FR2762000A1 - SYNTHESIS OF FLUORINE COPOLYMERS IN A HYDROCARBON MEDIUM - Google Patents

Abstract

The invention relates to the synthesis of fluorinated copolymers, and is intended for use in the hydrophobic and oil repellent treatment of textiles and leather. It specifically concerns a fluorinated copolymer solution in a hydrocarbonic solvent with a solubility factor of between 7 and 8 (cal/cm<3>)<1/2> and a flash point equal to or higher than 55 DEG C. The copolymer is formed from a mixture of monomers comprising at least one fluorinated (meth)acrylate, at least one non-fluorinated lipophilic monomer, and at least one silicated monomer.

Description

DESCRIPTION
The present invention relates to the field of fluorinated copolymers and more particularly relates to the synthesis of fluorinated copolymers in a hydrocarbon medium.

Fluorinated products intended for the hydrophobic and oleophobic treatment of textiles and leather can be applied in various forms, in particular during the dry cleaning of substrates or in the form of waterproofing aerosol. In all cases, they must be perfectly soluble in the solvents used.

For dry cleaning, there are two main classes of solvents. The first, widely used, is that of halogenated and in particular chlorinated solvents such as perchlorethylene; in this category are also used, but in a more specific way, hydrochlorofluorinated solvents such as l, l-dichloro-l-fluoro-ethane (HCFC 141b). Thus, US Patents 4,366,300 and US 3,341,497 describe fluorinated compositions used for hydrophobic and oleophobic treatment and presented in chlorinated solvents such as trichlorethylene, perchlorethylene and 1,1,1 -trichloroethane. Likewise, patent application WO 95/11949 proposes oleophobic and hydrophobic water-repellent fluorinated agents, used in dry cleaning and synthesized in a solvent of the hydrochlorofluorocarbon or hydrofluorocarbon type. However, most of these solvents have a negative effect on the ozone layer and recent decisions, taken on a global scale to protect this ozone layer, already prohibit the manufacture of solvents such as 1,1. , 2-trichloro-1, 2,2-trifluoroethane (CFC 113) and 1,1,1 -trichloroethane.

A second class of solvents which can be used for dry cleaning consists of petroleum or hydrocarbon solvents. Historically, white spirit was used for many years until the mid-1960s when it was gradually replaced by perchlorethylene; among the disadvantages associated with white spirit, we can mention its marked flammability with a flash point of 38 "C. The hydrocarbons available today for dry cleaning are characterized by lower flammability and also by a content of aromatic compounds. lower to avoid residual odors on clothing.These hydrocarbons, whose number of carbon atoms is generally between 10 and 15, are all flammable liquids of the second category with a flash point greater than or equal to 55 "C; their chemical structure is variable since n-paraffins (linear molecular skeletons), isoparaffins (branched molecular skeletons) and dearomatized paraffins (branched and cyclic molecular skeletons) can be used.

In terms of dry cleaning, the cleaning power of these hydrocarbons and their aggressiveness are at the same level as those of CFC 113 and lower than those of perchlorethylene. These properties allow their use on delicate textile structures and leathers. However, very few oleophobic and hydrophobic water-repellent fluorinated products have been proposed in such solvents; the essential difficulty of using hydrocarbons for the synthesis of fluorinated products is due to their low solubilization power of such products. Thus, in the case of a fluorinated copolymer, any increase in the relative proportion of perfluoroalkylated monomer is generally opposed to obtaining compositions of practical interest because it tends to be accompanied by a degradation of storage stability with , mainly, deposit formation. On the other hand, even if it can improve the stability, an increase in the relative proportion of fluorine-free monomers is most often done to the detriment of the hydrophobic and oleophobic performance. It may also be mentioned that the use of monomers comprising or not comprising polar groups capable of improving the adsorption of the polymer on the substrate to be treated or of allowing chemical reactions after application to the support (crosslinking for example) is problematic and may not occur. generally done at the expense of the storage stability of the final composition.

The difficulty linked to the choice of hydrocarbons as solvent can be circumvented by using for the synthesis a mixture of polar solvent and hydrocarbon, as proposed in patent applications JP 6 240 238 and
JP 6 248 257. Although these two patent applications provide for the possibility of using alone a hydrocarbon solvent such as decane, undecane or dodecane, they prefer to use a mixture of such a solvent with at least 10% by weight of a polar solvent. Likewise, US Pat. No. 5,284,902 claims the preparation of a fluorinated copolymer in a mixture of solvents, one of which is polar, followed by dilution in a hydrocarbon solvent.

