WO2023153403A1 - Water- and oil-repellent composition for nonwoven fabric, and nonwoven fabric product - Google Patents

Water- and oil-repellent composition for nonwoven fabric, and nonwoven fabric product Download PDF

Info

Publication number
WO2023153403A1
WO2023153403A1 PCT/JP2023/004006 JP2023004006W WO2023153403A1 WO 2023153403 A1 WO2023153403 A1 WO 2023153403A1 JP 2023004006 W JP2023004006 W JP 2023004006W WO 2023153403 A1 WO2023153403 A1 WO 2023153403A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
meth
oil repellent
group
nonwoven fabric
Prior art date
Application number
PCT/JP2023/004006
Other languages
French (fr)
Japanese (ja)
Inventor
晋一 南
佳介 中村
孝司 榎本
涛 陳
照偉 何
文旭 朱
Original Assignee
ダイキン工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ダイキン工業株式会社 filed Critical ダイキン工業株式会社
Publication of WO2023153403A1 publication Critical patent/WO2023153403A1/en

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/295—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present disclosure relates to a water and oil repellent composition for nonwoven fabrics and nonwoven fabric products.
  • Nonwovens are used in a variety of applications, particularly medical applications.
  • Major performance requirements for nonwoven fabrics, especially for medical nonwoven fabrics, include alcohol repellency, water pressure resistance, and antistatic properties.
  • the fluorine-containing water and oil repellent imparts alcohol repellency to the nonwoven fabric, but an antistatic agent is used in combination to prevent the nonwoven fabric from being charged.
  • antistatic agents impair alcohol repellency and water pressure resistance, it is a problem to achieve both alcohol repellency and water pressure resistance and antistatic properties.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2021-75608 discloses a water repellent composition containing an alkylketene dimer.
  • Patent Document 2 Japanese Unexamined Patent Publication No. 03-193972 discloses a water and oil repellent treatment agent for natural and recycled textile products containing a fluorine-containing water and oil repellent agent and a carbodiimide compound.
  • An object of the present disclosure is to provide a water and oil repellent composition that imparts good alcohol repellency, water pressure resistance, and antistatic properties to treated objects such as nonwoven fabrics.
  • the present disclosure provides a water and oil repellent composition containing a fluorine-containing water and oil repellent and a sizing agent.
  • Preferred aspects of the present disclosure are as follows.
  • Aspect 1 (1) A fluorine-containing water and oil repellent agent and (2) a sizing agent, comprising a water-based nonwoven fabric water and oil repellent composition.
  • Aspect 2 The water and oil repellent composition for non-woven fabrics according to aspect 1, which does not contain a carbodiimide compound and contains 20% by weight or more of water relative to the water and oil repellent composition.
  • the effective sizing component in the sizing agent is alkyl ketene dimer, alkenyl ketene dimer, wax, vinyl alcohol polymer, melamine/formalin polymer, styrene/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid ester copolymer.
  • the water and oil repellent composition for nonwoven fabrics according to any one of aspects 1 to 4, wherein the effective sizing component in the sizing agent comprises an alkyl ketene dimer and/or an alkenyl ketene dimer.
  • Aspect 6 The sizing active ingredient in the sizing agent is In addition to alkylketene dimers and/or alkenylketene dimers, Wax, vinyl alcohol polymer, melamine/formalin polymer, styrene/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid ester copolymer, styrene/(meth)acrylic acid/(meth)acrylic acid ester copolymer, styrene/maleic acid copolymer, isobutylene/(meth)acrylic acid copolymer, diisobutylene/maleic acid copolymer, propylene/maleic acid copolymer, ethylene/maleic
  • Oil repellent composition contains at least one selected from antistatic agents and penetrating agents, or the water and oil repellent composition is used in combination with at least one selected from antistatic agents and penetrating agents.
  • the water and oil repellent composition for nonwoven fabric according to any one of aspects 1 to 6.
  • Aspect 8 A nonwoven fabric water and oil repellent kit comprising (1) a water and oil repellent and (2) a sizing agent.
  • Aspect 9 A method for treating a nonwoven fabric, comprising treating a nonwoven fabric with the water and oil repellent composition for nonwoven fabric according to any one of aspects 1 to 7 or the water and oil repellent agent kit for nonwoven fabric according to aspect 8.
  • the water and oil repellent composition comprises a fluorine-containing water and oil repellent and a sizing agent.
  • the water and oil repellent composition is preferably water-based.
  • the water and oil repellent composition is preferably an aqueous dispersion.
  • the water and oil repellent composition may contain water in an amount of 20 wt % or more, 30 wt % or more, 50 to 99.9 wt %, or 60 to 99 wt % relative to the water and oil repellent composition.
  • the water and oil repellent composition preferably does not contain a carbodiimide compound.
  • the fluorine-containing water- and oil-repellent agent is preferably an aqueous dispersion (aqueous emulsion) containing a fluorine-containing polymer (that is, a water- and oil-repellent polymer) and water.
  • a fluorine-containing polymer is an active ingredient that imparts water repellency and water repellency.
  • the weight ratio of the active ingredient of the water and oil repellent (fluoropolymer) to the active ingredient of the sizing agent is 30:70 to 95:5, 55:45. may be ⁇ 90:10, 60:40-85:15 or 65:35-80:20
  • the fluoropolymer is a polymer having repeating units derived from a fluoromonomer having a fluoroalkyl group.
  • the fluoropolymer is A homopolymer having a repeating unit derived from a fluoromonomer having a fluoroalkyl group, or a repeating unit derived from a fluoromonomer having a fluoroalkyl group, and other copolymerizable compounds It may be a copolymer having repeating units derived from.
  • the fluoropolymer may be a random polymer or a block polymer.
  • the fluoropolymer (A) may consist only of repeating units derived from (A1) a fluoromonomer having a fluoroalkyl group, In addition to the repeating unit (A1), (A2) a repeating unit derived from a long-chain hydrocarbon group-containing monomer; It preferably has at least one repeating unit selected from (A3) a repeating unit derived from a non-crosslinkable monomer and (A4) a repeating unit derived from a crosslinkable monomer.
  • the fluorine- containing monomer is generally a polymerizable compound having a perfluoroalkyl group or perfluoroalkenyl group and an acrylic acid group, a methacrylic acid group or an ⁇ -substituted acrylic acid group.
  • X 11 is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (provided that X 1 and X 2 are hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted It may be a substituted phenyl group.
  • Specific examples of X 11 are H, CH 3 , Cl, Br, I, F, CN, CF 3 .
  • X 11 is preferably a hydrogen atom, a methyl group or a chlorine atom, particularly preferably a methyl group.
  • Y 11 is -O- or -NH-. Y 11 is preferably -O-.
