FORM 2
THE PATENT ACT 1970 (39 of 1970)
&
The Patents Rules, 2003 COMPLETE SPECIFICATION
(See Section 10, and rule 13)
1. TITLE OF INVENTION
COMB POLYMERS FOR THE HAIR
2. APPLICANT(S)
a) Name : COATEX
b) Nationality : FRENCH Company
c) Address : 35, RUE AMPERE,
F-69730 GENAY, FRANCE
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed : -

The present invention concerns the sector of additives used in cosmetic formulations intended to be applied to the scalp. It consists of the utilisation of (meth)acrylic comb copolymers with side chains of the hydroxy and alkoxy polyalkylene glycol type in which are present both ethylene oxide and propylene. In the field of hair care, compositions based on anionic, non-ionic and amphoteric surfactants oxide links. These copolymers give the shampoos in which they are incorporated a styling effect and an elimination of rinsing that is more pronounced than that of the comb copolymers of the prior art, manufactured from (meth)acrylic acid and side groups of the hydroxy or methoxy polyethylene glycol (MPEG) type.
In the field of hair care, compositions based on anionic, non-ionic and amphoteric surfactants are commonly used. They are applied to wet hair and the foam generated by massage or friction with the hands allows, after rinsing with water, elimination of the dirt initially present.
If these formulations have good washing power, their intrinsic cosmetic properties however remain limited, particularly because of the relatively aggressive nature of the treatment to which they subject the hair: it can cause more or less marked damage to the capillary fibre, including the gradual elimination of lipids and proteins contained in the hair.
It is also necessary to use additives whose function is to improve the cosmetic properties of the hair formulations in which they are incorporated. Among these properties, "the styling effect" is one that is sought in particular: It occurs through an ease of styling and maintenance of the hair after rinsing, and by a contribution to the volume and lightness at the dry hair level.
To do this, for a long time, use has been made of cationic polymers which, because of their strong affinity for capillary fibre which is anionic in nature, will have a persistent effect on the hair. Nevertheless, this phenomenon can lead product

deposits that are too significant: The feel of the hair becomes laden, unpleasant; the hair becomes stiff and there is an inter-fibre adhesion which affects styling.
A new generation of products has recently been developed to overcome these disadvantages. It is based on comb structured (meth)acrylic copolymers. The use of these products for hair care was described in documents EP 1 632 508 Al and EP 2 168 991 Al. It will be apparent that their use in a shampoo formulation allows not only an improvement in its styling effect, but also facilitates its elimination after rinsing with water.
The expression "(meth)acrylic comb copolymer" is intended to designate a copolymer consisting of a skeleton that is essentially linear and or a (meth)acrylic type on which are grafted at least 2 side segments consisting of at least one "macromonomer". The term "marcromonomer" refers to a water-soluble polymer or copolymer having at least one terminal group with an unsaturated ethylene function.
In the case of products developed for hair care and described in documents EP 1 632 508 Al and EP 2 168 991 Al, this macromonomer is of the hydroxyl methacrylate or methoxy polyethylene glycol type (MPEG or MAMPEG methacrylate). In summary, the comb copolymers described in these two documents are the result of the synthesis between a first anionic monomer which can be (meth)acrylic acid, and an alkoxy or hydroxy polyakylene glycol macromonomer with the formula R - (EO)n - R', with:
- EO designating ethylene oxide and n being an integer between 3 and 300,
- R designating an unsaturated polymerizable function such as the methacrylate function,
- R' representing hydrogen or a carbon radical with from 1 to 30 carbon atoms.