However, the introduction of a second solvent into the composition causes a complication during dry cleaning. The polar solvent can in particular become a source of pollution inside the dry cleaning machine.

On the other hand, it is more aggressive than hydrocarbon and can damage fragile textiles.

It has now been found new fluorinated copolymers which it is possible to synthesize in solution in a hydrocarbon solvent used alone (that is to say without having recourse to the use of a polar co-solvent) and which, after application to the support, are crosslinkable, which makes it possible to maintain the hydrophobic and oleophobic properties of the support after machine washing or dry cleaning.

dans laquelle RF représente un radical perfluoroalkyle, linéaire ou ramifié, contenant 2 à 20 atomes de carbone (de préférence 4 à 16), A représente un enchaînement bivalent lié à O par un atome de carbone et pouvant comporter un ou plusieurs atomes d'oxygène, de soufre etlou d'azote, et R1 représente un atome d'hydrogène ou un radical méthyle;
(b) 10 à 79 %, de préférence 20 à 60 %, d'un ou plusieurs monomères non fluorés lipophiles choisis parmi les composés de formules générales (II) et (III):

dans lesquelles R2 représente un atome d'hydrogène ou un radical méthyle, B est absent ou représente un enchaînement bivalent pouvant comporter un ou plusieurs atomes d'oxygène etlou d'azote, et R3 représente un radical alkyle, linéaire ou ramifié, contenant de 8 à 36 atomes de carbone (de préférence 12 à 24);
(c) 1 à 20 %, de préférence 1,5 à 10 %, d'un ou plusieurs monoméres siliciés choisis parmi les composés de formules générales (IV) et (V):

The subject of the invention is therefore a solution of fluorinated copolymer in a hydrocarbon solvent, characterized in that said solvent has a solubility parameter of between 7 and 8 (cal / cm3) 1/2 and a flash point greater than or equal at 55 "C and in that the fluorinated copolymer consists of units originating from a mixture of monomers comprising by weight:
(a) 20 to 89%, preferably 30 to 70%, of one or more fluorinated monomers corresponding to the general formula:

in which RF represents a perfluoroalkyl radical, linear or branched, containing 2 to 20 carbon atoms (preferably 4 to 16), A represents a divalent chain linked to O via a carbon atom and which may contain one or more oxygen atoms , sulfur and / or nitrogen, and R1 represents a hydrogen atom or a methyl radical;
(b) 10 to 79%, preferably 20 to 60%, of one or more nonfluorinated lipophilic monomers chosen from the compounds of general formulas (II) and (III):

in which R2 represents a hydrogen atom or a methyl radical, B is absent or represents a divalent chain which may contain one or more oxygen and / or nitrogen atoms, and R3 represents an alkyl radical, linear or branched, containing 8 36 carbon atoms (preferably 12-24);
(c) 1 to 20%, preferably 1.5 to 10%, of one or more silicon monomers chosen from the compounds of general formulas (IV) and (V):

dans lesquelles R4 représente un atome d'hydrogène ou un radical méthyle, D représente un enchaînement bivalent pouvant comporter un ou plusieurs atomes d'oxygène, d'azote eVou de soufre, R5 représente un radical alkyle contenant de 1 à 4 atomes de carbone, R6 et R7, identiques ou différents, représentent chacun un radical alkyle ou alcoxy contenant de 1 à 4 atomes de carbone ; et
(d) jusqu'à 30 %, de préférence 2 à 15 %, d'un ou plusieurs monomères quelconques autres que les monomères de formules 1,11,111, IV et V.

in which R4 represents a hydrogen atom or a methyl radical, D represents a divalent chain which may contain one or more oxygen, nitrogen or sulfur atoms, R5 represents an alkyl radical containing from 1 to 4 carbon atoms, R6 and R7, identical or different, each represent an alkyl or alkoxy radical containing from 1 to 4 carbon atoms; and
(d) up to 30%, preferably 2 to 15%, of any monomer or monomers other than the monomers of formulas 1,11,111, IV and V.