  • Z 11 is a direct bond, a linear or branched aliphatic group (especially an alkylene group) having 1 to 20 carbon atoms, such as the formula —(CH 2 ) x — (wherein x is 1 to 10) ), or an aromatic or cycloaliphatic group having 6 to 18 carbon atoms, or a group of the formula -R 2 (R 1 )N-SO 2 - or the formula -R 2 (R 1 )N- a group represented by CO— (wherein R 1 is an alkyl group having 1 to 10 carbon atoms and R 2 is a linear or branched alkylene group having 1 to 10 carbon atoms), Alternatively, the formula —CH 2 CH(OR 3 )CH 2 —(Ar—O) p — (wherein R 3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (e.g., formyl, acetyl, etc.) , Ar is an arylene group optionally
  • Z 11 is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cycloaliphatic group having 6 to 18 carbon atoms, or a —CH 2 CH 2 N(R 1 )SO 2 — group (with the proviso that R 1 is an alkyl group having 1 to 4 carbon atoms.), -CH2CH ( OZ1 ) CH2- (Ph-O) p- group (where Z1 is a hydrogen atom or an acetyl group, Ph is a phenylene group, and p is 0 or 1), -( CH2 ) n —Ph—O— group (where Ph is a phenylene group and n is 0 to 10), —(CH 2 ) m —SO 2 —(CH 2 ) n — group or —(CH 2 ) m It is preferably a -S-(CH 2 ) n - group (where m is 1 to 10 and n is 0 to 10
  • the aliphatic group is preferably an alkylene group (particularly having 1 to 4, eg 1 or 2, carbon atoms).
  • An aromatic or cycloaliphatic group may be substituted or unsubstituted.
  • the S group or SO2 group may be attached directly to the Rf group.
  • the Rf group is preferably a perfluoroalkyl group.
  • the Rf group preferably has 1 to 12 carbon atoms, such as 1 to 6 carbon atoms, especially 4 to 6 carbon atoms, especially 6 carbon atoms.
  • Rf groups are -CF3 , -CF2CF3 , -CF2CF2CF3 , -CF ( CF3 ) 2 , -CF2CF2CF2CF3 , -CF2CF ( CF3 ) 2 , -C( CF3 ) 3 , -( CF2 ) 4CF3 , -( CF2 ) 2CF ( CF3 ) 2 , -CF2C ( CF3 ) 3 , -CF( CF3 ) CF2 CF 2 CF 3 , -(CF 2 ) 5 CF 3 , -(CF 2 ) 3 CF(CF 3 ) 2 , -(CF 2 ) 4 CF(CF 3 ) 2
  • fluorine-containing monomer examples include, but are not limited to, the following.
  • the fluorine-containing monomer may be used singly or in combination of two or more.
  • combinations of two or more fluorine-containing monomers include a combination of monomer 1 in which X 11 is a hydrogen atom and monomer 2 in which X 11 is a methyl group; a combination of monomer 1 in which X 11 is a hydrogen atom and monomer 2 in which X 11 is a chlorine atom; a combination of monomer 1 in which X 11 is a methyl group and monomer 2 in which X 11 is a halogen atom; is mentioned.
  • the molar ratio of monomer 1 to monomer 2 may be from 10:90 to 90:10 or from 30:70 to 70:30.
  • A2 Long-chain hydrocarbon group-containing monomer
  • the long-chain hydrocarbon group-containing monomer does not have a fluoroalkyl group.
  • the long-chain hydrocarbon group-containing monomer does not contain fluorine atoms.
  • a long-chain hydrocarbon group is a saturated or unsaturated group.
  • the long-chain hydrocarbon group is preferably a saturated hydrocarbon group, especially an alkyl group.
  • the long-chain hydrocarbon group is preferably a straight or branched hydrocarbon group having 7 to 40 carbon atoms.
  • the number of carbon atoms in the linear or branched hydrocarbon group may be 10-40 or 12-40 or 18-40.
  • the linear or branched hydrocarbon group preferably has 12 to 40 carbon atoms, more preferably 12 to 30 carbon atoms, particularly 18 to 28 carbon atoms, especially 18 to 22 carbon atoms (or 18 to 24 carbon atoms), and generally A saturated aliphatic hydrocarbon group, particularly an alkyl group is preferred.
  • the long-chain hydrocarbon group is stearyl, icosyl or behenyl.
  • X may be a hydrogen atom, a methyl group, a halogen excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
  • Examples of X are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, cyano group.
  • X is preferably a hydrogen atom, a methyl group or a chlorine atom.
  • Y is a divalent to tetravalent group.
  • Y is preferably a divalent group.
  • R is preferably a linear or branched hydrocarbon group.
  • the hydrocarbon radicals may in particular be linear hydrocarbon radicals.
  • the hydrocarbon groups are preferably aliphatic hydrocarbon groups, especially saturated aliphatic hydrocarbon groups, especially alkyl groups.
  • the number of carbon atoms in the hydrocarbon group is preferably 12-30, for example 16-26, especially 18-22.
  • the acrylic monomer (a2) is a compound different from the acrylic monomer (a1).
  • Acrylic monomer (a1) is a long chain acrylate ester monomer in which Y 1 is —O— or a long chain acrylamide monomer in which Y 1 is —NH—.
  • X 1 may be a hydrogen atom, a methyl group, a halogen excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
  • Examples of X 1 are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, cyano group.
  • X 1 is preferably a hydrogen atom, a methyl group or a chlorine atom.
  • Y 1 is -O- or -NH-.
  • R is preferably a linear or branched hydrocarbon group.
  • the hydrocarbon radicals may in particular be linear hydrocarbon radicals.
  • the hydrocarbon groups are preferably aliphatic hydrocarbon groups, especially saturated aliphatic hydrocarbon groups, especially alkyl groups.
  • the carbon number of the hydrocarbon group may be 7-30 or 12-30, eg 16-26, especially 18-22 (or 18-24).
  • long chain acrylate ester monomers are nonyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, icosyl alpha chloro Acrylate, behenyl ⁇ -chloroacrylate.
  • long-chain acrylamide monomers are nonyl (meth)acrylamide, lauryl (meth)acrylamide, stearyl (meth)acrylamide, icosyl (meth)acrylamide, behenyl (meth)acrylamide.
  • the presence of the long-chain acrylate ester monomer or the long-chain acrylamide monomer enhances the water repellency, oil repellency, and texture provided by the fluoropolymer.
  • Acrylic monomer (a2) is a long chain acrylate ester monomer in which Y 2 is —O— or a long chain acrylamide monomer in which Y 2 is —NH—.
  • X2 may be a hydrogen atom, a methyl group, a halogen excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
  • Examples of X2 are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a cyano group.
  • X2 is preferably a hydrogen atom, a methyl group, or a chlorine atom, more preferably a hydrogen atom or a methyl group, because the less rigid the main chain of the resulting polymer is, the less the crystallinity of the side chain is impaired.
  • a hydrogen atom is preferred, and a hydrogen atom is particularly preferred.
  • Y 2 is -O- or -NH-.
