US20040026053A1 - Novel fluorinated copolymers, their use for coating and impregnating substrates, and resulting treated substrates - Google Patents
Novel fluorinated copolymers, their use for coating and impregnating substrates, and resulting treated substrates Download PDFInfo
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- US20040026053A1 US20040026053A1 US10/343,918 US34391803A US2004026053A1 US 20040026053 A1 US20040026053 A1 US 20040026053A1 US 34391803 A US34391803 A US 34391803A US 2004026053 A1 US2004026053 A1 US 2004026053A1
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- 0 C.C.C.C.C.C.C.C.C.[12*]C(=C)C(=O)OCC(=O)O[13*]C.[2*]C(=C)C(=O)OC[Rf].[3*]C(=C)C(=O)OC(C[N+]([4*])([4*])[5*])C[N-]([4*])([4*])[5*].[6*]C(=C)C(=O)OC(CN([7*])[7*])CN([7*])[7*].[8*]C(=C)C(=O)OC(CN([9*])[9*])C[N+]([9*])([9*])[10*] Chemical compound C.C.C.C.C.C.C.C.C.[12*]C(=C)C(=O)OCC(=O)O[13*]C.[2*]C(=C)C(=O)OC[Rf].[3*]C(=C)C(=O)OC(C[N+]([4*])([4*])[5*])C[N-]([4*])([4*])[5*].[6*]C(=C)C(=O)OC(CN([7*])[7*])CN([7*])[7*].[8*]C(=C)C(=O)OC(CN([9*])[9*])C[N+]([9*])([9*])[10*] 0.000 description 20
- PCIAAMOWQWAQLI-UHFFFAOYSA-N C=CC(=O)OCC[Rf] Chemical compound C=CC(=O)OCC[Rf] PCIAAMOWQWAQLI-UHFFFAOYSA-N 0.000 description 2
- HDFGHKYWINCNBL-UHFFFAOYSA-N C.C.C.C.C.C.C=C(C)C(=O)OCC(=O)OCC Chemical compound C.C.C.C.C.C.C=C(C)C(=O)OCC(=O)OCC HDFGHKYWINCNBL-UHFFFAOYSA-N 0.000 description 1
- NCOIOHHVCQRTNN-UHFFFAOYSA-N C.C.C.C.C.C.C=CC(=O)OCC(=O)OCC Chemical compound C.C.C.C.C.C.C=CC(=O)OCC(=O)OCC NCOIOHHVCQRTNN-UHFFFAOYSA-N 0.000 description 1
- IHSOFYQLCVEXMF-UHFFFAOYSA-N C.C=C(C)CC Chemical compound C.C=C(C)CC IHSOFYQLCVEXMF-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N C=C(C)C(=O)OCC1CO1 Chemical compound C=C(C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- UUGXDEDGRPYWHG-UHFFFAOYSA-N C=C(C)C(=O)OCN(C)C Chemical compound C=C(C)C(=O)OCN(C)C UUGXDEDGRPYWHG-UHFFFAOYSA-N 0.000 description 1
- QZOKULHDFHOORU-UHFFFAOYSA-N C=C(C)C(=O)OC[Rf] Chemical compound C=C(C)C(=O)OC[Rf] QZOKULHDFHOORU-UHFFFAOYSA-N 0.000 description 1
- CYFDUSRTALFMLF-UHFFFAOYSA-N C=CC(=O)NC.COC(O)OC Chemical compound C=CC(=O)NC.COC(O)OC CYFDUSRTALFMLF-UHFFFAOYSA-N 0.000 description 1
- KFXBAJCMBJYFEK-UHFFFAOYSA-N C=CC(=O)OC(C[N+](C)(C)Cc1ccccc1)C[N+](C)(C)Cc1ccccc1 Chemical compound C=CC(=O)OC(C[N+](C)(C)Cc1ccccc1)C[N+](C)(C)Cc1ccccc1 KFXBAJCMBJYFEK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N C=CC(=O)OCC Chemical compound C=CC(=O)OCC JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N C=CC(=O)OCCC Chemical compound C=CC(=O)OCCC PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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 subject of the present invention is novel fluorocopolymers and their use for the coating and the impregnation of various substrates, such as textiles, leather, wood, non-wovens, metal, concrete and, more particularly, paper and similar articles as well as textiles, for the purpose of making them oleophobic and hydrophobic.
- substrates such as textiles, leather, wood, non-wovens, metal, concrete and, more particularly, paper and similar articles as well as textiles, for the purpose of making them oleophobic and hydrophobic.
- the invention also relates to the substrates thus treated.
- European Patent EP-B-0 234 601 thus teaches cationic fluorocopolymers having a presentation in the form of a latex or emulsion, and obtained by copolymerization of:
- a (0) is a divalent linking group
- R (1) is H or methyl
- R (2) is a C 1 -C 6 alkylene group, the R (2) groups being identical or different;
- R (3) is a C 1 -C 20 alkyl or cycloalkyl group
- n is 0 to 10, provided that when n is 0, R (3) is a C 1 -C 16 alkyl or cycloalkyl group; or
- R (4) is a C 1 -C 6 alkylene or haloalkylene group, the R (4) groups being identical or different;
- R (5) is a C 1 -C 20 alkyl, cycloalkyl, haloalkyl or halocycloalkyl group;
- p is 0 or 1
- q is 0 to 10, provided that when q is 0, R (5) is a C 1 -C 16 haloalkyl or halocycloalkyl group;
- R (6) is H or methyl
- R (7) represents H or methyl
- Z (0) is an electron-withdrawing divalent group which activates the radical polymerization
- Y (0)+ is a cationic monovalent group
- X (0) ⁇ is an anion
- a (10) represents a divalent linking group which is linked to C by a carbon atom and which may comprise one or more oxygen, sulphur 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;
- R f represents a perfluorinated radical, having 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 (11) represents a linear or branched alkylene radical containing 1 to 4 carbon atoms
- R (12) and R (13) which are 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 R (12) and R (13) together with the nitrogen atom to which they are linked form a morpholino, piperidino or pyrrolidin-1-yl radical;
- R (14) may be an alkyl carboxylate or alkyl ether group containing from 1 to 18 carbon atoms
- copolymerization reaction leading to the fluorocopolymers described by that international application is carried out in solution in a water-miscible organic solvent or solvent mixture and is followed by a step of dilution with an aqueous solution of a mineral or organic acid. This dilution step is carried out in the presence of hydrogen peroxide or is followed by a treatment by means of an aqueous hydrogen peroxide solution.
- This commercial composition is thus in the form of a solution in a water/solvent (N-methylpyrrolidone) mixture, thereby giving it stability properties which are highly advantageous for its transportation and its storage.
- tertiary or quaternary amino monomers used for the preparation of the cationic fluorocopolymers described in the above documents possess a single tertiary amino group or a single quaternary amino group per molecule.