The fluorinated monomers of formula (I) are preferably chosen from the acrylates and methacrylates of the fluorinated alcohols of formulas (vol) to (VII):
RF- (CH2) n- (X) p- (CH2) mOH (Vl)
RF- (CH2) r (OCH2CH2) qOH (Vll)
RF-CH = CH- (CH2) mOH (Vlil) in which RF has the same meaning as in formula (I), X represents an oxygen or sulfur atom or a COO, S02, CONR or SO2NR group, R representing an alkyl radical containing 1 to 4 carbon atoms, n represents an integer ranging from 0 to 20 (preferably 0 to 2) but different from 0 if X is an oxygen or sulfur atom, p is equal to 0 or 1, the symbols m, q and r, identical or different, each represent an integer ranging from 1 to 20 (preferably equal to 1 or 2).

dans laquelle RF et R1 ont la même signification que dans la formule (I), R' représente un radical méthyle ou éthyle, p est égal à 0 ou 1, et n est égal à 0 ou 2.Fluorinated monomers of formula (I) which are particularly advantageous in the context of the invention are those corresponding to the general formula:

in which RF and R1 have the same meaning as in formula (I), R 'represents a methyl or ethyl radical, p is equal to 0 or 1, and n is equal to 0 or 2.

The monomers of formula (II) or (III) have an alkyl chain which is sufficiently lipophilic to ensure perfect solubility of the final copolymer in the hydrocarbons used for the synthesis. By way of nonlimiting examples of monomers (II), mention may be made of 2-ethylhexyl acrylate or methacrylate, octyl or isooctyl acrylate or methacrylate, ethyl acrylate or methacrylate. nonyl, lauryl acrylate or methacrylate, stearyl acrylate or methacrylate, arachidyl acrylate or methacrylate and behenyl acrylate or methacrylate. The monomers of formula (III) are advantageously chosen from alkylvinyl esters (B being an -O-CO- bridge), alkylallyl esters (B being a -CH2-O-CO- bridge), and alkylvinyl ethers (B = O). By way of nonlimiting examples, mention may be made of vinyl stearate, hexadecyl vinyl ether, dodecyl vinyl ether and octadecyl vinyl ether.

As examples of monomers of formula (IV), there may be mentioned [3 (methacryloyloxy) propyl] dimethylethoxysilane and especially [3 (methacryloyloxy) propyl] trimethoxysilane. As an example of monomers (V), there may be mentioned triethoxyvinylsilane.

dans laquelle R8 représente un atome d'hydrogène ou un radical méthyle, E représente un radical alkylène contenant 2 à 4 atomes de carbone et Y représente un groupe OH ou NR9R10, R9 représentant un radical alkyle contenant 1 à 4 atomes de carbone et R10 un atome d'hydrogène ou un radical alkyle contenant 1 à 4 atomes de carbone. Comme exemples de tels monomères, on peut citer plus particulièrement l'acrylate et le méthacrylate de 2-hydroxyéthyle, le méthacrylate de diméthylaminoéthyle et le méthacrylate de N-tertiobutylaminoéthyle.The monomer (s) (d) can be of very variable structure, but are preferably chosen from the acrylates and methacrylates of formula (X):

in which R8 represents a hydrogen atom or a methyl radical, E represents an alkylene radical containing 2 to 4 carbon atoms and Y represents an OH or NR9R10 group, R9 representing an alkyl radical containing 1 to 4 carbon atoms and R10 a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms. As examples of such monomers, there may be mentioned more particularly 2-hydroxyethyl acrylate and methacrylate, dimethylaminoethyl methacrylate and N-tert-butylaminoethyl methacrylate.

The products according to the invention are prepared according to a batch or semi-continuous process by radical copolymerization of the various monomers in solution in a hydrocarbon solvent or in a mixture of hydrocarbon solvents having a solubility parameter of between 7 and 8 (cal / cm3) 1 / 2 and a flash point greater than or equal to 55 ° C. These solvents can be n-paraffins, isoparaffins or dearomatized paraffins whose carbon number is between 10 and 15.

Isoparaffins are preferred.

