EP1311567A1

EP1311567A1 - Novel fluorinated copolymers, their use for coating and impregnating substrates, and resulting treated substrates

Info

Publication number: EP1311567A1
Application number: EP01956646A
Authority: EP
Inventors: Denis Tembou N'zudie; Yvon Legrand; Didier Juhue
Original assignee: Atofina SA
Current assignee: Arkema SA
Priority date: 2000-08-07
Filing date: 2001-07-26
Publication date: 2003-05-21
Also published as: US20040026053A1; FR2812643A1; AU2001278570A1; WO2002012361A1; JP2004506073A; FR2812643B1; CN1468266A; KR20030031966A

Abstract

The invention concerns a fluorinated cationic copolymer obtained from a composition comprising for 100 parts by weight: 5 to 92 parts by weight of at least a polyfluorinated monomer (I); 0.10 to 25 parts by weight of at least a monomer (II) (III) or (IV); 0 to 20 parts by weight of at least an anionic or potentially anionic monomer by Ph variation; 0 to 25 parts by weight of at least a vinyl monomer (V): CH2=CHR11; 0 to 60 parts by weight of at least a monomer (VI); 0 to 10 parts by weight of at least a monomer capable of inducing post-crosslinking of the fluorinated copolymer during or after the formation of a coating of said fluorinated copolymer on a substrate; and 0 to 25 parts by weight of at least a monomer (VII): R1, R2= H or one of the two = H and the other = C¿1?-C4 alkyl; A = bivalent chain formation bound to O by a carbon atom and capable of comprising one or several oxygen and/or sulphur and/or nitrogen atoms; Rf = perfluorinated C2-C20radical with linear or branched chain,; R?3, R6, R8, R12¿ = H or CH¿3?; R?4, R5, R7, R9, R10¿ = H, C¿1?-C18 alkyl, benzyl or hydroxyethyl; X?1Υ, X2Υ¿ = monovalent anion; R11 = alkylcarboxylate, alkylether, or C¿1?-C18 alkyl; m = 0 or 1; R?13 = C¿1-C6 alkylene capable of being substituted by at least a hal; m = 0 or an integer from 1 to 11, inclusively; R14 = C1-C32 alkyl capable of being substituted by at least a hal, or cycloalkyl capable of being substituted by at least a hal; R15 = H or C¿1?-C4 alkyl; A?2 = C¿1-C4 linear or branched alkylene; R16, R17 = H, C¿1?-C18 linear or branched alkyl or hydroxyethyl or benzyl, or R?16 and R17¿ together with the nitrogen atom to which they are bound from a morpholino, piperidino or pyrrolidinyl radical.

Description

NOVEL FLUORINATED COPOLYMERS, THEIR USE FOR THE COATING AND IMPREGNATION OF SUBSTRATES, AND THE SUBSTRATES THUS TREATED.

The present invention relates to new fluorinated copolyπières and their use for coating and impregnating various substrates such as textiles, leathers, wood, nonwovens, metals, concrete and, more particularly, papers and similar articles as well as

, textiles, for the purpose. to make them oleophobic and hydrophobic. It also relates to the substrates thus treated.

To achieve this goal, many cationic fluorinated derivatives have already been proposed in three types of presentation: (1) in the form of a latex or emulsion (dispersion in water of polymer particles stabilized by surfactants);

(2) in the form of a solution in a water / solvent mixture; or

(3) in the form of an aqueous dispersion after elimination of solvent in presentation (2).

European patent EP-B-0234601 teaches and cationic fluorine-containing copolymers having a presentation form of a latex or emulsion ^•, and obtained by copolymerization of: (a) 60 to 80% by weight of a fluorinated acrylate monomer of formula :

CH ≈ CH - C - O - A ⁽⁰⁾ - RW

II

0 in which:

- ^R f ^{is an} aliphatic perfluorinated radical having from 3 to 20 carbon atoms; and

- Α ^ 'is a bivalent concatenation; (b) 1 to 30% by weight of: (i) an alkyl or alkoxyalkyl (eth) acrylate monomer of formula (i): _R (D

CH = CC - [- 0-CH ₉ -C-] _nι - [- 0-R ⁽²⁾ -] _n -0R ⁽³⁾ (i)

II II 0 0 in which:

- R ^ ¹⁾ is H or methyl;

- R ' ² ) is a C 1 -C 6 alkylene group, the groups R ² ' being identical or different; - R ^ ³⁾ is a C ^ - ^ _Q alkyl or cycloalkyl group;

- m is 0 or 1; and

- n is 0 to 10, subject. that when n is 0, R ^ ³ 'is a C 1 -C 4 alkyl or cycloalkyl group; or

(ii) a halogenated alkyl or alkoxyalkyl acrylate monomer of formula (ii):

CH = CH-C - [- 0-CH -C-] _n - [- 0-R ⁽⁴⁾ -l -0R ⁽⁵⁾ (ii)

It II 0 0 in which:

- R ' ⁴ ^ is a C - ^ - Cg alkylene or haloalkylene group, the groups R' ⁴ ) being identical or different; - R (5) _e st alkyl, cycloalkyl, haloalkyl or halocycloalkyl C ₁ -C _20; at least one group R ^ ⁴ 'or R ^> containing a halogen atom; - p is 0 or 1; and

