EP1311567A1 - Neue fluorcopolymere, deren verwendung für die beschichtung und imprägnierung von substraten, und so behandelte substrate - Google Patents

Neue fluorcopolymere, deren verwendung für die beschichtung und imprägnierung von substraten, und so behandelte substrate

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Publication number
EP1311567A1
EP1311567A1 EP01956646A EP01956646A EP1311567A1 EP 1311567 A1 EP1311567 A1 EP 1311567A1 EP 01956646 A EP01956646 A EP 01956646A EP 01956646 A EP01956646 A EP 01956646A EP 1311567 A1 EP1311567 A1 EP 1311567A1
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EP
European Patent Office
Prior art keywords
monomer
weight
parts
alkyl
formula
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP01956646A
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English (en)
French (fr)
Inventor
Denis Tembou N'zudie
Yvon Legrand
Didier Juhue
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Arkema SA
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Atofina SA
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Publication of EP1311567A1 publication Critical patent/EP1311567A1/de
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/27—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of alkylpolyalkylene glycol esters of unsaturated carboxylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/273—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents

Definitions

  • the present invention relates to new fluorinated copoly ⁇ restaurants 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.
  • 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);
  • 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 :
  • R f is an aliphatic perfluorinated radical having from 3 to 20 carbon atoms
  • - 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;
  • R ⁇ 3 ' is a C 1 -C 4 alkyl or cycloalkyl group
  • - 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;
  • - R ''' represents H or methyl
  • - Z ⁇ 0 ' is a divalent electro-acceptor group which activates radical polymerization
  • _ ⁇ (0) ⁇ is a g rou p e monovalent cation
  • _ & ( 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;
  • 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;
  • R ' 11 ' represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms
  • a ' 1 -' represents an alkylene radical, linear or branched, containing 1 to 4 carbon atoms
  • R ⁇ 2 'and R ⁇ 13 ' identical or different, each represent a hydrogen atom, a linear alkyl radical or
  • R '- * - 4 ' may be an alkylcarboxylate or alkyl ether group containing from 1 to 18 carbon atoms;
  • 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.
  • 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.
  • 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.
  • 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:
  • 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
  • - R 3 represents H or -CH3
  • R 4 and R identical or different, each independently represent H, alkyl. in c ⁇ ⁇ c i8 'benzyl or hydroxyethyl;
  • R 7 represents H, C 1 -C 4 alkyl benzyl or hydroxyethyl
  • - 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 2 ⁇ represents a monovalent anion;
  • R 11 represents an alkylcarboxylate or alkyl ether group, or C 1 -C 4 -C 4 alkyl;
  • - 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;
  • 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
  • R 1 & and- R 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):
  • - R 4 represents -CH3; - R ⁇ represents -CH3 or benzyl; and
  • 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:
  • 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
  • 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:
  • 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
  • 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.
  • 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
  • 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, ⁇ -butyrolactone.
  • 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
  • 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 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 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.
  • 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.
  • peroxide type such as hydrogen peroxide
  • persalt such as the persulfates
  • azo type such as the 4,4 'azo bis acid (cyano -4 pentanoic) or azo-bis hydrochloride (aminidino propane).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • ketones for example, acetone, methyl ethyl ketone
  • alcohols for example isopropanol
  • ethers for example methyl ether
  • methyl isobutyl ketone or methyl ethyl ketone or a mixture of these with acetone it is preferred to use as solvent methyl isobutyl ketone or methyl ethyl ketone or a mixture of these with acetone.
  • N-vinyl-pyrrolidone 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.
  • initiators there can be used peroxides, such as benzoyl peroxide, lauroyl peroxide, succinyl peroxide and tertiary perpivalate.
  • 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 " .
  • 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.
  • the amount of acid is advantageously between 0 and 5 acid equivalents relative to the monomer (s) of formula
  • 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.
  • fluorinated copolymers in emulsion or in solution are applicable on various supports, such as leather, nonwovens, building materials, paper and cardboard.
  • they can be applied to textiles or paper using different techniques (in a size press
  • the present invention also relates to a solid substrate comprising at least one fluorinated copolymer according to the invention, as defined above.
  • textiles or papers, cardboards and similar materials 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.
  • 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.
  • 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.
  • fluorinated copolymers according to the invention 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%.
  • 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.
  • 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.
  • Vaseline Oil / n-Hexadecane (64/35)
  • 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.
  • 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).
  • 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).
  • 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 fluorinated cationic copolymer of the invention gives the treated paper excellent oleophobicity and hydrophobicity properties.
  • 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.
EP01956646A 2000-08-07 2001-07-26 Neue fluorcopolymere, deren verwendung für die beschichtung und imprägnierung von substraten, und so behandelte substrate Withdrawn EP1311567A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0010389A FR2812643B1 (fr) 2000-08-07 2000-08-07 Nouveaux copolymeres fluores, leur utilisation pour le revetement et l'impregnation de substrats, et les substrats ainsi traites
FR0010389 2000-08-07
PCT/FR2001/002457 WO2002012361A1 (fr) 2000-08-07 2001-07-26 Nouveaux copolymeres fluores, leur utilisation pour le revêtement et l'impregnation de substrats, et les substrats ainsi traites

