# US 10,117,824 B2 · Gradient copolymer, composition including same and cosmetic make-up or care method

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- Number: US 10,117,824 B2
- Document ID: US10117824B2
- Status: Granted
- Kind: B2
- Application number: 14/255,103
- Filed: 2014-04-17
- Published: 2014-08-14
- Granted: 2018-11-06
- Earliest claimed: 2004-06-11
- Assignees: L'oreal
- Applicants: L'oreal
- Inventors: Celine Farcet
- Web page: https://patentgrep.com/patent/US10117824B2

## CPC

- A61K 8/8152: {Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers}
- A61Q 1/02: Preparations containing skin colorants, e.g. pigments (preparations in powder form A61Q1/12)
- A61Q 1/06: Lipsticks
- A61Q 3/02: Nail coatings
- C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate}
- C08F 220/1804: {C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate}
- C08F 220/1811: {C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate}
- A61K 2800/54: Polymers characterized by specific structures/properties
- A61Q 1/10: for eyes, e.g. eyeliner, mascara
- A61Q 5/02: Preparations for cleaning the hair
- A61Q 5/06: Preparations for styling the hair, e.g. by temporary shaping or colouring
- A61Q 17/04: Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
- A61Q 19/00: Preparations for care of the skin
- C08F 220/1808: {C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate}
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- A61Q: SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Novel gradient copolymers including at least two different and specifically selected monomers, and cosmetic or skin-care compositions including same. The invention also relates to a cosmetic method for make-up or the care of keratin materials, in particular the skin of the body or of the face, the nails, the hair and/or the eyelashes, comprising the application of a cosmetic composition as defined above on said materials.

## Claims

### Claim 1

A cosmetic process for making up or caring for keratinous substances which comprises applying to said substances a cosmetic composition comprising, in a physiologically acceptable medium, at least one gradient copolymer comprising at least two different monomers chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate, wherein the copolymer is soluble in isododecane at 25° C., 1 atm., at a concentration of at least 1% by weight.

### Claim 2 (depends on 1)

The cosmetic process according to claim 1, wherein the keratinous substances are chosen from the skin of the body or face, the nails, the hair and the eyelashes.

### Claim 3 (depends on 1)

The cosmetic process according to claim 1, wherein a first monomer chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate is present in an amount ranging from 1 to 99% by weight, relative to the weight of the final copolymer.

### Claim 4 (depends on 3)

The cosmetic process according to claim 3, wherein said first monomer is present in an amount ranging from 30 to 70% by weight, relative to the weight of the final copolymer.

### Claim 5 (depends on 3)

The cosmetic process according to claim 3, wherein a second monomer chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate, but different from said first monomer, is present in an amount ranging from 1 to 99% by weight, relative to the weight of the final copolymer.

### Claim 6 (depends on 5)

The cosmetic process according to claim 5, wherein said second monomer is present in an amount ranging from 30 to 70% by weight, relative to the weight of the final copolymer.

### Claim 7 (depends on 1)

The cosmetic process according to claim 1, wherein said copolymer further comprises a third monomer, chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate, present in an amount ranging from 1 to 50% by weight, relative to the weight of the final copolymer.

### Claim 8 (depends on 7)

The cosmetic process according to claim 7, wherein said third monomer is present in an amount ranging from 10 to 35% by weight, relative to the weight of the final copolymer.

### Claim 9 (depends on 1)

The cosmetic process according to claim 1, wherein the total amount of monomers chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate in the final copolymer ranges from 50 to 100% by weight, relative to the weight of the final copolymer.

### Claim 10 (depends on 9)

The cosmetic process according to claim 9, wherein the total amount of monomers chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate in the final copolymer is present in an amount ranging from 90 to 95% by weight, relative to the weight of the final copolymer.