- q is 0 to 10, provided that when q is 0, R '~>) is a haloalkyl or halo-C 1-6 cycloalkyl group;

(c) 2 to 15% by weight (when the copolymer comprises units from monomer (i)) or 1 to 15% by weight (when the copolymer comprises units from monomer (ii)) of a monomer of formula : R (6)

CH = CC-0-CH ₉ CH-CH

It \ / 0 o in which R ^ 'is H or methyl; (d) 1 to 6% by weight of a cationic monomer of formula

_R (7) CH ₂ = c - Z <°> - Y <°> ^θ X <°> ^θ in which:

- R '''represents H or methyl; - Z ^ ⁰ 'is a divalent electro-acceptor group which activates radical polymerization; _ Γ ^{⁽⁰⁾ θ} _{is a} g _rou p _e monovalent cation; and

- χ ⁽ ° ^{) θ} is an anion; and

(e) 0 to 20% by weight of vinylidene chloride. International application WO 98/23657 deals with cationic fluorinated copolymers having a presentation in the form of a solution in a water / solvent mixture (N-vinyl pyrrolidone) obtained by copolymerization of: (a) 50 to 92% by weight of one or more polyfluorinated monomers of general formula:

_R (10)

CHR ⁽¹⁰⁾ = C - C - 0 - A ⁽¹⁰⁾ - R

II 0 in which:

_ & ⁽ l- ⁾ represents a bivalent chain linked to 0 by a carbon atom and which may contain one or more oxygen, sulfur and / or nitrogen atoms;

- one of the symbols R ^ ¹⁰ 'represents a hydrogen atom and the other a hydrogen atom or an alkyl radical ^• containing 1 to 4 carbon atoms; and - Rf represents a perfluorinated radical with a straight or branched chain, containing 2 to 20 carbon atoms, preferably 4 to 16 carbon atoms;

(b) 1 to 25% by weight of one or more monomers of general formula 5:

CH ₂ = C - C - 0 - A ⁽¹¹⁾ - N

10 0 R ⁽¹⁾ in which:

- R ' ¹¹ ' represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms;

15 - A ' ¹ -' represents an alkylene radical, linear or branched, containing 1 to 4 carbon atoms; and

- the symbols R ^ ² 'and R ^ ¹³ ', identical or different, each represent a hydrogen atom, a linear alkyl radical or

20. branched containing 1 to 18 carbon atoms. or a hydroxyethyl or benzyl radical, or R ^ ¹² 'and R ^' together with the nitrogen atom to which they are linked form a morpholino, piperidino or pyrrolidinyl-1 radical; (C) 1 to 25% by weight of a vinyl derivative of general formula:

CH ₂ ≈ CH-R ⁽¹⁴⁾ in which R '- * - ⁴ ' may be an alkylcarboxylate or alkyl ether group containing from 1 to 18 carbon atoms; and

(d) 0 to 10% of any monomer other than the monomers of the three preceding formulas.

The copolymerization reaction leading to the fluorinated copolymers described by this international application 35 is carried out in solution in a solvent or mixture of organic solvents miscible with water, and it is followed by a dilution step by a aqueous solution of a mineral or organic acid. This dilution step is carried out in the presence ^'of hydrogen peroxide or is followed treatment with an aqueous solution of hydrogen peroxide.

After said dilution step, it is necessary to carry out vacuum distillation or to sweep with an inert gas, for example nitrogen, to remove the volatile compounds, and obtain a composition which can be marketed, and applied to the substrate. treat.

The solvents exemplified in this application are essentially mixtures based on N-methyl-, pyrrolidone. These solvents, because of their boiling point,. are not completely eliminated by the distillation operation, so that significant quantities remain in the commercial composition.

This commercial composition is thus in the form of a solution in a water / solvent mixture (N-methyl-pyrrolidone), which gives it very advantageous stability properties for its transport and storage.

However, for some applications, ^{'particularly} for the treatment of papers or similar articles for the field of packaging food products, organic solvent the presence likely to come into contact with these foods is an inconvenience because of the risks for health. The international application WO 98/23657 mentions

(cf. page 5, lines 14-15) that the use of light solvents makes it possible to obtain, after distillation, a composition free of organic solvent, that is to say in the form of an aqueous dispersion of copolymer. Tertiary amino or quaternary monomers used for the preparation of fluorinated cationic copolymers described in the preceding document have one tertiary amino group or ^a single quaternary amino group per molecule. Unlike these known structures, it has now been found that other monomers having two tertiary amino groups, or two quaternary amino groups or a quaternary amino group associated with -a tertiary amino group, can be used for the preparation of new fluorinated cationic copolymers which give the same hydrophobic and oleophobic properties to various substrates, and in particular to paper and textiles, and which may also be in the form of aqueous compositions, in particular in the form of latex or emulsion , as a dispersion or as a solution in a water / solvent mixture.