- the subject of the present invention is therefore firstly a cationic fluorocopolymer, characterized in that it is obtained from a monomer composition comprising, per 100 parts by weight:
- R 1 and R 2 both represent a hydrogen atom or one of them represents a hydrogen atom and the other a C 1 -C 4 alkyl radical;
- a 1 represents a divalent linking group which is linked to 0 by a carbon atom and may comprise one or more oxygen and/or sulphur and/or nitrogen atom;
- R f represents a C 2 -C 20 perfluorinated radical with a straight or branched chain
- R 3 represents H or —CH 3 ;
- R 4 and R 5 which are identical or different, each independently represent H, C 1 -C 18 alkyl, benzyl or hydroxyethyl;
- x 1 represents a monovalent anion
- R 6 represents H or —CH 3 ;
- R 7 represents H, C 1 -C 18 alkyl, benzyl or hydroxyethyl
- R 8 represents H or —CH 3 ;
- R 9 and R 10 which are identical or 20 different, each independently represent hydrogen, C 1 -C18 alkyl, benzyl or hydroxyethyl;
- X 2 represents a monovalent anion
- R 1 represents a C 1 -C 18 alkyl or an alkyl carboxylate or alkyl ether group
- m is 0 or is an integer from 1 to 11, limits inclusive;
- R 14 represents a C 1 -C 32 alkyl residue possibly substituted with at least one halogen, or a cycloalkyl residue possibly substituted with at least one halogen;
- a 2 represents a linear or branched alkylene radical containing 1 to 4 carbon atoms
- R 16 and R 17 which are 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 R 16 and R 17 together with the nitrogen atom to which they are attached form a morpholino, piperidino or pyrrolidin-1-yl radical.
- the monomer or monomers (A) of formula (I) are especially those for which R f is a C 4 -C 16 perfluoroalkyl radical. More particularly, the monomer or monomers (A) of formula (I) are chosen from those of formula (Ia):
- R f represents a C 4 -C 16 perfluoroalkyl radical.
- the monomer or monomers (B) of formula (II) are chosen especially from those for which:
- R 3 represents H
- R 4 represents —CH 3 ;
- R 5 represents —CH 3 or benzyl
- X 1. represents Cl.
- the monomer (B) of formula (III) is especially that for which:
- R 6 represents H
- R 7 represents —CH 3 .
- the monomer or monomers (B) of formula (IV) are chosen especially from those for which:
- R 8 represents H
- R 9 represents —CH 3 ;
- R 10 represents —CH 3 or benzyl
- the anionic monomer(s) or monomer(s) potentially anionic by varying the pH (monomers (C)) are especially chosen from ethylenically unsaturated carboxylic acids and salts thereof and ethylenically unsaturated sulphonated monomers and salts thereof.
- the monomer (D) is especially vinyl acetate.
- the monomer or monomers (E) are especially chosen from behenyl acrylate, stearyl methacrylate, methoxyethyl acrylate and methoxyethyl methacrylate.
- R 18 represents H or —CH 3 ;
- R 21 represents H or —CH 3 ;
- R 22 , R 23 and R 24 which are identical or different, each represent H or a C 1 -C 4 alkyl.
- the monomer (F4) is especially N-methylolacrylamide.
- the monomer (F5) of formula (IX) is especially that for which:
- R 2 and R 22 each represent H
- R 23 and R 24 each represent —CH 3 .
- the monomer (G) is especially dimethylaminoethyl methacrylate.
- the organic solvents are compounds which can be at least partially diluted with water, such as propylene glycol, ethylene glycol, ethyl glycol, methoxypropanol, ethylene carbonate, propylene carbonate, the ethylic ether of ethylene glycol, the methyl ether of propylene glycol, N-methylpyrrolidone, acetone, methyl ethyl ketone, acetic acid, propionic acid, tetrahydrofuran, diacetone alcohol, methyl alcohol, ethyl alcohol, isopropyl alcohol and y-butyrolactone.
- water such as propylene glycol, ethylene glycol, ethyl glycol, methoxypropanol, ethylene carbonate, propylene carbonate, the ethylic ether of ethylene glycol, the methyl ether of propylene glycol, N-methylpyrrolidone, acetone, methyl ethyl ketone, acetic
- the amounts to be used in the water/solvent(s) mixture may vary between 40 and 95% by weight in the case of water and from 5 to 60% by weight in the case of the solvent mixture.
- the emulsion copolymerization is carried out in the presence of cationic surfactants which may or may not be combined with nonionic surfactants in an amount from 1 to 10% by weight with respect to the monomer mixture.
- the total concentration of monomers in the reaction mixture may range from 15 to 70% by weight and is preferably between 30 and 60% by weight.
- the molecular masses are adjusted by means of chain transfer agents, such as mercaptans, in an amount from 0.01 to 0.5% by weight with respect to the monomer mixture, or by the monomer introduction technique.
- chain transfer agents such as mercaptans
- the copolymerization may be initiated between 20 and 150° C. by means of initiators of the peroxide type (such as hydrogen peroxide) or persalt (such as persulphates) or of the azo type, such as 4,4′-azobis(4-cyano pentanoic acid) or azobis(aminidinopropane) hydro-chloride. They are used in an amount from 0.1 to 4% by weight with respect to the monomer mixture.
- initiators of the peroxide type such as hydrogen peroxide
- persalt such as persulphates
- azo type such as 4,4′-azobis(4-cyano pentanoic acid) or azobis(aminidinopropane) hydro-chloride.
- the amount of water-miscible solvent to be used may vary within wide limits and is generally between 10 and 80 parts by weight per 100 parts of the total of the monomers.
- high-energy emulsifying means may possibly be used, such as ultrasound or homogenizers of the Manton-Gaulin type.
- the polymerization step may be followed by a solvent distillation step so as to obtain an emulsion in water without any 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 a water-miscible organic solvent or in a mixture of such solvents.
- a distillable solvent will be used, in the form of a mixture with water in order to obtain a solventless product.
- the reaction mixture is then diluted with water in the presence of a mineral or organic acid in order to salify the macromolecules.
- this dilution step is carried out in the presence of hydrogen peroxide or is followed by a treatment by means of an aqueobus hydrogen peroxide soiution.
- water-miscible organic solvents distillable as a mixture with water, in which solvents the copolymerization is carried out
- ketones for example, acetone and methyl ethyl ketone
- alcohols for example, isopropanol
- ethers for example, methyl ether
- the total concentration of monomers in the organic solvent or organic solvent mixture may 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 from 0.1 to 2% by weight with respect to the total weight of monomers.
- initiators it is possible to use peroxides, such as benzoyl peroxide, lauroyl peroxide, succinyl peroxide and tert-butyl perpivalate, or azo compounds such as, for example, 2,2′-azobis(isobutyronitrile), 4-4′-azobis(4-cyanopentanoic) acid and azobis(amidinopropane).
- the copolymerization step may be carried out at a temperature ranging from 40° C. up to the boiling point of the reaction mixture. Preferably, it is carried out 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 organic or mineral acid, that is to say one whose dissociation constant or the first dissociation constant is greater than 10 ⁇ 5 .
- acetic acid As examples of such acids, mention may be made of hydrochloric, hydrobromic, sulphuric, nitric, phosphoric, acetic, formic, propionic and lactic acids, but it is preferred to use acetic acid.
- the amount of aqueous solution to be used and its acid concentration must be sufficient, on the one hand, to completely salify the amine functional groups provided by the monomer(s) of formulae (III), (IV) and (VII) and, on the other hand, to obtain a final copolymer solution having a solids content 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 with respect to the monomer(s) of formulae (III), (IV) and (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 with respect to the total initial weight of monomers.
- the treatment is carried out between 25 and 100° C., preferably from 70 to 85° C.
- emulsion or solution fluorocopolymers can be applied to various substrates, such as leather, non-wovens, building materials, paper and paperboard.
- substrates such as leather, non-wovens, building materials, paper and paperboard.
- they can be applied to textiles or to paper using various techniques (in a size-press or throughout the bulk of the material), thus giving the substrate excellent hydrophobic and oleophobic properties without requiring additives (sequestrants, retention agents, fixing resins).
