Novel ethylenic copolymers, compositions and methods of the same

• US 20060018863A1
• Filed: 07/13/2005
• Published: 01/26/2006
• Est. Priority Date: 07/13/2004
• Status: Abandoned Application

• Current Assignee: L'Oreal SA
• Original Assignee: L'Oreal SA
• Inventors: Mougin, Nathalie, Jegou, Gwenaelle
• Application Number:
  US11/179,469
• Publication Number:
  US 20060018863A1
• Time in Patent Office: Days
• US Class Current: 424/70.160
• CPC Class Codes: A61K 8/8152 Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
• CPC Class Codes: A61Q 5/02 Preparations for cleaning the hair
• CPC Class Codes: A61Q 5/06 Preparations for styling the hair, e.g. by temporary shaping or colouring
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 220/26 Esters containing oxygen in addition to the carboxy oxygen
• CPC Class Codes: C08F 220/387 and containing nitrogen and oxygen

Abstract

The present disclosure relates to novel ethylenic copolymers comprising from 10% to 80% by weight, of at least one monomer of polyethylene glycol (meth)acrylate type, from 20% to 90% by weight, of at least one anionic monomer, and from 0% to 70% by weight, at least one additional nonionic hydrophilic monomer. The disclosure also relates to a composition, such as cosmetic or pharmaceutical compositions, comprising the copolymers and to a method of using the same.

Claims

1. An ethylenic copolymer comprising:

a) from 10% to 80% by weight, relative to the total weight of the copolymer, of at least one monomer of formula (I);

wherein;

R₁ is chosen from a hydrogen atom and linear and branched hydrocarbon radicals C_pH_2p+1 wherein p is an integer ranging from 1 to 12 inclusive;

Z is a divalent group chosen from —

COO—

, —

CONH—

, —

CONCH₃—

, —

OCO—

, —

O—

, —

SO₂—

, —

CO—

O—

CO—

, and —

CO—

CH₂—

CO—

;

x is chosen from 0 and 1;

R₂ is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, divalent hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P;

m is chosen from 0 and 1;

n is an integer ranging from 3 to 300 inclusive;

R₃ is chosen from a hydrogen atom and linear, branched and cyclic, saturated and unsaturated, optionally aromatic, hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 20 heteroatoms chosen from O, N, S, F, Si, and P; and

salts thereof;

b) from 20% to 90% by weight, relative to the total weight of the copolymer, of at least one anionic monomer and salts thereof, chosen from maleic anhydride and monomers of formula (II);

wherein;

R₁ is chosen from a hydrogen atom and linear and branched hydrocarbon radicals C_pH_2p+1 wherein p is an integer ranging from 1 to 12 inclusive;

Z′

is a divalent group chosen from —

COO—

, —

OCO— and

—

O—

, —

SO₂—

, —

CO—

O—

CO—

, and —

CO—

CH₂—

CO—

;

x′

is chosen from 0 and 1;

R₂′

is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, divalent hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P;

m′

is chosen from 0 and 1; and

Y is a group chosen from —

COOH, —

SO₃H, —

OSO₃H, —

PO₃H₂, and —

OPO₃H₂; and

c) from 0% to 70% by weight, relative to the total weight of the copolymer, of at least one additional nonionic hydrophilic monomer.

2. The copolymer according to claim 1, wherein, in formula (I), R₁ is chosen from hydrogen and from methyl, ethyl, propyl and butyl radicals.

3. The copolymer according to claim 1, wherein, in formula (I), Z is chosen from —

COO— and

—

CONH—

.

4. The copolymer according to claim 1, wherein, in formula (I), R₂ is or comprises a radical chosen from:

an alkylene radical;

a phenylene radical —

C₆H₄—

(ortho, meta or para) optionally substituted by a C₁-C₂ alkyl radical optionally comprising from 1 to 25 heteroatoms chosen from O, N, S, F, Si, and P; and

a benzylene radical —

C₆H₄—

CH₂—

optionally substituted by a C₁-C₁₂ alkyl radical optionally comprising from 1 to 25 heteroatoms chosen from O, N, S, F, Si, and P;

a pyridinium radical of the formula;

wherein R′

₁ to R′

₄, which may be identical or different, are chosen from H and C₁-C₁₂ alkyl radicals optionally comprising from 1 to 8 heteroatoms chosen from O, N, S, F, Si, and P;