The present invention therefore firstly relates to a fluorinated cationic copolymer, characterized in that it is obtained from a composition of monomers comprising, per 100 parts by weight:

(A) 5 to 92 parts by weight, in particular 40 to 90 parts by weight, of at least one polyfluorinated monomer of formula (I):

R

CHR ¹ = C - C - 0 - A ^J R <(I) 0 in which

- R- ¹ - and R ² simultaneously represent a hydrogen atom or one of the two represents a hydrogen atom and the other, an alkyl radical

- A ¹ represents a divalent chain linked to 0 by a carbon atom and which may include one or more oxygen and / or sulfur and / or nitrogen atoms; and - R ^ represents a perfluorinated radical with a straight or branched chain, C ₂ -C _Q i

(B) 0.10 to 25 parts by weight, in particular 1 to 18 parts by weight, of at least one monomer chosen from those of formulas (II), (III) and (IV) below:

in which :

- R ³ represents H or -CH3;

- R ⁴ and R, identical or different, each independently represent H, alkyl. in ^c ι ~ ^c i8 'benzyl or hydroxyethyl; and

- X - "- ^θ represents a monovalent anion;

R ⁷

R ⁶ 0 /

1 // CH ₂ - N

2 = c - c

\ / R 7 '

0 - - CH (III)

R ⁷ \

/ CH ₂ - N

\ 7 R '

in which: - R ⁶ represents H or -CH3; and

- R ⁷ represents H, C 1 -C 4 alkyl benzyl or hydroxyethyl;

R ^b O /

I // CH ₉ - CH ₂ - C - C _N / - - ₉

O - CH. (IV) v - R ^y |

CH ₂ - - R ⁹ X ^2θ . R ¹⁰

in which :

- R ^ represents H or -CH3; - R ⁹ and R - * - 0, identical or different, each independently represent hydrogen, alkyl C _j _- _C] _8 benzyl or hydroxyethyl; and - X ^2Θ represents a monovalent anion;

(C) 0 to 20 parts by weight, in particular 1 to 10 parts by weight, of at least one anionic or potentially anionic monomer by variation of the pH;

(D) 0 to 25 parts by weight, in particular 2 to 10 parts by weight, of at least one vinyl monomer of general formula (V):

CH ₂ = CHR ¹¹ (V)

in which R ¹¹ represents an alkylcarboxylate or alkyl ether group, or C 1 -C 4 -C 4 alkyl;

(E) 0 to 60 parts by weight of at least one monomer of formula (VI):

in which :

- R ² represents H or -CH3; - m is 0 or 1;

- R ³ represents a C- _] _-C alkylene radical which can be substituted by at least one halogen;

- m is 0 or is an integer from 1 to 11, limits included; - R ⁴ represents an alkyl residue in which may be substituted by at least one halogen, or a cycloalkyl radical which may be substituted by at least one halogen; (F) 0 to 10 parts by weight of at least one monomer capable of inducing the post-crosslinking of the fluorinated copolymer during or after the formation of a coating of said fluorinated copolymer on a substrate; and

(G), 0 to 25 parts by weight of at least one monomer of general formula (VII):

R ¹⁵ R ¹⁶

/

CHo = C - C - 0 - A - N (VII) \

OR ¹⁷ in which:

- R ¹⁵ represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms;

- A ² represents an alkylene radical, linear or branched, containing 1 to 4 carbon atoms;

- the symbols R ^{1 &} and- R, identical or different, each represent a hydrogen atom, a linear or branched alkyl radical containing 1 to 18 carbon atoms or a hydroxyethyl or benzyl radical, or R16 and R17 together with the atom of nitrogen to which they are attached form a morpholino, piperidino or pyrrolidinyl-1 radical.

The monomer (s) (A) of formula (I) are in particular those for which Rf is a C 1 -C 4 perfluoroalkyl radical. More particularly, the monomer (s) of formula (I) are chosen from those of formula (la):

CH ₂ ≈CH-C-0-CH ₂ CH ₂ -R _f (la) O in which R _f represents a perfluoroalkyl radical in ^c 4 ^-c 16- The monomer (s) (B) of formula (II) are chosen in particular from those for which:

- R ³ represents H;

- R ⁴ represents -CH3; - R ^ represents -CH3 or benzyl; and

- X ^θ represents Cl ^θ .

The monomer (B) of formula (III) is in particular that for which:

- R ° represents H; - R ⁷ represents -CH3 ..

The monomer (s) (B) of formula (IV) are in particular chosen from those for which:

- R ⁸ represents H;

- R ⁹ represents -CH3; . ^" - R 0 represents -CH3 or benzyl; and X ^2θ represents Cl ^θ .

In the case of the copolymers according to the invention which are obtained in emulsion, it will be preferred to use, as compound (s) (B), a compound (II) in which R ³ = H; R ⁴ = -CH ₃ ; R ⁵ = -CH ₃ or -CH ₂ -CgH ₅ and X ^lθ = Cl ^θ and / or a compound (IV) in which R ⁸ = H; R ⁹ = -CH ₃ ; R ¹⁰ = -CH3 or -CH ₂ -CgH ₅ and X ^2θ = Cl ^θ .

In the case of the copolymers according to the invention which are obtained in solution, it will be preferred to use, as compound (s) (B), a compound (III) in which R ⁵ = H and R ⁷ ≈

-CH ₃ and / or a compound (IV) in which R ⁸ ≈ H; R ⁹ = -CH3;

R10 _β _ _C H _{3 or} -CH ₂ -CgH ₅ and X ^2θ = Cl ^θ .

