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  • 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
  • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
  • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
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  • C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
• • C—CHEMISTRY; METALLURGY
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  • C08F214/00—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 a halogen
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  • C08F2/00—Processes of polymerisation
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  • C08F214/00—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 a halogen
  • C08F214/18—Monomers containing fluorine
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  • C08F214/00—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 a halogen
  • C08F214/18—Monomers containing fluorine
  • C08F214/28—Hexyfluoropropene
  • C08F214/285—Hexyfluoropropene with non-fluorinated comonomers
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  • C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
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  • C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of 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 a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08L27/06—Homopolymers or copolymers of vinyl chloride
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of 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 a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08L27/08—Homopolymers or copolymers of vinylidene chloride
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of 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 a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08L31/00—Compositions of 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
  • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
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  • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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  • C09D131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
  • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
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  • 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
  • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
  • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
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  • 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
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  • 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
  • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
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  • 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
  • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
  • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
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  • 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
  • D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
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  • 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
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/53—Polyethers
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  • 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
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/55—Epoxy resins
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  • D06M2101/02—Natural fibres, other than mineral fibres
  • D06M2101/04—Vegetal fibres
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  • D06M2101/16—Synthetic fibres, other than mineral fibres
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  • D06M2200/12—Hydrophobic properties

Definitions

• the present invention relates to a water and oil repellent composition, a method for producing the same, and an article.
• an article As a method for imparting water and oil repellency to the surface of an article (textile product, etc.), an article is used using a water and oil repellent composition containing a fluorine-containing polymer having a unit based on a (meth) acrylate having a perfluoroalkyl group.
• a water and oil repellent composition containing a fluorine-containing polymer having a unit based on a (meth) acrylate having a perfluoroalkyl group.
• the ester bond in the unit based on (meth) acrylate is easily cleaved by hydrolysis with an alkali or the like. Therefore, the perfluoroalkyl group may be lost from the fluorine-containing polymer, and the water and oil repellency of the article may decrease.
• the water-repellent oil-repellent composition contains a fluorine-containing polymer having a perfluoroalkyl group and not having a unit based on (meth) acrylate.
• Oil composition is known.
• fluorine-containing polymer having a perfluoroalkyl group and not having a unit based on (meth) acrylate a fluorine-containing polymer having a unit based on (perfluoroalkyl) ethylene is known.
• Patent Document 1 describes a dispersion liquid having a polymer containing a unit based on (perfluoroalkyl) ethylene. Further, as a monomer that can polymerize with (perfluoroalkyl) ethylene, various monomers such as vinyl stearate, vinyl chloride, and 4-hydroxybutyl vinyl ether are disclosed. Example 10 shows a copolymer of (perfluorohexyl) ethylene (49.8 mol%) and vinyl stearate, and Example 29 shows a (perfluorohexyl) ethylene (40 mol%) and vinyl acetate. And vinyl chloride copolymers are disclosed.
• Patent Document 2 describes a surface treatment agent composition containing a fluorine-containing polymer having a unit based on a fluorine-containing olefin and a unit based on a hydrocarbon-based vinyl.
• Vinyl stearate is disclosed as a hydrocarbon-based vinyl.
• non-fluorine non-crosslinkable monomers such as vinyl halide and vinyl alkyl ether, and non-fluorine crosslinkable monomers are disclosed.
• Example 18 discloses a copolymer of (perfluorohexyl) ethylene (15 mol%) and vinyl stearate.
• the article treated with the water-repellent oil-repellent composition containing the fluorine-containing polymer described in the examples of Patent Documents 1 and 2 has insufficient water repellency and its durability.
• the present invention provides a water-repellent oil-repellent composition for obtaining an article having excellent water repellency and durability thereof, a method for producing the same, and an article having excellent water repellency and durability thereof.
• a unit based on a fluorine-containing olefin represented by the following formula (1), a unit based on vinyl carboxylate having an alkyl group having 12 or more carbon atoms, and a halogenated olefin or a derivative thereof other than the fluorine-containing olefin. Includes a fluorinated polymer with a unit based on The ratio of the unit based on the fluorine-containing olefin is 15 to 35 mol%, and the ratio of the unit based on the vinyl carboxylate is 30 to 60 mol% with respect to all the units constituting the fluorine-containing polymer.
• CH 2 CH-R f (1)
• R f is a perfluoroalkyl group having 1 to 8 carbon atoms.
• the fluorine-containing polymer further has a unit based on a crosslinkable monomer having a reactive group.
• the water repellency according to any one of [1] to [6] above, wherein the ratio of the units based on the crosslinkable monomer is 0.1 to 20 mol% with respect to all the units constituting the fluorine-containing polymer.
• Oil repellent composition [8] The water-repellent and oil-repellent composition of the above-mentioned [7], wherein the reactive group is a hydroxy group, an epoxy group or an amino group. [9] The water / oil repellent composition according to the above [7] or [8], wherein the crosslinkable monomer is a vinyl ether or an allyl ether.