In these 2 documents will be noted all the importance given to the specific macromonomers MPEG550 and MPEG2000, methoxypolyethylene glycol methacrylate with a mean molar mass by weight equal to 550 g/mol and 2,000 g/mol respectively.
Now quite surprisingly, the Applicant has developed the use of (meth)acrylic comb copolymers with a different structure that have proven to be more efficient at the level of the hair styling effect and in terms of elimination by rinsing with water. These polymers are constituted:
a) of at least one monomer which is (meth)acrylic acid
b) and or at least one macromonomer with the formula (1):
R-(PO)m-(EO)n-R' (I)
- m and n are non-zero integers less than 150,
- PO and EO respectively designate propylene oxide and ethylene oxide,
- R designates a polymerizable unsaturated function,
- R' represents hydrogen or an alkyl group with from 1 to 4 carbon atoms.
These structures differ from those mentioned in documents EP 1 632 508 Al and EP 2 168 991 Al in the sense that their macromonomer contains both ethylene oxide and propylene oxide links. There was nothing to suggest that such a modification would impact in such a beneficial way the properties of styling effect and rinseability of the shampoos in which these polymers would be incorporated.
In addition, it is stated that the macromonomer of formula (I) is well known and described in patent US 6 034 208. Also, the manufacture of the copolymers as indicated above, which are manufactured from this macromonomer, is well known to the person skilled in the art, notably in a continuous, semi-continuous or batch process (see documents US 6 815 513, US 6 214 958, US 6 664 360 and US 7 232 875).

Finally, other uses of these structures were already known: notably as additives in formulations of plaster (EP 1 377 533 Al, EP 1 615 860 Al), of cement (FR 2 939 128 Al and FR 2 939 428 Al) or in paper coating dispersions (French application not yet published and filed under number FR 10 54575).
Also, a first object of the present invention is the use as a styling agent in a cosmetic formulation of at least one (meth)acrylic comb copolymer characterized in that it consists:
a) of at least one monomer which is (meth)acrylic acid
b) and of at least one macromonomer with the formula (I):
R-(PO)m-(EO)n-R' (I)
- m and n are non-zero integers less than 150,
- PO and EO respectively designate propylene oxide and ethylene oxide,
- R designates a polymerizable unsaturated function,
- R'represents hydrogen or an alkyl group with from 1 to 4 carbon atoms.
This utilisation is also characterized in that the (meth)acrylic comb copolymer is constituted, expressed as a percentage by weight of each of its components:
a) of from 5% to 30%, preferentially from 15% to 25% of at least one monomer which is (meth)acrylic acid,
b) of from 70% to 95%, preferentially from 75% to 85% of at least one macromonomer with formula (I),
c) of from 0% to 20%, preferentially from 0% to 10% of at least one monomer which is an ester of (meth)acrylic acid, preferentially ethyl acrylate,
the sum of the percentages a), b), and c) being equal to 100%.

In a preferred way, this utilisation is characterized in that R designates the methacrylate or methacrylurethane function.
In a preferred way, this use is characterized in that R' obsignates hydrogen.
In a preferred way, this use is characterized in that n and m are between 10 and 90. Structures - (PO)m - (EO)n - designate both block structures as well statistical structures, and this is true for the entire Application.
This formulation is also characterized in that the (meth)acrylic comb copolymer presents a mean molar mass by weight of between 20,000 g/mol and 6,000,000 g/mol, preferentially between 40,000 and l,000,000 g/mdi.
The (meth)acrylic comb copolymer can be obtained by free radical polymerization in solution, in direct or inverse emulsion, in suspension or precipitation in solvents, in the presence of catalytic systems and transfer agents, or even in a controlled radical polymerization and preferentially in polymerization controlled by a nitroxides (NMP) or by cobaloxymes, in polymerization by atom transfer radical polymerization (ATRP), by controlled radical polymerization by sulphur derivatives, selected from among the carbamates, dithioesters or trithiocarbonates (RAFT) or the xanthates.
It may be fully or partially neutralized by one or more neutralizing agents with a monovalent or polyvalent cation, the said agents being preferentially being selected from ammonium hydroxide or among the hydroxides and/or oxides of calcium, magnesium, or among the hydroxides of sodium, potassium, lithium, or among the primary, secondary or tertiary aliphatic and/or cyclic amines such as preferentially stearylamine, ethanolamines (mono-, di-, triethanolamine), mono and diethylamine, cyclohexylamine, methylcyclohexylamine, amino methyl propanol, morpholine, and preferentially in that the neutralizing agent is chosen from among triethanolamine and sodium hydroxide.