The anionic or potentially anionic monomer (s) by variation of the pH (monomers (C)) are in particular chosen from ethylenically unsaturated carboxylic acids and their salts, and ethylenically unsaturated sulfonated monomers and their salts.

The ethylenically unsaturated carboxylic acid is in particular methacrylic acid, and the ethylenically unsaturated sulfonated monomers are in particular chosen from 2-acrylamido-2-methylpropanesulfonic acid and its salts. It is preferred to use methacrylic acid as the monomer (C).

The monomer (D) is in particular vinyl acetate.

The monomer (s) (E) are chosen in particular from behenyl acrylate, stearyl methacrylate, methoxyethyl acrylate and methoxyethyl methacrylate.

The monomer (s) (F), which can induce the cross-linking of the copolymer during or after the formation of the fluoropolymer coating on the substrate, are in particular chosen from:

(FI) silane ethylenically unsaturated monomers;

(F2) 2-hydroxy-3-chloropropyl (meth) acrylate; (F3) epoxy-functional (meth) acrylates;

(F4) the monomers of formula (VIII):

_R 18 R ¹⁹ ^• CH ₂ - C 1 /

C - CÇ - - NN (VIII)

II \

0 in which: v _° - R ^x ° represents H or -CH3; and - R ^x9 and R ^2, identical or different, each independently represent H, C ^c l ~ ^c 5 ^^ optionally contains one or more OH groups, or alkoxy (CL-C5) -alkyl

(F5) the monomers of formula (IX)

in which - R ^ represents H or -CH3; and

- R ²² , R ²³ and R ²⁴ , identical or different, each represents H or C 1 -C 4 alkyl. '

The monomer (F4) is in particular N-methylol-acrylamide.

The monomer (F5) of formula (IX) is in particular that for which: - R ° and R ¹⁹ each represent H; and - R ²⁰ and R ^2x each represent -CH3. The monomer (G) is in particular dimethylaminoethyl methacrylate.

Depending on the final presentation of the polymer, the fluorinated copolymers according to the present invention are prepared by radical copolymerization of the monomers according to two polymerization techniques, in particular emulsion polymerization (obtaining polymer in the form of latex or emulsion) or solution polymerization

(obtaining of polymer in the form of a solution in a water / solvent mixture or of an aqueous dispersion after elimination of solvent).

^'' EMULSION POLYMERIZATION:

In the case of emulsion polymerization, the implementation of the reaction requires the use of one or more organic solvents miscible with water. The present invention describes the composition of the water / solvent (s) mixture which can lead to a product with a flash point above 100 ° C.

Organic solvents are compounds, at least partially water-soluble, such as. propylene glycol, ethylene glycol, ethyl glycol, methoxypropanol, ethylene carbonate, propylene carbonate, ethyl ether of ethylene glycol, methyl ether of propylene glycol, N-methylpyrrolidone, l acetone, ethyl ethyl ketone, acetic acid, acid propionic acid, tetrahydrofuran, diacetone alcohol, methyl alcohol, ethyl alcohol, isopropyl alcohol, γ-butyrolactone.

The amounts to be used in the water / solvent (s) mixture can vary between 40 and 95% by weight for water, and from 5 to 60% by weight for the mixture of solvents.

The following solvents are preferably used:

- propylene glycol, N-methylpyrrolidone, propylene glycol methyl ether or acetic acid; in this case, the polymerization is not followed by a distillation because the mixture of solvents does not induce a flash point between 0 and 100 ° C;

- acetone; the water / acetone mixture leads to a flash point between 0 and 100 ° C; in this case, the distillation is carried out until elimination of the solvent in the emulsion.

The copolymerization in emulsion is carried out in the presence of cationic surfactants associated or not with nonionic surfactants used at a rate of 1 to 10% by weight relative to the mixture of monomers. The total concentration of monomers in the reaction mixture

(water / solvent / monomers / surfactant) can range from 15 to 70% by weight and is preferably between 30 and 60% by weight. Molecular ^weights' are adjusted using chain transfer agents such as mercaptans in an amount of 0.01 to 0.5% by weight relative to the monomer mixture or the monomer introduction of technical .

The copolymerization can be initiated between 20 and 150 ° C. by means of initiators of the peroxide type (such as hydrogen peroxide) or persalt (such as the persulfates) or of the azo type such as the 4,4 'azo bis acid (cyano -4 pentanoic) or azo-bis hydrochloride (aminidino propane). They are used in an amount of 0.1 to 4% by weight relative to the mixture of monomers.

The amount of water-miscible solvent to be used can vary within wide limits and is generally between 10 and 80 parts by weight per 100 parts of the total monomers. For the emulsification of the monomers, it is possible optionally to use energetic means of emulsification, such as ultrasounds or homogenizers of the Manton-Gaulin type. The polymerization step can be followed by a solvent distillation step in order to obtain an emulsion in water without organic solvent.

POLYMERIZATION IN SOLUTION:

This type of polymerization is used for copolymers having at least one tertiary amino group which is quaternized or salified by an acid at the end of polymerization.