The total concentration of the monomers and therefore that of the fluorinated copolymer in the final solution can vary from 5 to 60% by weight and, preferably, from 20 to 50%. The polymerization is carried out in the presence of initiator (s) which is used in an amount of 0.1 to 4%, and preferably 0.5 to 2% relative to the total weight of the monomers used. As initiators, one can use peroxides such as benzoyl peroxide, lauroyl peroxide, succinyl peroxide and tert-butyl perpivalate, or diazo compounds such as azo-2,2'-bis-isobuty ronitrile, Azo-4,4'-bis- (cyano-4-pentanoic) and azodicarbonamide. It is also possible to operate in the presence of UV radiation and photoinitiators such as benzophenone, 2-methyl-anthraquinone or 2-chloro-thioxanthone. The length of the polymer chains can, if desired, be adjusted using chain transfer agents such as alkyl mercaptans, carbon tetrachloride or triphenylmethane, used in an amount of 0.05 to 1% relative to to the total weight of monomers.

The reaction temperature can vary within wide limits, ranging from room temperature to the boiling point of the reaction mixture. Preferably, the operation is carried out between 60 and 95 ° C.

The fluorinated copolymer solutions according to the invention are more particularly intended for the hydrophobic and oleophobic treatment of textiles and leathers, and can be applied directly in the dry cleaning machine. They can also be used, on the same substrates, outside dry cleaning machines, in the form of waterproofing aerosol, by spraying or by impregnation in a bath.

The copolymer solutions according to the invention can also be applied with advantage on other supports, in particular on construction materials such as concrete, stones, tiles, bricks. In this case, the application is carried out under conditions well known to those skilled in the art: with a brush, with a roller, by spraying, etc.

For applications other than dry cleaning, the products can be diluted in any solvent or mixture of solvents compatible with the synthetic solvent.

In all cases, it is possible, in order to obtain a particular effect or a better fixation, to advantageously combine the fluorinated copolymers according to the invention with certain adjuvants (polymers, crosslinking products, catalysts). Mention may be made, for example, of hydrophobic extenders comprising aziridine or anhydride groups. At the time of application, the concentration of the fluorinated copolymers according to the invention is generally between 0.5 and 5% and preferably between 1 and 3%. The quantities of solution applied depend on the substrate to be treated; they can vary between 20 and 2000 g / m2.

After application, the treated substrates are generally dried at room temperature. They can also be dried by heating. The treated articles exhibit good hydrophobic and oleophobic properties which can be evaluated by the following application tests:
OlSophobia tests
The oleophobia is measured according to the test described in the standard "AATCC
Technical Manual ", Test Method 118 (1985) which evaluates the non-wettability of the substrate by a series of oily liquids whose surface tensions are increasingly low. The rating of the treated substrate is defined as the maximum value of the test liquid which does not wet the substrate after a contact time of 30 seconds The test liquids used in the evaluation are listed in the following table:

<tb> Rating <SEP> Test liquids <SEP> for <SEP> Surface tension <SEP><SEP> at
<tb><SEP> measure <SEP> the oleophobia <SEP> I <SEP> 25 C <SEP> (mN / m) <SEP>
<tb><SEP> 1 <SEP> Nujol <SEP> 31.5
<tb><SEP> 2 <SEP> Nujol / n-hexadecane <SEP> 29.6
<tb><SEP> (65/35 <SEP> in <SEP> volume)
<tb><SEP> 3 <SEP> n-hexadecane <SEP> 27.3
<tb><SEP> 4 <SEP> n-tetradecane <SEP> 26.4
<tb><SEP> 5 <SEP> n-dodecane <SEP> 24.7
<tb><SEP> 6 <SEP> n-decane <SEP> 23.5
<tb><SEP> 7 <SEP> n-octane <SEP> 21.4
<tb><SEP> 8 <SEP> n-heptane <SEP> 19.8
<tb>
Hydrophobicity tests
The hydrophobic effect is measured using test solutions numbered from 1 to 10 and consisting of water / isopropanol mixtures in the following weight proportions:

<tb> Test solutions <SEP> Water <SEP> Isopropanol
<tb><SEP> 1 <SEP> 90 <SEP> 10
<tb><SEP> 2 <SEP> 80 <SEP> 20
<tb><SEP> 3 <SEP> 70 <SEP> 30
<tb><SEP> 4 <SEP> 60 <SEP> 40
<tb><SEP> 5 <SEP> 50 <SEP> 50
<tb><SEP> 6 <SEP> 40 <SEP> 60
<tb><SEP> 7 <SEP> 30 <SEP> 70
<tb><SEP> 8 <SEP> 20 <SEP> 80
<tb><SEP> 9 <SEP> 10 <SEP> 90
<tb><SEP> 10 <SEP> 0 <SEP> 100
<tb>
The test consists of depositing drops of these mixtures on the treated substrates, then observing the effect produced. The number corresponding to the solution which contains the highest percentage of isopropanol and which has not penetrated or wetted the substrate after 30 seconds of contact is given as a value.