  • Z 1 is a direct bond, a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms (especially an alkyl group), and may have a branched structure.
  • Z 1 preferably has 2 to 4 carbon atoms, particularly 2 carbon atoms.
  • Specific examples of Z 1 include -CH 2 -, -CH 2 CH 2 - , -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH as a direct bond and a divalent group.
  • Z 1 is preferably not a direct bond.
  • Z 1 and Z 2 cannot be direct bonds at the same time.
  • R 2 is preferably a linear or branched hydrocarbon group.
  • the hydrocarbon radicals may in particular be linear hydrocarbon radicals.
  • the hydrocarbon groups are preferably aliphatic hydrocarbon groups, especially saturated aliphatic hydrocarbon groups, especially alkyl groups.
  • the number of carbon atoms in the hydrocarbon group is preferably 12-30, for example 16-26, especially 18-22 (or 18-24).
  • the acrylic monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate.
  • long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, behenyl isocyanate, and the like.
  • the acrylic monomer (a2) can also be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl isocyanate, with a long-chain alkylamine or a long-chain alkyl alcohol.
  • a long-chain alkylamine or a long-chain alkyl alcohol examples include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, behenylamine, and the like.
  • long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.
  • acrylic monomer (a2) are as follows.
  • the compounds of the following chemical formulas are acrylates in which the ⁇ -position is a hydrogen atom, and specific examples may be methacrylates in which the ⁇ -position is a methyl group and acrylates in which the ⁇ -position is a chlorine atom.
  • n is an integer of 7 to 40.
  • acrylic monomer (a2) is palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth) acrylate, behenic acid amide ethyl (meth) acrylate, and myristate amide ethyl (meth) acrylate.
  • amide group-containing monomers are carboxylic acid amide alkyl (meth)acrylates.
  • Specific examples of the amide group-containing monomer include ethyl palmitamide (meth)acrylate, stearamideethyl (meth)acrylate, behenamideethyl (meth)acrylate, myristateamideethyl (meth)acrylate, and laurateamideethyl (meth)acrylate.
  • Acrylates isostearic acid ethylamide (meth)acrylate, oleic acid ethylamide (meth)acrylate, tert-butylcyclohexylcaproic acid amide ethyl (meth)acrylate, adamantanecarboxylic acid ethylamide (meth)acrylate, naphthalenecarboxylic acid amideethyl (meth)acrylate, anthracenecarboxylic acid Acid amide ethyl (meth) acrylate, palmitamide propyl (meth) acrylate, stearamide propyl (meth) acrylate, palmitamide ethyl vinyl ether, stearamide ethyl vinyl ether, palmitamide ethyl allyl ether, stearamide ethyl allyl ether , or mixtures thereof.
  • the amide group-containing monomer is preferably stearamidoethyl (meth)acrylate.
  • the amide group-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate.
  • the amount of stearamide ethyl (meth)acrylate is, for example, 55 to 99% by weight, preferably 60 to 85% by weight, based on the total weight of the amide group-containing monomer. , more preferably 65 to 80% by weight, and the remaining monomer may be, for example, palmitamide ethyl (meth)acrylate.
  • Non-crosslinking monomer is a monomer other than the long-chain hydrocarbon group-containing monomer (A2).
  • a non-crosslinkable monomer (A3) is a monomer containing no fluorine atom.
  • a non-crosslinkable monomer (A3) does not have a crosslinkable functional group.
  • the non-crosslinkable monomer (A3) is non-crosslinkable, unlike the crosslinkable monomer (A4).
  • Non-crosslinkable monomer (A3) is preferably a monomer having an ethylenically unsaturated carbon-carbon double bond.
  • the non-crosslinkable monomer (A3) is preferably a fluorine-free vinyl monomer.
  • Non-crosslinking monomers (A3) are generally compounds having one ethylenically unsaturated carbon-carbon double bond.
  • A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom and an iodine atom)
  • T is a hydrogen atom, a chain or cyclic hydrocarbon group, or a chain or cyclic organic group having an ester bond (and optionally an oxyalkylene group).
  • A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom and an iodine atom)
  • T is a hydrogen atom, a chain or cyclic hydrocarbon group, or a chain or cyclic organic group having an ester bond (and optionally an oxyalkylene group).
  • A is a hydrogen atom, a methyl
  • linear or cyclic hydrocarbon groups include linear or branched aliphatic hydrocarbon groups having 1 to 40 carbon atoms, cycloaliphatic groups having 4 to 40 carbon atoms, carbon They are an aromatic hydrocarbon group having 6 to 40 carbon atoms and an araliphatic hydrocarbon group having 7 to 40 carbon atoms.
  • linear or cyclic organic groups having 1 to 300 or 1 to 41 carbon atoms having an ester bond
  • non-crosslinkable monomer (A3) examples include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, methoxypolypropylene Included are glycol (meth)acrylates and vinyl alkyl ethers.
  • Non-crosslinking monomers (A3) are not limited to these examples.
  • the non-crosslinkable monomer (A3) may be a (meth)acrylate ester having an alkyl group.
  • the number of carbon atoms in the alkyl group may be 1-17, 1-10, 1-6 or 1-4.
  • the non-crosslinkable monomer (A3) may be a (meth)acrylate monomer having a cyclic hydrocarbon group.
  • a (meth)acrylate monomer having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth)acrylate group.
  • the monovalent cyclic hydrocarbon group and the monovalent (meth)acrylate group are directly bonded.
  • Cyclic hydrocarbon groups include saturated or unsaturated monocyclic groups, polycyclic groups, bridged ring groups, and the like.
  • the cyclic hydrocarbon group is preferably saturated.
  • the cyclic hydrocarbon group preferably has 4 to 20 carbon atoms.
  • Cyclic hydrocarbon groups include cycloaliphatic groups having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, aromatic groups having 6 to 20 carbon atoms, and araliphatic groups having 7 to 20 carbon atoms.
  • the number of carbon atoms in the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less.
  • a carbon atom in the ring of the cyclic hydrocarbon group is preferably directly bonded to the ester group in the (meth)acrylate group.
  • the cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.
  • cyclic hydrocarbon group examples include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group and an adamantyl group.
  • the acrylate groups are preferably acrylate or methacrylate groups, with methacrylate groups being particularly preferred.
  • monomers having a cyclic hydrocarbon group include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.
  • dicyclopentenyl (meth)acrylate dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl -2-adamantyl (meth)acrylate and the like.
  • the non-crosslinkable monomer (A3) may be a halogenated olefin.
  • Halogenated olefins may be halogenated olefins having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine or iodine atoms.
  • the halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms.
  • halogenated olefins are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide.
  • a crosslinkable monomer (A4) may have repeating units derived from the crosslinkable monomer (A4).
  • a crosslinkable monomer (A4) is a monomer containing no fluorine atom.