- the subject of the present invention is also a solid substrate comprising at least one fluorocopolymer according to the invention, as defined above.
- substrates capable of being made oleophobic and hydrophobic with the products according to the invention it is preferred to use paper, paperboard and similar materials. It is also possible to use other highly varied materials such as, for example, woven or non-woven articles based on cellulose or regenerated cellulose, on natural, artificial or synthetic fibres such as cotton, cellulose acetate, wool, silk, polyamide, polyester, polyolefin, polyurethane or polyacrylonitrile fibres, leather, plastics, glass, wood, metals, porcelain and painted surfaces. It may also be advantageous to treat building materials such as concrete, stone, brick and tiles with the products according to the invention.
- compositions comprising a fluorocopolymer according to the invention are mainly applied diluted in an aqueous medium or in a mixture of water and solvents using known techniques, for example by coating, impregnation, immersion, spraying, brushing, padding or film-coating.
- fluorocopolymers according to the invention may also be advantageous to combine the fluorocopolymers according to the invention with one or more nonionic and/or cationic surfactants in order to improve the wetting of the substrate.
- the weight of this or these surfactants with respect to the total weight of copolymer may vary from 0 to 100%.
- Kit Test Volume of Volume of Volume of value castor oil toluene heptane 1 200 0 0 2 180 10 10 3 160 20 20 4 140 30 5 120 40 40 6 100 50 50 7 80 60 60 8 60 70 70 9 40 80 80 10 20 90 90 11 0 100 100 12 0 90 110
- the test consists in gently depositing drops of these mixtures on the treated paper. The drops are left on the paper for 15 seconds and then the appearance of the paper or paperboard is carefully observed and the wetting or penetration revealed by a browning of the surface is recorded.
- the number corresponding to the mixture containing the highest percentage of heptane, which does not penetrate or wet the paper, is the Kit Test value of the paper and is regarded as being the degree of oleophobicity of the treated paper. The higher the Kit Test value, the better the oleophobicity 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 by a square metre of paper supporting a water height of one centimetre.
- the test consists in depositing drops of these mixtures on the treated substrates and then in observing the effect of the drop after 30 seconds of contact.
- the rating is given by the number of the last drop of liquid which has neither penetrated nor wetted the substrate.
- This test is fully described by the AATCC 22-1989 standard. It consists in pouring, over a treated fabric, fixed to a substrate inclined at 45° C, 250 ml of water from a funnel fitted with a sprinkle rose over about twenty seconds and from a height of approximately 15 cm. The test reading is a visual one, the rating going from 0 (for a completely wetted fabric) to 100 (for a completely dry fabric).
- S-ADAMQUAT 2BZ a compound of formula:
- a reactor comprising 1000 parts by volume, heated by a thermostatted jacket and fitted with an anchor stirrer and with a reflux condenser, was charged with the following:
- a reactor comprising 1000 parts by volume, heated by a thermostatted jacket and fitted with an anchor stirrer and with a reflux condenser, was charged with the following:
- This composition was applied in the size press to a 70 g/m 2 gummed paper composed of bleached pulp. The degree of application was about 70%. After drying for 1 minute at 120° C., the paper thus treated was stored for one day at room temperature and then subjected to the various tests.
- the cationic fluorocopolymer of the invention gives the treated paper excellent oleophobic and hydrophobic 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 was prepared at room temperature.
- a polyester fabric was then padded in this bath, with 40% expression. After drying, the fabric was heat-set for 1 minute at 160° C. in a BENZ-type heat setter.
- the cationic fluorocopolymer of the invention gives the treated fabric excellent oleophobic and hydrophobic properties.
Abstract
This cationic fluorocopolymer is obtained from a composition comprising, per 100 parts by weight (pw): 5 to 92 pw of at least one polyfluorinated monomer (I); 0.10 to 25 pw of at least one monomer (II), (III) or (IV) ; 0 to 20 pw of at least one anionic monomer or monomer potentially anionic by varying the pH; 0 to 25 pw of at least one vinyl monomer (V) : CH2═CHR11; 0 to 60 pw of at least one monomer (VI); 0 to 10 pw of at least one monomer capable of causing postcrosslinking of the fluorocopolymer during or after the said fluorocopolymer has formed a coating on a substrate; and 0 to 25 parts by weight of at least one monomer (VII):
R1,R2═H or one of them ═H and the other ═C1-C4 alkyl; A=divalent linking group linked to 0 by a carbon atom and possibly comprising one or more oxygen and/or sulphur and/or nitrogen atoms; Rf═C2-C20 perfluorinated radical with a straight or branched chain; R, R, Rs, R1═H or —CH 3; R4, R5, R7, R9, R10═H, C1-C18 is alkyl, benzyl or hydroxyethyl; X1, X2.=monovalent anion; R11═C1-C18 alkyl carboxylate, alkyl ether or alkyl; m=0 or 1; R13═C1-C6 alkylene possibly substituted with at least one halogen; m=0 or an integer from 1 to 11, limits inclusive; R14═C1-C32 alkyl possibly substituted with at least one halogen, or cycloalkyl possibly substituted with at least one halogen; R15═H or C1-C4 alkyl; A2═C1-C4 linear or branched alkylene; R16, R17═H, C1-C18 linear or branched alkyl, or hydroxyethyl or benzyl, or R16 and R17 together with the nitrogen atom to which they are linked form a morpholino, piperidino or pyrrolidinyl radical.
Description
- The subject of the present invention is novel fluorocopolymers and their use for the coating and the impregnation of various substrates, such as textiles, leather, wood, non-wovens, metal, concrete and, more particularly, paper and similar articles as well as textiles, for the purpose of making them oleophobic and hydrophobic. The invention also relates to the substrates thus treated.
- To achieve this objective, many cationic fluoroderivatives have already been proposed, these having three types of presentation:
- (1) in the form of a latex or emulsion (a 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 removing the solvent in presentation (2).
- European Patent EP-B-0 234 601 thus teaches cationic fluorocopolymers having a presentation in the form of a latex or emulsion, and obtained by copolymerization of:
-
- in which:
- R(0) f is an aliphatic perfluorinated radical having from 3 to 20 carbon atoms; and
- A(0) is a divalent linking group;
- (b) 1 to 30% by weight of:
-
- in which:
- R(1) is H or methyl;
- R(2) is a C1-C6 alkylene group, the R(2) groups being identical or different;
- R(3) is a C1-C20 alkyl or cycloalkyl group;
- m is 0 or 1; and
- n is 0 to 10, provided that when n is 0, R(3) is a C1-C16 alkyl or cycloalkyl group; or
-
- in which:
- R(4) is a C1-C6 alkylene or haloalkylene group, the R(4) groups being identical or different;
- R(5) is a C1-C20 alkyl, cycloalkyl, haloalkyl or halocycloalkyl group;
- at least one R or R group containing a halogen atom;
- p is 0 or 1; and
- q is 0 to 10, provided that when q is 0, R(5) is a C1-C16 haloalkyl or halocycloalkyl group;
-
- in which R(6) is H or methyl;
-
- in which:
- R(7) represents H or methyl;
- Z(0) is an electron-withdrawing divalent group which activates the radical polymerization;
- Y(0)+ is a cationic monovalent group; and
- X(0)− is an anion; and
- (e) 0 to 20% by weight of vinylidene chloride.
