WO2012133622A1 - Composition contenant un copolymère fluoré - Google Patents

Composition contenant un copolymère fluoré Download PDF

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Publication number
WO2012133622A1
WO2012133622A1 PCT/JP2012/058319 JP2012058319W WO2012133622A1 WO 2012133622 A1 WO2012133622 A1 WO 2012133622A1 JP 2012058319 W JP2012058319 W JP 2012058319W WO 2012133622 A1 WO2012133622 A1 WO 2012133622A1
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group
fluorine
composition according
monomer
atom
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PCT/JP2012/058319
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English (en)
Japanese (ja)
Inventor
晋一 南
浩治 久保田
孝司 榎本
礼生 松田
光宏 薄ヶ谷
徹也 上原
育男 山本
佳代 楠見
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ダイキン工業株式会社
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395—Isocyanates
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    • 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
    • D06M15/295—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing fluorine
    • 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
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/01—Stain or soil resistance
    • 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

Definitions

  • the present invention relates to a composition
  • a composition comprising a fluorine-containing copolymer (in particular, an SR agent (antifouling agent or soil release agent)).
  • SR agent antifouling agent or soil release agent
  • the composition of the present invention has excellent water absorption and antifouling properties.
  • a (meth) acrylic acid ester having a fluoroalkyl group (hereinafter also referred to as a fluorine-containing compound) is used as an antifouling agent that imparts water and oil repellency to textile fabrics and makes it easy to remove dirt adhering to fibers by washing.
  • a hydrophilic group-containing compound are known (see JP-A-53-134786, JP-A-59-204980, JP-A-62-7782).
  • Rf groups perfluoroalkyl groups
  • the Rf group recedes and the hydrophilic group is oriented on the surface while exhibiting oiliness, and dirt is easily removed.
  • Flip-flop is a property in which the surface molecular structure changes depending on the environment in air and water, and is proposed by Sherman et al.
  • telomers for compounds containing an Rf group having 8 carbon atoms, which have recently been obtained by telomerization, Federal Register (FR Vol.68, No.73 / April 16,2003 [FRL-7303-8]) (http://www.epa.gov/opptintr/pfoa/pfoafr.pdf) EPA Environmental News FOR RELEASE: MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (Http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) or EPA OPPT FACT SHEET April 14, 2003 (http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf) allows telomers to produce perfluorooctanoic acid (hereinafter abbreviated as “PFOA”) by decomposition or metabolism It is announced that there is a
  • WO 2003/095083 describes a fluorine-containing graft polymer using an isocyanate group-containing vinyl monomer. Although it is described that this fluorine-containing graft polymer imparts antifouling properties, the resulting antifouling properties and / or water absorption are not sufficient.
  • JP-A-53-134786 JP 59-204980 A See JP-A-62-7782.
  • An object of the present invention is to provide a composition that imparts excellent water absorption, oil repellency, antifouling properties, and dirt release properties to textile fabrics and the like, and the Rf group has less than 8 carbon atoms.
  • An object of the present invention is to provide a composition having the same excellent properties even if it is shorter than conventional ones.
  • the simplest method for improving water absorption is to reduce the fluorine content in the soil release (SR) polymer and relatively increase the ratio of hydrophilic components. This certainly improves the water absorption to some extent, but conversely reduces the oil repellency and dirt release (SR property). It is important to improve water absorption without deteriorating oil repellency and SR property.
  • SR soil release
  • composition of the present invention (particularly, the soil release agent) is excellent in water absorption, and is excellent in antifouling properties and soil release properties.
  • the composition of the present invention comprises: (1) a fluorine-containing copolymer, (2) A blocked isocyanate compound and (3) a liquid medium.
  • the composition of the present invention is produced by adding a blocked isocyanate compound to a fluorinated copolymer liquid comprising a fluorinated copolymer and a liquid medium.
  • the fluorine-containing copolymer in the present invention generally does not have a repeating unit composed of a monomer having an amino group.
  • Amino groups generally have the formula: (R 11 ) (R 12 ) N- [Wherein, R 11 and R 12 are the same or different and each represents a monovalent group (for example, a hydrogen atom). ] It is group shown by these.
  • a monomer having an amino group generally has at least one carbon-carbon double bond in addition to the amino group.
  • a preferred example of X is a hydrogen atom.
  • the Rf group is generally a perfluoroalkyl group and / or a partially fluorinated fluoroalkyl group.
  • the Rf group is preferably a perfluoroalkyl group.
  • the Rf group has 1 to 6 carbon atoms. The carbon number of the Rf group may be 4, 5 or 6, in particular 6. Examples of Rf groups are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ).
  • n is 1 to 10, for example, 2 to 5.
  • n is 0 to 10, for example 1 to 6, in particular 2 to 5.
  • the fluorine-containing monomer (a) may be used alone or in combination of two or more.
