Hair laquer or hair setting composition containing a terpolymer

The present invention relates to new copolymers and in particular terpolymers which make it possible to produce cosmetic compositions which are in the form of lacquers or styling lotions.

It is known that natural or synthetic resins are currently used most often in alcoholic or alcoholic solutions to make hairsprays or styling lotions.

Among the various resins and polymers used to date, there may be mentioned in particular polyvinylpyrrolidone, polyvinylpyrrolidone / vinyl acetate copolymers, acrylic ester / unsaturated mono-carboxylic acid copolymers, maleic anhydride / vinyl alkyl ether copolymers, copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and other unsaturated monomers such as vinyl esters having 13 to 25 carbon atoms and allyl or methallyl esters having 14 to 27 carbon atoms, as well as copolymers of vinyl acetate, crotonic acid and branched vinyl esters having at least 7 carbon atoms.

Compared to these latter polymers, the terpolymers according to the invention have numerous advantages.

First of all they can be obtained more economically and with great purity. In addition, it is possible to obtain polymers of significantly lower molecular weight, which on the cosmetic level is very appreciable, without the need to use chain regulating agents.

In fact, when such agents are used, the polymer is contaminated at the same time, which in certain cases excludes any cosmetic use due either to residual odors or to parasitic reactions which may occur with the others.

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-2 constituents of cosmetic compositions.

Although other methods have been recommended for regulating the chains, namely mass or suspension polymerization with large quantities of initiators, or solution polymerization, these are difficult to put into practice and not very economical.

According to the invention, the polymerization of the various monomers leads, without having to regulate the chains, to terpolymers having a molecular weight not exceeding 30,000.

It follows purely from a cosmetic point of view the production of polymers having much better qualities than those previously described and commonly used.

Indeed, the terpolymers according to the invention have, in addition to the cosmetic qualities required for all lacquers or styling lotions, the highly sought-after property of being very easily removed by brushing and disentangling the hair.

Finally, the terpolymers according to the invention have excellent solubility in alcohols such as ethyl or isopropyl alcohol, which makes it possible to reduce the amount of this type of solvent to appreciable proportions.

The subject of the present invention is the new industrial product that constitutes a terpolymer resulting from the copolymerization:

(a) crotonic acid (b) vinyl acetate and (c) an allyl or methallyl ester corresponding to the following formula:

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in which :

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3R 'represents a hydrogen atom or a radical - CH₃ ;

R represents a linear or branched saturated hydrocarbon chain having from 1 to 6 carbon atoms;

R₂ represents either the radical - CH ^ or the radical

- HC (CH₃J ₂ ;

it being understood that R + R₂ must be less than or equal to 7 carbon atoms.

In accordance with the invention, the abovementioned terpolymers result from the copolymerization of 6-15% and preferably 7-12% of crotonic acid, 65-86% and preferably 71-83% of vinyl acetate, and 8-20% and preferably 10-17% of allyl or methallyl ester of formula (I).

Among the allyl or methallÿl esters of formula (I) there may be mentioned: allyl dimethyl propanoate, dimethyl pro15 methallyl panoate, 2,2-dimethyl allyl pentanoate, 2,2-dimethyl methallyl pentanoate, 2,2-dimethyl allyl hexanoate, 2,2-dimethyl methallyl hexanoate, 2,2-dimethyl allyl octanoate, 2,2-dimethyl methallyl octanoate etc ...

The terpolymers according to the invention preferably have a molecular weight of between 15,000 and 30,000.

According to the invention, the terpolymers can either be in heterogeneous form or in homogeneous form.

By homogeneous copolymers is meant the copolymers whose different macromolecular chains have substantially the same content of one of the monomers constituting them and this over the entire length of the chain, the content of this monomer not varying more than 2.5% relative to the average content of this monomer for all of the macromolecular chains and this over the entire length of the chains.

The use of homogeneous terpolymers in cosmetic compositions has many advantages over

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-41'use of these same polymers in heterogeneous form.

Indeed the use of homogeneous polymers brings important cosmetic qualities and in particular an absence of powdering of the resin between several applications of aerosol lacquers on the hair.

Obtaining homogeneous polymers in composition is a particularly delicate operation. This operation is particularly complicated when it comes to terpolymers.

In the case of terpolymers containing vinyl acetate and crotonic acid, the use of allyl or methallyl esters, the hydrocarbon chain of which is branched, is particularly recommended since their presence homogenizes the composition of the terpolymer throughout polymerization.