a radical of formula —

CH₂—

O—

CO—

O—

, —

CH₂—

CH₂—

O—

CO—

O—

, —

CH₂—

CO—

O—

, —

CH₂—

CH₂—

CO—

O—

, —

CH₂—

O—

CO—

NH—

, —

CH₂—

CH₂—

O—

CO—

NH—

, —

CH₂—

NH—

CO—

NH— and

—

CH₂—

CH₂—

NH—

CO—

NH—

, —

CH₂—

CHOH—

, —

CH₂—

CH₂—

CHOH—

, —

CH₂—

CH₂—

CH(NH₂)—

, —

CH₂—

CH(NH₂)—

, —

CH₂—

CH₂—

CH(NHR′

)—

, —

CH₂—

CH(NHR′

)—

, —

CH₂—

CH₂—

CH(NR′

R″

)—

, —

CH₂—

CH(NR′

R″

)—

, —

CH₂—

CH₂—

CH₂—

NR′

—

, —

CH₂—

CH₂—

CH₂—

O—

, and —

CH₂—

CH₂—

CHR′

—

O—

wherein R′ and

R″

are chosen from linear and branched C₁-C₂₂ alkyls optionally comprising from 1 to 12 heteroatoms chosen from O, N, S, F, Si, and P; and

mixtures thereof.

5. The copolymer according to claim 4, wherein the alkylene radical is chosen from methylene, ethylene, propylene, n-butylene, isobutylene, tert-butylene, n-hexylene, n-octylene, n-dodecylene, n-octadecylene, n-tetradecylene, and n-docosenylene.

6. The copolymer according to claim 1, wherein, in formula (I), n ranges from 5 to 200 inclusive.

7. The copolymer according to claim 6, wherein, in formula (I), n ranges from 9 to 50 inclusive.

8. The copolymer according to claim 1, wherein, in formula (I), R₃ is chosen from a hydrogen atom;

from succinimido, maleimido, mesityl, tosyl, triethoxysilyl, phthalimido and —

CH₂—

CH₂CN radicals;

from benzyl and phenyl radicals optionally substituted by a C₁-C₁₂ alkyl radical optionally comprising from 1 to 25 heteroatoms chosen from O, N, S, F, Si, and P; and

C₁-C₃₀ alkyl radicals optionally comprising from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P, wherein the the benzyl, phenyl and alkyl radicals may optionally comprise a functional group chosen from succinimido, glutarate-succinimido, glutarate, maleimido, mesityl, benzoate, tosyl, triethoxysilane, phthalimide, thioester, benzotriazole carbonate, butyraldehyde, acetaldehyde diethyl acetal, biotin, phospholipid, succinate N-hydroxysuccinimide, —

SO₃H, —

COOH, —

PO₄, —

NR₅R₆, and —

N⁺R₅R₆R₇, wherein R₅, R₆ and R₇, which may be identical or different, are chosen from H and linear, branched and cyclic C₁-C₁₈ alkyls, optionally comprising at least one heteroatom and/or at least one protective group.

9. The copolymer according to claim 1, wherein the at least one monomer of formula (I) is chosen from:

polyethylene glycol (meth)acrylate;

methylpolyethylene glycol (meth)acrylate;

alkylpolyethylene glycol (meth)acrylates;

phenylpolyethylene glycol (meth)acrylate;

a monomer of;

wherein n ranges from 3 and 100 inclusive,

and mixtures thereof.

10. The copolymer according to claim 9, wherein n ranges from 7 to 30 inclusive.

11. The copolymer according to claim 1, wherein the at least one monomer of formula (I) is present in an amount ranging from 20% to 70% by weight, relative to the total weight of the copolymer.

12. The copolymer according to claim 11, wherein the at least one monomer of formula (I) is present in an amount ranging from 30% to 60% by weight, relative to the total weight of the copolymer.

13. The copolymer according to claim 1, wherein, in formula (II), R₁ is chosen from hydrogen and from methyl, ethyl, propyl and butyl radicals.

14. The copolymer according to claim 1, wherein, in formula (II), Z′

is COO.