  • fluorine-containing monomer (a) include, but are not limited to, for example, the following.
  • R is preferably ethylene or propylene, particularly ethylene.
  • R in the general formula (II) may be a combination of two or more types of alkylene. In that case, at least one of R is preferably ethylene. Examples of the combination of R include an ethylene group / propylene group combination and an ethylene group / butylene group combination.
  • the alkoxy group-containing monomer (b) may be a mixture of two or more types.
  • alkoxy group-containing monomer (b) include, for example, the following, but are not limited thereto.
  • the fluorine-containing copolymer may contain (c) a crosslinkable monomer.
  • the crosslinkable monomer (c) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine.
  • the crosslinkable monomer (c) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanates, carboxyl groups, and the like. In the present invention, a monomer having an amino group is not used.
  • the crosslinkable monomer (c) is preferably a non-fluorine crosslinkable monomer, and particularly preferably di (meth) acrylate.
  • R ′′ has 2 to 10, for example, 2 to 6, particularly 2 to 4.
  • R ′′ is preferably an ethylene group.
  • q is preferably 1 to 30, for example 2 to 10.
  • crosslinkable monomer (c) examples include diacetone (meth) acrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3- Examples include, but are not limited to, chloro-2-hydroxypropyl (meth) acrylate, butadiene, chloroprene, glycidyl (meth) acrylate, 1,6-hexanediol acrylate, neopentyl glycol diacrylate, and the like.
  • crosslinkable monomer (c) examples include isocyanate group-containing (meth) acrylates such as glycerol (meth) acrylate, acetoacetoxyethyl (meth) acrylate, 2-isocyanatoethyl methacrylate, methyl ethyl ketoxime, etc. Those (meth) acrylates whose isocyanate groups are blocked with the blocking agent are exemplified.
  • the crosslinkable monomer (c) may be a mixture of two or more.
  • the fluorine-containing copolymer may contain (d) a non-crosslinkable monomer.
  • the non-crosslinkable monomer (d) is a monomer other than the alkoxy group-containing monomer (b), generally a non-fluorine monomer.
  • the non-crosslinkable monomer (d) preferably contains no fluorine and has a carbon-carbon double bond.
  • the non-crosslinkable monomer (d) is preferably a vinyl monomer that does not contain fluorine.
  • the non-crosslinkable monomer is generally a compound having one carbon-carbon double bond.
  • Non-crosslinkable monomers (d) include butadiene, chloroprene, maleic acid derivatives, vinyl halides such as vinyl chloride, vinylidene halides such as ethylene and vinylidene chloride, vinyl alkyl ethers, styrene, alkyl (meth) Examples include, but are not limited to, acrylate and vinyl pyrrolidone.
  • the non-crosslinkable monomer (d) may be a (meth) acrylic acid ester containing an alkyl group.
  • the alkyl group may have 1 to 30 carbon atoms, for example 6 to 30, for example 10 to 30 carbon atoms.
  • the fluorine-containing copolymer contains 100 parts by weight of the fluorine-containing monomer (a).
  • the amount of the alkoxy group-containing monomer (b) is 10 to 400 parts by weight, for example 25 to 150 parts by weight, particularly 43 to 100 parts by weight
  • the amount of the crosslinkable monomer (c) is 30 parts by weight or less, for example, 0.1 to 20 parts by weight, particularly 0.5 to 10 parts by weight
  • the amount of the non-crosslinkable monomer (d) is preferably 20 parts by weight or less, for example, 0.1 to 15 parts by weight, particularly 0.5 to 10 parts by weight.
  • the weight average molecular weight of the fluorinated copolymer in the present invention may be 1,000 to 1,000,000, preferably 5,000 to 500,000.
  • the weight average molecular weight is a value obtained by gel permeation chromatography in terms of polystyrene.
  • the polymerization of the fluorine-containing copolymer is not particularly limited, and various polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can be selected.
  • solution polymerization using an organic solvent or emulsion polymerization using water or an organic solvent and water in combination is generally selected.
  • the solution is prepared by diluting with water or adding an emulsifier and emulsifying in water.
  • organic solvents examples include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl acetate, glycols such as propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and low molecular weight polyethylene glycol.
  • examples thereof include alcohols such as ethyl alcohol and isopropanol.
  • the emulsifier when emulsifying in water by adding an emulsifier after emulsion polymerization or polymerization, various general anionic, cationic and nonionic emulsifiers can be used.
  • the polymerization initiator for example, a peroxide, an azo compound or a persulfuric acid compound can be used.
  • the polymerization initiator is generally water-soluble and / or oil-soluble.