• a method for producing a water-repellent oil-repellent composition containing a fluorine-containing polymer by polymerizing the monomer component in an emulsion containing an aqueous medium, a monomer component, a surfactant and a polymerization initiator.
• the monomer component contains a fluorine-containing olefin represented by the following formula (1), vinyl carboxylate having an alkyl group having 12 or more carbon atoms, and a halogenated olefin or a derivative thereof other than the fluorine-containing olefin.
• the ratio of the fluorine-containing olefin to the entire monomer component is 15 to 35 mol%, the ratio of the vinyl carboxylate is 30 to 60 mol%, and the ratio of the halogenated olefin or a derivative thereof is A method for producing a water-repellent oil-repellent composition, which is 5 to 55 mol%.
• CH 2 CH-R f (1)
• R f is a perfluoroalkyl group having 1 to 8 carbon atoms.
• an article having excellent water repellency and durability thereof can be obtained.
• a water-repellent oil-repellent composition capable of obtaining an article having excellent water repellency and durability thereof can be produced.
• the article of the present invention is excellent in water repellency and its durability.
• the meanings and definitions of the terms in the present invention are as follows.
• the "unit based on a monomer” is a general term for an atomic group directly formed by polymerizing one molecule of a monomer and an atomic group obtained by chemically converting a part of the atomic group.
• (Meta) acrylate” is a general term for acrylate and methacrylate.
• (meth) acryloyloxy group” is a general term for an acryloyloxy group and a metaacryloyloxy group.
• the number average molecular weight (hereinafter, also referred to as “Mn”) and the mass average molecular weight (hereinafter, also referred to as “Mw”) of the polymer are gel permeation using a calibration line prepared using a standard polymethylmethacrylate sample. It is a polymethylmethacrylate-equivalent molecular weight obtained by measuring by chromatography (hereinafter, also referred to as “GPC”).
• the solid content concentration is determined by (solid content mass / sample mass) ⁇ 100, where the mass of the sample before heating is the sample mass and the mass after drying the sample in a convection dryer at 120 ° C. for 4 hours is the solid content mass. It is calculated.
• the water- and oil-repellent agent composition of the present invention contains a specific fluorine-containing polymer (hereinafter, also referred to as “polymer (A)").
• the composition preferably contains an aqueous medium described below.
• the present composition is preferably a polymer dispersion containing the polymer (A), an aqueous medium, and a surfactant.
• the composition also includes the dispersion obtained by the method for producing the polymer (A) of the present invention, which will be described later, and the dispersion further diluted with an arbitrary aqueous medium for treating the article. ..
• the composition may contain other components, if necessary.
• the polymer (A) has a unit based on a fluorine-containing olefin represented by the following formula (1) (hereinafter, also referred to as “monomer a”) (hereinafter, also referred to as “unit a”) and a carbon number of carbon atoms.
• a unit based on a vinyl carboxylate having 12 or more alkyl groups hereinafter, also referred to as “monomer b”) (hereinafter, also referred to as “unit b”), a halogenated olefin other than the fluorine-containing olefin, or a halogenated olefin thereof.
• unit c based on a derivative (hereinafter, also referred to as “polymer c”).
• CH 2 CH-R f (1)
• R f is a perfluoroalkyl group having 1 to 8 carbon atoms.
• the polymer (A) has, if necessary, a unit based on a crosslinkable monomer having a reactive group (hereinafter, also referred to as “monomer d”) (hereinafter, also referred to as “unit d”). You may also have more.
• the polymer (A) is also referred to as a monomer other than the monomer a, the monomer b, the monomer c and the monomer d (hereinafter, also referred to as “monomer e”, if necessary. ) (Hereinafter, also referred to as “unit e”).
• the carbon number of R f is preferably 1 to 6 from the viewpoints that the conversion rate to the polymer (A) tends to be good, the availability of raw materials, and the ease of handling. ⁇ 6 is more preferable, and 6 is particularly preferable. R f is preferably linear.
• Two or more types of monomer a may be used in combination.
• the monomer b is preferably a monomer represented by the following formula (2).
• R 1 is an alkyl group having 12 or more carbon atoms.
• the carbon number of R 1 in the above formula (2) is 12 or more, preferably 16 or more, from the viewpoint of excellent water repellency and durability thereof.
• the carbon number of R 1 is preferably 30 or less, more preferably 20 or less, from the viewpoint of excellent availability and handleability.
• R 1 is preferably linear.
• Examples of the monomer b include vinyl myristate, vinyl palmitate, vinyl stearate, and vinyl oleate.
• vinyl myristate, vinyl palmitate, vinyl stearate is preferable, and vinyl stearate is more preferable.
• Two or more types of monomer b may be used in combination.
• examples of the halogenated olefin include vinyl halide, vinylidene halide, and fluoroethylene, and specific examples thereof include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and trifluoroethylene. Examples thereof include ethylene, chlorotrifluoroethylene and tetrafluoroethylene. Examples of the halogenated olefin derivative include perfluoro (alkyl vinyl ether).
• the monomer c vinyl halide or vinylidene halide is preferable, vinyl chloride or vinylidene chloride is more preferable, and vinyl chloride is further preferable. Two or more types of monomer c may be used in combination.
• the reactive group other functional groups (optionally, the functional group of the cross-linking agent contained in the present composition, the functional group existing on the surface of the article to be treated with the present composition, etc.) and the like.
• Any group may be used as long as it forms a crosslinked structure by the above reaction, and examples thereof include a hydroxy group, an epoxy group, an amino group, a monoalkylamino group, a dialkylamino group, a carboxy group, an isocyanate group, an oxazoline group, and a carbodiimide group.
• the number of carbon atoms of the alkyl group in the monoalkylamino group and the dialkylamino group is, for example, 1 to 4.
• a hydroxy group, an epoxy group or an amino group is preferable, and a hydroxy group is particularly preferable, from the viewpoint of excellent availability and handleability.
• the monomer d may be a monofunctional monomer having one polymerizable carbon-carbon double bond, or a polyfunctional monomer having two or more polymerizable carbon-carbon double bonds.
• a monofunctional monomer is preferable from the viewpoint of excellent polymerizable property.
• Examples of the monomer d include vinyl ether, allyl ether, (meth) acrylate, vinyl ester, and (meth) acrylamide compound.
• Examples of the vinyl ether include a compound represented by the following formula (3-1).
• Examples of the allyl ether include a compound represented by the following formula (3-2).
• Examples of the (meth) acrylate include compounds represented by the following formula (3-3).
• CH 2 CH-OZ (3-1)
• CH 2 CHCH 2 -O-Z (3-2)
• Z is an organic group having a reactive group.
• R is a hydrogen atom or a methyl group.
• Examples of Z include an aliphatic hydrocarbon group having a reactive group, an aryl group having a reactive group, and a cyclic group having a hetero atom substituted with a reactive group.
• Examples of the aliphatic hydrocarbon group include an alkyl group, a group having an oxygen atom between carbon atoms of the alkyl group, an alkenyl group, a group having an oxygen atom between carbon atoms of the alkenyl group, and a cycloalkyl group.
• the alkyl group and the alkenyl group have, for example, 1 to 6 carbon atoms.
• the number of carbon atoms forming the ring of the cycloalkyl group is, for example, 3 to 8.
• hetero atom examples include a nitrogen atom, an oxygen atom, and a sulfur atom.
• the cyclic group having a hetero atom is preferably saturated, preferably a 3- to 9-membered ring, and even more preferably a 3- to 6-membered ring.
• Z a hydroxyalkyl group is preferable.
• the hydroxyalkyl group preferably has 2 to 6 carbon atoms.
• vinyl ether or allyl ether is preferable, and allyl ether is more preferable, because it is excellent in copolymerizability with the monomers a to c and is not easily decomposed by alkali or the like.
• Examples of the monomer d include vinyl ethers having a hydroxy group (2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, cyclohexanedimethanol monovinyl ether, etc.), vinyl ethers such as glycidyl vinyl ether, etc.
• Allyl ethers having a hydroxy group (ethylene glycol monoallyl ether, diethylene glycol allyl ether, glycerin monoallyl ether, pentaerythritol triallyl ether, trimethylpropandiallyl ether, etc.), allyl ethers such as glycidyl allyl ether; hydroxyalkyl (meth) Acrylates (2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, etc.), glycidyl (meth) acrylate, 2-[(3, (Meta) acrylates such as 5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate; (meth) acrylamide compounds such as N-methylolacrylamide can be mentioned.
• vinyl ether having a hydroxy group and allyl ether having a hydroxy group are preferable, and 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, cyclohexanedimethanol monovinyl ether and ethylene glycol monoallyl ether are more preferable.
• Two or more types of monomer d may be used in combination.
• the monomer e may be any copolymerizable with the monomers a to c, and for example, vinyl esters other than the monomers a to c, allyl esters, vinyl ethers, allyl ethers, olefins, (meth). Examples thereof include acrylate, N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam and ethyl vinyl sulfide.
• Examples of the vinyl ester include vinyl carboxylate having an alkyl group having 11 or less carbon atoms, and specific examples thereof include vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, and vinyl laurate. Examples include vinyl benzoate, vinyl chloroacetate and divinyl adipate. As the vinyl ester, vinyl acetate or vinyl pivalate is particularly preferable from the viewpoint of obtaining an article having excellent oil repellency, alcohol repellency and water repellency. Examples of the allyl ester include allyl acetate and diallyl adipate.
• vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, stearyl vinyl ether, 1-chloromethyl vinyl ether, 2-chloroethyl vinyl ether, chloropropyl vinyl ether and cyclohexyl vinyl ether. Be done.
• allyl ether examples include allyl ethyl ether, diallyl ether, and 1,3-diallyloxy-2-propanol.
• olefin examples include ethylene and propylene.
• Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and behenyl.
• Alkyl (meth) acrylates such as (meth) acrylates; fluoroalkyl (meth) acrylates such as 2-perfluorohexylethyl (meth) acrylates may be mentioned.
• the polymer (A) preferably does not have a unit based on a (meth) acrylate having a perfluoroalkyl group, from the viewpoint that an article whose water and oil repellency is less likely to be lowered by alkali or the like can be obtained. Therefore, as the (meth) acrylate, a (meth) acrylate having no fluorine atom such as the above-mentioned alkyl (meth) acrylate is preferable.
• the ratio of the unit a in the polymer (A) is 15 to 35 mol%, preferably 18 to 32 mol%, and more preferably 20 to 30 mol% with respect to all the units constituting the polymer (A). ..
• the ratio of the unit a is equal to or higher than the lower limit value, the oil-repellent property of the article treated with the present composition is excellent.
• the ratio of the unit a is not more than the upper limit value, the water repellency of the article treated with the present composition is excellent.
• the ratio of the unit b in the polymer (A) is 30 to 60 mol%, preferably 32 to 58 mol%, and more preferably 34 to 56 mol% with respect to all the units constituting the polymer (A). ..
• the ratio of the unit b is not more than the lower limit value, the water repellency of the article treated with the present composition and its durability are excellent.
• the ratio of the unit b is not more than the upper limit value, the water repellency durability of the article treated with the present composition is excellent.
• the ratio of the unit c in the polymer (A) is 5 to 55 mol%, preferably 15 to 50 mol%, and more preferably 20 to 48 mol% with respect to all the units constituting the polymer (A). ..
• the ratio of the unit c is at least the above lower limit value, the oil-repellent property and the water-repellent durability of the article treated with the present composition are excellent.
• the ratio of the unit c is not more than the upper limit value, the water repellency of the article treated with the present composition is excellent.
• the ratio of the unit d in the polymer (A) is preferably 0.1 to 8 mol% with respect to all the units constituting the polymer (A), and 0. 5 to 6 mol% is more preferable, and 1 to 4 mol% is further preferable.
• the ratio of the unit d is not more than the lower limit value, the water repellency durability of the article treated with the present composition is further excellent.
• the ratio of the unit d is not more than the upper limit value, the water repellency of the article treated with the present composition and its durability are further excellent.
• the ratio of the unit e in the polymer (A) is preferably 10 mol% or less, more preferably 5 mol% or less, and may be 0 mol% with respect to all the units constituting the polymer (A). All the units constituting the polymer (A) are the sum of the unit a, the unit b, the unit c, the unit d and the unit e.
• the ratio of each unit can be calculated by 1 H-NMR and the reaction rate of each monomer component by gas chromatography.
• the ratio of each unit is based on the amount of the monomer component charged. May be calculated. The conversion rate is determined by the method described in Examples described later.
• the Mn of the polymer (A) is preferably 10,000 or more, more preferably 11,000 or more, and even more preferably 12,000 or more.
• the Mn of the polymer (A) is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less.
• the Mn of the polymer (A) is at least the above lower limit value, the water and oil repellency of the article treated with the present composition is further excellent.
• the Mn of the polymer (A) is not more than the above upper limit value, the water dispersibility of the polymer (A) is further excellent.
• the Mw of the polymer (A) is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more.
• the Mw of the polymer (A) is preferably 150,000 or less, more preferably 120,000 or less, and even more preferably 100,000 or less.
• the Mw of the polymer (A) is at least the above lower limit value, the water and oil repellency of the article treated with the present composition is further excellent.
• the Mw of the polymer (A) is not more than the above upper limit value, the water dispersibility of the polymer (A) is further excellent.
• aqueous medium examples include water and water containing a water-soluble organic solvent.
• the water-soluble organic solvent is an organic solvent that can be mixed with water in an arbitrary ratio.
• the water-soluble organic solvent at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols and aprotic polar solvents is preferable.
• the alcohol include t-butanol and propylene glycol.
• the ether alcohol include 3-methoxymethylbutanol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol.
• aprotic polar solvent examples include N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran (hereinafter, also referred to as “THF”), acetonitrile, acetone, 3-methoxy-N, N-dimethylpropanamide, 3-.
• THF tetrahydrofuran
• examples thereof include butoxy-N, N-dimethylpropanamide, 3-methoxy-3-methyl-1-butanol, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
• ether alcohol is preferable as the water-soluble organic solvent because the compatibility between the polymer (A) and the aqueous medium is improved and a uniform film can be easily formed on the article.
• Propylene glycol, tripropylene glycol and dipropylene glycol monomethyl ether are more preferred.
• the content of the water-soluble organic solvent is preferably 1 to 80 parts by mass, more preferably 5 to 60 parts by mass with respect to 100 parts by mass of water.
• surfactant As the surfactant, a surfactant having no fluorine atom is preferable.
• the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
• the surfactant since the dispersion stability of the aqueous dispersion containing the polymer (A) is excellent, the nonionic surfactant is used alone, the nonionic surfactant and the cationic surfactant or the amphoteric surfactant are used. It is preferable to use in combination with or an anionic surfactant alone, and it is more preferable to use a nonionic surfactant and a cationic surfactant in combination.
• the ratio of the nonionic surfactant to the cationic surfactant is preferably 100/0 to 40/60 (mass ratio), and is 97/3 to 40/60. (Mass ratio) is more preferable.
• mass ratio is more preferable.
• the total amount of the surfactant with respect to 100 parts by mass of the polymer (A) can be 5 parts by mass or less, which is caused by the surfactant. It is possible to reduce the adverse effect on the water and oil repellency of the article treated with the present composition.
• nonionic surfactant examples include the surfactants s1 to s6 described in paragraphs [0067] to [0995] of JP-A-2009-215370.
• the surfactant s1 polyoxyethylene alkyl ether is preferable.
• the surfactant s2 an acetylene glycol ethylene oxide adduct is preferable.
• the surfactant s3 an ethylene oxide propylene oxide polymer is preferable. Two or more kinds of nonionic surfactants may be used in combination.
• Examples of the cationic surfactant include the surfactant s7 described in paragraphs [0996] to [0100] of JP-A-2009-215370.
• As the surfactant s7 an ammonium salt in which one or more hydrogen atoms bonded to a nitrogen atom are substituted with an alkyl group, an alkenyl group or a polyoxyalkylene chain having a hydroxyl group at the terminal is preferable, and the following formula (s71) is used.
• the represented compound s71 is more preferable.
• R 21 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a polyoxyalkylene chain having a hydroxyl group at the end. ..
• the four R 21s may be the same or different, but the four R 21s are not hydrogen atoms at the same time.
• X - is a counterion. As X ⁇ , chlorine ion, ethyl sulfate ion, or acetate ion is preferable.
• Examples of the compound s71 include monostearyltrimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono (stearyl) monomethyldi (polyethylene glycol) ammonium chloride, monofluorohexyltrimethylammonium chloride, and di (beef fat alkyl) dimethylammonium chloride. , Dimethylmonococonutamine acetate. Two or more kinds of cationic surfactants may be used in combination.
• amphoteric surfactants include the surfactants s8 described in paragraphs [0101] to [0102] of JP-A-2009-215370. One of these may be used, or two or more thereof may be used in combination.
• a surfactant As a combination of surfactants, a surfactant is used because it has little adverse effect on the water and oil repellency of the article treated with this composition and is excellent in the dispersion stability of the dispersion containing the polymer (A).
• the combination with the surfactant s7 is preferable, and the above-mentioned combination in which the surfactant s7 is the compound s71 is more preferable.
• Examples of other components include a fluorine-containing polymer other than the polymer (A), a non-fluorine polymer, a non-fluorine water- and oil-repellent agent, and a water-soluble polymer resin (for example, hydrophilic polyester and its derivatives, hydrophilicity).
• a fluorine-containing polymer other than the polymer (A) a non-fluorine polymer, a non-fluorine water- and oil-repellent agent, and a water-soluble polymer resin (for example, hydrophilic polyester and its derivatives, hydrophilicity).
• Polyethylene glycol and its derivatives, hydrophilic polymer and its derivatives), cross-linking agents, penetrants for example, nonionic surfactants having an acetylene group in the center and a symmetrical structure, Dispanol manufactured by Nichiyu Co., Ltd.
• colloidal silica for example, Snowtex (registered trademark) series manufactured by Nissan Chemical Co., Ltd., Aderite series manufactured by ADEKA
• antifoaming agent for example, Orfin (registered trademark) manufactured by Nissin Chemical Co., Ltd.) Series, FS antifoam series manufactured by Toray Dow Corning
• film-forming aids for example, insect repellents, antifungal agents, preservatives, flame retardants, antistatic agents (for example, Directorol series manufactured by Meisei Chemical Co., Ltd.), wrinkle prevention Agents, softeners (eg, silicone emulsions, polyethylene wax emulsions, polyamide wax emulsions), pH adjusters (eg, diethanolamine, triethanolamine, acetic acid, citric acid).
• softeners eg, silicone emulsions, polyethylene wax emulsions, polyamide wax emulsions
• pH adjusters eg, diethanolamine, triethanolamine, acetic acid,
• the adhesiveness to the article is likely to be improved.
• a cross-linking agent an isocyanate-based cross-linking agent, a methylol-based cross-linking agent, a carbodiimide-based cross-linking agent, and an oxazoline-based cross-linking agent are preferable.
• the isocyanate-based cross-linking agent examples include an aromatic block-type isocyanate-based cross-linking agent, an aliphatic block-type isocyanate-based cross-linking agent, an aromatic non-blocking type isocyanate-based cross-linking agent, and an aliphatic non-blocking type isocyanate-based cross-linking agent.
• the isocyanate-based cross-linking agent is preferably an aqueous dispersion type emulsified with a surfactant or a self-aqueous dispersion type having a hydrophilic group.
• methylol-based cross-linking agent examples include a condensate or precondensate of urea or melamine and formaldehyde, methylol-dihydroxyethylene-urea and its derivatives, methylol-ethylene-urea, methylol-propylene-urea, methylol-triazone, and dicyandiamide.
• -Formaldehyde condensates, methylol-carbamate, methylol- (meth) acrylamide, and polymers thereof.
• the carbodiimide-based cross-linking agent is a polymer having a carbodiimide group in the molecule, and is a cross-linking agent that exhibits excellent reactivity with a carboxy group, an amino group, and an active hydrogen group of an article or the like.
• the oxazoline-based cross-linking agent is a polymer having an oxazoline group in the molecule, and is a cross-linking agent that exhibits excellent reactivity with a carboxy group of an article or the like.
• cross-linking agents include, for example, divinyl sulfone, polyamide and its cationic derivative, polyamine and its cationic derivative, epoxy derivative such as diglycidylglycerol, (epoxy-2,3-propyl) trimethylammonium chloride, N-methyl-N. -Halide derivatives such as (epoxy-2,3-propyl) morpholinium chloride, pyridinium salts of chloromethyl ether of ethylene glycol, polyamine-polyamine-epicrohydrin resin, polyvinyl alcohol or its derivatives, polyacrylamide or its derivatives, glyoxal resin Examples include anti-wrinkle agents.
• catalysts include, for example, inorganic amine salts and organic amine salts.
• examples of the inorganic amine salt include ammonium chloride.
• examples of the organic amine salt include aminoalcohol hydrochloride and semicarbazide hydrochloride.
• Examples of aminoalcohol hydrochloride include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanol hydrochloride, and 2-amino-2-methylpropanol hydrochloride.
• the content of the aqueous medium can be appropriately selected according to the desired solid content concentration of the present composition.
• the solid content concentration of the present composition is preferably 25 to 70% by mass, more preferably 30 to 60% by mass.
• the solid content concentration of the present composition is preferably 0.1 to 7% by mass, more preferably 0.2 to 5% by mass when the present composition is used for processing an article.
• the content of the surfactant in the present composition is preferably 1 to 6 parts by mass with respect to 100 parts by mass of the polymer (A) immediately after the production of the present composition.
• the content of the cross-linking agent in the composition is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polymer (A) when the composition is used for processing an article.
• the present composition is, for example, a water-repellent oil-repellent composition containing a fluorine-containing polymer by polymerizing the monomer component in an emulsion containing an aqueous medium, a monomer component, a surfactant and a polymerization initiator.
• a water-repellent oil-repellent composition containing a fluorine-containing polymer by polymerizing the monomer component in an emulsion containing an aqueous medium, a monomer component, a surfactant and a polymerization initiator.
• the monomer component includes a monomer a, a monomer b, and a monomer c.
• the monomer component may further contain the monomer d and the monomer e, if necessary.
• the ratio of the monomer a is 15 to 35 mol%, preferably 18 to 32 mol%, and more preferably 20 to 30 mol% with respect to the entire monomer component.
• the ratio of the monomer a is equal to or higher than the lower limit, the oil-repellent property of the article treated with the present composition is excellent.
• the proportion of the monomer a is not more than the upper limit, the water repellency of the article treated with the present composition is excellent.
• the ratio of the monomer b is 30 to 60 mol%, preferably 32 to 58 mol%, and more preferably 34 to 56 mol% with respect to the entire monomer component.
• the proportion of the monomer b is not less than the lower limit, the water repellency of the article treated with the present composition and its durability are excellent.
• the proportion of the monomer b is not more than the above upper limit value, the water repellency durability of the article treated with the present composition is excellent.
• the ratio of the monomer c is 5 to 55 mol%, preferably 15 to 50 mol%, and more preferably 20 to 48 mol% with respect to the entire monomer component.
• the proportion of the monomer c is at least the above lower limit value, the oil-repellent property and the water-repellent durability of the article treated with the present composition are excellent.
• the proportion of the monomer c is not more than the above upper limit value, the water repellency of the article treated with the present composition is excellent.
• the ratio of the monomer d is preferably 0.1 to 8 mol%, more preferably 0.5 to 6 mol% with respect to the entire monomer component. More preferably, 1 to 4 mol%.
• the proportion of the monomer d is not less than the lower limit, the water repellency durability of the article treated with the present composition is further excellent.
• the ratio of the monomer d is not more than the upper limit value, the water repellency of the article treated with the present composition and its durability are further excellent.
• the ratio of the monomer e is preferably 10 mol% or less, more preferably 5 mol% or less, and may be 0 mol% with respect to the entire monomer component.
• the entire monomer component is the total of the monomer a, the monomer b, the monomer c, the monomer d, and the monomer e.
• the polymerization initiator examples include a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, and an ionic polymerization initiator, and a radical polymerization initiator is preferable.
• a radical polymerization initiator for example, an azo-based polymerization initiator, a peroxide-based polymerization initiator, and a redox-based polymerization initiator are used depending on the polymerization temperature.
• an azo compound is preferable, and a salt of the azo compound is more preferable.
• the polymerization temperature is preferably 20 to 150 ° C.
• the amount of the polymerization initiator added is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the monomer component.
• a molecular weight modifier When polymerizing the monomer component, a molecular weight modifier may be used.
• the molecular weight adjusting agent for example, an aromatic compound, a mercapto alcohol, a mercaptocarboxylic acid, and an alkyl mercaptan are preferable, and a mercaptocarboxylic acid or an alkyl mercaptan is more preferable.
• the amount of the molecular weight adjusting agent added is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and may be 0 parts by mass with respect to 100 parts by mass of the monomer component.
• the emulsion can be prepared by mixing an aqueous medium, a monomer component, and a surfactant, dispersing them with a homogenizer, a high-pressure emulsifier, or the like, and then adding a polymerization initiator.
• the concentration of the monomer component in the emulsion is preferably 20 to 60% by mass, more preferably 30 to 50% by mass.
• concentration of the monomer component in the emulsion is within the above range, the conversion rate of the monomer component to the polymer (A) can be improved at the time of polymerization of the monomer component, and the polymer ( The molecular weight of A) can be sufficiently increased.
• the total amount of the surfactant in the emulsion is preferably 1 to 6 parts by mass with respect to 100 parts by mass of the monomer component.
• the total amount of the surfactant is not more than the lower limit of the above range, the dispersion stability of the emulsion is excellent.
• the total amount of the surfactant is not more than the upper limit of the above range, the adverse effect on the water and oil repellency of the article treated with the present composition is small.
• the dispersion of the polymer (A) obtained by polymerizing the monomer components in the emulsion may be used as it is as the present composition, or diluted with an aqueous medium to adjust the solid content concentration, and then the present composition. It may be a thing. Other components may be added to the composition.
• the conversion rate of the monomer component to the polymer (A) at the end of the polymerization is preferably 80% or more, more preferably 90% or more.
• the conversion rate By increasing the conversion rate, the molecular weight of the polymer (A) is also increased, and the water and oil repellency is also improved. Further, by setting the conversion rate to high, the performance deterioration due to the residual monomer is suppressed, and the amount of fluorine atoms contained in the polymer (A) is increased, so that the water and oil repellency is improved.
• the present composition capable of producing an article whose water and oil repellency is not easily lowered by alkali or the like can be produced. Can be manufactured. Further, in the method for producing the present composition, since the monomer component is polymerized in the emulsion, the molecular weight of the polymer (A) can be increased. Therefore, the present composition capable of producing an article having excellent water and oil repellency can be produced. In the method for producing the present composition, since the proportions of the monomer a, the monomer b and the monomer c contained in the monomer component are within a specific range, the water repellency and its durability thereof. The present composition capable of producing an article having excellent properties can be produced.
• the article of the present invention is an article processed using the present composition.
• Articles treated with this composition include, for example, fibers, textile fabrics (fiber woven fabrics, textile knitted fabrics, non-woven fabrics, brushed fabrics, etc.), and textile products including textile fabrics (keywear, rainwear, coats, bruzon, windbreakers, etc.).
• the porous resin is used, for example, as a filter.
• Examples of the material of the porous resin include polypropylene, polyethylene terephthalate, and polytetrafluoroethylene.
• Examples of the material of the porous fiber include glass fiber, cellulose nanofiber, carbon fiber, and cellulose acetate.
• a fiber, a woven fabric, and a textile product including the woven fabric are preferable.
• the type of fiber is not particularly limited, but includes natural fibers such as cotton, wool, silk or cellulose, synthetic fibers such as polyester, polyamide, acrylic or aramid, chemical fibers such as rayon, biscous rayon or lyocell, and natural fibers. Examples thereof include blended fibers with synthetic fibers and blended fibers with natural fibers and chemical fibers.
• the fiber when the fiber base material is a non-woven fabric include polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass and rayon.
• the thickness of the fiber cloth is not particularly limited, but is usually 0.01 to 5 mm.
• the method for treating the article may be any method as long as the water-repellent and oil-repellent composition can be attached to the article to be treated.
• the composition contains a liquid medium, coating, impregnation, dipping, spraying, brushing, etc.
• examples thereof include a method in which the dispersion liquid is treated on an article by a known coating method such as padding, a size press, and a roller, and then dried.
• the amount of solid content in the water-repellent and oil-repellent composition to be attached to the article to be treated is not particularly limited, but in the case of a fiber cloth, for example, it is 0.001 to 1.0 g / g with respect to the unit mass of the fiber cloth.
• Drying may be performed at room temperature or heated, and heating is preferable. When heating, the heating temperature is preferably 40 to 200 ° C.
• the water / oil repellent composition contains a cross-linking agent, it is preferable to heat the composition to a temperature higher than the cross-linking temperature of the cross-linking agent for curing, if necessary.
• Examples 1 to 13 are examples, and examples 14 to 21 are comparative examples.
• conversion rate From the theoretical value of the solid content concentration of the fluorine-containing polymer dispersion calculated from the amount of the raw material charged and the measured value of the solid content concentration of the fluorine-containing polymer dispersion, the monomer is calculated by the actual measurement value / theoretical value ⁇ 100.
• the conversion rate of the components to a fluorine-containing polymer was determined. A conversion rate of 90% or more was designated as "A” (good), 80% or more and less than 90% was designated as "B” (possible), and a conversion rate of less than 80% was designated as "C” (not possible).
• the test cloth evaluated for water repellency was washed 10 or 20 times according to the washing method of AATCC Monograph 6-2016. After washing, it was dried according to the tumble drying method of AATCC Monograph 6-2016, and then the water repellency was evaluated.
• Oil repellency The oil repellency was judged from the presence or absence of penetration by allowing the droplets of Nujor (diameter 5 mm) to stand still and visually observing the change of the droplet after 60 seconds. After 60 seconds, the case where the droplet remained spherical was evaluated as "A”, and the case where the droplet completely soaked into the test cloth was evaluated as "C”.
• PEL-12 10% by mass aqueous solution of polyoxyethylene lauryl ether (about 12 mol of ethylene oxide adduct, PEL-12, manufactured by Kao, Emargen 120)
• PEO-30 polyoxyethylene oleyl ether (about 30 mol of ethylene oxide adduct, 10% by mass aqueous solution of PEO-30, manufactured by Kao, Emargen 430)
• P104 10% by mass of a polymer of ethylene oxide and propylene oxide (average molecular weight 1670, containing 40% by mass of ethylene oxide, product name of Nichiyu Co., Ltd., Pronon # 104) Aqueous solution.
• P204 Polymer of ethylene oxide and propylene oxide (average molecular weight 3330, content of 40% by mass of ethylene oxide, NOF Corporation product name, pronon # 204)
• STMAC Alkyl chloride (carbon number: 16-18) trimethylammonium chloride (STMAC) 63% by mass water and isopropyl alcohol solution (Lion Specialty Chemicals Co., Ltd., Lipocard 18-63)
• Examples 1 to 21 Put the monomers shown in Tables 1 and 2 (excluding AcV and VCM), surfactant and medium in a glass container, heat at 55 ° C for 30 minutes, and then homomixer (Nippon Seiki Seisakusho Co., Ltd.).
• a mixed solution was obtained by mixing using a biomixer manufactured by Nissei Tokyo Office. While maintaining the obtained mixed solution at 55 ° C., it was pre-emulsified at 10 MPa using a high-pressure emulsifier (manufactured by APV Lanier, Minilab) and then treated at 40 MPa to obtain an emulsified solution. The obtained emulsion was placed in a stainless steel reactor and cooled to 30 ° C. or lower.
• the polymerization initiators shown in Tables 1 and 2 are added thereto to replace the gas phase with nitrogen, and then the amounts of AcV and VCM shown in Tables 1 and 2 are introduced, and the mixture is polymerized at 55 ° C. for 24 hours with stirring to contain the mixture.
• a dispersion containing a fluorine polymer was obtained.
• Tables 1 and 2 show the conversion rate of the monomer to the fluorine-containing polymer, the solid content concentration of the dispersion liquid, and Mn and Mw of the fluorine-containing polymer in the dispersion liquid.
• the numerical values in parentheses attached to the right side of each monomer (vinyl carboxylate) in the columns of monomers b and e are the carbon number of the alkyl group possessed by vinyl carboxylate.
• the charged amount (g) of the surfactant and the polymerization initiator is the total amount including the mass of the medium.
• the fluorine-containing polymer dispersion is diluted with tap water to adjust the solid content concentration to 2.0% by mass, and then an isocyanate-based cross-linking agent (Meikanate TP-10, manufactured by Meisei Chemical Industry Co., Ltd.) is added at a concentration of 1.0% by mass. Was added to obtain a water-repellent and oil-repellent composition.
• Polyethylene terephthalate (PET) wooly taffeta, nylon taslan taffeta, or cotton broadcloth is dipped in the obtained water- and oil-repellent composition, and wet pickup is performed from 50 to 60% by mass for PET wooly taffeta and 55 to 55 to nylon taslan taffeta.
• the articles of Examples 1 to 13 treated with the composition containing the fluorine-containing polymer having the unit a, the unit b and the unit c in a specific ratio have sufficient oil repellency, water repellency and durability thereof. It was excellent in (water-repellent washing durability).
• Example 14 since the unit a in the fluorine-containing polymer was less than 15 mol%, the oil repellency of the article was inferior to that of Examples 1 to 13.
• Examples 15 and 21 since the unit a in the fluorine-containing polymer was more than 35 mol%, the water repellency of the article and its durability (water-repellent washing durability) were insufficient.
• the oil repellency of the article was inferior to that of Examples 1 to 13.
• Example 16 and 19 since the unit b in the fluorine-containing polymer was less than 30 mol%, the water repellency of the article and its durability (water-repellent washing durability) were insufficient.
• Examples 17 and 18 since the fluorine-containing polymer has a unit based on vinyl carboxylate having an alkyl group having less than 12 carbon atoms instead of the unit b, the water repellency of the article and its durability (water-repellent washing durability) Sex) was inadequate.
• Example 20 since the unit a in the fluorine-containing polymer is more than 35 mol%, and the fluorine-containing polymer has a unit based on vinyl carboxylate having an alkyl group having less than 12 carbon atoms instead of the unit b. , The water repellency of the article and its durability (water repellency washing durability) were insufficient.

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