15. The copolymer according to claim 1, wherein, in formula (II), R₂′

is or comprises a radical chosen from;

an alkylene radical;

a phenylene radical —

C₆H₄—

(ortho, meta or para) optionally substituted by a C₁-C₁₂ alkyl radical optionally comprising from 1 to 5 heteroatoms chosen from N, O, S, F, Si, and/or P; and

a benzylene radical —

C₆H₄—

CH₂—

optionally substituted by a C₁-C₁₂ alkyl radical optionally comprising from 1 to 5 heteroatoms chosen from O, N, S, F, Si, and P;

a radical of formula —

CH₂—

O—

CO—

O—

, —

CH₂—

CH₂—

O—

CO—

O—

, —

CH₂—

CO—

O—

, —

CH₂—

CH₂—

CO—

O—

, —

CH₂—

O—

CO—

NH—

, —

CH₂—

CH₂—

O—

CO—

NH—

, —

CH₂—

NH—

CO—

NH—

, —

CH₂—

CH₂—

NH—

CO—

NH—

, —

CH₂—

CHOH—

, —

CH₂—

CH₂—

CHOH—

, —

CH₂—

CH₂—

CH—

O—

, and —

CH₂—

CH₂—

CHR′

—

O—

wherein R′

is chosen from linear and branched C₁-C₂₂ alkyl radicals optionally comprising from 1 to 12 heteroatoms chosen from O, N, S, F, Si, and P; and

mixtures thereof.

16. The copolymer according to claim 15, wherein the alkylene radical is chosen from methylene, ethylene, propylene, n-butylene, isobutylene, tert-butylene, n-hexylene, n-octylene, n-dodecylene, n-octadecylene, n-tetradecylene, and n-docosenylene.

17. The copolymer according to claim 1, wherein the at least one anionic monomer is chosen from maleic anhydride, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, 2-carboxyethyl acrylate, styrenesulphonic acid, vinylbenzoic acid, vinylphosphonic acid, sulphopropyl (meth)acrylate, sulphatoethyl (meth)acrylate, and salts thereof.

18. The copolymer according to claim 17, wherein the salts thereof comprise ammonium salts.

19. The copolymer according to claim 1, wherein the at least one anionic monomer is present in an amount ranging from 30% to 80% by weight, relative to the total weight of the copolymer.

20. The copolymer according to claim 19, wherein the at least one anionic monomer is present in an amount ranging from 40% to 70% by weight, relative to the total weight of the copolymer.

21. The copolymer according to claim 1, wherein the at least one additional nonionic hydrophilic monomer exhibits a log P ranging from −

8 to 2.

22. The copolymer according to claim 21, wherein the at least one additional non-ionic hydrophilic monomer exhibits a log P ranging from −

6 to 0.

23. The copolymer according to claim 1, wherein the at least one additional nonionic hydrophilic monomer is chosen from those of formula (III), alone or as a mixture:

wherein;

R′

₁ is chosen from hydrogen and —

CH₃;

Z″

is a divalent group chosen from —

COO—

, —

CONH—

, —

CONCH₃—

, —

OCO—

, —

SO₂—

, —

CO—

O—

CO—

, —

CO—

CH₂—

CO—

, and —

O—

;

x″

is chosen from 0 and 1; and

R″

is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P.

24. The copolymer according to claim 23, wherein the hydrocarbon radical of R″

is chosen from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, benzyl and furfuryl, and radicals of formula —

CH₂—

CH₂—

CH₂OH, —

CH₂—

CH₂—

OH, and —

CH₂—

CH₂—

CH₂—

OH.

25. The copolymer according to claim 1, wherein the at least one additional nonionic hydrophilic monomer is chosen from:

methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, ethoxyethyl methacrylate, ethoxyethyl acrylate, N-isopropylacrylamide, N-isopropylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, vinyl acetate, methyl vinyl ether, ethyl vinyl ether, vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, hydroxypropyl acrylate, N-vinyllactam, acrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-methyl-N-vinylacetamide, N-vinylformamide, N-methyl-N-vinylformamide, and vinyl alcohol, copolymerized in the vinyl acetate form and then hydrolyzed.

26. The copolymer according to claim 1, wherein the at least one additional nonionic hydrophilic monomer is present in an amount ranging from 0.1% to 35% by weight, relative to the total weight of the copolymer.