  • Specific examples of the oil-soluble polymerization initiator include 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl4-methoxyvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), dimethyl 2,2′-azobis (2 -Methylpropionate), 2,2'-azobis (2-isobutyronitrile), benzoyl peroxide, di-tertiary-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxy Pivalate, diisopropyl peroxydicarbon
  • water-soluble polymerization initiator examples include 2,2′-azobisisobutylamidine dihydrochloride, 2,2′-azobis (2-methylpropionamidine) hydrochloride, 2,2′-azobis [ 2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] sulfate hydrate, 2,2′-azobis [2- Preferred examples include (5-methyl-2-imidazolin-2-yl) propane] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, and the like.
  • the polymerization initiator is preferably an organic peroxide having a 10-hour half-life temperature of 40 ° C. or higher. It is particularly preferred that the polymerization initiator is t-butyl peroxypivalate.
  • the polymerization initiator is used in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the monomer.
  • a chain transfer agent such as a mercapto group-containing compound may be used, and specific examples thereof include 2-mercaptoethanol, thiopropionic acid, alkyl mercaptan and the like.
  • the mercapto group-containing compound is used in an amount of 10 parts by weight or less and 0.01 to 5 parts by weight based on 100 parts by weight of the monomer.
  • the fluorine-containing copolymer can be produced as follows.
  • solution polymerization a method is adopted in which a monomer is dissolved in an organic solvent, after substitution with nitrogen, a polymerization initiator is added, and the mixture is heated and stirred, for example, in the range of 40 to 120 ° C. for 1 to 10 hours.
  • the polymerization initiator may generally be an oil-soluble polymerization initiator.
  • organic solvent examples include those which are inert to the monomer and dissolve them, such as acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, Tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichloro And trifluoroethane.
  • the organic solvent is used in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total mono
  • emulsion polymerization a method is adopted in which a monomer is emulsified in water in the presence of an emulsifier and the like, after substitution with nitrogen, a polymerization initiator is added, and the mixture is stirred and polymerized in the range of 40 to 80 ° C. for 1 to 10 hours. Is done.
  • Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used.
  • the polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
  • the monomer is finely divided into water using an emulsifier that can give strong crushing energy such as a high-pressure homogenizer or ultrasonic homogenizer, and is oil-soluble. It is desirable to polymerize using a polymerization initiator.
  • an emulsifier various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers.
  • a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers.
  • water-soluble organic solvent examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water.
  • the low molecular weight monomer examples include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers.
  • it may be used in the range of 10 to 40 parts by weight.
  • a blocked isocyanate compound is an isocyanate that is blocked by at least one blocking agent.
  • the blocked isocyanate compound is a compound that has a blocked isocyanate group, does not have a polymerizable unsaturated group, and has an isocyanate residue of an isocyanate blocked by a blocking agent.
  • the blocked isocyanate compound may be modified with a compound having a hydrophilic group.
  • hydrophilic groups examples include nonionic hydrophilic groups (eg, hydroxyl groups, amino groups, and polyoxyalkylene groups (particularly polyoxyethylene groups)); and ionic (cationic or anionic) hydrophilic groups (eg, Carboxyl group, sulfate group, sulfone group, sulfonate group and sulfite group).
  • nonionic hydrophilic groups eg, hydroxyl groups, amino groups, and polyoxyalkylene groups (particularly polyoxyethylene groups)
  • ionic (cationic or anionic) hydrophilic groups eg, Carboxyl group, sulfate group, sulfone group, sulfonate group and sulfite group.
  • isocyanates examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), MDI oligomer, naphthalene-1,5-diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate (HDI), 4,4-dicyclohexylmethane diisocyanate, norbornane diisocyanate.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • 4,4-dicyclohexylmethane diisocyanate norbornane diisocyanate.
  • Isophorone diisocyanate IPDI
  • adducts eg TDI or HDI TMP (trimethylolpropane) adduct
  • allophanate modified products biuret modified products (eg biuret made from HDI)
  • isocyanurate modified products Products (for example, isocyanurates produced from TDI, isocyanurates produced from HDI, isocyanurates produced from IPDI) DOO, and isocyanurates) prepared from TDI and HDI, or a carbodiimide-modified product or a urethane prepolymer, the foregoing compounds.
  • blocking agents include (i) oximes, (ii) phenols, (iii) alcohols, (iv) mercaptans, (v) amides, (vi) imides, (vii) imidazoles, ( viii) ureas, (ix) amines, (x) imines, (xi) pyrazoles, and (xii) active methylene compounds.
  • Other examples of blocking agents include pyridinols, thiophenols, diketones and esters.
  • the blocked isocyanate compound may be modified with a compound having a hydrophilic group.
  • Oxime examples include formamide oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime and cyclohexanone oxime.