- International Application WO 98/23657 relates to cationic fluorocopolymers having a presentation in the form of a solution in a water/solvent (N-vinylpyrrolidone) mixture, which are obtained by the polymerization of:
-
- in which:
- A(10) represents a divalent linking group which is linked to C by a carbon atom and which may comprise one or more oxygen, sulphur 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, having a straight or branched chain, containing 2 to 20 carbon atoms, preferably 4 to 16 carbon atoms,
-
- in which:
- R(11) represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms;
- A(11) represents a linear or branched alkylene radical containing 1 to 4 carbon atoms; and
- the symbols R(12) and R(13), which are 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 R(12) and R(13) together with the nitrogen atom to which they are linked form a morpholino, piperidino or pyrrolidin-1-yl radical;
- (c) 1 to 25% by weight of a vinyl derivative of general formula:
- CH2═CH—R(14)
- in which R(14) may be an alkyl carboxylate 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 above three formulae.
- The copolymerization reaction leading to the fluorocopolymers described by that international application is carried out in solution in a water-miscible organic solvent or solvent mixture and is followed by a step of dilution with an aqueous solution of a mineral or organic acid. This dilution step is carried out in the presence of hydrogen peroxide or is followed by a treatment by means of an aqueous hydrogen peroxide solution.
- After the said dilution step, it is necessary to carry out a vacuum distillation or to flush with an inert gas, for example nitrogen, in order to remove the volatile compounds and to obtain a composition that can be sold and applied to the substrate to be treated.
- The solvents exemplified in that application are, mostly, mixtures based on N-methylpyrrolidone. Because of their boiling point, these solvents are not completely removed by the distillation operation so that significant quantities of them remain in the commercial composition.
- This commercial composition is thus in the form of a solution in a water/solvent (N-methylpyrrolidone) mixture, thereby giving it stability properties which are highly advantageous for its transportation and its storage.
- However, for some applications, and especially for the treatment of papers or similar articles intended for the field of packaging food products, the presence of an organic solvent liable to come into contact with these food products is a drawback because of the health risks.
- 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 containing no organic solvent, that is to say in the form of an aqueous copolymer dispersion.
- The tertiary or quaternary amino monomers used for the preparation of the cationic fluorocopolymers described in the above documents possess a single 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 one quaternary amino group combined with one tertiary amino group can be used to prepare novel cationic fluorocopolymers which give various substrates, and especially paper and textiles, the same hydrophobic and oleophobic properties and which, in addition, may be in the form of aqueous compositions, especially in the form of a latex, emulsion or dispersion, or in the form of a solution in a water/solvent mixture.
- The subject of the present invention is therefore firstly a cationic fluorocopolymer, characterized in that it is obtained from a monomer composition comprising, per 100 parts by weight:
-
- in which:
- R1 and R2 both represent a hydrogen atom or one of them represents a hydrogen atom and the other a C1-C4 alkyl radical;
- A1 represents a divalent linking group which is linked to 0 by a carbon atom and may comprise one or more oxygen and/or sulphur and/or nitrogen atom; and
- Rf represents a C2-C20 perfluorinated radical with a straight or branched chain;
-
- in which:
- R3 represents H or —CH3;
- R4 and R5, which are identical or different, each independently represent H, C1-C18 alkyl, benzyl or hydroxyethyl; and
-
- in which:
- R6 represents H or —CH3; and
-
- in which:
- R8 represents H or —CH3;
- R9 and R10, which are identical or 20 different, each independently represent hydrogen, C1-C18 alkyl, benzyl or hydroxyethyl; and
- X2. represents a monovalent anion;
- (C) 0 to 20 parts by weight, in particular 1 to 10 parts by weight, of at least one anionic monomer or a monomer which is potentially anionic by varying the
- (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):
- CH2═CHR11 (V)
- in which R1 represents a C1-C18 alkyl or an alkyl carboxylate or alkyl ether group;
-
- in which:
- R12 represents H or —CH3;
- m is 0 or 1;
- R13 represents a C1-C6 alkylene residue possibly substituted with at least one halogen;
- m is 0 or is an integer from 1 to 11, limits inclusive;
- R14 represents a C1-C32 alkyl residue possibly substituted with at least one halogen, or a cycloalkyl residue possibly substituted with at least one halogen;
- (F) 0 to 10 parts by weight of at least one monomer capable of causing the postcrosslinking of the fluorocopolymer during or after the said fluorocopolymer has formed a coating on a substrate; and
-
- in which:
- R15 represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms;
- A2 represents a linear or branched alkylene radical containing 1 to 4 carbon atoms;
- the symbols R16 and R17, which are 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 nitrogen atom to which they are attached form a morpholino, piperidino or pyrrolidin-1-yl radical.
-
- in which Rf represents a C4-C16 perfluoroalkyl radical.
- The monomer or monomers (B) of formula (II) are chosen especially from those for which:
- R3 represents H;
- R4 represents —CH3;
- R5 represents —CH3 or benzyl; and
- X1. represents Cl.
- The monomer (B) of formula (III) is especially that for which:
- R6 represents H; and
- R7 represents —CH3.
- The monomer or monomers (B) of formula (IV) are chosen especially from those for which:
- R8 represents H;
- R9 represents —CH3;
- R10 represents —CH3 or benzyl; and
- X2. represents Cl.
- In the case of the copolymers according to the invention which are obtained in an emulsion, it will be preferred to use, as compound(s) (B), a compound (II) in which R3═H; R4═—CH3; R5═—CH3 or —CH2-C6H5 and X1.═Cl. and/or a compound (IV) in which R8═H; R9-CH3; R10═—CH3 or -CH2-C6H5 and X2., ═Cl.
- 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 R6═H and R7═—CH3 and/or a compound (IV) in which R8═H; R9═—CH3; R10═—CH3 or —CH2-C6H5 and X2. ═Cl.
- The anionic monomer(s) or monomer(s) potentially anionic by varying the pH (monomers (C)) are especially chosen from ethylenically unsaturated carboxylic acids and salts thereof and ethylenically unsaturated sulphonated monomers and salts thereof.
- The ethylenically unsaturated carboxylic acid is especially methacrylic acid and the ethylenically unsaturated sulphonated monomers are especially chosen from 2-acrylamido-2-methylpropanesulphonic acid and salts thereof. It is preferred to use methacrylic acid as monomer (C).
- The monomer (D) is especially vinyl acetate.
- The monomer or monomers (E) are especially chosen from behenyl acrylate, stearyl methacrylate, methoxyethyl acrylate and methoxyethyl methacrylate.
- The monomer or monomers (F), which can cause postcrosslinking of the polymer during or after the fluorocopolymer has formed a coating on the substrate, are especially chosen from:
- (F1), ethylenically unsaturated silane monomers;
- (F2), 2-hydroxy-3-chloropropyl (meth)acrylate;
- (F3), (meth)acrylates with an epoxy functional group;
-
- in which:
- R18 represents H or —CH3; and
- R19 and R20, which are identical or different, each independently represent H or a C1-C5 alkyl, which possibly includes one or more OH groups, or a (C1-C5)alkoxy-(C1-C5)alkyl; and
-
- in which:
- R21 represents H or —CH3; and
- R22, R23 and R24, which are identical or different, each represent H or a C1-C4 alkyl.
- The monomer (F4) is especially N-methylolacrylamide. The monomer (F5) of formula (IX) is especially that for which:
- R2 and R22 each represent H; and
- R23 and R24each represent —CH3.
- The monomer (G) is especially dimethylaminoethyl methacrylate.