Water resistance tests (spray test
This test, described in the standard "AATCC Technical Manual", Test Method 22 (1985), makes it possible to evaluate the resistance to wetting of the treated fabrics. 250 ml of water are poured from a height of 15 cm, through a funnel terminated by an aluminum spray head, on the sample of tissue stretched on a frame of diameter 15.2 cm and tilted at 45 "C. When all the water is discharged, tap the frame on a hard surface to remove excess water and visually note the wetting level against a series of 6 values shown on a photographic reference published in the standard The following table indicates the rating of the test according to the level of wetting:

<tb> Rating <SEP> Level <SEP> of <SEP> anchorage
<tb><SEP> 0 <SEP> wetting <SEP> complete <SEP> of <SEP> all <SEP> sample
<tb><SEP> 50 <SEP> complete <SEP> wetting <SEP> of <SEP> center <SEP> of <SEP> sample
<tb><SEP> 70 <SEP> wetting <SEP> partial <SEP> of <SEP> all <SEP> the sample
<tb><SEP> 80 <SEP> anchorage <SEP> localized <SEP> on <SEP> some <SEP> isolated <SEP> points
<tb><SEP> 90 <SEP> very <SEP> weak <SEP> wetting <SEP> on <SEP> a few isolated <SEP><SEP> points
<tb><SEP> 100 <SEP> M <SEP> none <SEP> wetting <SEP> of <SEP> sample
<tb>
The application tests can also be repeated after machine wash (s) or dry cleaning of the treated articles, in particular in the case of textiles.

Machine washes at 40 "C are carried out according to cycle 6A described in the standard
NF G 07-136 (1994). The fabrics are then dried in a tumble dryer at a temperature of the order of 55 ° C.

The dry cleanings are carried out as follows: the treated textiles are immersed for half an hour in perchlorethylene or in an isoparaffin, then drained in an upright position and dried at room temperature for 48 hours.

EXAMPLES
The following examples, in which the parts are expressed by weight, unless otherwise indicated, illustrate the invention without limiting it.

EXAMPLE 1
In a reactor of 1000 parts by volume, equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet and a heating device, are introduced 220 parts of an isoparaffin (ISOPAR H of the Company
EXXON Chemical), having a boiling point of the order of 1800C, a flash point of 58 "C and a solubility parameter of 7.3 (caVcm3), 75 parts of stearyl methacrylate, 14.4 parts of 2-hydroxyethyl methacrylate, 6 parts of [3 (methacryloyloxy) propyl] trimethoxysilane and 110 parts of a mixture of fluorinated alcohol acrylates of the formula:
CF3 (CF2) nC2H400C-CH = CH2 where n is equal to 5, 7, 9, 11, 13, in respective average weight ratios of 11631251913.

The mixture is heated to 80 ° C. under a nitrogen atmosphere and 2.4 parts of azo2,2′-bis-isobutyronitrile are introduced in suspension in 86 parts of ISOPAR H. The reaction is allowed to proceed for 4 hours, then 0.5 part of azo-2,2'-bisisobutyronitrile is introduced and the reaction medium is maintained for one hour at 80 ° C. The reaction mixture is then diluted with 160 parts of ISOPAR H, then the product is allowed to cool. A clear solution (S1) is obtained comprising 30% by weight of copolymer according to the invention.

EXAMPLE 2
The procedure is the same as in Example 1, but without the addition of 2-hydroxyethyl methacrylate. A clear solution (S2) is obtained comprising 29.1% by weight of copolymer according to the invention.

EXAMPLE 3
The procedure is the same as in Example 1, but replacing the 2-hydroxyethyl methacrylate with the same weight of dimethyllaminoethyl methacrylate. A clear solution (S3) is obtained comprising 30% by weight of copolymer according to the invention.