  • Phenols examples include phenols optionally having at least one (preferably one or two) C 1-10 alkyl group. Specific examples of phenols include: phenol; monoalkylphenol (eg, cresol, ethylphenol, propylphenol, butylphenol, hexylphenol, 2-ethylhexylphenol and octylphenol); and dialkylphenol (eg, diethylphenol, dipropylphenol, Dipropylcresol, dibutylphenol, di-2-ethylhexylphenol, dioctylphenol and dinonylphenol). Specific examples of phenols include styrenated phenols and hydroxybenzoate esters.
  • monoalkylphenol eg, cresol, ethylphenol, propylphenol, butylphenol, hexylphenol, 2-ethylhexylphenol and octylphenol
  • dialkylphenol eg, diethylphenol,
  • Alcohols examples include (preferably monovalent) alcohols (particularly alkanols) having a C 1 -C 30 alkyl group. Specific examples of alcohols include methanol, ethanol, propanol, 1-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxy-1-propanol, and 3- And methyl-2-penten-4-in-1-ol. (iv) Mercaptans Specific examples of mercaptans include butyl mercaptan and dodecyl mercaptan.
  • amides include acetanilide, acetic acid amide, ⁇ -propiolactam, ⁇ -butyrolactam, ⁇ -valerolactam, ⁇ -caprolactam, laurolactam, stearolactam, N-methyl- ⁇ -caprolactam and pyrrolidinone.
  • Imides Specific examples of imides include acid imides such as maleic imide and succinimide.
  • Imidazoles Specific examples of imidazoles include imidazole and 2-methylimidazole.
  • Ureas Specific examples of ureas include urea, thiourea and ethyleneurea.
  • Amines Specific examples of the amines include diphenylamine, aniline, carbazole, diethylamine, dipropylamine and propylethylamine.
  • Imines Specific examples of imines include ethyleneimine and polyethyleneimine.
  • (xi) Pyrazoles As specific examples of pyrazoles, 2-methyl-pyrazole, 3-methyl-pyrazole, 4-methyl-pyrazole, 2,4-dimethyl-pyrazole, 2,5-dimethyl-pyrazole, 3,4-dimethyl-pyrazole, 3,5-dimethyl-pyrazole, Examples include 4-nitro-3,5-dimethyl-pyrazole and 4-bromo-3,5-dimethyl-pyrazole.
  • Active methylene compounds examples include malonate esters (eg, C 1-30 -alkyl malonic acid esters), acetoacetate esters (eg, C 1-30 -alkyl acetoacetate esters) And acetylacetone.
  • the blocking agent for forming the blocked isocyanate compound is preferably a pyrazole compound or a malonate ester compound.
  • each R 11 is the same or different and is an alkyl group, an alkenyl group, an aralkyl group, an N-substituted carbamyl group, a phenyl group, NO 2 , a halogen atom, or a —C ( ⁇ O) OR 12 group (R 12 is an alkyl group having 1 to 4 carbon atoms.) n is 0, 1, 2 or 3. ] It may be shown by.
  • pyrazole compounds include 2-methyl-pyrazole, 3-methyl-pyrazole, 4-methyl-pyrazole, 2,4-dimethyl-pyrazole, 2,5-dimethyl-pyrazole, 3,4-dimethyl-pyrazole, 3,5-dimethyl-pyrazole, Examples include 4-nitro-3,5-dimethyl-pyrazole and 4-bromo-3,5-dimethyl-pyrazole.
  • the malonate ester compound is a reaction product (monoester or diester (preferably diester)) of malonic acid and alcohol (for example, monohydric alcohol).
  • the alcohol has a hydrocarbon group having 1 to 30 carbon atoms bonded to a hydroxyl group.
  • the hydrocarbon group is preferably an alkyl group, especially an alkyl group having 1 to 4 carbon atoms.
  • malonate ester examples include dimethyl malonate, diethyl malonate, dipropyl malonate, dibutyl malonate, methyl malonate, ethyl malonate, propyl malonate and butyl malonate. Diesters are preferred. Preferred specific examples of malonate esters include dimethyl malonate, diethyl malonate, dipropyl malonate and dibutyl malonate.
  • the blocked isocyanate compound may be modified with a compound having a hydrophilic group.
  • the compound having a hydrophilic group may be a compound having a nonionic hydrophilic group or a compound having an ionic hydrophilic group.
  • a compound having a hydrophilic group is a reaction between a compound having a nonionic hydrophilic group or a compound having an ionic hydrophilic group and an isocyanate, usually active hydrogen (eg, —OH or —NH 2 ) And an isocyanate group (—NCO).
  • Each of the compound having a nonionic hydrophilic group and the compound having an ionic hydrophilic group preferably has a number average molecular weight of 100 to 4000, particularly 200 to 2000.
  • a compound having a nonionic hydrophilic group is particularly preferred.
  • the compound having a nonionic hydrophilic group is preferably a compound having an active hydrogen and a polyethylene oxide chain at one end.