### Claim 11 (depends on 1)

The cosmetic process according to claim 1, wherein said copolymer comprises at least one of the following combinations of monomers:
isobornyl acrylate and isobornyl methacrylate;
isobornyl acrylate and isobutyl acrylate;
isobornyl acrylate and isobutyl methacrylate;
isobornyl acrylate and 2-ethylhexyl acrylate;
isobornyl methacrylate and isobutyl acrylate;
isobornyl methacrylate and isobutyl methacrylate;
isobornyl methacrylate and 2-ethylhexyl acrylate;
isobornyl acrylate, isobornyl methacrylate and 2-ethylhexyl acrylate;
isobornyl acrylate, isobornyl methacrylate and isobutyl acrylate;
isobornyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate;
isobornyl acrylate, isobutyl methacrylate and isobutyl acrylate; and
isobornyl methacrylate, isobutyl methacrylate and isobutyl acrylate.

### Claim 12 (depends on 1)

The cosmetic process according to claim 1, wherein said copolymer further comprises at least one additional monomer, other than those chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate.

### Claim 13 (depends on 12)

The cosmetic process according to claim 12, wherein the at least one additional monomer is present in an amount ranging from 0 to 50% by weight, relative to the weight of the final copolymer.

### Claim 14 (depends on 13)

The cosmetic process according to claim 13, wherein the at least one additional monomer is present in an amount ranging from 5 to 10% by weight, with respect to the weight of the final copolymer.

### Claim 15 (depends on 12)

The cosmetic process according to claim 12, wherein the at least one additional monomer is chosen, alone or as a mixture, from:
(i) (meth)acrylates of formula CH2═CHCOOR or CH2═C(CH3)COOR wherein R is chosen from:
a linear or branched alkyl group comprising 1 to 30 carbon atoms in which is optionally inserted at least one heteroatom chosen from O, N, S and P, said alkyl groups being optionally substituted by at least one substituent chosen from —OH, halogen atoms chosen from Cl, Br, I, and F, —NR4R5 groups, wherein R4 and R5, which are identical or different, are each independently chosen from hydrogen atoms, linear or branched C1 to C6 alkyl groups, phenyl groups; and polyoxyalkylene groups composed of the repetition of 5 to 30 oxyalkylene units;
a C3 to C12 cycloalkyl group, said cycloalkyl group optionally comprising, in its chain, at least one heteroatom chosen from O, N, S and P and being optionally substituted by at least one substituent chosen from —OH and halogen atoms chosen from Cl, Br, I, and F;
a C4 to C20 aryl group or a C5 to C30 aralkyl group wherein the alkyl portion is a C1 to C8 alkyl;
(ii) (meth)acrylamides of formula CH2═CHCONR4R5 or CH2═C(CH3) CONR4R5 wherein R4 and R5, which are identical or different, are each independently chosen from hydrogen atoms and:
a) linear or branched alkyl groups comprising from 1 to 18 carbon atoms in which is optionally inserted at least one heteroatom chosen from O, N, S and P; said alkyl group being optionally substituted by at least one substituent chosen from hydroxyl groups, halogen atoms chosen from Cl, Br, I, and F and Si(R4R5) groups, wherein R4 and R5, which are identical or different, are each independently chosen from C1 to C6 alkyl groups and phenyl groups;
b) C3 to C12 cycloalkyl groups, and heterocycloalkyl groups having an alkyl portion of 1 to 4 carbon atoms,
c) C4 to C20 aryl groups,
d) C5 to C30 aralkyl groups, wherein said alkyl portion has C1 to C8 alkyl groups,
(iii) monomers possessing at least one ethylenic unsaturation comprising at least one functional group chosen from carboxylic acids, phosphoric acids, sulfonic acids, and anhydrides, and the salts thereof;
(iv) vinyl ethers of formula R6O—CH═CH2 and vinyl esters of formula R6—COO—CH═CH2
wherein R6 is chosen from a linear or branched alkyl group comprising from 1 to 22 atoms, a cyclic alkyl group comprising from 3 to 6 carbon atoms, and an aromatic group;
(v) vinyl compounds of formula CH2═CH—R9, CH2═CH—CH2—R9 or CH2═C(CH3)—CH2—R9
wherein R9 is chosen from a hydroxyl group, a halogen group chosen from Cl and F, an NH2 group, an OR10 group, wherein R10 is chosen from a phenyl group and a C1 to C12 alkyl group such that the monomer is a vinyl or allyl ether, an acetamide group (NHCOCH3), an OCOR11 group, wherein R11 is a linear or branched alkyl group of 2 to 12 carbons such that the monomer is a vinyl or allyl ester, and a group chosen from:
a linear or branched alkyl group of 1 to 18 carbon atoms in which is optionally inserted at least one heteroatom chosen from O, N, S and P, said alkyl group additionally being optionally substituted by at least one substituent chosen from hydroxyl groups, halogen atoms chosen from Cl, Br, I, and F and Si(R4R5) groups, wherein R4 and R5, which are identical or different, are each independently chosen from C1 to C6 alkyl groups and phenyl groups;
a C3 to C12 cycloalkyl group,
a C3 to C20 aryl group,
a C4 to C30 aralkyl group (C1 to C8 alkyl groups),
a 4- to 12-membered heterocyclic group comprising at least one heteroatom chosen from O, N and S, the ring being aromatic or nonaromatic,
a heterocycloalkyl group wherein said alkyl portion comprises 1 to 4 carbon atoms,
(vi) styrene and its derivatives;
(vii) monomers possessing ethylenic unsaturation comprising at least one silicon atom;
and salts and mixtures thereof;
with the proviso that the at least one additional monomer is not chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate.