27. The copolymer according to claim 26, wherein the at least one additional non-ionic hydrophilic monomer is present in an amount ranging from 5% to 9.5% by weight, relative to the total weight of the copolymer.

28. The copolymer according to claim 1, wherein the copolymer exhibits a weight-average molecular mass (Mw) ranging from 500 to 5,000,000.

29. The copolymer according to claim 28, wherein the copolymer exhibits a weight-average molecular mass (Mw) ranging from 8,000 to 100,000.

30. The copolymer according to claim 1, wherein the copolymer is conveyed in an aqueous medium.

31. The copolymer according to claim 30, wherein the aqueous medium is water-dispersible or water-soluble.

32. The copolymer according to claim 1, wherein the copolymer exhibits a viscosity in water ranging from 1 mPa·

s to 1000 mPa·

s, measured at 25°

C.

33. The copolymer according to claim 32, wherein the copolymer exhibits a viscosity in water ranging from 2 mPa·

s to 500 mPa·

s, measured at 25°

C.

34. The copolymer according to claim 1, wherein the copolymer exhibits a glass transition temperature (Tg) ranging from −

150°

C. to 20°

C.

35. The copolymer according to claim 34, wherein the copolymer exhibits a glass transition temperature (Tg) ranging from −

100°

C. to 0°

C.

36. The copolymer according to claim 1, wherein the copolymer exhibits a water uptake ranging from 3% to 150% by weight, at 75% relative humidity (75% RH), and/or the copolymer exhibits a water uptake ranging from 5% to 90% by weight, at 85% relative humidity (85% RH).

37. The copolymer according to claim 36, wherein the copolymer exhibits a water uptake ranging from 4.5% to 90% by weight, at 75% relative humidity (75% RH), and/or the copolymer exhibits a water uptake ranging from 15% to 60% by weight, at 85% relative humidity (85% RH).

38. A composition comprising, in a physiologically acceptable medium, at least one copolymer comprising:

a) from 10% to 80% by weight, relative to the total weight of the copolymer, of at least one monomer of formula (I);

wherein;

R₁ is chosen from a hydrogen atom and linear and branched hydrocarbon radicals C_pH_2p+1 wherein p is an integer ranging from 1 to 12 inclusive;

Z is a divalent group chosen from —

COO—

, —

CONH—

, —

CONCH₃—

, —

OCO—

, —

O—

, —

SO₂—

, —

CO—

O—

CO—

, and —

CO—

CH₂—

CO—

;

x is chosen from 0 and 1;

R₂ is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, divalent hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P;

m is chosen from 0 and 1;

n is an integer ranging from 3 to 300 inclusive;

R₃ is chosen from a hydrogen atom and linear, branched and cyclic, saturated and unsaturated, optionally aromatic, hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 20 heteroatoms chosen from O, N, S, F, Si, and P; and

salts thereof;

b) from 20% to 90% by weight, relative to the total weight of the copolymer, of at least one anionic monomer and salts thereof, chosen from maleic anhydride and monomers of formula (II);

wherein;

R₁ is chosen from a hydrogen atom and linear and branched hydrocarbon radicals C_pH_2p+1 wherein p is an integer ranging from 1 to 12 inclusive;

Z′

is a divalent group chosen from —

COO—

, —

OCO— and

—

O—

, —

SO₂—

, —

CO—

O—

CO—

, and —

CO—

CH₂—

CO—

;

x′

is chosen from 0 and 1;

R₂′

is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, divalent hydrocarbon radicals with from 1 to 30 carbon atoms which optionally comprises from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P;

m′

is chosen from 0 and 1; and

Y is a group chosen from —

COOH, —

SO₃H, —

OSO₃H, —

PO₃H₂, and —

OPO₃H₂; and

c) from 0% to 70% by weight, relative to the total weight of the copolymer, of at least one additional nonionic hydrophilic monomer.

39. The composition according to claim 38, wherein the composition is in a form chosen from a cosmetic and pharmaceutical composition.

40. The composition according to claim 38, wherein the copolymer is present in an amount ranging from 0.01% to 50% by weight on a dry basis, relative to the total weight of the composition.

41. The composition according to claim 40, wherein the copolymer is present in an amount ranging from 3% to 20% by weight on a dry weight basis, relative to the total weight of the composition.

