LU83703A1 - NOVEL COSMETIC COMPOSITION AND ITS APPLICATION TO PERMANENT DEFORMATION OF HAIR - Google Patents

Description

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Patent application, h. &> h. .....

Designation of the Inventor - »« »- C) The undersigned ......... Jean ... Waxweil.gr .................... .................................................. .................................................. ....................................

21-25, Allée Scheffer, Luxembourg acting as ci6Xîë | S8SâHf - as agent for the depositor - (j) L'OREAL S.A. 14, rue Royale, 75008 PARIS, France (5) of the invention concerning:

New cosmetic composition and its application to permanent deformation of the hair.

designates as inventor (s):, * Grollier Jean-François 1. Surname and first names __________________________________________________-_______________________________________________________________________________________: _______________________

Address 16bis, Boulevard Morland, 75004 PARIS- France_________ 2. Last and first names —Madr.ang.a .... Ann.ie .., ___________________________________________________________________________________________________________________________________

Address 4, rue du Prieuré, 78100 ST. GERMAIN-EN-LAYE, France 3. Full name _________________________________________________________________________________________________________________________________________________________________________________

Address ..._________________________________________________________________________________________________________________________________________________________________________________________________

He affirms the sincerity of the aforementioned indications and declares to assume full responsibility for them.

Luxembourg on January 21, 19 82

AT

_________ [MÀ __________ (signature) A ¢ 8026_j_ (') Last name, first names, company, address. ^

Pl Klnm nrZnnmr n / iracea rlii #lar "Aennf" Ionene C8 - permanent "L- ^ Gsg t,

NEW PATENT APPLICATION TO BE FILED IN LUXEMBOURG IN SUPPORT OF AN INVENTION PATENT APPLICATION

On behalf of the so-called Anonymous Company: L'OREAL

For: "New cosmetic composition and its application to permanent hair deformation".

'Xi - 1 -: ί * The present invention relates to a new cosmetic composition / as well as its application to permanent deformation of the hair.

It is known that the conventional technique for carrying out permanent deformation of the hair consists in / firstly, in opening the disulphide bonds of the keratin using a composition containing a reducing agent (reduction step), then , after having preferably rinsed the hair, to reconstitute in a second time said connections by applying, to the hair under tension, an oxidizing composition, (oxidation step, also called fixing) so as to give the hair the desired shape . It is also known that this technique makes it possible to carry out the waving of the hair as well as its straightening or straightening.

The reducing and oxidizing compositions are well known and described in most of the cosmetology works, in particular in the book by E. SIDI and C. ZVIAK, Problèmes Capillaires Paris, 1966 (Gauthier Villard).

The compositions for the first stage of a perming operation contain, in addition to the reducing agent, adjuvants making it possible to present them in the form of lotions, creams, gels or powders to be diluted in a liquid support.

It is well known that the processes of permanent deformation of the hair have the defect of weakening them and of harming their general appearance.

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.! i * We have already recommended the use in compositions - 2 - -. In hair cosmetics, various cationic polymers and in particular polymers of the ionene type, and French patent application No. 76.20261, published under No. 2.316.27l, has described certain asymmetric ionenes and their use in various cosmetic compositions in particular for hair. The use of these cationic polymers in. cosmetic compositions generally confer on these compositions interesting properties which have been explained in part by the fact that these polymers generally have a good affinity for keratin fibers.

We have now discovered that by using certain particular asymmetric ionenes, we unexpectedly obtain significant protection against the effect of hair degradation on contact with the reducing solutions used in the first stage of the deformation operations. permed.

More specifically, it has been observed that by using particular asymmetric ionenes having a relative proportion of short chain side substituents and chain side substituents having 6 to 10 carbon atoms, significant protection of the hair is observed, whereas neighboring analogous products with shorter or longer lateral substituents protect the hair only in markedly lesser proportions, as will be shown below in the experimental section.

It has also been observed that the use of the ionenes of formula (I) in the reducing composition of the first stage of an operation for permanent deformation of the hair leads to less degradation of the mechanical properties / "nhiavonv v I

- 3 - '»Λ j>' In addition, it has been verified that the ionenes of formula I do not have an unfavorable effect on the degree of crimping of the permed hair.