  • a compound having a nonionic hydrophilic group can be produced by addition reaction of an alkylene oxide, particularly ethylene oxide, with a monoalcohol such as methanol (for example, having 1 to 30 carbon atoms).
  • the ethylene oxide content is preferably at least 50% by weight based on the alkylene oxide (the upper limit of the ethylene oxide content is 100% by weight, for example 90% by weight, based on the alkylene oxide).
  • the compound having a nonionic hydrophilic group may contain propylene oxide units in an amount of 0 to 50% by weight, for example 0 to 20% by weight, in particular 1 to 10% by weight, based on the alkylene oxide.
  • the compound having an ionic hydrophilic group is preferably an anionic compound (for example, hydroxycarboxylic acid, amino acid, aminosulfonic acid and hydroxysulfonic acid).
  • a cationic compound such as a tertiary amino compound having a hydroxy group can be used as the compound having an ionic hydrophilic group.
  • a tertiary amino compound having a hydroxy group is reacted with an isocyanate and then neutralized with an acid or reacted with a quaternizing agent (eg, benzyl chloride) to give a quaternized salt.
  • a quaternizing agent eg, benzyl chloride
  • Examples of compounds having a hydrophilic group include monovalent to tetravalent alcohols having aliphatic groups (eg C 1 -C 30 ) and monovalents having at least one oxyalkylene group (eg C 3 -C 200 ).
  • Examples include alcohol. This can be prepared by adding (eg C 2 -C 5 ) alkylene oxide to (eg C 1 -C 30 ) monohydric alcohols.
  • R (O—CH 2 CH 2 ) n —OH
  • R is a C 1 -C 10 aliphatic (or alkyl) group (eg, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 ), and n is 2 to 50, preferably Is 5-25.
  • R is a C 1 -C 10 aliphatic (or alkyl) group (eg, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 ), and n is 2 to 50, preferably Is 5-25. ]
  • the compound shown by these is mentioned.
  • the blocked isocyanate compound is an isocyanate [isocyanate is A (NCO) m (where A and m are the same as described below (for example, A is a group remaining after the isocyanate-reactive group is removed, and m is It may be indicated by an integer from 2 to 8.]]
  • the blocking agent is indicated by RH (wherein R is a hydrocarbon group which may be substituted by a heteroatom such as a nitrogen atom and an oxygen atom, and H is a hydrogen atom). Good. ] Can be made to react.
  • the blocked isocyanate compound has the formula: AY m
  • A represents an m-valent aliphatic group, alicyclic group, heterocyclic group or aromatic group (where m is an integer of 2 to 8);
  • Y is the same or different, (However, each R 11 is the same or different and is an alkyl group, an alkenyl group, an aralkyl group, an N-substituted carbamyl group, a phenyl group, NO 2 , a halogen atom or a —C ( ⁇ O) OR 12 group (R 12 Is an alkyl group having 1 to 4 carbon atoms), n is 0, 1, 2 or 3.
  • R 21 is a hydrocarbon group having 1 to 30 carbon atoms or a monovalent group having a hydrophilic group.
  • R 31 is an alkylene group having 2 to 5 carbon atoms;
  • R 32 is an aliphatic group (or alkyl group) having 1 to 10 carbon atoms, such as CH 3 , C 2 H 5 , C 3 H 7 and C 4 H 9 , k is 2 to 50, preferably 5 to 25.
  • m is 1 to 10, in particular 2 to 5.
  • the amount of the blocked isocyanate compound may be 0.5 to 50 parts by weight, for example, 1 to 20 parts by weight with respect to 100 parts by weight of all the monomers or the fluorinated copolymer.
  • the liquid medium is a solvent composed of water and / or an organic solvent.
  • the liquid medium may be a mixture of water and an organic solvent.
  • the liquid medium is preferably a solvent used when a monomer is polymerized to produce a fluorinated copolymer.
  • a solvent may be added after producing the fluoropolymer.
  • the solvent added after the polymerization may be the same as or different from the solvent used during the polymerization.
  • the amount of the liquid medium may be such that the concentration of the fluorine-containing copolymer and the blocked isocyanate compound in the composition is 0.02 to 70% by weight, for example 1 to 50% by weight.
  • the composition of the present invention (that is, the treatment agent (particularly, the soil release agent)) is preferably in the form of a solution, an emulsion or an aerosol.
  • the treating agent comprises a fluorine-containing copolymer and a medium (for example, a liquid medium such as an organic solvent and water).
  • the concentration of the fluorinated copolymer may be, for example, 0.01 to 50% by weight, particularly 0.1 to 40% by weight.
  • the fluorine-containing polymer (fluorine-containing copolymer) in the present invention can be prepared by any method depending on the type of article to be treated and the preparation form (emulsion, organic solvent solution, aerosol, etc.). Can be applied to the article to be treated.
  • a method of adhering to a surface of an object to be processed and drying by a known method of coating processing such as dip coating or spray coating can be employed. At this time, if necessary, heat treatment such as curing may be performed. If necessary, other blenders can be used together.
  • water / oil repellent, wrinkle preventive, anti-shrink agent, flame retardant, crosslinking agent, antistatic agent, softener, water-soluble polymer such as polyethylene glycol and polyvinyl alcohol, wax emulsion, antibacterial agent, pigment, paint, etc. is there.
  • These blenders may be used by being added to the object to be treated and the treatment bath at the time of treatment, or in advance, if possible, mixed with the fluoropolymer in the present invention.
  • the article to be treated is not particularly limited, but besides textiles, stones, filters (for example, electrostatic filters), dust masks, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, Mention may be made of ceramic products, plastics, painted surfaces and plasters. It is particularly useful for textile products.
  • textile products Various examples can be given as textile products.
  • animal and vegetable natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.
  • the fiber product may be in the form of fiber, yarn, cloth or the like.
  • the article to be treated is treated with a treatment agent (particularly, a soil release agent).
  • a treatment agent particularly, a soil release agent.
  • Treatment means that a treatment agent is applied to an object to be treated by dipping, spraying, coating, or the like.
  • the fluoropolymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.
  • ⁇ Water absorption test droplet method> Using a micropipette, gently place 10 ⁇ L of drinking water (20 ⁇ 2 ° C.) on the test cloth. Measure the time (unit: seconds) from when a water drop is placed on the test cloth until the water drop soaks into the test cloth and disappears.
  • the disappearance of water droplets means a state where the specular reflection of water disappears and only moisture remains. Five locations are measured and the average water absorption time is taken as the measured value.
  • the test cloth is cut into strips having a length of 16 cm and a width of 2.5 cm. This is set in a 200 ml beaker containing 200 g of pure water so that the tip of the test cloth is immersed in water by 5 to 10 mm. After 30 minutes, the height from the surface of the water rising from the cloth by capillary action is read.
  • Oil repellency test (OR test)> The oil repellency test was conducted according to AATCC-TM118-2000 using a textile product. That is, the test cloth is spread horizontally, a few drops of the test solution shown in Table 3 is dropped, and the infiltration state after 30 seconds is determined. When the oil repellency is low, oil stains enter the article to be treated in the air, making it difficult to remove them. This is an important evaluation index along with the soil detachability (SR property) test.
  • SR property soil detachability
  • SR test Soil detachment test
  • Corn oil corn oil
  • mineral oil mineral oil
  • chili oil was used as the soil for the test.
  • the ballast cloth is added to the test cloth to make 1.8 kg, and 100 g of detergent (AATCC standard WOB detergent) is used, and the bath volume is 64 liters in the AATCC standard washing machine (manufactured by Kenmore, USA). After washing and rinsing at 38 ° C. for 12 minutes, the test cloth is dried with an AATCC standard tumbler dryer (manufactured by Kenmore, USA). The state of residual stain on the dried test cloth is compared with a standard photographic plate for judgment, and the dirt removal performance is expressed by the corresponding judgment grade (see Table 4).
  • the standard photographic plate for judgment was AATCC-TM130-2000 (American Association of Textile Chemists and Colorists-Test Method 130-2000).
  • Washing by AATCC-135 method is repeated 10 or 20 times, and the subsequent water absorption, oil repellency (OR property) and SR property are evaluated (HL-10, HL-20).
  • PV perbutyl PV
  • PV perbutyl PV
  • MEK was distilled off from the resulting solution at about 70 ° C. under reduced pressure to obtain a pale yellow polymer residue.
  • 121.2 g of water and 0.6 g of acetic acid were added, and the internal temperature was about 80 ° C. After maintaining for 1 hour or more, the mixture was cooled to prepare an aqueous dispersion having a solid concentration of about 20% by weight.
  • Example 1 20 parts aqueous dispersion of fluorine-containing copolymer obtained in Synthesis Example 1 3.0 parts aqueous dispersion of blocked isocyanate obtained in Synthesis Example 2 0.25 parts Tap water 96.75 parts Synthesis at the above ratio
  • the fluorine-containing copolymer dispersion obtained in Example 1 and the blocked isocyanate aqueous dispersion obtained in Synthesis Example 2 were diluted with water to prepare a processing solution. 100% cotton cloth and 100% PET cloth were immersed in the treatment solution thus obtained and squeezed with a roll so that the wet pickup (WPU) was 60 mass%.
  • WPU wet pickup
  • the soil release agent treatment was completed by drying and heat-treating the fabric at 160 ° C. for 3 minutes. These fabrics were measured for water absorption (water droplet method, wicking method), soil release (SR) and oil repellency (OR). The results are shown in Table 3.
  • Example 2 Except for changing the amount of the 20% aqueous dispersion of the fluorine-containing copolymer obtained in Synthesis Example 1 to 6.0 parts, a treatment solution was prepared and cloth-treated in the same manner as in Example 1 to remove soil. And oil repellency were measured. The results are shown in Table 3.
  • Example 3 20 parts aqueous dispersion of fluorine-containing copolymer obtained in Synthesis Example 1 3.0 parts aqueous dispersion obtained in Synthesis Example 3 1.0 part tap water 96.75 parts The obtained fluorine-containing copolymer dispersion and the blocked isocyanate aqueous dispersion obtained in Synthesis Example 3 were diluted with water to prepare a processing solution. 100% cotton cloth and 100% PET cloth were immersed in the treatment solution thus obtained and squeezed with a roll so that the wet pickup (WPU) was 60 mass%. Next, the soil release agent treatment was completed by drying and heat-treating the fabric at 160 ° C. for 3 minutes. These fabrics were measured for water absorption (water droplet method, wicking method), soil detachment property and oil repellency. The results are shown in Table 3.
  • Example 4 Except for changing the amount of the 20% aqueous dispersion of the fluorinated copolymer obtained in Synthesis Example 1 to 6.0 parts, a treatment solution was prepared and cloth-treated in the same manner as in Example 3 to remove dirt. And oil repellency were measured. The results are shown in Table 3.
  • Example 5 20% aqueous dispersion of fluorine-containing copolymer obtained in Synthesis Example 1 3.0 parts aqueous dispersion of blocked isocyanate obtained in Synthesis Example 2 0.25 parts Becamine NS-19 (Glyoxal Resin, Dainippon Ink Chemistry) 8.0 parts Becamine X-80 (Glyoxal Resin Catalyst, Dainippon Ink & Chemicals) 2.4 parts tap water 78.35 parts Fluorine-containing copolymer dispersion obtained in Synthesis Example 1 in the above proportion The blocked isocyanate aqueous dispersion obtained in Synthesis Example 2 was diluted with water to prepare a processing solution.
  • Example 6 Except for changing the amount of the 20% aqueous dispersion of the fluorinated copolymer obtained in Synthesis Example 1 to 6.0 parts, a treatment solution was prepared and cloth-treated in the same manner as in Example 3 to remove dirt. And oil repellency were measured. The results are shown in Table 4.
  • Example 2 A treatment liquid was prepared in the same procedure as in Example 1, except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 1. After treatment, the soil release and oil repellency were measured. The results are shown in Table 5.
  • Example 3 A treatment liquid was prepared in the same procedure as in Example 2, except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 1. After treatment, the soil release and oil repellency were measured. The results are shown in Table 5.
  • Example 4 A treatment liquid was prepared in the same procedure as in Example 5 except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 1. After treatment, the soil release and oil repellency were measured. The results are shown in Table 6.
  • Example 5 A treatment liquid was prepared in the same procedure as in Example 6 except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 1. After treatment, the soil release and oil repellency were measured. The results are shown in Table 6.
  • Example 6 A treatment liquid was prepared in the same procedure as in Example 1, except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 2. After treatment, the soil release and oil repellency were measured. The results are shown in Table 5.
  • Example 7 A treatment liquid was prepared in the same procedure as in Example 2, except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 2. After treatment, the soil release and oil repellency were measured. The results are shown in Table 5.
  • Example 8 A treatment liquid was prepared in the same procedure as in Example 5, except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 2. After treatment, the soil release and oil repellency were measured. The results are shown in Table 6.
  • Example 9 A treatment liquid was prepared in the same procedure as in Example 6, except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 2. After treatment, the soil release and oil repellency were measured. The results are shown in Table 6.
  • composition of the present invention can be used as a soil release agent having excellent water absorption, antifouling properties and soil release properties.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

La présente invention concerne une composition qui peut conférer d'excellentes propriétés d'absorption de l'eau et de répulsion de l'huile, et d'excellentes propriétés anti-tâches et de facilité de détachage à des textiles en fibres tissées et équivalents, et qui présente d'excellentes propriétés similaires à celles des compositions conventionnelles, malgré un nombre d'atomes de carbone par groupe Rf inférieur à 8, ce qui est plus faible que dans les compositions conventionnelles. La composition comprend : (1) un copolymère fluoré qui comprend, comme composants essentiels, (a) un monomère fluoré représenté par la formule générale CH2=C(-X)-C(=O)-Y-[-(CH2)m-Z-]p-(CH2)n-Rf (I) [dans laquelle X représente un atome d'hydrogène, un groupe méthyle, un atome de fluor, un atome de chlore, un atome de brome, un atome d'iode ou équivalent ; Z représente une liaison simple, -S- ou -SO2- ; Rf représente un groupe fluoroalkyle ayant de 1 à 6 atomes de carbone ; m vaut 1 à 10 ; n vaut 0 à 10 ; et p vaut 0 ou 1] et(b) un monomère contenant un groupe alcoxy représenté par la formule générale CH2=C(X')-C(=O)-O-(RO)q-H (II) [dans laquelle X' représente un atome d'hydrogène ou un groupe méthyle ; R représente un groupe alkylène ayant de 2 à 4 atomes de carbone dans lequel tout ou partie des atomes d'hydrogène peuvent être remplacés par un groupe hydroxy ; et q représente un entier allant de 1 à 50], et qui ne contient aucun monomère contenant un groupe amino ; (2) un composé isocyanate protégé ; et (3) un milieu liquide.
PCT/JP2012/058319 2011-03-31 2012-03-29 Composition contenant un copolymère fluoré WO2012133622A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013077451A1 (fr) * 2011-11-25 2013-05-30 日産化学工業株式会社 Polymère hyper-ramifié fluoré réactif et composition durcissable le contenant
CN104120198A (zh) * 2014-07-17 2014-10-29 张红 一种苯酚鞣剂的制作方法
US9695263B2 (en) 2013-03-06 2017-07-04 Unimatec Co., Ltd. Fluorine-containing oligomer, nano-silica composite particles using the same, and methods for producing both
WO2020075652A1 (fr) * 2018-10-09 2020-04-16 Ａｇｃ株式会社 Composition d'agent antisalissure, et article et produit fibreux traités au moyen de cette composition

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2617214T3 (es) 2011-04-25 2017-06-15 Teijin Frontier Co., Ltd. Tejidos y producto textil
CN104039861B (zh) 2012-01-17 2016-08-17 Dic株式会社 活性能量射线固化型水性树脂组合物、活性能量射线固化型水性涂料、以及用该涂料涂装后的物品
KR20210127129A (ko) * 2018-11-06 2021-10-21 임박스 슈케어 에이/에스 의복 함침 방법 및 의복 함침 장치

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6119684A (ja) * 1984-07-06 1986-01-28 Meisei Kagaku Kogyo Kk 耐久性の改良された撥水撥油剤
WO2004035708A1 (fr) * 2002-10-15 2004-04-29 Asahi Glass Company, Limited Composition hydrophobe et oleophobe
WO2005097851A1 (fr) * 2004-04-05 2005-10-20 Daikin Industries, Ltd. Détachant contenant du fluoropolymère
WO2006001214A1 (fr) * 2004-06-25 2006-01-05 Daikin Industries, Ltd. Agent anti-salissures contenant un copolymere renfermant du fluor et son procede de production
JP2006508226A (ja) * 2002-12-02 2006-03-09 ランベルティ ソシエタ ペル アチオニ 非イオン性ブロックポリイソシアネートの安定な水溶性分散剤
JP2009102463A (ja) * 2007-10-22 2009-05-14 Yunimatekku Kk 撥水撥油剤

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4630955B2 (ja) * 2004-05-19 2011-02-09 大原パラヂウム化学株式会社 親水・撥油加工剤で処理する繊維布帛の加工方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6119684A (ja) * 1984-07-06 1986-01-28 Meisei Kagaku Kogyo Kk 耐久性の改良された撥水撥油剤
WO2004035708A1 (fr) * 2002-10-15 2004-04-29 Asahi Glass Company, Limited Composition hydrophobe et oleophobe
JP2006508226A (ja) * 2002-12-02 2006-03-09 ランベルティ ソシエタ ペル アチオニ 非イオン性ブロックポリイソシアネートの安定な水溶性分散剤
WO2005097851A1 (fr) * 2004-04-05 2005-10-20 Daikin Industries, Ltd. Détachant contenant du fluoropolymère
WO2006001214A1 (fr) * 2004-06-25 2006-01-05 Daikin Industries, Ltd. Agent anti-salissures contenant un copolymere renfermant du fluor et son procede de production
JP2009102463A (ja) * 2007-10-22 2009-05-14 Yunimatekku Kk 撥水撥油剤

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013077451A1 (fr) * 2011-11-25 2013-05-30 日産化学工業株式会社 Polymère hyper-ramifié fluoré réactif et composition durcissable le contenant
US9546298B2 (en) 2011-11-25 2017-01-17 Nissan Chemical Industries, Ltd. Reactive fluorine-containing highly branched polymer and curable composition containing the same
US9695263B2 (en) 2013-03-06 2017-07-04 Unimatec Co., Ltd. Fluorine-containing oligomer, nano-silica composite particles using the same, and methods for producing both
CN104120198A (zh) * 2014-07-17 2014-10-29 张红 一种苯酚鞣剂的制作方法
WO2020075652A1 (fr) * 2018-10-09 2020-04-16 Ａｇｃ株式会社 Composition d'agent antisalissure, et article et produit fibreux traités au moyen de cette composition

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