- Depending on the final presentation of the polymer, the fluorocopolymers according to the present invention are prepared by radical copolymerization of the monomers using two polymerization techniques, especially emulsion polymerization (to obtain a polymer in latex or emulsion form) or solution polymerization (to obtain the polymer in solution form in a water/solvent mixture or in the form of an aqueous dispersion after solvent removal).
- In the case of emulsion polymerization, to carry out the reaction one or more water-miscible organic solvents must be used. The present invention describes the composition of the water/solvent(s) mixture which can result in a-product with a flash point above 100° C. =p The organic solvents are compounds which can be at least partially diluted with water, such as propylene glycol, ethylene glycol, ethyl glycol, methoxypropanol, ethylene carbonate, propylene carbonate, the ethylic ether of ethylene glycol, the methyl ether of propylene glycol, N-methylpyrrolidone, acetone, methyl ethyl ketone, acetic acid, propionic acid, tetrahydrofuran, diacetone alcohol, methyl alcohol, ethyl alcohol, isopropyl alcohol and y-butyrolactone.
- The amounts to be used in the water/solvent(s) mixture may vary between 40 and 95% by weight in the case of water and from 5 to 60% by weight in the case of the solvent mixture.
- The following solvents are preferably used:
- propylene glycol, N-methylpyrrolidone, the methyl ether of propylene glycol or acetic acid; in this case, the polymerization is not followed by a distillation as the solvent mixture does not result in a flash point between 0 and 100° C.;
- acetone; the water/acetone mixture results in a flash point between 0 and 100° C.; in this case, the distillation is carried out until the solvent is removed from the emulsion.
- The emulsion copolymerization is carried out in the presence of cationic surfactants which may or may not be combined with nonionic surfactants in an amount from 1 to 10% by weight with respect to the monomer mixture. The total concentration of monomers in the reaction mixture (water/solvent/monomers/surfactants) may range from 15 to 70% by weight and is preferably between 30 and 60% by weight.
- The molecular masses are adjusted by means of chain transfer agents, such as mercaptans, in an amount from 0.01 to 0.5% by weight with respect to the monomer mixture, or by the monomer introduction technique.
- The copolymerization may be initiated between 20 and 150° C. by means of initiators of the peroxide type (such as hydrogen peroxide) or persalt (such as persulphates) or of the azo type, such as 4,4′-azobis(4-cyano pentanoic acid) or azobis(aminidinopropane) hydro-chloride. They are used in an amount from 0.1 to 4% by weight with respect to the monomer mixture.
- The amount of water-miscible solvent to be used may vary within wide limits and is generally between 10 and 80 parts by weight per 100 parts of the total of the monomers. For the emulsion of the monomers, high-energy emulsifying means may possibly be used, such as ultrasound or homogenizers of the Manton-Gaulin type.
- The polymerization step may be followed by a solvent distillation step so as to obtain an emulsion in water without any 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 a water-miscible organic solvent or in a mixture of such solvents. Preferably, a distillable solvent will be used, in the form of a mixture with water in order to obtain a solventless product. The reaction mixture is then diluted with water in the presence of a mineral or organic acid in order 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 by means of an aqueobus hydrogen peroxide soiution.
- As water-miscible organic solvents distillable as a mixture with water, in which solvents the copolymerization is carried out, mention may be made, by way of non-limiting examples, of ketones (for example, acetone and methyl ethyl ketone), alcohols (for example, isopropanol) and ethers (for example, methyl ether).
- To implement the invention, it is preferred to use as solvent methyl isobutyl ketone or methyl ethyl ketone, or a mixture of these with acetone.
- As water-miscible organic solvents not distillable as a mixture with water, in which solvents the copolymerization is carried out, mention may be made by way of a non-limiting example of N-vinylpyrrolidone.
- The total concentration of monomers in the organic solvent or organic solvent mixture may 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 from 0.1 to 2% by weight with respect to the total weight of monomers. As initiators, it is possible to use peroxides, such as benzoyl peroxide, lauroyl peroxide, succinyl peroxide and tert-butyl perpivalate, or azo compounds such as, for example, 2,2′-azobis(isobutyronitrile), 4-4′-azobis(4-cyanopentanoic) acid and azobis(amidinopropane). The copolymerization step may be carried out at a temperature ranging from 40° C. up to the boiling point of the reaction mixture. Preferably, it is carried out 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 organic or mineral acid, that is to say one whose dissociation constant or the first dissociation constant is greater than 10−5.
- As examples of such acids, mention may be made of hydrochloric, hydrobromic, sulphuric, nitric, phosphoric, acetic, formic, propionic and lactic acids, but it is preferred to use acetic acid. The amount of aqueous solution to be used and its acid concentration must be sufficient, on the one hand, to completely salify the amine functional groups provided by the monomer(s) of formulae (III), (IV) and (VII) and, on the other hand, to obtain a final copolymer solution having a solids content between 5 and 30% by weight, preferably between 20 and 30% by weight. For complete salification of the amine functional groups, the amount of acid is advantageously between 0 and 5 acid equivalents with respect to the monomer(s) of formulae (III), (IV) and (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 with respect to the total initial weight of monomers. The treatment is carried out between 25 and 100° C., preferably from 70 to 85° C.
- These emulsion or solution fluorocopolymers can be applied to various substrates, such as leather, non-wovens, building materials, paper and paperboard. In particular, they can be applied to textiles or to paper using various techniques (in a size-press or throughout the bulk of the material), thus giving the substrate excellent hydrophobic and oleophobic properties without requiring additives (sequestrants, retention agents, fixing resins).
- The subject of the present invention is also a solid substrate comprising at least one fluorocopolymer 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 paper, paperboard and similar materials. It is also possible to use other highly varied materials such as, for example, woven or non-woven articles based on cellulose or regenerated cellulose, on natural, artificial or synthetic fibres such as cotton, cellulose acetate, wool, silk, polyamide, polyester, polyolefin, polyurethane or polyacrylonitrile fibres, leather, plastics, glass, wood, metals, porcelain and painted surfaces. It may also be advantageous to treat building materials such as concrete, stone, brick and tiles with the products according to the invention.
- The compositions comprising a fluorocopolymer according to the invention are mainly applied diluted in an aqueous medium or in a mixture of water and solvents using known techniques, for example by coating, impregnation, immersion, spraying, brushing, padding or film-coating.
- The products according to the invention can be applied in aqueous solution to paper, either onto the surface of the already completed substrate (preferably in an amount of 0.05 to 0.2% fluorine with respect to the weight of paper) or into the body of the material, that is to say into the paper pulp (preferably in an amount of 0.2 to 0.4% fluorine with respect to the weight of pulp).
- The substrates thus treated exhibit good oleophobic and hydrophobic properties after simple drying at room temperature or at high temperature, optionally followed by a heat treatment which can range, depending on the nature of the substrate, up to 200° C.
- To obtain good attachment of the fluorocopolyniers according to the invention to the substrates to which they have been applied, and, in addition, to confer a specific effect, it is sometimes advantageous to combine them with certain additives, polymers, thermocondensable products and catalysts capable of promoting their crosslinking with the substrate. Mention may be made, as such, of urea-formaldehyde or melamine-formaldehyde condensates or precondensates, 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 fluorocopolymers according to the invention with one or more nonionic and/or cationic surfactants in order to improve the wetting of the substrate. The weight of this or these surfactants with respect to the total weight of copolymer may vary from 0 to 100%.