  • Crosslinking monomers (A4) may be fluorine-free compounds having at least two reactive groups and/or ethylenically unsaturated carbon-carbon double bonds.
  • Crosslinking monomer (A4) is a compound having at least two ethylenically unsaturated carbon-carbon double bonds, or at least one ethylenically unsaturated carbon-carbon double bond and at least one reactive group It may be a compound. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.
  • crosslinkable monomer (A4) examples include diacetone acrylamide, (meth)acrylamide, N-methylolacrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl ( meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butadiene, isoprene, chloroprene, glycidyl (meth)acrylate, etc. Examples include, but are not limited to.
  • the monomer may be polymerized in the presence of at least one compound selected from the group consisting of blocked isocyanate compounds and organopolysiloxane compounds.
  • the amount of blocked isocyanate compound (or organopolysiloxane compound) may be 0 to 100 parts by weight, for example 1 to 50 parts by weight, based on 100 parts by weight of the monomer.
  • a polymer having a blocked isocyanate group is obtained by polymerizing the monomer in the presence of the blocked isocyanate compound.
  • a blocked isocyanate compound is an isocyanate that is blocked with at least one blocking agent.
  • blocking agents include oximes, phenols, alcohols, mercaptans, amides, imides, imidazoles, ureas, amines, imines, pyrazoles, and 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.
  • the fluoromonomer (A1) may be 30 to 100% by weight, preferably 32 to 98% by weight, for example 35 to 95% by weight, particularly 40 to 90% by weight, relative to the fluoropolymer.
  • the amount of the long-chain hydrocarbon group-containing monomer (A2) is 1000 parts by weight or less, for example 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight
  • the amount of the non-crosslinkable monomer (A3) is 1000 parts by weight or less, for example 0.1 to 300 parts by weight, especially 1 to 200 parts by weight
  • the amount of crosslinkable monomer (A4) may be 50 parts by weight or less, for example 30 parts by weight or less, especially 0.1 to 20 parts by weight.
  • the amount of the fluorine-containing monomer (A1) is 30 to 90% by weight, for example 35 to 80% by weight, particularly 40 to 70% by weight;
  • the amount of the long-chain hydrocarbon group-containing monomer (A2) is 1 to 60% by weight, for example 5 to 50% by weight, especially 10 to 40% by weight;
  • the amount of non-crosslinking monomer (A3) is 1 to 60% by weight, for example 5 to 50% by weight, especially 10 to 40% by weight;
  • the amount of crosslinkable monomers (A4) may be up to 30% by weight, for example 0.1 to 20% by weight, especially 1 to 10% by weight.
  • the number average molecular weight (Mn) of the fluoropolymer may generally be from 1,000 to 1,000,000, for example from 2,000 to 500,000, especially from 3,000 to 200,000.
  • the number average molecular weight (Mn) of the fluoropolymer is generally measured by GPC (gel permeation chromatography).
  • GPC gel permeation chromatography
  • the water and oil repellent is an aqueous emulsion
  • it preferably contains a surfactant.
  • the surfactant may be at least one selected from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants.
  • nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides, and their polyoxyalkylene (especially ethylene) adducts.
  • cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazolines and imidazolinium salts.
  • anionic surfactants include fatty acid salts, sulfonates, and sulfate ester salts.
  • amphoteric surfactants include alanines, imidazolinium betaines, amidobetaines, and betaine acetate.
  • the amount of the surfactant may be 0.1 to 50 parts by weight, for example 1 to 20 parts by weight, with respect to 100 parts by weight of the fluoropolymer (or the total amount of monomers).
  • the fluorine-containing polymer can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.
  • the fluorine-containing polymer is preferably produced by an emulsion polymerization method or a solution polymerization method.
  • the water and oil repellent preferably forms a fluoropolymer dispersion by emulsion polymerization.
  • the water and oil repellent is preferably an aqueous dispersion, more specifically, an aqueous dispersion in which fluoropolymer particles are dispersed in an aqueous medium.
  • water or an aqueous medium
  • water may be added after the fluoropolymer is produced by polymerization.
  • water is added to the polymer mixture, the organic solvent is distilled off, and the fluoropolymer is dissolved in water. You can disperse it. It is not necessary to distill off the organic solvent.
  • a surfactant may be added before or after polymerization, or may not be added. Good aqueous dispersions are obtained even when no surfactant is added.
  • Sizing agents are commonly used sizing agents for paper.
  • the sizing agent has the function of suppressing the permeability of liquid such as ink to paper and preventing set-off and bleeding.
  • the sizing agent is preferably one that is used as an internal or external sizing agent in the manufacture of paper, for example, as an external sizing agent (ie, surface sizing agent).
  • the sizing agent preferably contains an active ingredient of the sizing agent (a component that suppresses liquid permeability) and water.
  • the active ingredient of the sizing agent may be referred to as "active sizing ingredient”.
  • the size active ingredient is not particularly limited, but for example, ketene dimers such as alkyl ketene dimers and alkenyl ketene dimers; Alkyl succinic anhydride, alkenyl succinic anhydride; wax; vinyl alcohol polymers such as polyvinyl alcohol and modified polyvinyl alcohol; melamine/formalin polymers; Styrene/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid ester copolymer, styrene/(meth)acrylic acid/(meth)acrylic acid ester copolymer, styrene/maleic acid copolymer, etc.
  • ketene dimers such as alkyl ketene dimers and alkenyl ketene dimers
  • Alkyl succinic anhydride alkenyl succinic anhydride
  • wax vinyl alcohol polymers such as polyvinyl alcohol and modified polyvinyl alcohol
  • styrene polymer styrene polymer
  • Olefin polymers such as isobutylene/(meth)acrylic acid copolymer, diisobutylene/maleic acid copolymer, propylene/maleic acid copolymer, ethylene/maleic acid copolymer
  • Poly(meth)acrylic homopolymers and copolymers such as (meth)acrylate/acrylonitrile copolymers may be mentioned.
  • the alkyl and alkenyl groups may have 3-40, 4-36 or 4-24, eg 12-24, carbon atoms.
  • Waxes include paraffin waxes, microcrystalline waxes, Fischer-Tropsch waxes, polyethylene waxes, animal and plant waxes, mineral waxes, and the like. Examples include normal alkanes.
  • the wax may have 20 to 60 carbon atoms, such as 25 to 45 carbon atoms.
  • the wax may have a molecular weight of 150-1000 or 300-700.
  • (Meth) acrylic acid esters alcohol residues are hydrocarbon alcohols (especially aliphatic hydrocarbon alcohols such as saturated aliphatic hydrocarbon alcohols and saturated alicyclic hydrocarbon alcohols) (hydrocarbon groups with 1 to 40 carbon atoms) or 3 to 30). Copolymers of two or more (meth)acrylic acid alkyl esters with different alkyl chain lengths, or (meth)acrylic acid alkyl esters and cross-linking groups such as —OH and/or —COOH groups (meth) ) copolymers with acrylic acid esters are preferred.