The present invention also relates to the new industrial product which constitute the terpolymers described above which have undergone the salification of their acid function with the aid of an organic base such as: monoethanolamine, diethanolamine, triethanolamine, isopropanolamines, morpholine, as well as certain amino alcohols such as 2-amino-2-methyl-propanol and 2-amino-2-methyl-propanediol-1,3.

According to the invention, the terpolymers can advantageously be neutralized using one of the bases mentioned above in an amount equal for example to 10 to 150% and preferably to 50 to 120% of the amount corresponding to a neutralization stoichiometric.

The terpolymers according to the invention can be prepared by liquid phase copolymerization, for example in a solvent such as alcohol or benzene. However, it is preferable to carry out the polymerization in bulk or in suspension in a solvent such as water.

These polymerizations can be carried out in the presence of a

BSB / MV / 24514.

polymerization catalyst such as benzoyl peroxide, lauroyl peroxide, and azobis-isobutyronitrile, the concentration of catalyst being for example between 0.5 and 6% and preferably between 1 and 4% by weight relative to the total weight of the monomers reacted.

The suspension polymerization which makes it possible to obtain the copolymers in the form of beads is carried out as described above in water in the presence of a protective colloid such as polyvinyl alcohol or polyacrylic acid or hydroxyethylcellulose.

The concentration of the protective colloid can for example be between 0.1 and 1% by weight relative to the total weight of the monomers.

The present invention also relates to the new industrial product which constitutes a cosmetic composition characterized in that it contains at least one terpolymer as defined above, optionally neutralized, in solution in a suitable cosmetic vehicle.

The cosmetic product according to the invention may for example be a hairspray which may or may not be in aerosol form, a styling lotion or even a treatment composition for the hair.

For example, an aerosol hairspray can be produced by conditioning in an aerosol can of 1 to 4% by weight of a terpolymer according to the invention optionally neutralized from 6 to 30% and preferably from 8 to 15% in weight of an alcohol and 65 to 90% by weight of a pressurized liquefied propellant, such as dichlorodifluoromethane and trichlorofluoromethane and mixtures thereof.

As alcohol, ethyl alcohol or isopropyl alcohol is preferably used.

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A styling lotion according to the invention can for example be made by introducing into a hydroalcoholic solution having, as 20 to 66% in alcohol, 1 to 3% by weight of a terpolymer according to the invention preferably neutralized.

The cosmetic compositions according to the invention can also contain conventional cosmetic adjuvants such as perfumes, dyes, preservatives, plasticizers, cationic products, non-ionic products, silicones to improve the shine or other cosmetic resins. .

In order to better understand the invention we will now describe by way of illustration and without any limiting character, various examples of implementation.

EXAMPLE 1

Preparation of a copolymer. Crotonic acid 10%,

Vinyl acetate 75%, Allyl dimethyl propanoate 15%.

75 g of vinyl acetate, 15 g of allyl dimethyl propanoate are introduced into a 500 ml flask fitted with a mechanical stirrer, a nitrogen inlet, a condenser and a thermometer. 10 g of crotonic acid, 1.2 g of benzoyl peroxide and 200 g of water containing 1.6 g of Cellosize.

The mixture is heated to reflux with stirring for 10 hours; the copolymer is recovered in the form of beads.

Efficiency: 90%

Acid number: 67

Viscosity: 2.0 cp (in 5% solution in dimethylformamide (DMF) at 34.6 ° C).

Molecular weight: 24,000 (by osmometry in solution in dioxane).

EXAMPLE 2:

According to Example 1, the following are copolymerized:

- 10 g of crotonic acid

- 75 g of vinyl acetate

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7- 15 g of 2,2-dimethyl allyl pentanoate

- in the presence of 2 g of benzoyl peroxide. Yield: 95%

Acid number: 70

Viscosity: 1.84 cp (5% DMF at 34.6 ° C). EXAMPLE 3 According to Example 1, the following are copolymerized:

- 10 g of crotonic acid

- 80 g of vinyl acetate

- 10 g of allyl dimethyl propanoate

- in the presence of 1.2 g of benzoyl peroxide

Yield: 95%

Acid number: 75

Viscosity: 2.04 cp (5% DMF at 34.6 ° C)

EXAMPLE 4:

According to Example 1, the following are copolymerized:

- 10 g of crotonic acid

- 78 g-vinyl acetate

- 12 g of allyl dimethyl propanoate

- in the presence of 1.2 g of benzoyl peroxide

Efficiency: 88%

Acid number: 71.

Viscosity: 2.05 cp (5% DMF at 34.6 ° C).