EXAMPLE 4 (Comparative)
The procedure is the same as in Example 1, but without the addition of [3- (methacryloyloxy) propyl] trimethoxysilane. A clear solution (Sa) is obtained comprising 30% by weight of a copolymer not in accordance with the invention.

EXAMPLE 5
The solutions (S1), (S2), (S3) and (Sa) are diluted with isopar H to a concentration by mass of 2% of copolymer. The solutions obtained are applied by spraying onto cotton at a rate of the order of 50 g / m2. The treated fabrics are then dried at room temperature for 48 hours, then subjected to application tests before and after machine washing. The following tables bring together the results obtained.

- results before washing.

<tb>

Solution <SEP> Spray <SEP> Test <SEP> Hydrophobia <SEP> Oleophobia
<tb><SEP> SI <SEP> S1 <SEP><SEP> 80 <SEP> 10 <SEP> 5
<tb><SEP> S2 <SEP> 70-80 <SEP> 8 <SEP> 4
<tb><SEP> 83 <SEP> 70-80 <SEP> 8 <SEP> 4
<tb><SEP> Sa <SEP> 80 <SEP> 8 <SEP> 4
<tb> - results after washing.

<tb>

Spray <SEP> Spray <SEP> Test <SEP> Hydrophobia <SEP> Oleophobia
<tb><SEP> IF <SEP> 50 <SEP> 8 <SEP> 4 <SEP>
<tb><SEP> S2 <SEP> 50 <SEP> 6 <SEP> 1
<tb><SEP> 83 <SEP> 50 <SEP> 3 <SEP> I
<tb><SEP> Sa <SEP> 0 <SEP> 2 <SEP> 0
<tb>
Examination of the above tables shows that, although the presence of [3 (methacryloyloxy) propyl] trimethoxysilane has little influence on the application results before washing, it is on the other hand decisive for improving the durability of the fluoride treatment subjected to machine washing.

EXAMPLE 6
The solution (S1) is diluted with isopropyl acetate or heptane to a concentration by mass of 1% of copolymer. The solutions obtained are applied by spraying onto lambskin (stain from the company Desprat) at a rate of the order of 100 g / m2. The treated leathers are dried at room temperature for 48 hours, then subjected to application tests.

<tb>

Solvent <SEP> Solvent <SEP> Hydrophobia <SEP> Oleophobia <SEP>
<tb> Isopropyl acetate <SEP><SEP> 9 <SEP> 6
<tb><SEP> Heptane <SEP> 9 <SEP> 5
<tb>
EXAMPLE 7
The solutions (S1) and (Sa) are diluted with perchlorethylene to a concentration by mass of 2% of copolymer. The solutions obtained are applied by spraying onto cotton at a rate of the order of 50 g / m2. The treated fabrics are then dried at room temperature for 48 hours, then subjected to application tests before and after dry cleaning in perchlorethylene. The following tables bring together the results obtained.

- results before dry cleaning.

<tb>

<SEP> Solution <SEP> Spray <SEP> Test <SEP> Hydrophobia <SEP><SEP> Oleophobia <SEP>
<tb> S1 <SEP> 70 <SEP> 10 <SEP> 6
<tb><SEP> Sa <SEP> 50-70 <SEP> 8 <SEP> 5 <SEP>
<tb> - results after dry cleaning.

<tb>

Solution <SEP> Spray <SEP> Test <SEP> Hydrophobia <SEP><SEP> i <SEP> Oleophobia <SEP>
<tb><SEP> S1 <SEP> 70 <SEP> 10 <SEP> 5
<tb><SEP> Sa <SEP> 50 <SEP> 3 <SEP> 0
<tb>
Examination of the above tables shows that the presence of [3 (methacryloyloxy) propyl] trimethoxysilane is decisive for improving the durability of the fluorine treatment subjected to dry cleaning with perchlorethylene.

EXAMPLE 8
The solutions (S1) and (Sa) are diluted with isopar H to a concentration by mass of 2% of copolymer. The solutions obtained are applied by spraying onto polyester at a rate of the order of 50 g / m2. The treated fabrics are then dried at room temperature for 48 hours, then subjected to application tests before and after dry cleaning in lsopar H. The following tables summarize the results obtained.

results before dry cleaning.