  • (meth)acrylic acid means acrylic acid and methacrylic acid.
  • Preferred sizing agents are alkyl ketene dimers, alkenyl ketene dimers, waxes, styrene/(meth)acrylic acid copolymers, styrene/acrylic acid ester copolymers, styrene/(meth)acrylic acid/(meth)acrylic acid ester copolymers.
  • polymers, styrene polymers such as styrene/maleic acid copolymers, isobutylene/acrylic acid copolymers, diisobutylene/maleic acid copolymers, propylene/maleic acid copolymers, ethylene/maleic acid copolymers.
  • More preferred sizing agents are alkylketene dimers, alkenylketene dimers, alkylketene dimers, styrene polymers and copolymers, and mixtures thereof.
  • Alkyl ketene dimers and alkenyl ketene dimers are particularly preferred because they have higher alcohol resistance.
  • alkyl ketene dimers and alkenyl ketene dimers are sometimes indicated as "AKD".
  • Alkyl ketene dimers and alkenyl ketene dimers have the formula: [In the formula, R 1 and R 2 may be the same or different and each represents an alkyl group or an alkenyl group having 4 to 24 carbon atoms. ] It may be a compound represented by
  • a sizing agent can be used individually or in combination of 2 or more types.
  • the sizing agent may contain, in addition to the alkyl ketene dimer and/or the alkenyl ketene dimer, other active ingredients as described above, such as waxes.
  • the weight ratio of alkyl ketene dimer and/or alkenyl ketene dimer and other active ingredient is 10:90 to 90:10 or 30:70 to It may be 70:30.
  • the sizing agent is preferably an aqueous solution or aqueous dispersion (aqueous liquid).
  • Aqueous dispersions of sizing agents can be prepared, for example, by dispersing the sizing agent in water in the presence of a surfactant.
  • the sizing agent is an aqueous emulsion, it preferably contains a surfactant.
  • the surfactant may be at least one selected from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants. Examples of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants are the same as those described for the fluorine-containing polymer.
  • the amount of surfactant may be from 0.1 to 50 parts by weight, for example from 1 to 20 parts by weight, based on 100 parts by weight of the size active ingredient.
  • the surfactant may be cationic or amphoteric.
  • the water and oil repellent kit has a water and oil repellent (1) and a sizing agent (2).
  • a water and oil repellent agent kit means a combination of a water and oil repellent agent (1) and a sizing agent (2).
  • the water/oil repellent (1) generally comprises a fluoropolymer and a liquid medium.
  • Sizing agent (2) generally comprises a sizing active ingredient and a liquid medium.
  • it is not necessary to pre-form the water and oil repellent composition by mixing the water and oil repellent (1) and the sizing agent (2).
  • the water and oil repellent agent (1) and the sizing agent (2) may be separately prepared and added to the treatment liquid.
  • the water and oil repellent composition is preferably in the form of dispersion, solution, emulsion or aerosol.
  • the water and oil repellent composition preferably contains a medium (especially a liquid medium such as an organic solvent and/or water) in addition to the fluorine-containing copolymer and the sizing active ingredient.
  • a medium especially a liquid medium such as an organic solvent and/or water
  • the concentration of the fluoropolymer and the sizing active ingredient may be, for example, 0.01 to 50% by weight.
  • the liquid medium contained in the water and oil repellent composition is preferably an aqueous medium.
  • aqueous medium refers to a medium consisting only of water, and an organic solvent in addition to water (the amount of the organic solvent is 80 parts by weight or less, for example, 0.1 to 100 parts by weight per 100 parts by weight of water). 50 parts by weight, especially 5 to 30 parts by weight).
  • the water and oil repellent composition can be applied to the object to be treated (substrate) by any appropriate method, for example, the substrate can be treated with the water and oil repellent composition.
  • “treatment” means applying a water and oil repellent agent or a treatment agent containing the same to an object to be treated by immersion, spraying, coating, or the like. Due to the treatment, the fluorine-containing polymer, which is the active ingredient of the treatment agent, permeates into the material to be treated and/or adheres to the surface of the material to be treated.
  • the treatment methods of the present disclosure are generally capable of rendering treated objects water- and oil-repellent (or water-repellent/hydrophobic and oil-repellent/oleophobic) as well as alcohol-repellent.
  • the water and oil repellent composition (or the water and oil repellent and the sizing agent) is dispersed in water and diluted to form a treatment liquid, which is applied to known methods such as dip coating, spray coating and foam coating.
  • a method of adhering to an object to be treated and drying can be adopted.
  • the water and oil repellent composition may be used together with a suitable cross-linking agent, applied to the object to be treated, and cured.
  • the water and oil repellent composition can be used in combination with antistatic agents, penetrants, insect repellents, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, and the like.
  • the concentration of the fluoropolymer and sizing active ingredient in the treatment liquid when brought into contact with the object to be treated may be 0.01 to 10% by weight (especially in the case of dip coating), for example 0.05 to 10% by weight. .
  • the water and oil repellent composition contains an antistatic agent and/or a penetrating agent, or that the water and oil repellent composition is used in combination with an antistatic agent and/or a penetrating agent.
  • Antistatic agents include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
  • the anionic surfactant includes a phosphate compound such as ZELEC TY (manufactured by Stepan) as a butyl phosphate metal salt.
  • nonionic surfactants include polyoxyethylene compounds
  • cationic surfactants include alkylammonium chloride
  • amphoteric surfactants include amidoalkylbetaine compounds. You may use an antistatic agent individually by 1 type or in combination of 2 or more types.
  • the amount of the antistatic agent is 0.01-1.0% by weight or 0.1-. It may be 5% by weight. Alternatively, the amount of the antistatic agent may be 1 to 1000 parts by weight or 10 to 500 parts by weight with respect to 100 parts by weight of the fluoropolymer.
  • the penetrant allows the water and oil repellent composition to penetrate into the hydrophobic substrate.
  • Penetrants include alcohols, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like.
  • Specific examples of penetrants include nonionic emulsifier emulsified dispersions of alcohols having alkyl groups of 1 to 10 carbon atoms, polyoxyethylene alkyl ethers, n-hexanol or n-decanol.
  • Penetrants may be used singly or in combination of two or more.
  • the amount of the penetrant is 0.01 to 1.0% by weight or 0.1 to . It may be 5% by weight. Alternatively, the amount of penetrant may be 1 to 1000 parts by weight or 10 to 500 parts by weight with respect to 100 parts by weight of the fluoropolymer.
  • a fibrous base material is preferable as the object (base material) to be treated with the water and oil repellent composition.
  • a textile product can be obtained by treating a textile substrate with the water and oil repellent composition.
  • the water and oil repellent composition is treated with a treatment liquid containing the water and oil repellent composition according to any suitable method for treating a fiber base material with a liquid.