EXAMPLE 5:

According to Example 1, we polymerize:

7.5 g crotonic acid

- 77.5 g of vinyl acetate

- 15 g of allyl dimethyl propanoate

- in the presence of 1.2 g of benzoyl peroxide

Efficiency: 90%

Acid number: 54

Viscosity: 2.06 cp (5% DMF at 34.6®C)

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-8 EXAMPLE G.:

According to Example 1, the following are copolymerized:

8g crotonic acid

- 77 g of vinyl acetate

- 15 g of allyl dimethyl propanoate

- in the presence of 1.2 g of benzoyl peroxide

Efficiency: 96%

Acid number: 53.5

Viscosity: 1.99 cp (5% DMF at 34.6 ° C)

EXAMPLE 7:

According to Example 1, the following are copolymerized:

- 10 g of crotonic acid

- 75 g of vinyl acetate

- 15 g of 2,2-dimethyl allyl octanoate

- in the presence of 4 g of benzoyl peroxide

Yield: 92%

Acid number: 72

EXAMPLE 8

Preparation of a homogeneous terpolymer in composition Preparation of a polymer:

- Crotonic acid ............... 10%

- Vinyl acetate .............. 75%

- Allyl dimethyl propanoate ... 15%

75 g of vinyl acetate, 15 g of allyl dimethyl propanoate are introduced into a one-liter flask fitted with a mechanical stirrer, a nitrogen supply, a condenser and a thermometer , 10 g of crotonic acid, 1.2 g of benzoyl peroxide, g of ethylene glycol and 200 g of water containing 1.6 g of Cellosize.

The mixture is heated to reflux with stirring for 11 hours, the copolymer is recovered in the form of pearls.

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Efficiency: 85%

Acid number: 65. Viscosity: 1.84 cp (5% DMF at 34.6 ° C).

COMPOSITION EXAMPLES

Example A

A hair spray is prepared according to the invention by mixing the following ingredients:

Polymer prepared according to Example 1 ............. 8 g

2-amino-2-methyl-1,3-propanediol qs ......... pH 7

Ethyl alcohol .......... qs ............. 100 gg of this solution are packaged in an aerosol can with 45 g of trichlorofluoromethane and 30 g of dichlorodif luoromethane.

Example B

According to the invention, a styling lotion is prepared by mixing the following ingredients:

Polymer according to Example 1 ...................... 2 g

2-amino-2-methyl-propanol-1 qs ............ pH 7

Ethyl alcohol .............................. 45 g

Water ....................... qsp ............. 100 g

Example C

A hair spray is prepared according to the invention by mixing the following ingredients:

Polymer prepared according to Example 4 ............ 3 g

2-amino-2-methyl-1,3-propanediol qs ........ pH 7

Perfume ............................'............ 0.1g

Ethyl alcohol qs ........................ 12 g

This solution is packaged in an aerosol can with:

49.7 g of trichlorofluoromethane and

35.3 g of dichlorodifluoromethane.

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-10 Example D

A hair spray is prepared according to the invention by mixing the following ingredients:

Polymer prepared according to Example 5 ........... 3g

2-amino-2-methyl-propanediol-1,3 qs ....... pH 7

Perfume ....................................... 0.1g

Ethyl alcohol ................. qs ..... 12 g

This solution is packaged in an aerosol can with:

49.7 g of trichlorofluoromethane and

35.3 g of dichlorodifluoromethane.

Example E

A hair spray is prepared according to the invention by mixing the following ingredients:

Polymer prepared according to Example 5 ............ 2 g

2-amino-2-methyl-1,3-propanediol qs ..... pH 7

Perfume ...................................... 0.1g

Ethyl alcohol ......... qs ............. 8 g

This solution is packaged in an aerosol can with:

52.7 g of trichlorofluoromethane and

37.3 g of dichlorodifluoromethane.

Example F

A hair spray is prepared according to the invention by mixing the following ingredients:

Polymer prepared according to Example 6 ............... 2 g

2-amino-2-methyl-1,3-propanediol qs .......... pH 7

Perfume ................... 0.1g

Ethyl alcohol ................................. 8 g

This solution is packaged in an aerosol can with

59 g of trichlorofluoromethane and g of dichlorodifluoromethane.

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-11 Example G

We. according to the invention, a hair spray is prepared by mixing the following ingredients:

Polymer prepared according to Example 3 .............. 3 g

2-amino-2-methyl-2,3-propanediol qs ........ pH 7

Perfume .......................................... 0.1 g

Ethyl alcohol ................................ 12 g

This solution is packaged in an aerosol can with:

g of trichlorofluoromethane and g of dichlorodifluoromethane.

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-12and (c) of an e.ster following formula:

R -CCO- CH „ ² I II ² ch₃ 0 in which: