CH622024A5 - Process for the preparation of new terpolymers and higher polymers of N-alkyl acrylamide or methacrylamide and cosmetic composition containing these polymers - Google Patents

Description

The present invention relates to a process for the preparation of new terpolymers and higher polymers based on N-alkyl acrylamide or methacrylamide and a cosmetic composition containing them, in particular lacquers and styling lotions.

A large number of synthetic polymers have already been proposed for use in lacquers or styling lotions.

The titular Company has just noted that it was also possible to produce excellent lacquers and styling lotions using a new class of copolymers.

These polymers, unlike those previously used, make it possible to give lacquers and styling lotions excellent properties and in particular good hold of the hairstyle.

These new copolymers result from the copolymerization:

(a) at least one monomer of formula:

r,

r2

I

CH2 = C -C -NH-C - (X) n — R II I o r3

(I)

in which:

R represents an alkyl radical, linear or branched, having from 1 to 10 carbon atoms,

Ri, R2 and R3 represent either a hydrogen atom or a methyl radical,

and n is 0 or 1; when n = 1, X represents an oxygen atom,

(b) of at least one monomer of formula:

R4-CH = C - (CH2) m-CONH2 I

Rs

(II)

where: m is 0 or 1

622,024

4

if m = 0 R4 is either a hydrogen atom or the radical (v) CH2 = CH-Q-R10 (VII) -COOH

and R5 is a hydrogen atom or a radical -CH3, Hans which:

if m = l R4 is a hydrogen atom R10 represents a linear or branched saturated alkyl radical

and Rs represents the radical -COOH 5 having from 1 to 17 carbon atoms,

and (c) at least one monomer taken from the group consisting

with styrene, N-vinylpyrrolidone and the monomers of the following Rn formulas: |

and (vi) R13 -CH = C - (CH2) p-CON -Z ^ OH (vni)

(i) ch2 = c-cn (in) 10 i

1 Rl2

r6

in which:

in which: Rj t represents a hydrogen atom or a methyl radical,

R6 represents a hydrogen atom or a methyl radical, 15 z represents a linear or branched alkylene radical from 1 to 6

carbon atoms, whether or not substituted by one or two functions

(ii) CH2 = C -C -0-R8 (IV) hydroxymethyls, and p is 0 or 1.

I II if p = Q, Rj3 is either a hydrogen atom or the radical r7 o - cor14

R14 being -OH or the radical -NH-R15, R15 being an atom in which: hydrogen or the radical —Z-OH, and R12 is a hydrogen atom

R7 represents a hydrogen atom or a methyl gene radical or the radical -CH3

and Rg represents a linear or branched alkyl radical having if p — 1, RI3 is a hydrogen atom and R12 is the from 1 to 18 carbon atoms, a radical: radical - COR14, R14 having the same meaning as above .

- (CH2) 2-N (CH3) 2, quaternized or not, a radical In the formula (VIII) above, the radical Z is preferably

-CH2CH2OH, a radical -CH2-CH-CH2OH and a rence radical taken from the group consisting of:

OH - CH2

- (CH2-CH20) i R 'in which R' represents a methyl radical - (CH2) 2-

or ethyl and / is 12, 30 ~ CH (C2H5) -CH2-

-C (CH3) 2-CH2-

(iii) R9-C —0-CH = CH2 (V) - C (CH2OH) 2-CH2-

II -C (CH3) 2-CH2-CH (CH3) -

o and - C (CH3) (CH2OH) -CH2-

35

in which: As indicated above, the copolymers thus obtained are

Rg represents a linear or branched alkyl radical preferably having 1 terpolymers. However, according to a variant with 16 carbon atoms, the copolymers can be tetra, or penta-polymers or higher polymers.

(iv) CH -COOR "(VI) 4 (i In this case the copolymers result from the copolymerization of more than one monomer of formula (I) and / or more than one CH -COOR '' monomer of formula (II) and / or of more than one of the monomers represented by formulas (III) to (VIII) above.

The copolymers prepared by the process, according to the invention in which: 45 Can be represented by the following general formula:

R "represents an alkyl radical having from 1 to 3 carbon atoms r.

-ch2 o c = o_

I R?

I I2

nh - c -

I

r.,

w

(x) - r n

R4 R5

-ch-

(CH9) lx. .2. YOU

-M-

Jy

C = o * 2

^ -Lh,

5,622,024

in which: 2-amino-2-methyl propanol and 2-amino methyl-2-propan-

the radicals R, R1; R2, R3, R4 and R5, n, m and X have the 1,3-diol.

meanings given above for formulas (I) and (II), w The carboxylic functions can be neutralized with corresponds to 5 to 90% by weight, x corresponds to 5 to 90% by weight these organic bases in a proportion between 10 and and y corresponds to 5 to 60% by weight, and M represents a unit 5 150%.

styrene, an N-vinylpyrrolidone unit or a unit of a mono- These copolymers can be prepared by copolymerization

unsaturated mother such as those of formulas (III) to (VIII) given tion in solution in an organic solvent such as alcohols, the above. esters, ketones or hydrocarbons.

Among the monomers of formula (I), it is possible in particular. Among these solvents, mention may in particular be made of: methanol,

quote: N-tertiobutyl acrylamide, N-octyl acrylamide, N-de-10 isopropanol, ethanol, ethyl acetate, ethyl methyl ketone, cyl acrylamide, N-dodecyl acrylamide, N - [(dimethyl-l, l) benzene, etc ...

propyl-1] acrylamide, N - [(dimethyl-l, l) butyl-1] acrylamide, The copolymerization can also take place in suspen-la N- [(dimethyl-1,1) pentyl-l] acrylamide, N-isobutoxymation or as an emulsion in an inert solvent such as water, thylacrylamide and the corresponding methacrylamides. The copolymerization can also take place in bulk.

Among the monomers of formula (II), it is possible in particular. These polymerizations can be carried out in the presence of: acrylamide, methacrylamide, maleamic acid, and a polymerization catalyst generating free radicals, itaconamic acid, such as benzoyl peroxide, lauroyl peroxide, azo

Among the monomers of formula (III) to (VIII) there may be bis-isobutyronitrile, hydrogen peroxide, the various pairs of oxido-particular cite: acrylonitrile, methacrylonitrile, reduction acrylates such as (NH4) 4 S2Og, FeCI2 etc ... and methyl, ethyl, propyl, isopropyl methacrylates, 20 The catalyst concentration varies between 0.2 and 10% in butyl, tert-butyl, hexyl, decyl , dodecyl, Weight Relative to the monomers reacted and depending on the octadecyl, 2-hydroxyethyl and N, N-dimethylamino-2 Molecular weight of the copolymers which it is desired to obtain, quaternized ethyl or not , and the acrylates and methacrylates of <u- The present invention further relates to a compound

methyl or ethyl polyethylene glycol; vinyl acetate, the cosmetic tion containing the new copolymers described above

vinyl propionate, vinyl butyrate, vinyl laurate, above.

vinyl stearate, vinyl pivalate, neoheptanoate This cosmetic composition can be in vinyl form, vinyl neooctanoate, vinyl neodecanoate, lacquer or styling lotions.

vinyl tetramethyl-2,2,4,4 valerate, 2-isopropyl dimethyl- This cosmetic composition can be, for example, a

2.3 vinyl butyrate; dimethyl maleate, Iaclue maleate for hair which may or may not be present in aero-diethyl form, dimethyl itaconate, diethyl itaconate; the soil> a styling lotion, a treatment composition for methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, hair, a dye support, a shampoo or an isopropyl vinyl ether, l octyl vinyl ether, the dodecyl vinyl ether so-called “rinse” composition which is applied to the hair after octadecyl vinyl ether; N-hydroxymethyl acrylamide, N-washing of the hair with a shampoo.

droxymethyl methacrylamide, N - [(hydroxy-2) ethyl] acryl- For example an aerosol hair spray may be amide, N - [(hydroxy-2) ethyl] methacrylamide, N-hy- acid 35 produced by conditioning in an aerosol can of 0.2 to 8% droxymethyl maleamic, N-hydroxymethyl maleamide, the by weight of a copolymer according to the invention, from 6 to 30% and N, N'-dihydroxymethyl maleamide , N-hydroxymethyl acid ita- preferably from 8 to 25% by weight of an alcohol, the remainder being conamic, N-hydroxymethyl itaconamide, N, N-dihydroxy- essentially consisting of a propellant liquefied under methyl itaconamide , N- [(hydroxymethyl-1) propyl] acryl-pressure such as dichlorodifluoromethane, trichlorofluoro-amide, N - [(hydroxymethyl-1) propyl] methacrylamide, 40 methane, nitrous oxide or gas carbonic or N - [(methyl-1 hydroxymethyl-1) ethyl-1] acrylamide, N - [(mixtures thereof.

thyl-1 hydroxymethyl-1) ethyl-1] methacrylamide, N- [tris ^ As the alcohol, ethanol or

(hydroxymethyl) -1.1, l methyl] acrylamide, laN- [tris (hydroxy- isopropanol.

methyl) -1, 1,1 methyl] methacrylamide, N - [(3-hydroxy-dimé) The setting lotions can be for example réali-thyl-1,1) butyl] acrylamide, N - [(hydroxy -3 dimethyl-1,1) fired by introducing into a hydroalcoholic solution having a tyl] methacrylamide, N - [(2-hydroxy) ethyl] N-methyl acryl- titer of 20 to 66% in alcohol, 0.3 to 6% by weight of an amide, N - [(2-hydroxy) ethyl] N-methyl methacrylamide, the copolymer obtained by the process according to the invention.

N- [bis (hydroxymethyl) -1,1 ethyl] acrylamide and N- [bis (hy- The cosmetic composition may also contain droxymethyl) -1,1 ethyl] methacrylamide. conventional cosmetic adjuvants such as perfumes,

The copolymers prepared by the process according to the invention 50 dyes, preservatives, plasticizers, catio-products preferably have a molecular weight of between 1000 and nics, non-ionic products, silicones to improve 500,000 and more particularly a molecular weight including gloss or other cosmetic resins.

between 2000 and 200,000. In order to better understand the invention, we will

In a particular embodiment, the copolymers now described by way of illustration and without any character are crosslinked with a crosslinking agent in a limiting proportion 55 various examples of preparation of the copolymers thus comprised between 0.01 and 2% by weight relative to by total weight as different examples of compositions based thereon. monomers reacted.

Examples of the preparation of copolymers

Among the various crosslinking agents which can be used, mention may in particular be made of: diethyl dimethacrylate. Example 1

Iene glycol, diallyl ether, tetra allyloxyethane, dimeth- In a one liter flask fitted with a condenser, a stirrer

ethylene glycol acrylate and ethylene glycol diacrylate. mechanical torch and a nitrogen adductor tube, we introduce:

According to a particular embodiment when the radical R4 represents a free carboxylic acid function, the latter - 400 g of ethanol,

can be neutralized with at least one organic base, such as 65 - 55 g of N-tertiobutyl acrylamide,

as monoethanolamine, diethanolamine, triethanol - - 27.5 g of acrylamide,

amine, isopropanolamines such as tri-isopropanol - - 17.5 g of methyl methacrylate,

amine, morpholine as well as certain amino alcohols such as and -1 g of azo isobutyronitrile.

The reaction mixture is heated at 80 ° C for 8 hours using a thermostatically controlled device and then allowed to cool to room temperature.

The solution is then poured, drop by drop, into a container containing, as precipitator, ethyl acetate. The precipitated polymer is then filtered and dried under reduced pressure.

Efficiency: 76%

Viscosity: 2.95 cPo (in 5% solution in DMF at 34.6 ° C).

Example 2

According to the same procedure as that described in Example 1 above, the following are copolymerized:

- 65 g of N-tertiobutyl acrylamide

- 20 g of acrylamide

- 15 g of N-hydroxymethyl acrylamide and - 1 g of azo bis isobutyronitrile.

Viscosity: 2.61 cPo (in 5% solution in DMF at 34.6 ° C).

Other examples of copolymers (Examples 3 to 17) are given in Table I. All of these copolymers were prepared according to Example 1, only the nature of the precipitant is different.

ON M

O M

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

50

40

50

60

60

50

35

40

40

40

40

30

20

35

30

25

20

30

30

15

35

15

40

40

40

20

30

55

25

5

25

40

20

20

Table I Examples

N-T-butyl acrylamide Acrylamide N-vinyl pyrrolidone Acrylonitrile

Styrene 10

Hydroxy-2-ethyl methacrylate 25

Methyl methacrylate 15 10 25

Stearyl methacrylate 5

Vinyl acetate 20

Diethyl maleate 20

Butyl vinyl ether

Dimethyl methacrylate 20

aminoethyl 35

Polyethylene methacrylate 40

glycol monomethyl ether 40 20 40

N - [(methyI-l hydroxymethyl-

1) ethyl-1] acrylamide 25

Precipitating © © © © © © @ © © © © © ©

Viscosity (at 5% in the

DMF) 34.6 ° C 2.22 2.32 2.00 2.10 2.18 2.54 2.31 1.85 1.60 2.15 2.05 2.90 2.35 2.18 2 , 18

Ref. : © Petroleum ether © Diethyl ether © Acetone @ Heptane

7

622,024

Examples of composition

Example A

A styling lotion is prepared according to the invention by mixing the following ingredients:

Polymer prepared according to Example 1 2

Perfume 0.1

Ethanol 45

Water q.s.p. 100

This conventionally applied styling lotion gives the hair a shiny appearance and excellent hold over time.

In this example, the copolymer prepared according to example 1 can be replaced by an equal amount of the copolymer prepared according to examples 5, 10-12 and 15.

93 g of this solution are then packaged in an aerosol can and carbon dioxide is introduced so as to bring the internal pressure to approximately 8 bars.

In this example, the polymer prepared according to example 11 5 can advantageously be replaced by the same amount of one g of the polymers prepared according to examples 12, 14 and 16.

g g Example D

g A styling lotion is prepared according to the invention by m mixing the following ingredients:

Polymer prepared according to Example 9 (quaternized with dimethyl sulfate) 2 g

Perfume 0.1 g

Isopropanol 45 g

15 Water q.s.p. 100g

Example B

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

Polymer prepared according to Example 2 4 g 20

Perfume 0.3 g

Ethanol q.s.p. 100g

25 g of this solution are conditioned in an aerosol can with 47 g of trichlorofluoromethane and 28 g of dichlorodifluo-romethane. 25

By spraying this lacquer, a beautiful shiny appearance of the hair is obtained as well as a strong lacquering power.

The hair is soft to the touch and the hairspray is easily removed by combing or brushing.

In this example the copolymer prepared according to Example 2 can be replaced by an equal amount of copolymer prepared according to Examples 3,4,6-8 and 10.

Example C

An aerosol hair lacquer is prepared according to the invention by mixing the following ingredients:

Polymer prepared according to Example 11 5 g

Perfume 0.07 g

Ethanol q.s.p. 100g

This conventionally applied styling lotion gives the hair a shiny appearance and excellent hold over time. The polymer according to Example 9 can advantageously be replaced by the same amount of the polymer according to Example 13 also quaternized.

Example E

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

Polymer prepared according to Example 2 4 g

Perfume 0.3 g

Ethanol 100 g

25 g of this solution are conditioned in an aerosol can with 47 g of trichlorofluoromethane and 28 g of dichlo-rodifluoromethane.

By spraying this lacquer, a beautiful shiny appearance of the hair is obtained as well as a strong lacquering power.

The hair is soft to the touch and the hairspray is easily removed by combing or brushing.

In this example, the polymer according to Example 2 can advantageously be replaced by the same amount of the polymer according to Example 17.

VS

Claims (16)

622,024 2 CLAIMS (iv) C H -COOR " 1. Process for the preparation of new copolymers, charac- [| terrified by the fact that it consists in reacting en masse, pending çjj -COOR " sion or emulsion, in a suitable solvent, in the presence of a polymerization catalyst: 5 (a) at least one monomer of formula: (in which: R "represents an alkyl radical having from 1 to 3 atoms of Ri ^ 2 carbon, (VI) I CHU = C -C -NH- C - (X) „- R II I o r3 (!) io (v) CH2 = CH-0-R1i (VII) in which: R10 represents a linear or branched saturated alkyl radical, in which: having from 1 to 17 carbon atoms, R represents an alkyl radical, linear or branched having from 1 to 10 to 10 carbon atoms, R 1, R 2 and R 3 represent either an atom ^ of hydrogen, i.e. a methyl radical, 111 and n is 0 or 1; when n = 1, X represents an atom and (vi) R - CH = C -CCH) -CON -Z-OH oxygen, 13 | p (^ at least one monomer of formula: 20 r (Wine) M2 R4-CH = C - (CH2) m-CONH2 I R5 (he) in which: m is 0 or 1 if m = 0 R .; is either a hydrogen atom or the radical - COOH and R5 is a hydrogen atom or a radical -CH3, if m = 1 R4 is a hydrogen atom and R5 represents the radical - COOH and (c) at least one monomer taken from the group consisting of styrene, the N-vinylpyrrolidone and the monomers of the following formulas: 35 (i) CH2 = C -CN I rfi (III) 40 in which: R6 represents a hydrogen atom or a methyl radical, (ii) CH2 = C —C — O — r8 I II r7 o (IV) < in which: R7 represents a hydrogen atom or a methyl radical and R8 represents a linear or branched alkyl radical having from 1 to 18 carbon atoms, a radical: - (CH2) 2-N (CH3) 2, quaternized or not, a radical -CH2-CH2OH, the radical -CH2-CH -CH2OH and the radical I OH - (CH2 -CH20) / - R ' in which R ′ represents a methyl or ethyl radical and / is 12, 55 (iii) R, -C -0-CH = CHn II O (V) in which: R9 represents a linear or branched alkyl radical having from 1 to 16 carbon atoms, in which: rn represents a hydrogen atom or a methyl radical, Z represents a linear or branched alkylene radical of 1 to 6 carbon atoms, substituted or not by one or two hydroxymethyl functions and p is 0 or 1 if p = 0, R13 is either a hydrogen atom or the radical —COR14 Ri4 being -OH or the radical -NH-R15, R15 being a hydrogen atom or the radical —Z-OH, and RI2 is a hydrogen atom or the radical -CH3 if p = 1, R13 is a hydrogen atom and r12 is the radical -CORJ4, R14 having the same meaning as above. 2. Method according to claim 1, characterized in that the copolymers obtained result from the copolymerization of 5 to 90% by weight of at least one monomer of formula (I), from 5 to 90% by weight of at least a monomer of formula (H) and from 5 to 60% by weight of styrene, of N-vinylpyrrolidone or of at least one monomer corresponding to those of formulas (III) to (VIII). 3. Method according to one of claims 1 and 2, characterized in that the monomers of formula (I) are taken from the group consisting of: N-tertiobutyl acrylamide, N-octyl acrylamide, N-decyl acrylamide , N-dodecyl acrylamide, N - [(dimethyl-l, l) propyl-1] acrylamide, laN - [(dimethyl-l, l) butyl-1] acrylamide, N - [(dimethyl-l, l ) pentyl-1] acrylamide, N-isobutoxymethylacrylamide and the corresponding methacrylamides. 