  • a treatment liquid containing the water and oil repellent composition according to any suitable method for treating a fiber base material with a liquid.
  • the water and oil repellent composition water and oil repellent and sizing agent
  • the amount of each of the fluorine-containing polymer and the sizing active ingredient attached to the substrate surface is 0.001 g/m 2 to 10 g/m 2 (on one side) or 0.01 g/m 2 to 1 g/m 2 ( solid content).
  • the fibrous base material can be in any form such as fiber, thread, cloth, etc., and typically can be cloth.
  • the fiber base material is immersed in a treatment liquid prepared by dispersing and diluting the water and oil repellent composition in an aqueous medium, and then the fiber base material (for example, cloth) is taken out from the treatment liquid and rolled or the like. Excess treatment liquid is removed by pressing (for example, between rolls) and dried to leave the active ingredient of the water and oil repellent composition on the fiber substrate, thereby imparting water and oil repellency and alcohol repellency. You can get a finished textile product.
  • the water and oil repellent composition has high processing stability, and even if mechanical impact (or shear force) is applied to the treatment liquid when the fiber base material enters the treatment liquid during such treatment, the emulsion particles It can be stably maintained, and can effectively prevent polymer (fluoropolymer) lumps from adhering to a roll or the like or adhering to a fiber base material. Such an effect is particularly remarkable when the fluoroalkyl group of the fluoropolymer has 6 or less carbon atoms.
  • the water and oil repellent composition may be applied to the fibrous substrate by a cleaning method, for example, it may be applied to the fibrous substrate in a laundering application or dry cleaning method.
  • the fibrous substrate is typically in the form of cloth (which may also be referred to as fabric), which includes woven, knitted and nonwoven fabrics (eg medical nonwoven fabrics), clothing form fabrics and carpets.
  • the fibrous substrate may be in other forms, such as fibers, yarns or intermediate textile products such as sliver or roving.
  • the fibrous substrate is preferably a nonwoven fabric, especially a medical nonwoven fabric.
  • Natural fibers include, for example, vegetable fibers such as cotton and hemp, animal fibers such as wool and silk, and mineral fibers such as asbestos, and animal and plant natural fibers are preferably used.
  • Chemical fibers include refined fibers such as lyocell, regenerated fibers such as rayon (including viscose rayon, etc.), semi-synthetic fibers such as acetate, polyamide (including nylon, aramid, etc.), polyvinyl alcohol, and polyvinyl chloride.
  • Synthetic fibers such as polyester, polyacrylonitrile, polyolefin (including polyethylene, polypropylene, etc.), polyether ester, polyurethane, etc., inorganic fibers such as glass fiber, carbon fiber, refined fiber, semi-synthetic Fibers and synthetic fibers are preferably used.
  • the material of the fiber base material may be a mixture of two or more materials selected from the group consisting of the fiber materials exemplified above (for example, a mixture of any natural fiber and any synthetic fiber, etc.) It may be in the form of mixed fiber, composite fiber, mixed yarn, mixed woven yarn, etc.).
  • the water and oil repellent composition can impart water and oil repellency and alcohol repellency to both hydrophilic and hydrophobic textile materials.
  • hydrophilic fibrous materials include cellulosics (such as cotton or rayon).
  • hydrophobic fiber materials include polyolefins (polyethylene, polypropylene, polyethylene blends, etc.), polyvinyl chlorides, polyamides (nylon, etc.), polyesters, and polystyrenes.
  • the water and oil repellent composition is used as a fiber base material for nonwoven fabrics in order to produce nonwoven fabric products such as medical nonwoven fabrics that can be used for textile products that require high alcohol repellency, such as medical gowns and surgical gowns.
  • nonwoven fabrics for medical use may typically be nonwoven fabrics composed of hydrophobic fibrous materials, such as polypropylene (PP) nonwoven fabrics, polyethylene terephthalate (PET) nonwoven fabrics, composite nonwoven fabrics of polypropylene and polyethylene, polyethylene nonwoven fabrics, and the like.
  • PP polypropylene
  • PET polyethylene terephthalate
  • the fiber base material may be leather.
  • the water and oil repellent composition is added in aqueous solution at various stages of leather processing, for example during wet processing of leather or during finishing of leather, in order to render the leather hydrophobic and oleophobic. Or it may be applied to leather from an aqueous emulsion.
  • the fiber base material may be paper.
  • the repellent composition may be applied to preformed paper or may be applied at various stages of papermaking, such as during drying of the paper.
  • a treatment liquid 1000 g was prepared by diluting the water and oil repellent with pure water and adding chemicals such as a sizing agent.
  • a polypropylene non-woven fabric 45 g/m 2
  • a sheet of polypropylene non-woven fabric (45 g/m 2 ) (510 mm x 205 mm) was immersed in this treatment solution, passed between mangle rolls, and treated with a pin tenter at 120°C for 2 minutes.
  • the obtained test cloth (treated cloth) was evaluated for alcohol repellency. Specifically, it was tested and evaluated as follows in accordance with AATCC test method 193-2007.
  • the treated cloth is stored in a thermo-hygrostat at a temperature of 21° C. and a humidity of 50% for 4 hours or more.
  • Test liquids are also stored at a temperature of 21°C and used.
  • the test is performed in a constant temperature and humidity room with a temperature of 21° C. and a humidity of 50%.
  • the alcohol repellency is scored based on the maximum isopropyl alcohol (IPA) content (% by volume) of the test solution that passes, and the water repellency ranges from poor water repellency to good level Fail, 0, 1, 2, 3, 4. , 5, 6, 7, 8, 9, and 10. The larger the series, the higher the alcohol repellency.
  • IPA isopropyl alcohol
  • a charging voltage (IOOV) was applied to the evaluation sample according to WSP40.1, and the surface electrical resistivity was measured after 30 seconds.
  • Fluorine-containing water and oil repellent agent A Production example 1 Fluorine-Containing Water and Oil Repellent B: Production Example 2 PERGLUTIN K 175 EP: Polymer solution with high cationic charge density, acrylate copolymer from BK Giulini GmbH PERGLUTIN K 485: Cationic polymer dispersion, styrene-acrylate copolymer from BK Giulini GmbH AD1602: Seiko PMC cationic, alkyl ketene dimer AD1606: Seiko PMC weak cationic, alkyl ketene dimer Basoplast 265D: BASF Cationic dispersion, Styrene-Butylacrylate copolymer Basoplast 2023LC: BASF Standard dispersion, AKD FennoSize S A466: Amphoteric surface sizing agent from Kemira Hydrores 166M: Kemira Alkylketendimer wax
  • Example 1 After diluting the fluorine-containing water and oil repellent agent A with pure water, a sizing agent, an antistatic agent and a penetrating agent are added to obtain 0.8% of the fluorine-containing water and oil repellent agent A, 0.33% of the sizing agent, A treatment solution (1000 g) containing 0.3% antistatic agent and 0.6% penetrant was prepared. A polypropylene non-woven fabric (45 g/m 2 ) was used as the fabric to be treated (fiber substrate). A sheet of polypropylene non-woven fabric (45 g/m 2 ) (510 mm x 205 mm) was immersed in this treatment solution, passed between mangle rolls, and treated with a pin tenter at 120°C for 2 minutes. Alcohol repellency, water pressure resistance and surface resistivity were measured. Table 2 shows the results.