The solution polymerization is carried out in an organic solvent miscible with water or in a mixture of such solvents. Preferably, a distillable solvent will be chosen in the form of a mixture with water to obtain a product without solvent. The reaction medium is then diluted with water in the presence of a mineral or organic acid to salify the macromolecules.

According to a preferred variant of the invention, this dilution step is carried out in the presence of hydrogen peroxide, or is followed by a treatment using an aqueous solution of hydrogen peroxide.

As water-miscible and distillable organic solvents mixed with water, in which the copolymerization is carried out, non-limiting mention may be made of ketones (for example, acetone, methyl ethyl ketone), alcohols ( for example isopropanol), ethers (for example methyl ether).

For the implementation of the invention, it is preferred to use as solvent methyl isobutyl ketone or methyl ethyl ketone or a mixture of these with acetone.

As organic solvents miscible with water and non-distillable in admixture with water, in which the copolymerization is carried out, non-limiting mention may be made of N-vinyl-pyrrolidone. The total concentration of the monomers in the organic solvent or mixture of organic solvents can range from 15 to 70% by weight and is preferably between 30 and 60% by weight. The copolymerization is carried out in the presence of at least one initiator, used in an amount of 0.1 to 2% by weight relative to the total weight of monomers. As initiators, there can be used peroxides, such as benzoyl peroxide, lauroyl peroxide, succinyl peroxide and tertiary perpivalate. -butyl, or azo compounds such as, for example, azo-2,2 '-bis-isobutyronitrile, azo-4, 4' -bis (cyano-4-pentaoic) and .. azobis (amidinopropane ). The copolymerization step can be carried out at a temperature ranging from 40 ° C. to the boiling point of the reaction mixture. Preferably, one operates between 60 and 90 ° C.

The dilution step consists in adding to the organic solution of the copolymer an aqueous solution of a strong or moderately strong mineral or organic acid, that is to say of which the dissociation constant or the first dissociation constant is greater than 10 ^" .

Examples of such acids include hydrochloric, hydrobromic, sulfuric, nitric, phosphoric, acetic, formic, propionic or lactic acids, but preferably acetic acid is used. The quantity of aqueous solution to be used and its acid concentration must be sufficient, on the one hand, to completely salify the amino functions provided by the monomer (s) of formula (III), (IV), (VII ) and, on the other hand, to obtain a solution _. final copolymer having a dry matter content of between 5 and 30% by weight, preferably - between. 20 and 30% by weight. For the complete salification of the amino functions, the amount of acid is advantageously between 0 and 5 acid equivalents relative to the monomer (s) of formula

(III), (IV), (VII), preferably between 1 and 2 equivalents.

The amount of hydrogen peroxide used is between 0 and 10% by weight, preferably from 0.5 to 4% by weight relative to the total weight of initial monomers. The treatment is carried out between 25 and 100 ° C, preferably from 70 to 85 ° C.

These fluorinated copolymers in emulsion or in solution are applicable on various supports, such as leather, nonwovens, building materials, paper and cardboard. In particular, they can be applied to textiles or paper using different techniques (in a size press

("size-press") or in the mass), thus giving the support, without the need for adjuvants (sequestrants, retention agents, fixing resins), excellent hydrophobic and oleophobic properties.

The present invention also relates to a solid substrate comprising at least one fluorinated copolymer according to the invention, as defined above.

As substrates capable of being made oleophobic and hydrophobic with the products according to the invention, it is preferred to use textiles or papers, cardboards and similar materials. Other very diverse materials can also be used, such as, for example, woven or non-woven articles based on cellulose or regenerated cellulose, natural, artificial or synthetic fibers such as cotton, cellulose acetate, wool, silk, polyamide, polyester, polyolefin, polyurethane fibers or polyacrylonitrile, leather, plastics, glass, wood, metals, porcelain, painted surfaces. May also be treated with favor the ^{'construction} aterials such as concrete, stone, brick and tiles with the products according to the invention.

The compositions comprising a fluorinated copolymer according to the invention are applied mainly diluted in an aqueous medium or in a mixture of water and of solvents, according to known techniques, for example by coating, impregnation, immersion, spraying, brushing, padding , sleeping. On paper, the products according to the invention can be applied in aqueous solution either superficially on the support already finished (preferably at a rate of 0.05 to 0.2% of fluorine relative to the weight of paper), or in the mass , that is to say, in the paper pulp in the pulp (preferably in an amount of 0.2 to 0.4% fluorine with respect ^'to the weight of pulp).

The supports thus treated have good oleophobic and hydrophobic properties after a simple drying,. at room temperature or at elevated temperature, possibly followed by a heat treatment which can range, depending on the nature of the support, up to 200 ° C.

To obtain good fixation of the copolymers. fluorinated according to the invention on the substrates on which they are applied and to give in addition a particular effect, it is sometimes advantageous to combine them with certain adjuvants, polymers, thermally condensable products and catalysts capable of promoting their crosslinking with the support. As such, mention may be made of condensates or precondensates of urea formaldehyde or melamine formaldehyde, epoxy derivatives such as diglycidylglycerol, polyamine-epichlorohydrin resins, glyoxal and its derivatives, polyvinyl alcohols and cationic, oxidized and amphoteric starches. It may also be advantageous to combine the fluorinated copolymers according to the invention with one or more nonionic and / or cationic surfactants to improve the wetting of the support. The weight of this or these surfactants relative to the total weight of copolymer can vary from 0 to 100%.