42. The composition according to claim 38, wherein the physiologically acceptable medium comprises at least one constituent chosen from water;

hydrophilic organic solvents;

waxes, pasty fatty substances, gums and their mixtures of animal, vegetable, mineral and synthetic origin;

lipophilic organic solvents;

oils of animal, vegetable, mineral and synthetic origin;

synthetic esters and ethers;

pentaerythritol esters;

fatty alcohols comprising from 12 to 26 carbon atoms;

partially hydrocarbon-comprising and/or silicone-comprising fluorinated oils;

volatile or nonvolatile and linear or cyclic silicone oils which are liquid or pasty at ambient temperature;

pigments, pearlescent agents and fillers;

water-soluble dyes and fat-soluble dyes;

polymers;

additional agents which are able to form a film;

surfactants;

vitamins, fragrances, pearlescent agents, thickeners, gelling agents, trace elements, softening agents, sequestering agents, basifying and acidifying agents, preservatives, sunscreens, antioxidants, agents for combating hair loss, antidandruff agents, propellants and ceramides; and

mixtures thereof.

43. The composition according to claim 38, wherein the composition is in the form of a suspension, a dispersion;

an optionally thickened oily solution;

an oil-in-water, water-in-oil or multiple emulsion;

a gel or a foam;

an oily or emulsified gel;

a dispersion of vesicles;

a two-phase or multiphase lotion;

a spray;

of a lotion, a cream, an ointment, a soft paste, a salve, a cast or molded solid, or a compacted solid.

44. The composition according to claim 38, wherein the composition is a product for caring for and/or making up the skin of the body or face, the lips and the hair;

an antisun or self-tanning product;

or a hair product.

45. The composition according to claim 38, wherein the composition is in the form of a hair composition;

a rinse-out or leave-in conditioner;

a perming, hair straightening, dyeing or bleaching composition;

or a rinse-out composition, applied before or after a dyeing, bleaching, perming or a hair straightening or between the two stages of a perming or hair straightening composition.

46. A method for treating keratinous substances comprising applying, to the keratinous substances, a cosmetic composition comprising, in a physiologically acceptable medium, at least one copolymer comprising:

a) from 10% to 80% by weight, relative to the total weight of the copolymer, of at least one monomer of formula (I);

wherein;

R₁ is chosen from a hydrogen atom and linear and branched hydrocarbon radicals C_pH_2p+1 wherein p is an integer ranging from 1 to 12 inclusive;

Z is a divalent group chosen from —

COO—

, —

CONH—

, —

CONCH₃—

, —

OCO—

, —

O—

, —

SO₂—

, —

CO—

O—

CO—

, and —

CO—

CH₂—

CO—

;

x is chosen from 0 and 1;

R₂ is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, divalent hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P;

m is chosen from 0 and 1;

n is an integer ranging from 3 to 300 inclusive;

R₃ is chosen from a hydrogen atom and linear, branched and cyclic, saturated and unsaturated, optionally aromatic, hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally, comprising from 1 to 20 heteroatoms chosen from O, N, S, F, Si, and P; and

salts thereof;

b) from 20% to 90% by weight, relative to the total weight of the copolymer, of at least one anionic monomer and salts thereof, chosen from maleic anhydride and monomers of formula (II);

wherein;

R₁ is chosen from a hydrogen atom and linear and branched hydrocarbon radicals C_pH_2p+1 wherein p is an integer ranging from 1 to 12 inclusive;

Z′

is a divalent group chosen from —

COO—

, —

OCO— and

—

O—

, —

SO₂—

, —

CO—

O—

CO—

, and —

CO—

CH₂—

CO—

;

x′

is chosen from 0 and 1;

R₂′

is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, divalent hydrocarbon radicals with from 1 to 30 carbon atoms which optionally comprises from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P;

m′

is chosen from 0 and 1; and

Y is a group chosen from —

COOH, —

SO₃H, —

OSO₃H, —

PO₃H₂, and —

OPO₃H₂; and

c) from 0% to 70% by weight, relative to the total weight of the copolymer, of at least one additional nonionic hydrophilic monomer.

47. The method according to claim 46, wherein said keratinous substances are chosen from the skin of the body or face, the nails, the hair, and the eyelashes.