  • Example 2-18 The same procedure as in Example 1 was repeated except that the agents shown in Table 2 were used. Table 2 shows the results.
  • the water and oil repellent composition of the present disclosure is useful for fiber substrates, particularly nonwoven fabrics such as medical nonwoven fabrics.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A water- and oil-repellent composition for a nonwoven fabric, which comprises (1) a fluorine-containing water- and oil-repellent agent and (2) a sizing agent and is water-based, can impart good alcohol repellency, water pressure resistance, and antistatic properties to an object to be treated, such as a nonwoven fabric. The water- and oil-repellent composition for a nonwoven fabric does not contain a carbodiimide compound and may contain at least 20 wt% of water with respect to the water- and oil-repellent composition. The active ingredient of the sizing agent may include an alkylketene dimer and/or an alkenylketene dimer. The water- and oil-repellent composition may further contain an antistatic agent and a penetrant. A treated substrate is preferably a nonwoven fabric.

Description

不織布用撥水撥油剤組成物および不織布製品Water and oil repellent composition for nonwoven fabric and nonwoven fabric product
　本開示は、不織布用撥水撥油剤組成物および不織布製品に関する。 The present disclosure relates to a water and oil repellent composition for nonwoven fabrics and nonwoven fabric products.
　不織布が種々の用途、特に医療用途において使用されている。不織布、特に医療用不織布の主要な要求性能としては、撥アルコール性、耐水圧性および帯電防止性が挙げられる。
　含フッ素撥水撥油剤が不織布に撥アルコール性を付与するが、不織布の帯電を防止するために、帯電防止剤が併用される。しかし、帯電防止剤は撥アルコール性および耐水圧性を阻害するので、撥アルコール性および耐水圧性と帯電防止性の両立が課題である。例えば、従来の含フッ素撥水撥油剤では、撥アルコール性、耐水圧性および帯電防止性の最良のバランスを取ることが難しく、特に、帯電防止剤併用時に耐水圧性が低下しない撥水撥油剤の選定が難しい状況であった。 Nonwovens are used in a variety of applications, particularly medical applications. Major performance requirements for nonwoven fabrics, especially for medical nonwoven fabrics, include alcohol repellency, water pressure resistance, and antistatic properties.
The fluorine-containing water and oil repellent imparts alcohol repellency to the nonwoven fabric, but an antistatic agent is used in combination to prevent the nonwoven fabric from being charged. However, since antistatic agents impair alcohol repellency and water pressure resistance, it is a problem to achieve both alcohol repellency and water pressure resistance and antistatic properties. For example, with conventional fluorine-containing water and oil repellents, it is difficult to achieve the best balance between alcohol repellency, water pressure resistance, and antistatic properties. was in a difficult situation.
　特許文献１（特開２０２１－７５６０８号公報）は、アルキルケテンダイマーを含む撥水剤組成物を開示している。
　特許文献２（特開平０３－１９３９７２号公報）は、含フッ素撥水撥油剤及びカルボジイミド化合物を含有する天然および再生繊維製品用撥水撥油処理剤を開示している。 Patent Document 1 (Japanese Patent Application Laid-Open No. 2021-75608) discloses a water repellent composition containing an alkylketene dimer.
Patent Document 2 (Japanese Unexamined Patent Publication No. 03-193972) discloses a water and oil repellent treatment agent for natural and recycled textile products containing a fluorine-containing water and oil repellent agent and a carbodiimide compound.
特開２０２１－７５６０８号公報Japanese Patent Application Laid-Open No. 2021-75608 特開平０３－１９３９７２号公報JP-A-03-193972
　本開示の目的は、良好な撥アルコール性、耐水圧性および帯電防止性を不織布などの被処理物に与える撥水撥油剤組成物を提供することにある。 An object of the present disclosure is to provide a water and oil repellent composition that imparts good alcohol repellency, water pressure resistance, and antistatic properties to treated objects such as nonwoven fabrics.
　本開示は、含フッ素撥水撥油剤とサイズ剤を含む撥水撥油剤組成物を提供する。
　本開示の好ましい態様は次のとおりである。
態様１：
　（１）含フッ素撥水撥油剤および（２）サイズ剤を含み、水系である不織布用撥水撥油剤組成物。
態様２：
　カルボジイミド化合物を含まず、撥水撥油剤組成物が撥水撥油剤組成物に対して２０重量％以上の水を含む態様１に記載の不織布用撥水撥油剤組成物。
態様３：
　含フッ素撥水撥油剤が、式：
ＣＨ２＝Ｃ（－Ｘ１１）－Ｃ（＝Ｏ）－Ｙ１１－Ｚ１１－Ｒｆ
［式中、Ｘ１１は、水素原子、一価の有機基またはハロゲン原子であり、
Ｙ１１は、－Ｏ－または－ＮＨ－であり、
Ｚ１１は、直接結合または二価の有機基であり、
Ｒｆは、炭素数１～２０のフルオロアルキル基である。］
で示される単量体から形成されている繰り返し単位を有する含フッ素重合体を含んでなる態様１または２に記載の不織布用撥水撥油剤組成物。
態様４：
　サイズ剤におけるサイズ有効成分が、アルキルケテンダイマー、アルケニルケテンダイマー、ワックス、ビニルアルコール重合体、メラミン／ホルマリン重合体、スチレン／（メタ）アクリル酸共重合体、スチレン／（メタ）アクリル酸エステル共重合体、スチレン／（メタ）アクリル酸／（メタ）アクリル酸エステル共重合体、スチレン／マレイン酸共重合体、イソブチレン／（メタ）アクリル酸共重合体、ジイソブチレン／マレイン酸共重合体、プロピレン／マレイン酸共重合体、エチレン／マレイン酸共重合体、ポリ（メタ）アクリル単独重合体および共重合体、ならびに（メタ）アクリル酸エステル／アクリロニトリル共重合体からなる群から選択された少なくとも１種である態様１～３のいずれかに記載の不織布用撥水撥油剤組成物。
態様５：
　サイズ剤におけるサイズ有効成分が、アルキルケテンダイマーおよび／またはアルケニルケテンダイマーを含む態様１～４のいずれかに記載の不織布用撥水撥油剤組成物。
態様６：
　サイズ剤におけるサイズ有効成分が、
アルキルケテンダイマーおよび／またはアルケニルケテンダイマーに加えて、
ワックス、ビニルアルコール重合体、メラミン／ホルマリン重合体、スチレン／（メタ）アクリル酸共重合体、スチレン／（メタ）アクリル酸エステル共重合体、スチレン／（メタ）アクリル酸／（メタ）アクリル酸エステル共重合体、スチレン／マレイン酸共重合体、イソブチレン／（メタ）アクリル酸共重合体、ジイソブチレン／マレイン酸共重合体、プロピレン／マレイン酸共重合体、エチレン／マレイン酸共重合体、ポリ（メタ）アクリル単独重合体および共重合体、ならびに（メタ）アクリル酸エステル／アクリロニトリル共重合体からなる群から選択された少なくとも１種をも含む態様１～５のいずれかに記載の不織布用撥水撥油剤組成物。
態様７：
　撥水撥油剤組成物が、帯電防止剤および浸透剤から選択された少なくとも１種を含んでなるか、あるいは撥水撥油剤組成物を帯電防止剤および浸透剤から選択された少なくとも１種と併用する態様１～６のいずれかに記載の不織布用撥水撥油剤組成物。
態様８：
（１）撥水撥油剤、および
（２）サイズ剤
を有する不織布用撥水撥油剤キット。
態様９：
　不織布を態様１～７のいずれかに記載の不織布用撥水撥油剤組成物または態様８に記載の不織布用撥水撥油剤キットで処理する不織布の処理方法。
態様１０：
　態様１～７のいずれかに記載の不織布用撥水撥油剤組成物または態様８に記載の不織布用撥水撥油剤キットにおける撥水撥油重合体およびサイズ有効成分が付着している不織布製品。 The present disclosure provides a water and oil repellent composition containing a fluorine-containing water and oil repellent and a sizing agent.