To evaluate the performance of the substrates treated according to the invention, the following tests were used:

. INCREASABILITY TEST OR NUMBER OF KIT (KIT VALUE)

This test, described in Tappi, vol. 50, n ° 10, pages 152A and 153A, standard RC 338 and UM 511, allows measure the greaseproofness of the substrates with mixtures of castor oil, toluene and heptane. These contain varying amounts of these three products:

The test consists in gently depositing drops of these mixtures on the treated paper. The drops are left on the paper for 15 seconds, then the appearance of the paper or cardboard is carefully observed and the wetting or penetration evidenced by browning of the surface is noted. The number corresponding to the mixture containing the highest percentage of heptane, which does not penetrate or wet the paper, is the Kit Number of the paper and is considered to be the oleophobicity rate of the treated paper. The higher the Kit Number, the better the oil repellency of the paper.

• COBB TEST.

The Cobb test [NF EN 20535-ISO 535 (1994)] consists in measuring the weight (in g) of water absorbed during one minute per one square meter of paper supporting a water height of one centimeter.

'' OLEOPHOBIA TEST

On certain supports, the oleophobia was measured according to ^' the method described in "AATCC Technical Manual", Test Method 118-1972, which' evaluates the non-wettability of the substrate by a series of oily liquids numbered from 1 to 8:

- N ^υ 1 Vaseline Oil; - - NN °° 2 2: Vaseline oil / n-Hexadecane (64/35)

- N ° 3: n-Hexadecane

- N ° 4: n-Tetradecane

- N ° 5: n-Dodecane

- N ° 6: n-Decane - - NN °° 7 7: n-Octane

- N ° 8 n-Heptane

The test consists of depositing drops of these mixtures on the treated substrates, then observing the effect of the drop after 30 seconds of contact. The listing is done by giving the value of the number of the last drop of liquid which has neither penetrated nor wetted the substrate.

* HYDROPHOBIA TEST

This so-called "spray-test" is fully described by the AATCC 22-1989 standard. It consists in pouring onto a treated fabric, fixed on a support inclined at 45 °, 250 ml of water from a funnel fitted with a sprinkler in about twenty seconds and a height of approximately 15 cm. . The reading of the test is visual, the rating going from 0 (for a completely wet fabric) to 100 (for a completely dry fabric). The following examples illustrate the invention without, however, limiting its scope. The parts and percentages indicated are by weight, unless otherwise indicated, and the abbreviation according to a _. been used:.

• S-ADAMQUAT 2BZ: compound of formula:

In Examples 1 and 2, a mixture of polyfluorinated acrylates of formula:

CH ^ CH-CO-CH ^ oC ^ Ho- ^ C- _^ pF ^: p + l

O where p is equal to 8, 10, 12 and 14 in respective weight ratios of 63: 25: 10: 2.

EXAMPLE 1

In a reactor of 1000 parts by volume, heated by a thermostated double jacket and provided with a anchor stirring and a reflux condenser, the following are introduced:

383 parts of demineralized water;

• 140 parts of acetone; • 3.75 parts of trimethyloleyl ammonium chloride;

• 3.43 parts of a mixture of oxyethylenated alkylphenols' de'HLB 15;

• 176.9 parts of the mixture of polyfluorinated acrylates defined above; , • 43.2 parts of methoxyethyl acrylate;

25 parts of 48% N-methylolacrylamide in water;

• • 12.8 parts of a 75% aqueous solution of S-,

ADAMQUAT 2BZ; and

• 0.48 part of n-dodecylmercaptan.

After inerting with nitrogen and heating to 70 ° C., priming is initiated. polymerization with 1.2 parts of azo bis hydrochloride (amidino propane) dissolved in 8 parts of water. After 2 hours of polymerization at 70 ° C., 796 parts of an emulsion with 30.2% dry matter content are obtained.

The acetone is then distilled at 90 ° C., which leads to a latex with 36% dry extract, which is then diluted with water to obtain an emulsion which is perfectly stable at 25% solids. This product does not have a flash point between 0 and 100 ° C, in closed cup (according to the Sétaflash NF.T.300.50 method).

EXAMPLE 2

In a reactor of 1000 parts by volume, heated by a thermostated double jacket and provided with anchor stirring and a reflux condenser, the following are introduced:

257.4 parts of demineralized water; 91.8 parts of acetone;

• 8.98 parts of trimethyloleyl ammonium chloride; 2361

22

• 8.22 parts of a mixture of oxyethylenated alkylphenols of HLB 15;

• 118.7 parts of the mixture of polyfluorinated acrylates defined above; ^' • 50.3 parts of behenyl acrylate;

• 5.74 parts of 48% N-methylolacrylamide in water;

• 7.30 parts of 50% solution of the monomer of formula:

OCH ₃ ^' /

CH ≈CH-C-NH-CHOH-CH

Il \ o OCH ₃

• 2.80 parts of 75% aqueous solution of S-ADAMQUAT 2BZ;

• 8.45 parts of methyl acrylate; and

• 0.18 part of n-dodecylmercaptan.