- The following tests were used to evaluate the performance of the treated substrates according to the invention:
- This test, described in TAPPI, Vol. 50, No. 10, pages 152A and 153A and in the RC338 and UM511 standards, makes it possible to measure the grease resistance of substrates using mixtures of castor oil, toluene and heptane. These mixtures contain variable amounts of these three products:
Kit Test Volume of Volume of Volume of value castor oil toluene heptane 1 200 0 0 2 180 10 10 3 160 20 20 4 140 30 30 5 120 40 40 6 100 50 50 7 80 60 60 8 60 70 70 9 40 80 80 10 20 90 90 11 0 100 100 12 0 90 110 - The test consists in gently depositing drops of these mixtures on the treated paper. The drops are left on the paper for 15 seconds and then the appearance of the paper or paperboard is carefully observed and the wetting or penetration revealed by a browning of the surface is recorded. The number corresponding to the mixture containing the highest percentage of heptane, which does not penetrate or wet the paper, is the Kit Test value of the paper and is regarded as being the degree of oleophobicity of the treated paper. The higher the Kit Test value, the better the oleophobicity 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 by a square metre of paper supporting a water height of one centimetre.
- The oleophobicity was measured on certain substrates using the method described in “AATCC Technical Manual”, Test Method 118-1972, which evaluates the non-wettability of the substrate using a series of oily liquids numbered 1 to 8:
- No. 1: liquid paraffin
- No. 2: liquid paraffin/n-hexadecane (64/35)
- No. 3: n-hexadecane
- No. 4: n-tetradecane
- No. 5: n-dodecane
- No. 6: n-decane
- No. 7: n-octane
- No. 8: n-heptane.
- The test consists in depositing drops of these mixtures on the treated substrates and then in observing the effect of the drop after 30 seconds of contact. The rating is given by the number of the last drop of liquid which has neither penetrated nor wetted the substrate.
- This test, called a spray test, is fully described by the AATCC 22-1989 standard. It consists in pouring, over a treated fabric, fixed to a substrate inclined at 45° C, 250 ml of water from a funnel fitted with a sprinkle rose over about twenty seconds and from a height of approximately 15 cm. The test reading is a visual one, the rating going from 0 (for a completely wetted fabric) to 100 (for a completely dry fabric).
- The following examples illustrate the invention without, however, limiting the scope thereof. The parts and percentages given are by weight, unless otherwise. indicated, and the following abbreviation has been used:
-
-
- was used, in which p is equal to 8, 10, 12 and 14 in respective proportions by weight of 63/25/10/2.
- A reactor comprising 1000 parts by volume, heated by a thermostatted jacket and fitted with an anchor stirrer and with a reflux condenser, was charged with the following:
- 383 parts of demineralized water;
- 140 parts of acetone;
- 3.75 parts of trimethyloleylammonium chloride;
- 3.43 parts of a mixture of ethoxylated alkylphenols (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 an aqueous 75% S-ADAMQUAT 2BZ solution; and
- 0.48 parts of n-dodecylmercaptan.
- After inerting with nitrogen and heating to 70° C., the polymerization was initiated using 1.2 parts of azobis (amidinopropane) hydrochloride dissolved in 8 parts of water. After 2 hours of polymerization at 70° C., 796 parts of an emulsion having a solids content of 30.2% was obtained.
- Next, the acetone was distilled off at 90° C., resulting in a latex having a solids content of 36%; this was then diluted with water in order to obtain a perfectly stable emulsion having a solids content of 25%. This product did not have a flash point between 0 and 100° C. in the closed cup test (using the Setaflash NF.T.300.50 method).
- A reactor comprising 1000 parts by volume, heated by a thermostatted jacket and fitted with an anchor stirrer and with a reflux condenser, was charged with the following:
- 257.4 parts of demineralized water;
- 91.8 parts of acetone;
- 8.98 parts of trimethyloleylammonium chloride;
- 8.22 parts of a mixture of ethoxylated alkylphenols (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;
-
- 2.80 parts of an aqueous 75% S-ADAMQUAT 2BZ solution;
- 8.45 parts of methyl acrylate; and
- 0.18 parts of n-dodecylmercaptan.
- After inerting with nitrogen and heating to 70° C., the polymerization was initiated using 0.9 parts of azobis (amidinopropane) hydrochloride dissolved in 9 parts of water. After 2 hours of polymerization at 70° C., 573 parts of an emulsion having a solids content of 36% was obtained.
- Next, the acetone was distilled off at 90° C., resulting in a latex having a solids content of 40%; this was then diluted with water in order to obtain a perfectly stable emulsion having a solids content of 20%. This product did not have a flash point between 0 and 100° C. in the closed cup test (using the Setaflash NF.T.300.50 method).
- An aqueous size-press bath containing 16 g/l of the emulsion obtained in Example 1 was prepared.
- This composition was applied in the size press to a 70 g/m2 gummed paper composed of bleached pulp. The degree of application was about 70%. After drying for 1 minute at 120° C., the paper thus treated was stored for one day at room temperature and then subjected to the various tests.
- The results are given in Table 1 below:
TABLE 1 PAPER TREATED TESTS WITH THE BATH UNTREATED PAPER KIT TEST VALUE 12 0 COBB VALUE (g/m2) 17 >20 - The cationic fluorocopolymer of the invention gives the treated paper excellent oleophobic and hydrophobic 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 was prepared at room temperature. A polyester fabric was then padded in this bath, with 40% expression. After drying, the fabric was heat-set for 1 minute at 160° C. in a BENZ-type heat setter.
- The hydrophobicity and oleophobicity of the fabric were then tested. The results obtained are given in Table 2 below:
TABLE 2 FABRIC TREATED TESTS WITH BATH UNTREATED FABRIC SPRAY TEST 100 0 OLEOPHOBICITY 5 0 - The cationic fluorocopolymer of the invention gives the treated fabric excellent oleophobic and hydrophobic properties.
Claims (23)
1. Cationic fluorocopolymer, characterized in that it is obtained from a monomer composition comprising, per 100 parts by weight:
(A) 5 to 92 parts by weight of at least one polyfluorinated monomer of formula (I):
in which:
R1 and R2 both represent a hydrogen atom or one of them represents a hydrogen atom and the other a C1-C4 alkyl radical;
A1 represents a divalent linking group which is linked to 0 by a carbon atom and may comprise one or more oxygen and/or sulphur and/or nitrogen atom; and
Rf represents a C2-C20 perfluorinated radical with a straight or branched chain;
(B) 0.10 to 25 parts by weight of at least one monomer chosen from those of the following formulae (II), (III) and (IV):
in which:
R3 represents H or —CH3;
R4 and R5, which are identical or different, each independently represent H, C1-C18 alkyl, benzyl or hydroxyethyl; and
x1. represents a monovalent anion;
in which:
R6 represents H or —CH3; and
R7 represents H, C1-C18 alkyl, benzyl or hydroxyethyl;
in which:
R8 represents H or —CH3;
R9 and R10, which are identical or different, each independently represent hydrogen, C1-C18 alkyl, benzyl or hydroxyethyl; and
X2. represents a monovalent anion;
(C) 0 to 20 parts by weight of at least one anionic monomer or a monomer which is potentially anionic by varying the pH;
(D) 0 to 25 parts by weight of at least one vinyl monomer of general formula (V):
CH2═CHR11 (V)
in which R11 represents a C1-C18 alkyl or an alkyl carboxylate or alkyl ether group;
(E) 0 to 60 parts by weight of at least one monomer of formula (VI):
in which:
R12 represents H or —CH3;
m is 0 or 1;
R13 represents a C1-C6 alkylene residue possibly substituted with at least one halogen;
m is 0 or is an integer from 1 to 11, limits inclusive;
R14 represents a C1-C32 alkyl residue possibly substituted with at least one halogen, or a cycloalkyl residue possibly substituted with at least one halogen;
(F) 0 to 10 parts by weight of at least one monomer capable of causing the postcrosslinking of the fluorocopolymer during or after the said fluorocopolymer has formed a coating on a substrate; and
(G) 0 to 25 parts by weight of at least one monomer of general formula (VII):
in which:
R15 represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms;
A2 represents a linear or branched alkylene radical containing 1 to 4 carbon atoms;
the symbols R16 and R17, which are 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 nitrogen atom to which they are attached form a morpholino, piperidino or pyrrolidin-1-yl radical.