The subject of the present invention is a cosmetic reducing composition for the first stage of a permanent hair deformation operation, said reducing composition comprising, in a usual excipient, at least one reducing agent and at least one cationic polymer of the ionene type, characterized by the fact that said ionene consists of recurring units of formula I: 1) - 4 -

R R

-N® - A - N®-B- 2ΧΘ (I)

!, I

R 'R

in which: A and B, identical or different, represent a divalent hydrocarbon-based group which can be substituted and / or contain heteroatoms, the substituents R, equal or different, represent an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, X is a anion, and R 'represents a hydrocarbon radical having 6 to 10 carbon atoms.

In polymers with units of formula

Q

(I), X is preferably a halide anion, in particular chloride, bromide or iodide; R is preferably a methyl group; R ′ is in particular an alkyl group having from 6 to 10 carbon atoms, a phenyl-alkyl group in which the alkyl has from 1 to 3 carbon atoms or a cyclohexyl group; preferably R 'is a group having 8 carbon atoms and in particular an n-octyl group; A and B represent hydrocarbon groups optionally substituted (in particular by groups -OH and = O) and optionally comprising heteroatoms, one of the groups A and B possibly containing from 2 to 20 carbon atoms and the other from 3 to 20 carbon atoms; A and B may in particular represent linear or branched alkylene or alkenylene groups (the branching groups preferably having 1 to 3 carbon atoms), which may contain, intercalated in the main chain, one or more rings or heteroatoms; for example A and B can represent groups of formula - (Cf ^^ - Z- (QE ^) n ~ in which m and n are whole numbers which can vary from 1 to 10, and Z 2Γ ΘΌΓ 11ΠΑ 1 T 3 1 ζΠΠ 1 ÄrvhiÄ Hironfû nr * ûf ûrnafnmû f.

- 5 - / or group of heteroatoms such as -0-, -S-, -S0-, -S09-SS-, Φ Θ -N (R ") -, -N (R") (R "') -.Y, -CHOH-, -NH-CO-NH-, -C0-N (R ") -, -CO-O-, -N (R1) - (C0-D1) yN (R2) -, - N (R ^^) -SC ^ -N (R2> - or -0-C0NH-, ^

Q

and R2 being hydrogen or lower alkyl, Y representing an anion derived from a mineral or organic acid, R "being hydrogen or lower alkyl, R '" being lower alkyl; or Z also represents an arylene, diaminoalkylene, diaminocycloalkylene or diaminoarylene group; for example Z can represent a group —CgH ^ -Z'-C ^ H ^, (and in this case m and n can moreover represent the number zero) Z ′ being in particular a direct covalent bond or a group -CH2-, - C (CH3) 2-, -CO-, -0-, -CHOH- or —S02 ~.

In what follows, for simplicity, the polymers whose recurring units correspond to formula (I) will be designated by the expression "polymer of formula (I)".

Generally, the molecular mass of the polymers of formula (I) used in the compositions of the invention varies from 1000 to 100,000.

The polymers of formula (I) can be prepared according to the method described in the French patent application No. 76.20261 already cited, or by an analogous method, starting from di-tertiary diamines and suitable dihalides.

representing an alkylene optionally interrupted by a group -SS-, an alkenylene, an arylene, a diaminoalkylene, a diaminoarylene, a dioxyalkylene, a polyoxyalkylene or a dioxyarylene, or alternatively, representing a direct covalent bond, there being a number equal to 0 or 1.

il -: »- * To prepare the polymers of formula (I): - 6 -4 a) or else a di-tertiary diamine of formula is subjected to a polycondensation reaction:

R R

I [

NOPE

I I

R 'R

and a di-halide of formula X-B-X, in which A, B, R, R 'and X have the meanings mentioned above, b) or else a ditertiary diamine of formula is subjected to a polycondensation reaction:

R R

I!

N-B-N

I I

R 'R

and a di-halide of formula: X-A-X.

The polycondensation reaction is carried out, for example, according to method a) or b) above, in a solvent or in a mixture of solvents favoring the quaternization reactions, such as water, dimethylformamide, acetonitrile, lower alcohols, especially lower alcohols, such as methanol, etc.

The reaction temperature generally varies between 10 and 150 ° C approximately, and preferably between 20 and 100 ° C.

The reaction time depends on the nature of the solvent, the starting reagents and the degree of polymerization desired.

The starting reagents are generally reacted in equimolar quantities, but it is possible to use either the diamine or the di-halide in slight excess, this excess being less than 20 mol%.

io - 7 -

It is possible to adjust the average length of the chains by adding at the start or during the reaction a small amount (1 to 15 mol% relative to one of the reagents) of a monofunctional reagent such as a tertiary amine or a mono-halide. In this case, at least part of the terminal groups of the polymer I obtained is constituted either by the tertiary amine group used, or by the hydrocarbon group of the mono-halide.