After inerting with nitrogen and heating to 70 ° C., the polymerization is started with 0.9 part of azo bis hydrochloride (amidino propane) dissolved in 9 parts of water. After 2 hours of polymerization at. 70 ° C, 573 parts of an emulsion with 36% dry matter content are obtained.

The acetone is then distilled at 90 ° C., which leads to a latex with 40% dry extract, which is then diluted with water to obtain an emulsion which is perfectly stable at 20% solids. This product does not have a flash point between 0 and 100 ° C, in closed cup (according to the Sétaflash NF.T.300.50 method).

EXAMPLE 3

An aqueous size press press bath containing 16 g / l of the emulsion obtained in Example 1 is prepared.

This composition is applied to the sizing press. On a paper composed of bleached paste, glued, 70 g / m ² . The take-up rate is around 70%. After drying for one minute at 120 ° C, the paper thus treated is stored for 1 day at room temperature, then subjected to the various tests.

The results are collated in the following Table 1:

TABLE 1 ^'

The fluorinated cationic copolymer of the invention gives the treated paper excellent oleophobicity and hydrophobicity properties.

EXAMPLE 4

A padding bath containing 20 g / l of the emulsion obtained in Example 2 and 1.5 g / l of acetic acid in water is prepared at room temperature. A polyester fabric is then scarfed in this bath, with a rate of expression of 40%. After drying, the fabric is therixed for one minute at 160 ° C in a BENZ type thermocondenser.

The fabric is then tested for hydrophobicity and oleophobia. The results obtained are collated in the following Table 2.: TABLE 2

The cationic fluorinated copolymer of the invention

-confers to the treated fabric excellent properties of oleophobia and hydrophobia.

Claims

CLAIMS 1 - Fluorinated cationic copolymer, characterized in that it is obtained from a composition of monomers comprising, per 100 parts by weight:

(A) 5 to 92 parts by weight of at least one polyfluorinated monomer of formula (I):

R ² CHR ¹ = C - C - O - A ¹ - Rp (I)

0 in which

- R and R ² simultaneously represent a hydrogen atom or one of the two represents a hydrogen atom and the other, a C _χ -C ₄ alkyl radical; ' - A ¹ represents a bivalent chain linked to O by a carbon atom and which may include one or more atoms of oxygen and/or sulfur and/or nitrogen; And

- R represents a perfluorinated radical with a straight ^or branched chain, in C -CQ;

(B) 0.10 to 25 parts by weight of at least one monomer chosen from those of the following formulas (II), (III) and (IV):

(II)

in which: - R ³ represents H or -CH3; R ⁴ and R, identical or different, each independently represent H, C- _{j_} -C _-] _g alkyl, benzyl or hydroxyethyl; and X represents a monovalent anion;

in which :

- R° represents H or -CH3; And

"7

- R' represents H, C^-C^alkyl benzyl or hydroxyethyl;

^R8

| CHo - C - •

in which :

- R° represents H or -CH3; - R ⁹ and R ^x , identical or different, each independently represent hydrogen, C^-C^g alkyl, benzyl or hydroxyethyl; And

Op.,

- X ^ώW represents a monovalent anion;

(C) 0 to 20 parts by weight of at least one anionic or potentially anionic monomer by variation of pH; (D) 0 to 25 parts by weight of at least one vinyl monomer of general formula (V):

CH ₂ ≈ CHR ¹¹ (V)

in which R ^x represents an alkylcarboxylate or alkylether group, or Cχ-C- alkyl _| _g ;

(E) 0 to 60 parts by weight of at least one monomer of formula (VI):

^R12

CH ₂ =CC- [-0-CH ₂ -C-] _m - [-0-R ¹³ -] _n -OR ¹⁴ (VI )

O O

in which :

- R ^ώ represents H or -CH3;

- mr. is 0 or 1. ; •

- R ^x3 represents a C^-Cg alkylene residue which can be substituted by at least one halogen; - m is 0 or is an integer from 1 to 11, limits included;

- R ^x4 represents a C- _{j_} -C3 ₂ alkyl residue which can be substituted by at least one halogen, or a cycloalkyl residue which can be substituted by at least one halogen;

(F) 0 to 10 parts by weight of at least one monomer capable of inducing post-crosslinking of the fluoro copolymer during or after the formation of a coating of said fluoro copolymer on a substrate; And

(G) 0 to 25 parts by weight of at least one monomer of general formula (VII): in which ^' :

- R ¹⁵ represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms; o

- A^ represents an alkylene radical, linear or branched, containing 1 to 4 carbon atoms;

- the symbols R ¹⁶ and R ^x7 , identical or different, each represent a hydrogen atom, a linear or branched alkyl radical containing 1 to 18 carbon atoms or a hydroxyethyl or benzyl radical, or R16 and R17 together with the atom of nitrogen to which they are linked form a morpholino, piperidino or pyrrolidinyl-1 radical.

2 - Fluorinated cationic copolymer according to claim 1, characterized in that the monomer(s) (A) represent 40 to 90 parts by weight per 100 parts by weight of the total monomers.

3 - Fluorinated cationic copolymer according to one of claims 1 and 2, characterized in that the monomer(s) (A) of formula (I) are those for which Rf is a C^-C^g perfluoroalkyl radical.