It can also be separated into several phases according to static or dynamic processes by one or more polar solvents preferentially belonging to the group consisting of water, methanol, ethanol, propanol, isopropanol, the butanols, acetone, tetrahydrofuran or their mixtures.
This utilisation is also characterized in that the cosmetic formulation comprises from 0.01% to 50%, preferentially from 0.1% to 30%, very preferentially from 3% to 20% by dry weight of the said copolymer with respect to its total weight.
This utilisation is also characterized in that the formulation includes at least one constituent chosen from among water, hydrophilic organic solvents and preferentially alcohols, preferentially monoakohols, linear or branched in CI - C6 and polyols and glycol ethers, preferentially in C2, and aldehydes in C2 - C4 hydrophylic, waxes, pasty fats, gums and their mixtures, of animal, vegetable, mineral or synthetic origin, lipophilic organic solvents, oils of animal, vegetable, mineral or synthetic origin, synthesis esters and ethers, pentaerythritol esters, the fatty alcohols with 12 to 26 carbon atoms, fluorinated oils, partially hydrocarbonated and/or siliconated, siliconated oils, volatile or not, linear or cyclical, liquid or pasty at room temperature, pigments, nacres, fillers, water-soluble dyes, fat-soluble dyes, filmification agents, surfactants, vitamins, perfumes, nacrating agents, thickeners, gelling agents, trace elements, softeners, retention aids, perfumes, alkalinizing or acidifying agents, preservatives, solar filters, anti-oxidants, the anti hair loss agents, anti-dandruff agents, propellant agents, ceramides and their mixtures.
This utilisation is also characterized in that the formulation presents in the form of a capillary composition, preferentially for the maintenance of hair styling or the shaping of hair, very preferentially in the form of shampoos, gels, waving lotions, brushing lotions, of setting and styling compositions chosen from the lacquers or sprays, after-shampoos whether rinsed or not, compositions for permanents, straightening, dyeing or bleaching or again, in the form of compositions for rinsing, for application before or after a dyeing, a bleaching, a permanent or a straightening, or again between the two steps of a permanent or a straightening.

Another object of the present invention consists of a cosmetic formulation containing at least one (meth)acrylic comb copolymer characterized in that it consists:
a) of at least one monomer which is (meth)acrylic acid
b) and of at least one macromonomer with the formula (I):
R-(PO)m-(EO)n-R' (I)
- m and n are non-zero integers less than 150,
- PO and EO respectively designate propylene oxide and ethylene oxide,
- R designates a polymerizable unsaturated function,
- R1 represents hydrogen or an alkyl group with from 1 to 4 carbon atoms.
This formulation is also characterized in that the (meth)acrylic comb copolymer is constituted, expressed as a percentage by weight of each of its components:
a) of 5% to 30%, preferentially of 15% to 25% of at least one monomer which is (meth)acrylic acid,
b) of 70% to 95%, preferentially of 75% to 85% of at least one macromonomer with formula (I),
c) of 0% to 20%, preferentially of 0% to 10% of at least one monomer which is an ester of (meth)acrylic acid, preferentially ethyl acrylate,
the sum of the percentages a), b), and c) being equal to 100%.
In a preferred way, this formulation is characterized in that for the said copolymer, R designates the methacrylate or methacrylurethane function.
In a preferred way, this formulation is characterized in that for the said copolymer, Rl designates hydrogen.

In a preferred way, this formulation is characterized in that for the said copolymer, n and m are between 10 and 90.
This formulation is also characterized in that for the said copolymer it presents a mean molar mass by weight of between 20,000 g/mol and 6,000,000 g/mol, preferentially between 40,000 g/mol and 1,000,000 g/mol.
This formulation is also characterized in that the cosmetic formulation comprises from 0.01% to 50%, preferentially from 0.1% to 30%, very preferentially from 3% to 20% by dry weight of the said copolymer with respect to its total weight.
This formulation is also characterized in that it includes at least one constituent chosen from among water, hydrophilic organic solvents and preferentially alcohols, preferentially monoalcohols, linear or branched in Cl - C6 and polyols and glycol ethers, preferentially in C2, and aldehydes in C2 - C4 hydrophylic, waxes, pasty fats, gums and their mixtures, of animal, vegetable, mineral or synthetic origin, lipophilic organic solvents, oils of animal, vegetable, mineral or synthetic origin, synthesis esters and ethers, pentaerythritol esters, the fatty alcohols with 12 to 26 carbon atoms, fluorinated oils, partially hydrocarbonated and/or siliconated, siliconated oils, volatile or not, linear or cyclical, liquid or pasty at room temperature, pigments, nacres, fillers, water-soluble dyes, fat-soluble dyes, filmification agents, surfactants, vitamins, perfumes, nacrating agents, thickeners, gelling agents, trace elements, softeners, retention aids, perfumes, alkalinizing or acidifying agents, preservatives, solar filters, anti-oxidants, the anti hair loss agents, anti-dandruff agents, propellant agents, ceramides and their mixtures.
This formulation is also characterized in that it presents in the form of a capillary composition, preferentially for the maintenance of hair styling or the shaping of hair, very preferentially in the form of shampoos, gels, waving lotions, brushing lotions, of setting and styling compositions chosen from the lacquers or sprays, after-shampoos whether rinsed or not, compositions for permanents, straightening,