### Claim 16 (depends on 12)

The cosmetic process according to claim 12, wherein the at least one additional monomer is chosen from methyl (meth)acrylates, n-propyl (meth)acrylates, isopropyl (meth)acrylates, n-butyl (meth)acrylates, t-butyl (meth)acrylates, cyclohexyl (meth)acrylates, methoxyethyl (meth)acrylates, ethoxyethyl (meth)acrylates, trifluoroethyl (meth)acrylates, dimethylaminoethyl (meth)acrylates, diethylaminoethyl (meth)acrylates, 2-hydroxypropyl (meth)acrylates, 2-hydroxyethyl (meth)acrylates, acrylic acid, methacrylic acid, (meth) acrylamide, methacryloyloxy-propyltrimethoxysilane, and methacryloyloxypropyltris(trimethylsiloxy)silane, and salts and mixtures thereof.

### Claim 17 (depends on 12)

The cosmetic process according to claim 12, wherein the at least one additional monomer is chosen, alone or as a mixture, from carbon-based or silicone macro-monomers having at least one polymerizable end group and their salts.

### Claim 18 (depends on 17)

The cosmetic process according to claim 17, wherein said carbon-based or silicone macro-monomers having at least one polymerizable end group, and salts thereof, are chosen from
(i) linear or branched C8-C22 alkyl (meth)acrylate homopolymers and copolymers comprising a polymerizable end group chosen from vinyl and (meth)acrylate groups;
(ii) polyolefins comprising an end group having ethylenic unsaturation; and
(iii) polydimethylsiloxanes comprising a mono(meth)-acrylate end group.

### Claim 19 (depends on 1)

The cosmetic process according to claim 1, wherein the copolymer is soluble in isododecane at 25° C., 1 atm., at a concentration of at least 10% by weight.

### Claim 20 (depends on 1)

The cosmetic process according to claim 1, wherein the copolymer has a weight polydispersity index of less than or equal to 3.

### Claim 21 (depends on 20)

The cosmetic process according to claim 20, wherein the copolymer has a weight polydispersity index ranging from 1.2 to 1.8.

### Claim 22 (depends on 1)

The cosmetic process according to claim 1, wherein the copolymer is present in an amount ranging from 0.1 to 95% by weight, relative to the total weight of the composition.

### Claim 23 (depends on 1)

The cosmetic process according to claim 1, wherein the copolymer is present in an amount ranging from 5 to 70% by weight, relative to the total weight of the composition.

