein the polyquaternium is selected from the group consisting of polyquaternium-10, polyquaternium-1 1 , polyquaternium-22, polyquaternium-34, polyquaternium-53, polyquaternium-67, and combinations thereof.

18. The hair care composition of claim 16, wherein the cationic polymer of (d) is present in an amount of about 0.01 to about 10 wt.%, based on the total weight of the hair care composition.

19. The hair care composition of any one of the above claims, wherein the nonionic surfactant of (e) is selected from a polyol ester, a glycerol ether, an oxyethylenated ether, an oxypropylenated ether, an ethylene glycol polymer, and combinations thereof.

20. The hair care composition of claim 19, wherein the nonionic surfactant of (e) comprises a combination of a polyol ester and an ethylene glycol polymer.

21 . The hair care composition of claim 20, wherein the nonionic surfactant of (e) comprises a combination of glyceryl stearate, PEG-100 stearate, and steareth-20.

22. The hair care composition of any one of the above claims, wherein the nonionic surfactant of (e) is present in an amount of about 0.01 to about 20 wt.%, based on the total weight of the hair care composition.

23. The hair care composition of any one of the above claims in the form of an emulsion.

25. A hair care composition comprising:

(a) about 0.01 to about 10 wt.% of an acrylate latex polymer;

(b) about 0.01 to about 10 wt.% of a polyurethane latex polymer;

(c) about 0.01 to about 10 wt.% of an amino silicone;

(d) optionally, a cationic polymer; and

(e) a nonionic surfactants.

26. The hair care composition of claim 25, wherein the weight ratio of the acrylate latex polymer of (a) to the polyurethane latex polymers of (b) is 1 :5 to 5:1 .

27. The hair care composition of claim 25 or 26, wherein the acrylate latex polymer of (a) and/or the polyurethane latex polymer of (b) are particles dispersed in the hair care compositions.

28. The hair care composition of any one of claims 25-27, wherein the acrylate latex polymer is selected from the group consisting of an ammonium acrylate copolymer, an acrylates copolymer, a (meth)acrylate copolymer, a butyl acrylate/hydroxypropyl dimethicone acrylate copolymer, an acrylates/Ci 2-C₂2 alkylmethacrylate copolymer, an acrylates copolymer in combination (or dispersed) in isododecane, an acrylates/octylacrylamide copolymer, and combinations thereof.

29. The hair care composition of claim 28, wherein the acrylate latex polymer is acrylates copolymer.

30. The hair care composition of any one of claims 25-29, wherein the acrylate latex polymer of (a) is present in an amount of about 0.01 to about 10 wt.%, based on the total weight of the hair care composition.

31 . The hair care composition of any one of claims 25-30, wherein the polyurethane latex polymer is selected from the group consisting of polyurethane-32, polyurethane-34, polyurethane-35, and combinations thereof.

32. The hair care composition of claim 31 , wherein the polyurethane latex polymer is polyurethane-34.

33. The hair care composition of any one of claims 25-32 wherein the polyurethane latex polymer of (b) is present in an amount of about 0.01 to about 10 wt.%, based on the total weight of the hair care composition.

34. The hair care composition of any one of claims 25-33, wherein the (c) amino silicone is selected from the group consisting of a polyether amino silicone, amodimethicone, a modified amodimethicone (such as bis-cetearyl amodimethicone and bis-hydroxy/methoxy amodimethicone), an amino gum silicone, and combinations thereof.

35. The hair care composition of any one of claims 25-34, wherein the amino silicone of (c) is selected from the group consisting of amodimethicone, bis- cetearyl amodimethicone, amodimethicone/morpholinomethyl silsesquioxane copolymer, PEG-40/PPG-8 methylaminopropyl/hydroxypropyl dimethicone copolymer, bisamino

PEG/PPG-41/3 aminoethyl PG-propyl dimethicone, and combinations thereof.

36. The hair care composition of any one of claims 25-35, wherein the amino silicone of (c) is a quaternized polysiloxane selected from the group consisting of silicone quaternium 22, silicone quaternium 12, amodimethicone, bis-cetearyl amodimethicone, bis-amino PEG/PPG-41/3 aminoethyl PG-propyl dimethicone PEG-

40/PPG-8 methylaminopropyl hydroxypropyl dimethicone copolymer, silicone quaterium

16 (and) undeceth-1 1 (and) butyloctanol (and) undeceth-5, bis-isobutyl/PEG/PPG-

20/35/amodimethicone copolymer, and combinations thereof.

37. The hair care composition of any one of claims 25-36, wherein the amino silicone of (c) is present in an amount of about 0.01 to about 10 wt.%, based on the total weight of the hair care composition.

38. The hair care composition of any one of claims 25-37 comprising the cationic polymer of (d), wherein the cationic polymer of (d) is a polyquaternium.

39. The hair care composition of claim 38, wherein the polyquaternium is selected from the group consisting of polyquaternium-10, polyquaternium-1 1 , polyquaternium-22, polyquaternium-34, polyquaternium-53, polyquaternium-67, and combinations thereof.

40. The hair care composition of any one of claim 38, wherein the cationic polymer of (d) is present in an amount of about 0.01 to about 10 wt.%, based on the total weight of the hair care composition.

41 . The hair care composition of any one of claims 25-40, wherein the nonionic surfactant of (e) is selected from a polyol ester, a glycerol ether, an oxyethylenated, an oxypropylenated ether, an ethylene glycol polymer, and combinations thereof.

42. The hair care composition of claim 41 , wherein the nonionic surfactant of (e) comprises a combination of a polyol ester and an ethylene glycol polymer.

43. The hair care composition of claim 42, wherein the nonionic surfactant of (e) comprises a combination of glyceryl stearate, PEG-100 stearate, and steareth-20.

44. The hair care composition of any one of claims 25-44, wherein the nonionic surfactant of (e) is present in an amount of about 0.01 to about 10 wt.%, based on the total weight of the hair care composition.

45. The hair care composition of any one of claims 25-44 in the form of an emulsion.

46. The hair care composition of any one of the preceding claims, further comprising:

(f) oil.

47. The hair care composition of claim 46, wherein the oil of (f) is a hydrocarbon-based oil.

48. The hair care composition of claim 47, wherein the hydrocarbon- based oil is mineral oil.

49. The hair care composition of any one of the preceding claim having an acidic pH, i.e., a pH less than 7.

50. The hair care composition of claim 49, wherein the pH is from 4 to less than 7, from 5 to less than 7, or from 5 to 6.

51 . The hair care composition of any one of the preceding claims in the form of a spray, a gel, a mousse, a foam, a cream, a lotion, a serum, or an adhesive.

52. A method for:

(i) improving or retaining curl definition of hair;

(ii) imparting humidity resistance to hair;

(iii) reducing hair frizz;

(iv) controlling hair volume;

(v) styling hair;

(vi) straightening hair; or

(vi) improving the appearance of hair;

comprising applying a hair care composition of any one of the proceeding claims to hair.

53. The method of claim 52, wherein the hair is naturally curly.

54. A method of imparting durable styling or shaping properties and/or frizz control to hair comprising applying a hair care composition of any one of the preceding claims to hair.