dyeing or bleaching or again, in the form of compositions for rinsing, for application before or after a dyeing, a bleaching, a permanent or a straightening, or again between the two steps of a permanent or a straightening.
A last object of the present invention consists of a cosmetic hair treatment process characterized in that it consists of applying to the hair a cosmetic formulation as defined above.
The following examples will allow a better understanding of the invention, without however limiting its scope.
EXAMPLES
A shampoo composition is prepared that comprises the following components (in weight %):
- 7.5% of lauryl ether sulphate,
- 2.5% of coconut betaine amphoteric surfactant (Dehyton AB30 from Cognis™).
- 5% of coconut polyglucoside surfactant (Plantacare 818 UP from Cognis™),
- 3% (by dry weight) of the polymer to be tested,
- QS100% water.
Test No. 1
This test demonstrates the prior art, and implements a copolymer consisting of,
expressed in % by weight of each of its monomers:
a) 20% methacrylic acid,
b) 80% of a macromonomer with formula (I):

R-(PO)m-(EO)n-R' (I)
- m = 0, n = 48,
- PO and EO respectively designate propylene oxide and ethylene oxide,
- R designates the methacrylate function,
- R' represents the methyl radical.
totally neutralized by sodium hydroxide and with a mean molecular mass by weight equal to 25,000 g/mol.
Macromonomer (I) is thus here MPEG methacrylate with a mean molar mass equal to 2,000 g/ mol (illustrated in documents EP1 632 508 Al and EP 2168 991 Al).
Test No. 2
This test demonstrates the prior art, and implements a copolymer consisting of,
expressed in % by weight of each of its monomers:
a) 20% methacrylic acid,
b) 80% of a macromonomer with formula (I):
R - (FO)m - (EO)„ - R' (I)
- m = 0, n = 110,
- PO and EO respectively designate propylene oxide and ethylene oxide,
- R designates the methacrylate function,
- R' represents the methyl radical,
totally neutralized by sodium hydroxide and with a mean molecular mass by weight equal to 60,000 g/ mol.

Macromonomer (I) is thus here MPEG methacrylate with a mean molai mass by weight equal to 5,000 g/mol.
Test No. 3
This test demonstrates the invention, and implements a copolymer consisting of,
expressed in % by weight of each of its monomers:
a) 20% methacrylic acid,
b) 80% of a macromonomer with formula (1):
R-(PO)m-(EO)n-R' (I)
- m = 15, n = 46,
- PO and EO respectively designate propylene oxide and ethylene oxide,
- R designates the methacrylate function,
- R' represents the hydroxy radical,
totally neutralized by sodium hydroxide and with a mean molecular mass by weight equal to 60,000 g/mol.
In humid and dry environments, good untangling properties and an improved styling in the case of the polymer No. 3 according to the invention are observed. It is also apparent there is a more pronounced capacity of this polymer to be eliminated by rinsing the hair in water.
Test n° 4
This test illustrates the invention and uses a copolymer consisting, expressed as a %
by weight of each of its monomers, of:
a) 8 % of acrylic acid and 2.5 % of methacrylic acid,
b) 89.5 % of a macromonomer with formula (I):