4. Method according to one of claims 1 and 2, characterized in that the monomers of formula (II) are taken from the group consisting of: acrylamide, methacrylamide, maleamic acid and itaconamic acid. 5. Method according to one of claims 1 and 2, characterized in that the monomers of formulas (DI) to (VIII) are taken from the group consisting of: acrylonitrile, methacrylo-nitrile, acrylates and methacrylates methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, decyl, dodecyl, octadecyl, 2-hydroxyethyl, NN-2-dimethylaminoethyl, quaternized or not and of o-methyl or ethyl polyethylene glycol; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, tetramethyl vinyl, vinyl pivalate, vinyl neoheptanoate, vinyl neoctanoate, vinyl neodecanoate, tetramethyl-2 , 2,4,4 vinyl valerate, 2,3-isopropyl-2,3-dimethyl vinyl butyrate; dimethyl maleate, diethyl maleate, dimethyl itaco-nate, diethyl itaconate, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isopropyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether; N-hydroxymethyl acrylamide, N-hydroxymethyl methacry-Iamide, N - [(hydroxy-2) ethyl] acrylamide, N - [(hydroxy-2) ethyl] methacrylamide, N-hydroxymethyl maleamic acid, N -hydroxymethyl maleamide, N, N'-dihydroxymethyl maleea-mide, N-hydroxymethyl itaconamic acid, N-hydroxymethyl itaconamide, N, N-dihydroxymethyl itaconamide, N - [(hydroxymethyl-1) propyl] acrylamide, N- [hydroxymé-thyl-1) propyl] methacrylamide, laN - [(methyl-l hydroxymé-thyl-1) ethyl-1] acrylamide, N - [(methyl-l hydroxymethyl-1) ethyl-1] methacrylamide , N- [tris (hydroxymethyl-1,1,1 methyl] acrylamide, N- [tris (hydroxymethyl) -1,1,1 methyl] methacrylamide, N - [(3-hydroxy-dimethyl-1,1) butyl] acryla- J 622 024 mide, N - [(3-hydroxy-1,1-dimethyl) butyl] methacrylamide, N- [(2-hydroxy) ethyl] N-methyl acrylamide, laN- [(2-hydroxy) ethyl] N-methyl methacrylamide , N- [bis (hydroxymethyl) -1.1 ethyl] acrylamide and N- [bis (hydroxymethyl) -1.1 ethyl], methacrylamide. 6. Method according to one of claims 1 and 2, characterized in that the copolymers have a molecular weight between 1000 and 500,000 and preferably between 2000 and 200,000. n, 7. Method according to one of claims 1 and 2, characterized in that the copolymers obtained correspond to the following general formula: R, ■ CH .. L o R. NH - C! R. i4 -CH w (X) n - R Rr (CEL) 2 m C = O NEL -M x: in which: the radicals R, Rb R2, R3, R4 and R5, n, m and X have the same meanings as those given in claim 1, w. corresponds to 5 to 90% by weight, x corresponds to 5 to 90% and y corresponds to 5 to 60% by weight, and M represents a styrene unit, an N-vinylpyrrolidone unit or a unit of an unsaturated monomer such as those of formulas (III) to (VIII) given in claim 1. 8. Method according to claim 1, characterized in that the polymerization reaction is carried out in the presence of a crosslinking agent in a proportion of between 0.01 and 2% by weight relative to the total weight of the monomers. 9. Method according to claim 8, characterized in that the crosslinking agent is taken from the group consisting of: diethylene glycol dimethacrylate, diallyl ether, tetra allyloxyethane, ethylene glycol dimethacrylate and di - ethylene glycol acrylate. 10. Method according to claim 1, characterized in that the catalyst concentration varies from 0.2 to 10% by weight relative to the monomers reacted. 11. Cosmetic composition, characterized in that it contains in a cosmetic vehicle at least one copolymer obtained by the process according to claim 1. 12. Composition according to claim 11, characterized in that it is packaged in an aerosol can and contains from 0.2 to 8% by weight of copolymer, from 6 to 30% and preferably from 8 to 25% by weight of an alcohol, the remainder being essentially constituted by a propellant gas liquefied under pressure. 13. Composition according to claim 11, characterized in that it is a hydroalcoholic solution containing from 0.3 to 6% by weight of copolymer and constitutes a styling lotion. 14. Composition according to one of claims 11 to 13, characterized in that it also contains perfumes, dyes, preservatives, plasticizers, cationic products, non-ionic products, silicones or other cosmetic resins. 40 45