2. Cationic fluorocopolymer according to claim 1 , characterized in that the monomer or monomers (A) represent 40 to 90 parts by weight per 100 parts by weight of total monomer.
3. Cationic fluorocopolymer according to either of claims 1 and 2, characterized in that the monomer or monomers (A) of formula (I) are those for which Rf is a C4-C16 perfluoroalkyl radical.
5. Cationic fluorocopolymer according to one of claims 1 to 4 , characterized in that the monomer or monomers (B) represent 1 to 18 parts by weight per 100 parts by weight of total monomer.
6. Cationic fluorocopolymer according to one of claims 1 to 5 , characterized in that:
the monomer or monomers (B) of formula (II) are chosen from those for which:
R3 represents H;
R4 represents —CH3;
R5 represents —CH3 or benzyl; and
x1. represents Cl.;
the monomer (B) of formula (III) is that for which:
R6 represents H;
R7 represents —CH3; and
the monomer or monomers (B) of formula (IV) are chosen from those for which:
R8 represents H;
R9 represents —CH3;
R10 represents —CH3 or benzyl; and
x2. represents Cl.
7. Cationic fluorocopolymer according to one of claims 1 to 6 , characterized in that the monomer or monomers (C) represent 1 to 10 parts by weight per 100 parts by weight of total monomer.
8. Cationic fluorocopolymer according to one of claims 1 to 7 , characterized in that the monomer or monomers (C) are chosen from ethylenically unsaturated carboxylic acids and salts thereof and ethylenically unsaturated sulphonated monomers and salts thereof.
9. Cationic fluorocopolymer according to claim 8 , characterized in that the ethylenically unsaturated carboxylic acid is methacrylic acid and the ethylenically unsaturated sulphonated monomers are chosen from 2-acrylamido-2-methylpropanesulphonic acid and salts thereof.
10. Cationic fluorocopolymer according to one of claims 1 to 9 , characterized in that the monomer or monomers (D) represent 2 to 10 parts by weight per 100 parts by weight of total monomer.
11. Cationic fluorocopolymer according to one of claims 1 to 10 , characterized in that the monomer (D) is vinyl acetate.
12. Cationic fluorocopolymer according to one of claims 1 to 11 , characterized in that the monomer or monomers (E) are chosen from behenyl acrylate, stearyl methacrylate, methoxyethyl acrylate and methoxyethyl methacrylate.
13. Cationic fluorocopolymer according to one of claims 1 to 12 , characterized in that the monomer or monomers (F) are chosen from:
(F1), ethylenically unsaturated silane monomers;
(F2), 2-hydroxy-3-chloropropyl (meth)acrylate;
(F3), (meth)acrylates with an epoxy functional group;
(F4), monomers of formula (VIII):
in which:
R18 represents H or —CH3; and
R19 and R20, which are identical or different, each independently represent H or a C1-C5 alkyl, which possibly includes one or more OH groups, or a (C1-C5)alkoxy-(C5)alkyl; and
(F5), monomers of formula (IX):
in which:
R21 represents H or —CH3; and
R22, R23 and R24, which are identical or different, each represent H or a C1-C4 alkyl.
14. Cationic fluorocopolymer according to claim 13 , characterized in that the monomer (F4) is N-methylolacrylamide
15. Cationic fluorocopolymer according to claim 13 , characterized in that the monomer (F5) of formula (IX) is that for which:
R21 and R22 each represent H; and
R23 and R24 each represent —CH3.
16. Cationic fluorocopolymer according to one of claims 1 to 15 , characterized in that the monomer (G) of formula (VII) is dimethylaminoethyl methacrylate.
17. Cationic fluorocopolymer according to one of claims 1 to 16 , characterized in that it was obtained by emulsion copolymerization in at least one water-miscible organic solvent, the said copolymerization possibly being followed by a solvent distillation step so as to obtain an emulsion in water without any organic solvent.
18. Cationic fluorocopolymer according to one of claims 1 to 16 , characterized in that it was obtained by solution copolymerization in a water-miscible organic solvent or a mixture of water-miscible organic solvents, and being followed by a step of dilution with an aqueous solution of a mineral or organic acid, the said step possibly being carried out in the presence of hydrogen peroxide or having been followed by a treatment by means of an aqueous hydrogen peroxide solution.
19. Application of the cationic fluorocopolymer as defined in one of claims 1 to 18 for the oleophobic and hydrophobic treatment of solid substrates, particularly of paper and paperpaperboard.
20. Application according to claim 19 to the surface of a paper in an amount from 0.05 to 0.2% of fluorine with respect to the weight of the paper.
21. Application according to claim 19 into the bulk of a paper pulp in an amount from 0.2 to 0.4% of fluorine with respect to the weight of pulp.