R - (PO)m - (EO)n - R' (I)
- m = 15, n = 46,
- PO and EO designate respectively propylene oxide and ethylene oxide
- R designates the methacrylate group,
- R' represents the hydroxy radical,
totally neutralised by sodium hydroxide and of average molecular mass by weight equal to 120,000 g/mol.
Test n° 5
This test illustrates the prior art and uses a copolymer consisting, expressed as a %
by weight of each of its monomers, of:
a) 6 % of acrylic acid and 1.8 % of methacrylic acid,
b) 92.2% of a macromonomer with formula (I):
R - (PO)m - (EO)n - R' (I)
- m = 0, n = 45,
- PO and EO designate respectively propylene oxide and ethylene oxide
- R designates the methacrylate group,
- R' represents the methyl radical,
totally neutralised by sodium hydroxide and of average molecular mass by weight equal to 100,000 g/mol.
The polymers according to tests n° 4 and 5 were also tested in the shampoo formulation described in the introduction to the examples.

In a moist and dry environment satisfactory untangling properties are observed, and improved hair condition in the case of polymer n° 4 according to the invention, at a level comparable with that obtained with the polymer according to test n° 3. A more pronounced aptitude for this polymer to be eliminated by rinsing the hair in water is also observed.
In comparison, the properties obtained with the polymer according to test n° 5 remain comparable with those obtained with the polymers according to tests n° 1 and 2.

WE CLAIM:
1 - Use as a hair styling agent in a cosmetic formulation of at least one
(meth)acrylic comb copolymer characterized in that it consists:
a) of at least one monomer which is (meth)acrylic acid,
b) and of at least one macromonomer with the formula (I):
R-(PO)m-(EO)n-R' (I)
- m and n are non-zero integers less than 150,
- PO and EO respectively designate propylene oxide and ethylene oxide,
- R designates a polymerizable unsaturated function,
- R1 represents hydrogen or an alkyl group with from 1 to 4 carbon atoms.
2 - Utilisation according to claim 1 characterized in that the (meth)acrylic comb
copolymer is constituted, expressed as a percentage by weight of each of its components:
a) of 5% to 30%, preferentially from 15% to 25% of at least one monomer which is (meth)acrylic acid,
b) of 70% to 95%, preferentially of 75% to 85% of at least one macromonomer with formula (I),
c) of 0% to 20%, preferentially of 0% to 10% of at least one monomer which is an ester of (meth)acrylic acid, preferentially ethyl acrylate,
the sum of the percentages a), b), and c) being equal to 100%.
3 - Utilisation according to one of claims 1 or 2 characterized in that R designates
the methacrylate or methacrylurethane function.

4 - Utilisation according to one of claims 1 to 3 characterized in that R' designates
hydrogen.
5 - Utilisation according to one of claims 1 to 4 characterized in that n and m are
between 10 and 90.
6 - Utilisation according to one of claims 1 to 5 characterized in that the
(meth)acrylic comb copolymer presents a mean molar mass by weight of between 20,000 g/mol and 6,000,000 g/mol, preferentially between 40,000 g/mol and 1,000,000 g/mol.
7 - Utilisation according to one of claims 1 to 6 characterized in that the cosmetic
formulation comprises from 0.01% to 50%, preferentially from 0.1% to 30%, very preferentially from 3% to 20% by dry weight of the said copolymer with respect to its total weight.
8 - Utilisation according to one of claims 1 to 7 characterized in that the
formulation includes at least one constituent chosen from among water, hydrophilic organic solvents and preferentially alcohols, preferentially monoalcohols, linear or branched in C1 - C6 and polyols and glycol ethers, preferentially in C2, and aldehydes in C2 - C4 hydrophylic, waxes, pasty fats, gums and their mixtures, of animal, vegetable, mineral or synthetic origin, lipophilic organic solvents, oils of animal, vegetable, mineral or synthetic origin, synthesis esters and ethers, pentaerythritol esters, the fatty alcohols with 12 to 26 carbon atoms, fluorinated oils, partially hydrocarbonated and/or siliconated, siliconated oils, volatile or not, linear or cyclical, liquid or pasty at room temperature, pigments, nacres, fillers, water-soluble dyes, fat-soluble dyes, filmification agents, surfactants, vitamins, perfumes, nacrating agents, thickeners, gelling agents, trace elements, softeners, retention aids, perfumes, alkalinizing or acidifying agents, preservatives, solar filters,

anti- oxidants, the anti hair loss agents, anti-dandruff agents, propellant agents, ceramides and their mixtures.
9 - Utilisation according to one of claims 1 to 8 characterized in that the formulation presents in the form of a capillary composition, preferentially for the maintenance of hair styling or the shaping of hair, very preferentially in the form of shampoos, gels, waving lotions, brushing lotions, of setting and styling compositions chosen from the lacquers or sprays, after-shampoos whether rinsed or not, compositions for permanents, straightening, dyeing or bleaching or again, in the form of compositions for rinsing, for application before or after a dyeing, a bleaching, a permanent or a straightening, or again between the two steps of a permanent or a straightening.
10 - Cosmetic formulation containing at least one (meth)acrylic comb copolymer
characterized in that it consists:
a) of at least one monomer which is (meth)acrylic acid,
b) and of at least one macromonomer with the formula (I):
R-(PO)m - (EO)n - R' (I)
- m and n are non-zero integers less than 150,
- PO and EO respectively designate propylene oxide and ethylene oxide,
- R designates a polymerizable unsaturated function,
- R1 represents hydrogen or an alkyl group with from 1 to 4 carbon atoms.
11 - Formulation according to claim 10 characterized in that the (meth)acrylic
comb copolymer is constituted, expressed as a percentage by weight of each of its components:
a) of 5% to 30%, preferentially from 15% to 25% of at least one monomer which is (meth)acrylic acid,

b) of 70% to 95%, preferentially of 75% to 85% of at least one macromonomer with formula (I),
c) of 0% to 20%, preferentially of 0% to 10% of at least one monomer which is an ester of (meth)acrylic acid, preferentially ethyl acrylate,
the sum of the percentages a), b), and c) being equal to 100%.
12 - Formulation according to one of claims 10 or 11 characterized in that for the
said copolymer, R designates the methacrylate or methacrylurethane function.
13 - Formulation according to one of claims 10 to 12 characterized in that for the
said copolymer, R' designates hydrogen.
14 - Formulation according to one of claims 10 to 13, characterized in that for the
said copolymer, it presents a mean molar mass by weight of between 20,000 g/mol and 6,000,000 g/mol, preferentially between 40,000 g/mol and 1,000,000 g/mol.
15 - Formulation according to one of claims 10 to 14 characterized in that the
cosmetic formulation comprises from 0.01% to 50%, preferentially from 0.1% to 30%, very preferentially from 3% to 20% by dry weight of the said copolymer with respect to its total weight.
16 - Formulation according to one of claims 10 to 15 characterized in that the
formulation includes at least one constituent chosen from among water, hydrophilic organic solvents and preferentially alcohols, preferentially monoalcohols, linear or branched in C1 - C6 and polyols and glycol ethers, preferentially in C2, and aldehydes in C2 - C4 hydrophylic, waxes, pasty fats, gums and their mixtures, of animal, vegetable, mineral or synthetic origin, lipophilic organic solvents, oils of animal, vegetable, mineral or synthetic origin, synthesis esters and ethers, pentaerythritol esters, the fatty alcohols

with 12 to 26 carbon atoms, fluorinated oils, partially hydrocarbonated and/or siliconated, siliconated oils, volatile or not, linear or cyclical, liquid or pasty at room temperature, pigments, nacres, fillers, water-soluble dyes, fat-soluble dyes, filmification agents, surfactants, vitamins, perfumes, nacrating agents, thickeners, gelling agents, trace elements, softeners, retention aids, perfumes, alkalinizing or acidifying agents, preservatives, solar filters, antioxidants, the anti hair loss agents, anti-dandruff agents, propellant agents, ceramides and their mixtures.
17 - Formulation according to one of claims 10 to 16 characterized in that the formulation presents in the form of a capillary composition, preferentially for the maintenance of hair styling or the shaping of hair, very preferentially in the form of shampoos, gels, waving lotions, brushing lotions, of setting and styling compositions chosen from the lacquers or sprays, after-shampoos whether rinsed or not, compositions for permanents, straightening, dyeing or bleaching or again, in the form of compositions for rinsing, for application before or after a dyeing, a bleaching, a permanent or a straightening, or again between the two steps of a permanent or a straightening.
18 - Cosmetic hair treatment process characterized in that consists of the application to the hair of a cosmetic formulation according to one of claims 10 to 17.