### Claim 24 (depends on 1)

The cosmetic process according to claim 1, wherein said composition comprises at least one oil and/or solvent chosen from volatile or nonvolatile oils which can be chosen from optionally branched, carbon-based, hydrocarbon or fluorinated, natural or synthetic oils, alone or as a mixture; ethers and esters having more than 6 carbon atoms; ketones having more than 6 carbon atoms; aliphatic fatty monoalcohols having 6 to 30 carbon atoms, wherein the hydrocarbon chain does not comprise a substituent group.

### Claim 25 (depends on 24)

The cosmetic process according to claim 24, wherein the at least one oil and/or solvent is chosen from volatile or nonvolatile alkanes chosen from decane, heptane, dodecane, isododecane, isohexa-decane, cyclohexane and mixtures thereof.

### Claim 26 (depends on 1)

The cosmetic process according to claim 1, wherein said composition comprises at least from 0.01 to 95% by weight of at least one oil and/or solvent, relative to the total weight of the composition.

### Claim 27 (depends on 1)

The cosmetic process according to claim 1, wherein said composition comprises at least from 30 to 80% by weight of at least one oil and/or solvent, relative to the total weight of the composition.

### Claim 28 (depends on 1)

The cosmetic process according to claim 1, wherein said composition further comprises a constituent chosen from a hydrophilic medium comprising water or a mixture of water and of hydrophilic organic solvent; waxes; gums; coloring materials; fillers; polymers; vitamins, thickeners, gelling agents, trace elements, softening agents, sequestering agents, fragrances, basifying or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, agents for combating hair loss, antidandruff agents, propellants, ceramides and mixtures thereof.

### Claim 29 (depends on 1)

The cosmetic process according to claim 1, wherein the composition is in a form chosen from a suspension, a dispersion, a solution a gel, an emulsion, a cream, a foam, a dispersion of vesicles, a two-phase or multiphase lotion, a spray, a powder, a paste and in the anhydrous form, for example of an anhydrous paste.

### Claim 30 (depends on 29)

The cosmetic process according to claim 29, wherein the composition is in a form chosen from an organic solution; oil-in-water (O/W), water-in-oil (W/O), or a multiple (W/O/W or polyol/O/W or O/W/O) emulsion, a cream, a foam, a dispersion of vesicles comprising ionic or nonionic lipids; a soft paste; and an anhydrous paste.

### Claim 31 (depends on 1)

The cosmetic process according to claim 1, wherein the composition is chosen from a makeup composition; a product for the lips; a concealer; a blusher, a mascara, an eyeliner; a product for making up the eyebrows, a lip pencil, an eye pencil; a product for the nails; a product for making up the body; a product for making up the hair; a composition for protecting or caring for the skin of the face, of the neck, of the hands or of the body; an antisun or artificial tanning composition; and a hair composition.

### Claim 32 (depends on 30)

The cosmetic process according to claim 30, wherein the composition is chosen from a foundation, a face powder or an eye shadow.

### Claim 33 (depends on 31)

The cosmetic process according to claim 31, wherein the composition is in the form chosen from a foundation, a face powder, an eyeshadow, a lipstick, a lip care product, a nail varnish, a nail care product, hair mascara, hair lacquer, a composition for combating wrinkles or fatigue, a moisturizing composition, a treating composition and a hair composition, form the form retention of the hairstyle or the shaping of the hair.

### Claim 34 (depends on 1)

The cosmetic process according to claim 1, wherein said first monomer is isobornyl acrylate and is present in an amount ranging from comprising from 30 to 70% by weight, relative to the weight of the final copolymer and wherein said second monomer is isobornyl methacrylate and is present in an amount ranging from comprising from 30 to 70% by weight, relative to the weight of the final copolymer; and wherein the total amount of monomers isobornyl acrylate and isobornyl methacrylate in the final copolymer ranges from 50 to 100% by weight, relative to the weight of the final copolymer.

### Claim 35 (depends on 33)

The cosmetic process according to claim 33, which further comprises isobutyl acrylate as a third monomer in an amount of 10 to 35% by weight, relative to the weight of the final copolymer.

### Claim 36 (depends on 33)

The cosmetic process according to claim 33, which further comprises 2-ethylhexyl acrylate as a third monomer in an amount of 10 to 35% by weight, relative to the weight of the final copolymer.