<tb>

Solution <SEP> Spray <SEP> Test <SEP> Hydrophobia <SEP> Oleophobia <SEP>
<tb><SEP> S1 <SEP> 80 <SEP> 10 <SEP> 6
<tb><SEP> Sa <SEP> 80 <SEP><SEP> 8 <SEP> 5 <SEP>
<tb> - results after dry cleaning.

<tb>

<SEP> Solution <SEP> Spray <SEP> Test <SEP> Hydrophobia <SEP> Oleophobia <SEP>
<tb><SEP> S1 <SEP> 70-80 <SEP> 8 <SEP> 5
<tb><SEP> Sa <SEP> 70 <SEP> 5 <SEP> 3
<tb>

Claims (10)

1. Fluorinated copolymer solution in a hydrocarbon solvent, characterized in that said solvent has a solubility parameter of between 7 and 8 (cal / cm3) 1/2 and a flash point greater than or equal to 55 "C and in that the fluorinated copolymer consists of units originating from a mixture of monomers comprising by weight: (a) 20 to 89% of one or more fluorinated monomers corresponding to the general formula:

in which RF represents a perfluoroalkyl radical, linear or branched, containing 2 to 20 carbon atoms, A represents a divalent chain linked to O through a carbon atom and which may contain one or more oxygen, sulfur and / or nitrogen atoms , and R1 represents a hydrogen atom or a methyl radical; (b) 10 to 79% of one or more non-fluorinated lipophilic monomers chosen from the compounds of general formulas:

(d) up to 30% of any one or more monomers other than the monomers of formulas 1,11,111, IV and V. in which R4 represents a hydrogen atom or a methyl radical, D represents a divalent chain which may contain one or more oxygen, nitrogen and / or sulfur atoms, R5 represents an alkyl radical containing from 1 to 4 carbon atoms , R6 and R7, identical or different, each represent an alkyl or alkoxy radical containing from 1 to 4 carbon atoms; and

(c) 1 to 20% of one or more silicon monomers chosen from the compounds of general formulas: CH2 = CH-B-R3 (III) in which R2 represents a hydrogen atom or a methyl radical, B is absent or represents a bivalent chain which may contain one or more oxygen and / or nitrogen atoms, and R3 represents an alkyl radical, linear or branched, containing from 8 to 36 carbon atoms; 2. Solution according to claim 1, in which the hydrocarbon solvent is a paraffin or a mixture of paraffins containing from 10 to 15 carbon atoms, preferably an isoparaffin or a mixture of isoparaffins. 3. Solution according to claim 1 or 2, in which the copolymer results from the polymerization of a mixture of monomers comprising: - 30 to 70% of monomer (s) of formula (I), - 20 to 60% of monomer (s) of formula (II) or (III), - 1.5 to 10% of monomer (s) of formula (IV) or yes), and - 2 to 15% of monomer (s) other (s) than those of formula I, 11, III, IV and V. 4. Solution according to one of claims 1 to 3 wherein the RF radical contains 4 to 16 carbon atoms and R3 contains 12 to 24 carbon atoms. 5. Solution according to one of claims 1 to 4 in which the monomer (s) of formula (I) corresponds to the general formula:

in which R 'is a methyl or ethyl radical, p is equal to 0 or 1, and n is equal to 0 or 2. 6. Solution according to one of claims 1 to 5 wherein the one or more Monomers of formula (II) are chosen from 2 ethylhexyl, octyl, isooctyl, nonyl, lauryl, stearyl, arachidyl and behenyl acrylates and methacrylates. 7. Solution according to one of claims 1 to 5 wherein the monomer (s) of formula (III) are chosen from hexadecyl vinyl ether, dodecyl vinyl ether and octadecyl vinyl ether. 8. Solution according to one of claims 1 to 7 wherein the monomer of formula (IV) is [3- (methacryloyloxy) propyl] -trimethoxysilane. 9. Solution according to one of claims 1 to 8 wherein the monomer (d) is 2-hydroxyethyl acrylate or methacrylate, dimethyl laminoethyl methacrylate or N-tert-butylaminoethyl methacrylate. 10. Solution according to one of claims 1 to 9 containing 5 to 60% by weight of fluorinated copolymer, preferably 20 to 50%. He. Use of a solution according to one of Claims 1 to 10 for the hydrophobic and oleophobic treatment of textiles, leathers and other supports.