It is also possible to use, instead of the starting reagent, either a mixture of di-tertiary diamines, or a mixture of di-halides, or else a mixture of di-tertiary diamines and a mixture of di-halides, provided that the ratio total molar amounts of diamines or di-halides is close to 1;

The di-tertiary diamines used as starting materials in the process described above are known or can be prepared by application of known methods.

For example, the diamines of formula:

R R

/ "- (CH2> —N \

R 'R

with n ^ = 3 can be obtained by cyanoethylation of secondary amines

R

NH

R 'according to Whitmore et al. JACS 6d> p. 725 (1944), then reduction of the propionitrile amine and methylation according to the Eschweiler - Clarke method using the formaldehyde - formic acid mixture (cf. Chem. Ber. _38 p. 880 (1905) and JACS _55 P. 4571 (1933) Other diamines used as starting materials in the present application can be prepared for example by methylation according to the method described above of diamines R \ H \ y NA-NH2 OR > NA-NH2 R 'R' themselves obtained by a method deriving from that described by HE Franck et al., JACS 67_ p. 882 (1945) or else by analogy with the method described in US Patent No. 3,234. 139.

L) t '* - 9 -

The terminal groups of the polymers of formula (I) vary in particular with the proportions of the starting reactants.

They can be of the type (R) (R ') N-A-, (R) 2N- or X-B-,

Among the polymers of formula (I), there may be mentioned in particular the following polymers, for which: - A = (CH2) 3, B = (CH2) 6, R = CH3, R '^ CgH ^ and X = C1 or Br; - a = (CH2) 3, B = p-xylylényle, R = CH3, R '= CgH ^ and X = Br or Cl; - A = (CH2) 3, B = -CH2CHOHCH2-, R = CH3, R '= C8H17 and X = Br or Cl; - A = (CH2) 6, B = (CH2) 4, R = CH3, R '= C8H17, and X = Br or Cl; - A = (CH2) 10, B = (CH2) 2-0- (CH2) 2-, R = CH3, R '= CgHl7 and X = Br or Cl; - A = (CH2) 3, B = (CH2) g, R = CH3, R '= benzyl and X = Cl or Br; - A = (CH2) 3, B = (CH2) 4, R = CH3, R '= CgHl7 or cyclohexyl and X = C1 or Br

The reducing composition of the invention is of the same type as those commonly used in perming operations, that is to say preferably consists of a solution containing at least one reducing agent such as for example a mercapta'n, an alkali or ammonium sulfite or bi-sulfite, said composition having a pH generally between 6.5 and 10.

Preferably the reducing agent is present in the composition at a concentration of 2 to 25% by weight relative to the total weight of the reducing composition. This reducing agent, which is a reducing agent usually used in

V

- 10 - »* * operations of permanent deformation of the hair, can be for example thioglycolic acid or thiolactic acid or a mixture of these acids? in this case the concentration of these reducing agents is generally between 2 and 11% by weight.

The reducing agent can also be a sulfite or an alkali or ammonium bi-sulfite; in this case the concentration is generally between 2 and 15%.

The reducing agent can also be an ester of thioglycolic or thiolactic acid (for example glycerol or glycol monothioglycolate), at a concentration of for example between 5 and 25% by weight.

The reducing agent can also be cysteine or one of its derivatives, for example its salts such as the hydrochloride.

The pH of the reducing compositions is generally obtained using alkaline agents such as for example ammonia, monoethanolamine, diethanolamine, triethanolamine, a carbonate or an alkali or ammonium bicarbonate.

The reducing compositions of the invention can also be of the exothermic type, that is to say causing a certain heating during application to the hair, which brings a certain pleasure to the person who undergoes the first time of permanent deformation. .

The polymer of formula I is generally present in the reducing compositions at a concentration of between 0.2 and 5% by weight relative to the total weight of the composition.

- 11 - ”. Of course, if desired, the compositions of the invention can be presented either with the ionene I already dissolved in the reducing solution, or with the ionene presented separately and then having to be added at the time of use of the reducing solution. This is of course specified in the instructions for use of the composition.