4 - Fluorinated cationic copolymer according to one of claims 1 to 3, characterized in that the monomer(s) (A) of formula (I) are chosen from those of formula (la):

CH ₂ =CH-C-0-CH ₂ CH ₂ -R _f (la)

O

in which R represents a C ₄ -C ₁₆ perfluoroalkyl radical.

5 - Fluorinated cationic copolymer according to one of claims 1 to 4, characterized in that the one or more monomers (B) represent 1 to 18 parts by weight per 100 parts by weight of total monomers.

6 - Fluorinated cationic copolymer according to one of claims 1 to 5, characterized in that:

• the monomer(s) (B) of formula (II) are chosen from those for which:

- R ³ represents H;

- R ⁴ represents -CH3;

Rl ⁵ " ³ rreepprréésseennttee --CCHH33 or benzyl; and - X ^lθ represents Cl ^θ

the monomer (B) of formula (III) is that for which:

- R ⁶ represents H;

- R ⁷ represents -CH3; And

• the monomer(s) (B) of formula (IV) are chosen from those for which:

- R ⁸ represents H;

- R ⁹ represents -CH3;

- R ⁰ represents -CH3 or benzyl; And

X ^2θ represents Cl ^θ .

7 - Fluorinated cationic copolymer according to one of claims 1 to 6, characterized in that the monomer(s) (C) represent 1 to 10 parts by weight per 100 parts by weight of the total monomers. 8 - Fluorinated cationic copolymer according to one of claims 1 to 7, characterized in that the monomer(s) (C) are chosen from ethylenically unsaturated carboxylic acids and their salts, and sulfonated ethylenically unsaturated monomers and their salts . 9 - Fluorinated cationic copolymer according to claim 8, characterized in that the ethylenically unsaturated carboxylic acid is methacrylic acid, and the sulfonated ethylenically unsaturated monomers are chosen from 2-acrylamido-2-methylpropanesulfonic acid and its salts. 10 - Fluorinated cationic copolymer according to one of claims 1 to 9, characterized in that the monomer(s) (D) represent 2 to 10 parts by weight per 100 parts by weight of the total monomers. 11 - Fluorinated cationic copolymer according to one of claims 1 to 10, characterized in that the monomer (D) is vinyl acetate.

12 - Fluorinated cationic copolymer according to one of claims 1 to 11, characterized in that the monomer(s) (E) are chosen from behenyl acrylate, stearyl methacrylate, methoxyethyl acrylate and behenyl methacrylate. methoxyethyl.

13 - Fluorinated cationic copolymer according to one of claims 1 to 12, characterized in that the monomer(s) (F) are chosen from:

(FI) ethylenically unsaturated silanated monomers;

(F2) 2-hydroxy-3-chloropropyl (meth)acrylate;

(F3) epoxy-functional (meth)acrylates;

(F4) the monomers of formula (VIII):

_R18 ^R19

1

2 ⁼ = c ~ c - - N (VIII)

II

0 ^X _R 20

in which

- R ^x8 represents H or -CH3; and - R ⁹ and R ²⁰ , identical or different, each independently represent H, C -Cc alkyl; which possibly includes one or more groups

OH, or (C1-C5 alkoxy)-C2-C5 alkyl; And

(F5) the monomers of formula (IX):

R ²¹ OR ²³

in which :

- represents H or -CH ₃ ; And

- R ²² , R ²³ and R ²⁴ , identical or different, each represent H or C- _{j_} -C ₄ alkyl.

14 - Fluorinated cationic copolymer according to claim 13, characterized in that the monomer (F4) is N-methylolacrylamide.

15 - Fluorinated cationic copolymer according to claim 13, characterized in that the monomer (F5) of formula (IX) is that for which:

- R ^2x and R ²² each represent H; And

- R ²³ and R ²⁴ each represent -CH3.

16 - Fluorinated cationic copolymer according to one of claims 1 to 15, characterized in that the monomer (G) of formula. (VII) is dimethylaminoethyl methacrylate.

17 - Fluorinated cationic copolymer according to one of claims 1 to 16, characterized in that it was obtained by emulsion copolymerization in at least one organic solvent miscible with water, said copolymerization possibly having been followed by a step solvent distillation in order to obtain an emulsion in water without organic solvent.

18 - Fluorinated cationic copolymer according to one of claims 1 to 16, characterized in that it was obtained by copolymerization in solution in an organic solvent or a mixture of organic solvents miscible with water, and being followed by a step of dilution with an aqueous solution of a mineral or organic acid, said step being able to be carried out in the presence of hydrogen peroxide or to have been followed by treatment using an aqueous solution of hydrogen peroxide.

19 - Application of the cationic fluorinated copolymer as defined in one of claims 1 to 18 for the oleophobic and hydrophobic treatment of solid substrates, in particular paper and cardboard.- 20 - Application according to claim 19 to the surface of a paper at a rate of 0.05 to 0.2% fluorine relative to the weight of the paper.

21 - Application according to claim 19 in the mass of paper pulp at a rate of 0.2 to 0.4% fluorine relative to the weight of pulp.

22 - Solid substrate comprising at least one fluorinated copolymer as defined in one of claims 1 to 18. 23 - Solid substrate according to claim 22 characterized in that it is paper or cardboard.