22. Solid substrate comprising at least one fluorocopolymer as defined in one of claims 1 to 18 .
23. Solid substrate according to claim 22 , characterized in that it is made of paper or paperpaperboard.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0010389A FR2812643B1 (en) | 2000-08-07 | 2000-08-07 | NOVEL FLUORINATED COPOLYMERS, THEIR USE FOR COATING AND IMPREGNATION OF SUBSTRATES, AND SUBSTRATES THUS PROCESSED |
PCT/FR2001/002457 WO2002012361A1 (en) | 2000-08-07 | 2001-07-26 | Novel fluorinated copolymers, their use for coating and impregnating substrates, and resulting treated substrates |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040026053A1 true US20040026053A1 (en) | 2004-02-12 |
Family
ID=8853364
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/343,918 Abandoned US20040026053A1 (en) | 2000-08-07 | 2001-07-26 | Novel fluorinated copolymers, their use for coating and impregnating substrates, and resulting treated substrates |
Country Status (8)
Country | Link |
---|---|
US (1) | US20040026053A1 (en) |
EP (1) | EP1311567A1 (en) |
JP (1) | JP2004506073A (en) |
KR (1) | KR20030031966A (en) |
CN (1) | CN1468266A (en) |
AU (1) | AU2001278570A1 (en) |
FR (1) | FR2812643B1 (en) |
WO (1) | WO2002012361A1 (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070010591A1 (en) * | 2003-09-05 | 2007-01-11 | Piet Vanneste | Process for the preparation of (meth)acrylate di-ammonium salts and their use as monomers for the synthesis of polymers |
GB2439947A (en) * | 2006-07-31 | 2008-01-16 | Vernacare Ltd | Mouldable paper pulp composition |
US20100120970A1 (en) * | 2006-12-12 | 2010-05-13 | University Of Leeds | Reversible micelles and applications for their use |
US20120325419A1 (en) * | 2010-02-15 | 2012-12-27 | Daikin Industries, Ltd. | Water and oil resistant agent for paper and paper treatment process |
WO2013004704A1 (en) | 2011-07-04 | 2013-01-10 | Syngenta Limited | Formulation |
WO2014097309A1 (en) | 2012-12-17 | 2014-06-26 | Asian Paints Ltd. | Stimuli responsive self cleaning coating |
KR101431298B1 (en) | 2007-05-30 | 2014-08-20 | 아사히 가라스 가부시키가이샤 | Stain-proofing agent composition, method for producing the same and article processed with the same |
GB2519059A (en) * | 2013-08-07 | 2015-04-15 | Hpc Healthline Uk Ltd | A method of manufacturing a moulded pulp object |
WO2016040525A1 (en) * | 2014-09-09 | 2016-03-17 | Honeywell International Inc. | Low voc and high solid fluoropolymer for coating applications |
US11225585B2 (en) | 2015-11-20 | 2022-01-18 | Honeywell International Inc. | Gloss retentive fluorocopolymers for coating applications |
US11453731B2 (en) | 2013-10-22 | 2022-09-27 | Honeywell International Inc. | Curable fluorocopolymer formed from tetrafluoropropene |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8071489B2 (en) * | 2007-07-10 | 2011-12-06 | E. I. Du Pont De Nemours And Company | Amphoteric fluorochemicals for paper |
KR101037589B1 (en) * | 2009-01-19 | 2011-05-31 | 심현섭 | Led display apparatus practicable free-production |
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US5558940A (en) * | 1994-07-27 | 1996-09-24 | Bayer Aktiengesellschaft | Oil- and water-repellent papers, processes for their production and new fluorine-containing copolymers for this purpose |
US5798415A (en) * | 1994-11-29 | 1998-08-25 | Elf Atochem S.A. | Cationic fluoro copolymers for the oleophobic and hydrophobic treatment of building materials |
US6111043A (en) * | 1996-11-27 | 2000-08-29 | Elf Atochem S.A. | Fluorocopolymers for oil repelling and waterproofing treatment of various substrates |
US6153675A (en) * | 1997-09-12 | 2000-11-28 | Nippon Mektron, Limited | Fluorinated water-and oil-repellent agents with improved freeze-thaw stability |
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DE4426537A1 (en) * | 1994-07-27 | 1996-02-01 | Bayer Ag | Fluorine-contg. copolymers for oil- and water-proofing paper |
-
2000
- 2000-08-07 FR FR0010389A patent/FR2812643B1/en not_active Expired - Fee Related
-
2001
- 2001-07-26 EP EP01956646A patent/EP1311567A1/en not_active Withdrawn
- 2001-07-26 AU AU2001278570A patent/AU2001278570A1/en not_active Abandoned
- 2001-07-26 JP JP2002518331A patent/JP2004506073A/en not_active Abandoned
- 2001-07-26 CN CNA018169740A patent/CN1468266A/en active Pending
- 2001-07-26 US US10/343,918 patent/US20040026053A1/en not_active Abandoned
- 2001-07-26 WO PCT/FR2001/002457 patent/WO2002012361A1/en not_active Application Discontinuation
- 2001-07-26 KR KR10-2003-7001816A patent/KR20030031966A/en not_active Application Discontinuation
Patent Citations (4)
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US5558940A (en) * | 1994-07-27 | 1996-09-24 | Bayer Aktiengesellschaft | Oil- and water-repellent papers, processes for their production and new fluorine-containing copolymers for this purpose |
US5798415A (en) * | 1994-11-29 | 1998-08-25 | Elf Atochem S.A. | Cationic fluoro copolymers for the oleophobic and hydrophobic treatment of building materials |
US6111043A (en) * | 1996-11-27 | 2000-08-29 | Elf Atochem S.A. | Fluorocopolymers for oil repelling and waterproofing treatment of various substrates |
US6153675A (en) * | 1997-09-12 | 2000-11-28 | Nippon Mektron, Limited | Fluorinated water-and oil-repellent agents with improved freeze-thaw stability |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
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US7799944B2 (en) | 2003-09-05 | 2010-09-21 | Taminco N.V. | Process for the preparation of (meth)acrylate di-ammonium salts and their use as monomers for the synthesis of polymers |
US20070010591A1 (en) * | 2003-09-05 | 2007-01-11 | Piet Vanneste | Process for the preparation of (meth)acrylate di-ammonium salts and their use as monomers for the synthesis of polymers |
GB2439947A (en) * | 2006-07-31 | 2008-01-16 | Vernacare Ltd | Mouldable paper pulp composition |
EP2047032A2 (en) | 2006-07-31 | 2009-04-15 | Vernacare Limited | Paper pulp composition and article formed therefrom |
US20090260152A1 (en) * | 2006-07-31 | 2009-10-22 | Vernacare Limited | Paper pulp composition and article formed therefrom |
GB2439947B (en) * | 2006-07-31 | 2011-05-18 | Vernacare Ltd | Washbowl formed from paper pulp composition |
AU2007279051B2 (en) * | 2006-07-31 | 2011-11-17 | Vernacare Limited | Paper pulp composition and article formed therefrom |
US20100120970A1 (en) * | 2006-12-12 | 2010-05-13 | University Of Leeds | Reversible micelles and applications for their use |
KR101431298B1 (en) | 2007-05-30 | 2014-08-20 | 아사히 가라스 가부시키가이샤 | Stain-proofing agent composition, method for producing the same and article processed with the same |
US20120325419A1 (en) * | 2010-02-15 | 2012-12-27 | Daikin Industries, Ltd. | Water and oil resistant agent for paper and paper treatment process |
US8992733B2 (en) * | 2010-02-15 | 2015-03-31 | Daikin Industries, Ltd. | Water and oil resistant agent for paper and paper treatment process |
WO2013004704A1 (en) | 2011-07-04 | 2013-01-10 | Syngenta Limited | Formulation |
WO2014097309A1 (en) | 2012-12-17 | 2014-06-26 | Asian Paints Ltd. | Stimuli responsive self cleaning coating |
GB2519059A (en) * | 2013-08-07 | 2015-04-15 | Hpc Healthline Uk Ltd | A method of manufacturing a moulded pulp object |
GB2519059B (en) * | 2013-08-07 | 2017-07-05 | Hpc Healthline Uk Ltd | A method of manufacturing a moulded pulp object |
US11453731B2 (en) | 2013-10-22 | 2022-09-27 | Honeywell International Inc. | Curable fluorocopolymer formed from tetrafluoropropene |
WO2016040525A1 (en) * | 2014-09-09 | 2016-03-17 | Honeywell International Inc. | Low voc and high solid fluoropolymer for coating applications |
US11111405B2 (en) | 2014-09-09 | 2021-09-07 | Honeywell International Inc. | Low VOC and high solid fluoropolymer for coating applications |
US11225585B2 (en) | 2015-11-20 | 2022-01-18 | Honeywell International Inc. | Gloss retentive fluorocopolymers for coating applications |
Also Published As
Publication number | Publication date |
---|---|
EP1311567A1 (en) | 2003-05-21 |
KR20030031966A (en) | 2003-04-23 |
FR2812643B1 (en) | 2002-09-13 |
FR2812643A1 (en) | 2002-02-08 |
CN1468266A (en) | 2004-01-14 |
WO2002012361A1 (en) | 2002-02-14 |
AU2001278570A1 (en) | 2002-02-18 |
JP2004506073A (en) | 2004-02-26 |
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