In addition to the reducing agent and ionene I, the reducing compositions can also contain various ingredients such as, for example, softening agents and in particular quaternary ammoniums, lanolin derivatives, protein hydrolysates, waxes, opacifying agents, perfumes, colorants, nonionic or cationic surfactants or treating agents, as well as other cationic polymers, and in particular ionenes other than those of formula I.

In the case of a straightening or straightening operation, the reducing composition is preferably presented in particular in the form of a cream so as to keep the hair as straight as possible. These creams are produced in the form of "heavy" emulsions, for example based on glyceryl stearate, glycol stearate, self-emulsifying waxes, fatty alcohols, etc. It is also possible to use liquids or gels containing thickening agents such as carboxyvinyl polymers or copolymers which "stick" the hair and keep it in the smooth position during the setting time.

The invention also relates to a process for permanent deformation of the hair, consisting firstly in reducing the disulfide bonds of keratin by application of a reducing composition containing a cationic polymer, then in a second time in reforming said bonds. - 12 -,. »Sounds by application of an oxidizing composition, this process being characterized in that said cationic polymer is a polymer of formula (I) as defined above.

The hair to which the permanent deformation treatment is applied must of course be subjected, in a known manner, to an extension allowing, during the fixing step, to reform the keratin bonds of the hair while the latter are in the new form. desired.

In the case of waving, the new shape is obtained by the use of rollers or curlers. In the case of straightening, the new shape is obtained, for example by straightening the hair.

In the case where the method of the invention is a method of waving the hair, the reducing composition is applied to wet hair previously wound on rollers having 4 to 20 mm in diameter or else the composition is applied as and as it is being rolled up, it is left to act for a time of 5 to 60 minutes, in particular from 5 to 30 minutes, it is rinsed thoroughly after which the oxidizing composition is applied to the coiled hair.

After having allowed the said composition to act for a time of between 2 and 10 minutes, the rollers are removed and the hair is rinsed thoroughly and then dried.

In the case of a straightening or straightening operation, the mechanical deformation of the hair allowing it to be fixed in its new shape is generally obtained by an operation of straightening the hair after application of the reducing composition, with a comb with large teeth, with the back of a comb or by hand. After an exposure time of 5 to 60 minutes, in particular 5 to 30 minutes, one generally proceeds to a new smoothing, however, avoiding drawing too much - 13 - d * * on the hair, then rinsing thoroughly and applying the <4 oxidizing or fixing composition which is left to act for 2 to 10 minutes approximately. Then rinse the hair thoroughly.

The oxidizing compositions used in the second stage of the process of the invention are the conventional oxidizing compositions used in the operations of permanent deformation of the hair. It is known that these compositions contain, as oxidizing agent, hydrogen peroxide, an alkaline bromate or a persalt or a mixture of alkaline bromate and a persal.

The concentration of hydrogen peroxide can vary from 3 to 10 volumes, the concentration of alkali bromate from 2 to 12% and the concentration of parsley from 0.1 to 15% by weight, relative to the total weight of the oxidizing composition.

The oxidizing compositions can also contain various ingredients and in particular stabilizing agents, preserving agents, softening agents, surface-active agents, opacifying agents, perfumes, dyes, sequestering agents, acidifying or basifying agents, etc. ..

The oxidizing compositions for carrying out the process of the invention can also be like the reducing compositions of the exothermic type, that is to say of the type developing during application a certain amount of heat making it possible on the one hand to accelerate the reconstitution of the disulfide bonds and on the other hand to bring an approval for the person to whom the treatment of permanent deformation is applied. Such compositions are described in particular in French patent No. 2,179,025.

i - 14 - »The invention also relates to a complex composition intended to implement the process of 1-'invention. This complex composition, consisting of the reducing and oxidizing compositions described above, intended to be applied one after the other, is contained in a packaging suitable for several compartments, provided with instructions for use.

The following examples illustrate the invention without, however, limiting it.

V

- 15 -. ”EXAMPLE 1

Permanent deformation is carried out by applying the following reducing composition to all of the hair: - Thioglycolic acid ............. 6.0 g - Thiolactic acid ........ ....... 3.0g - Ammonia at 22 ° Be .............. 10.0g - Ammonium bicarbonate ........... 6 , 0g - Sequestering agent ................ 0.4g - Polymer 1 (in active material) ... 2.0g * - Oleic alcohol 20 OE ...... ..... 1.0g - Protein hydrolysates ......... 0.5g - Perfume, color, opacifying agent, deionized water qs ............. 100ml

Polymer 1 is an ionene corresponding to formula I with A = (CH2) 3 B, = (CH2) 6 R "CH3, R '= CgHl7 and X = Cl.