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JP (1) JP2004506073A (de)
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GB2439947B8 (en) * 2006-07-31 2021-08-18 Vernacare Ltd Washbowl formed from paper pulp composition
GB0624729D0 (en) * 2006-12-12 2007-01-17 Univ Leeds Reversible micelles and applications for their use
CA2686440A1 (en) * 2007-05-30 2008-12-11 Asahi Glass Company, Limited Antifouling composition, method for its production and article treated therewith
US8071489B2 (en) * 2007-07-10 2011-12-06 E. I. Du Pont De Nemours And Company Amphoteric fluorochemicals for paper
KR101037589B1 (ko) * 2009-01-19 2011-05-31 심현섭 자유로운 발광연출이 가능한 엘이디 디스플레이 장치
ES2563205T3 (es) * 2010-02-15 2016-03-11 Daikin Industries, Ltd. Agente resistente al agua y al aceite para papel y proceso de tratamiento de papel
GB201111439D0 (en) 2011-07-04 2011-08-17 Syngenta Ltd Formulation
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GB2519059B (en) * 2013-08-07 2017-07-05 Hpc Healthline Uk Ltd A method of manufacturing a moulded pulp object
EP3060590B1 (de) 2013-10-22 2020-03-04 Honeywell International Inc. Härtbares fluorcopolymer aus tetrafluorpropen
US10435580B2 (en) 2015-11-20 2019-10-08 Honeywell International Inc. Gloss retentive fluorocopolymers for coating applications
EP3194165B1 (de) 2014-09-09 2021-03-03 Honeywell International Inc. Fluorpolymer mit niedrigem gehalt an flüchtigen organischen verbindungen und hohem gehalt an feststoffen für beschichtungsanwendungen

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EP0701020A2 (de) * 1994-07-27 1996-03-13 Bayer Ag Öl- und wasserabweisende Papiere, Verfahren zu ihrer Herstellung und neue fluorhaltige Copolymerisate hierzu
FR2727417B1 (fr) * 1994-11-29 1997-01-03 Atochem Elf Sa Copolymeres fluores cationiques pour le traitement oleophobe et hydrophobe des materiaux de construction
FR2756290B1 (fr) * 1996-11-27 1998-12-31 Atochem Elf Sa Copolymeres fluores pour le traitement oleophobe et hydrophobe de substrats divers
JP3876495B2 (ja) * 1997-09-12 2007-01-31 ユニマテック株式会社 撥水撥油剤およびその製造法

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WO2002012361A1 (fr) 2002-02-14
AU2001278570A1 (en) 2002-02-18
KR20030031966A (ko) 2003-04-23
US20040026053A1 (en) 2004-02-12
CN1468266A (zh) 2004-01-14
FR2812643B1 (fr) 2002-09-13
JP2004506073A (ja) 2004-02-26
FR2812643A1 (fr) 2002-02-08

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