O.E stands for "ethylene oxide".

The hair is then rolled up on rollers having a diameter of 10mm and then the composition is left to act for a period of 15 minutes.

After rinsing, the following oxidizing composition is then applied to the reduxed hair: - Stabilizer ...................... 0.05g - Peptizing agent .... .............. 1.0g - Perfume ........................... 0.3g - H202 ............. qs 8 volumes - Citric acid ..... qs pH 3 - Deionized water qs ............. 100ml

The oxidizing composition is left to act for 5 minutes, then the hair is rinsed with water and the rollers are then removed.

EXAMPLE 2

The procedure is as in Example 1 but using the following reducing composition: - 16 - * '- Sodium bisulphite .............. 4.0g - Ammonium sulphite ... ............ 3.0g - Mo no ethano lamin ................. 4.0 g - Sequestering agent ...... .......... 0.3g - Polymer 1 (in active material) ... 1.0g - Homopolymer of dimethyldiallyl ammonium chloride of PM less than 100,000 sold by the company MERCK under the name MERQUAT 100 (active ingredient) 0.5g - Polyoxyethylenated nonylphenol with 9 moles of ethylene oxide ....... 1.0g - Perfume .................. ......... 0.5g - Colorant, opacifier, deionized water qs ............. 100ml EXAMPLE 3

The procedure is as in Example 1, but using the following reducing composition: - Thioglycolic acid ............. 7.0 g - Ammonia at 22 ° Bé ......... ..... 6.0g - Monoethanolamine ................. 1.0g - Ammonium bicarbonate ........... 3.0g - Sequestering agent ................ 0.5g - Polymer 1 (in active matter) ... 0.5g - Polymer 2 (in active matter) ... 1.0g - Polyoxyethylene oleic alcohol containing 20 moles of ethylene oxide ...... 1.0g - Perfume ........................... 0.5g - Colorant, opacifier, deionized water qs ................. 100ml

Polymer 2 is an ionene which has units similar to those of formula I, with A = (Ci ^) ^, B = (CE ^) ^, and X = Cl, but for which R 'would represent, as well as R , a methyl group.

4o - 17 - EXAMPLE 4 t v

The procedure is as in Example 1 but using the following reducing composition: - Thioglycolic acid ............. 5.0 g - Ammonium bicarbonate .......... 5.0g - Sequestering agent ................ 0.3g - Polymer 1 (in active material) ... 1.0g - Polyoxyethylene oleic alcohol with 20 moles of oxide ethylene ...... 1.0g - Perfume .................. ........ 0.5g - Colorant, opacifier, deionized water qs ................. 100ml EXAMPLE 5

Study of the protective effect provided by the ionenes of formula I.

It is known that treatment with a reducing solution attacks hair which undergoes weight loss.

To study the protective effect provided by the ionenes of formula I, the weight loss was measured after immersion in the reducing agent and drying.

Procedure

For each composition studied, four wicks of 0.50 g - 0.03 g were used.

The locks are then kept in a desiccator for 12 hours and then weighed (weight Po).

The locks are then immersed in the reducing composition for 90 minutes, the liquid / lock ratio being approximately 20.

The locks are then rinsed three times in 100ml of water for 15 minutes.

They are then placed in an oven for 12 hours at 105 - 5 ° C and then cooled for 45 minutes in a desiccator and weighed (weight PI).

The weight loss is then calculated in% for each lock, determined according to the following formula:

- io »L

T

- 18 -

The reducing composition of the following formula was used: - Thioglycolic acid ............. 8g - Thiolactic acid ............... 2g - Ammonia at 22 ° Be .............. 10.5g - Ammonium bicarbonate ........... 7g - Sequestering agent ........... ..... 0.2g - Peptizing agent .................. 0.9g - Deionized water qs ............. 100ml pH 8.2

This reducing composition also contained, with the exception of the control reducing composition, 3% by weight of an ionene (as active material) corresponding or analogous to formula I with A = (CH ^ g, B = (Cî ^ Jg, R = CH ^, X = Cl, and R 'respectively representing a methyl group (ionene C1), butyl (ionene C ^), octyl (ionene Cg), dodecyl (ionene C. ^) and octadecyl (ionene C ^ g) · The ionene Cg is the polymer called "Polymer 1" in the previous examples.

The results obtained are summarized in Table I

following:

PAINTINGS

Composition Weight reduction x reduction in% without ionene 16.1 - 0.8 C1 13.6 - 0.5 C4 11.0 - 1.3 C8 0 C12 12.5 ί 1.1

Cl8 14.7 - 0.2

It can be seen from the results of Table I that the percentage of weight loss, which is high with a short side chain (C ion) ionene, decreases only slightly with the C ^ ionene. On the other hand, the weight loss is minimum with the Cg ionene. Then the percentage of weight loss increases when the side chain length increases as shown by the results obtained with the ionenes

Claims (11)

1 IR ′ R in which: A and B, which are identical or different, represent a divalent hydrocarbon-based group which can be substituted and / or contain heteroomes, the substituents R, equal or different, represent an alkyl or hydroxyalkyl group having from 1 Θ to 3 carbon atoms, X is an anion, and R 'represents a hydrocarbon radical having from 6 to 10 carbon atoms. 1. Cosmetic reducing composition for the first stage of a permanent hair deformation operation, said reducing composition comprising, in a usual excipient, at least one reducing agent and at least one "cationic polymer of the ionene type, characterized in that said ionene consists of recurring units of formula (I): RR -N®-- AN®-B- 2X® (I) 2. Composition according to Claim 1, characterized in that A and B represent hydrocarbon-based groups optionally substituted by groups -OH or = 0, and optionally comprising heteroomes, one of the groups A and B possibly containing from 2 to 20 carbon atoms and the other from 3 to 20 carbon atoms. 3. Composition according to claim 2, characterized in that A and B are linear or branched alkylene or alkenylene groups which may contain, interspersed in the main chain, one or more rings or heteretomas. 4. Composition according to claim 3, characterized in that A and B are alkylene groups. r 5. Composition according to any one of the preceding claims, characterized in that R is a methyl group. 6. Composition according to any one of the preceding claims, characterized in that R 'is an alkyl group having from 6 to 10 carbon atoms. 7. Composition according to claim 6, characterized in that R 'is a group having 8 carbon atoms. * 8. Composition according to claim 7, characterized in that R 'is an n-octyl group. 9. Composition according to any one of the preceding claims, characterized in that the said polymer is present in the reducing composition at a concentration of between 0.2 and 5% by weight relative to the total weight of the composition. 10. A method of permanent deformation of the hair, consisting firstly in reducing the disulfide bonds of keratin by application of a reducing composition containing a cationic polymer and then in a second step in reforming said bonds by application of an oxidizing composition, characterized in that said reducing composition is a composition as defined in any one of the preceding claims. 11. Composition according to Claim 2, characterized in that A and B represent hydrocarbon groups optionally substituted (in particular by groups -OH and = 0): and optionally comprising heteroatoms, one of the groups A and B possibly containing from 2 to 20 carbon atoms and the other from 3 to 20 carbon atoms; A and B may represent in particular linear or branched alkylene or alkenylene groups (the branching groups preferably having 1 to 3 carbon atoms), which may contain, intercalated in the main chain, one or more rings or heteroatoms; for example A and B can represent groups of formula - (CH, J -Z- (CH „) - in which m and n are integers which can vary from 1 to 10, and Z represents a direct covalent bond, a heteroatom or group of heteroatoms such as ® θ -O-, -S-, -SO-, -S02-, -SS-, -N (R ") -, -N (R") (R "') -. Y , -CHOH-, -NH-CO-NH-, -CO-N (R ") -, -CO-O-, -N (R ^) - (CO-D ^^ - N (R2) -, - N (R) -S02 “N (R2) - or -O-CONH-, R ^ and R2 being hydrogen or lower alkyl, representing an alkylene optionally interrupted by a group -SS-, an alkenylene, a diaminoalkylene , a diaminoarylene, a dioxyalkylene, a polyoxyalkylene or a dioxyarylene, or else representing a direct covalent bond @, y being a number equal to 0 or 1, Y representing an anion derived from a mineral or organic acid, R "being hydrogen or lower alkyl; or alternatively Z represents an arylene, diaminoalkylene, diaminocycloalkylene or diaminoarylene group; for example Z can represent a group -CgH ^ -Z'-CgH ^ -, (and in this case m and n can also represent the number zero), Z 'being in particular a direct covalent bond or a group -CH2 ~, -C (CH3) 2-, -CO-, -O-, -CHOH- or -S02 ~. * 1