Preferred aspects of the present disclosure are as follows.
Aspect 1:
(1) A fluorine-containing water and oil repellent agent and (2) a sizing agent, comprising a water-based nonwoven fabric water and oil repellent composition.
Aspect 2:
The water and oil repellent composition for non-woven fabrics according to aspect 1, which does not contain a carbodiimide compound and contains 20% by weight or more of water relative to the water and oil repellent composition.
Aspect 3:
The fluorine-containing water and oil repellent has the formula:
CH 2 =C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf
[Wherein, X 11 is a hydrogen atom, a monovalent organic group or a halogen atom;
Y 11 is —O— or —NH—;
Z 11 is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
3. The water and oil repellent composition for nonwoven fabric according to aspect 1 or 2, comprising a fluoropolymer having a repeating unit formed from the monomer represented by:
Aspect 4:
The effective sizing component in the sizing agent is alkyl ketene dimer, alkenyl ketene dimer, wax, vinyl alcohol polymer, melamine/formalin polymer, styrene/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid ester copolymer. coalescence, styrene/(meth)acrylic acid/(meth)acrylic acid ester copolymer, styrene/maleic acid copolymer, isobutylene/(meth)acrylic acid copolymer, diisobutylene/maleic acid copolymer, propylene/ At least one selected from the group consisting of maleic acid copolymers, ethylene/maleic acid copolymers, poly(meth)acrylic homopolymers and copolymers, and (meth)acrylate/acrylonitrile copolymers The water and oil repellent composition for nonwoven fabric according to any one of certain aspects 1 to 3.
Aspect 5:
5. The water and oil repellent composition for nonwoven fabrics according to any one of aspects 1 to 4, wherein the effective sizing component in the sizing agent comprises an alkyl ketene dimer and/or an alkenyl ketene dimer.
Aspect 6:
The sizing active ingredient in the sizing agent is
In addition to alkylketene dimers and/or alkenylketene dimers,
Wax, vinyl alcohol polymer, melamine/formalin polymer, styrene/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid ester copolymer, styrene/(meth)acrylic acid/(meth)acrylic acid ester copolymer, styrene/maleic acid copolymer, isobutylene/(meth)acrylic acid copolymer, diisobutylene/maleic acid copolymer, propylene/maleic acid copolymer, ethylene/maleic acid copolymer, poly( The water repellent material for nonwoven fabrics according to any one of aspects 1 to 5, further comprising at least one selected from the group consisting of meth)acrylic homopolymers and copolymers, and (meth)acrylic acid ester/acrylonitrile copolymers. Oil repellent composition.
Aspect 7:
The water and oil repellent composition contains at least one selected from antistatic agents and penetrating agents, or the water and oil repellent composition is used in combination with at least one selected from antistatic agents and penetrating agents. The water and oil repellent composition for nonwoven fabric according to any one of aspects 1 to 6.
Aspect 8:
A nonwoven fabric water and oil repellent kit comprising (1) a water and oil repellent and (2) a sizing agent.
Aspect 9:
A method for treating a nonwoven fabric, comprising treating a nonwoven fabric with the water and oil repellent composition for nonwoven fabric according to any one of aspects 1 to 7 or the water and oil repellent agent kit for nonwoven fabric according to aspect 8.
Aspect 10:
A nonwoven fabric product to which the water and oil repellent polymer and the sizing active ingredient in the water and oil repellent composition for nonwoven fabric according to any one of aspects 1 to 7 or the water and oil repellent agent kit for nonwoven fabric according to aspect 8 are adhered.
　被処理物（特に不織布）に、良好な撥アルコール性、帯電防止性および耐水圧性を与える。 Gives good alcohol repellency, antistatic properties, and water pressure resistance to the object to be treated (especially nonwoven fabric).
　撥水撥油剤組成物は、含フッ素撥水撥油剤およびサイズ剤を含んでなる。
　撥水撥油剤組成物は、水系であることが好ましい。例えば、撥水撥油剤組成物は、水性分散液であることが好ましい。撥水撥油剤組成物が、撥水撥油剤組成物に対して、２０重量％以上、３０重量％以上、５０～９９.９重量％、または６０～９９重量％の水を含んでよい。
　撥水撥油剤組成物は、カルボジイミド化合物を含まないことが好ましい。 The water and oil repellent composition comprises a fluorine-containing water and oil repellent and a sizing agent.
The water and oil repellent composition is preferably water-based. For example, the water and oil repellent composition is preferably an aqueous dispersion. The water and oil repellent composition may contain water in an amount of 20 wt % or more, 30 wt % or more, 50 to 99.9 wt %, or 60 to 99 wt % relative to the water and oil repellent composition.
The water and oil repellent composition preferably does not contain a carbodiimide compound.
＜（１）含フッ素撥水撥油剤＞
　含フッ素撥水撥油剤は、含フッ素重合体（すなわち、撥水撥油性重合体）および水を含んでなる水性分散液（水性エマルション）であることが好ましい。含フッ素重合体が、撥水性および撥水性を与える有効成分である。 <(1) Fluorine-containing water and oil repellent>
The fluorine-containing water- and oil-repellent agent is preferably an aqueous dispersion (aqueous emulsion) containing a fluorine-containing polymer (that is, a water- and oil-repellent polymer) and water. A fluorine-containing polymer is an active ingredient that imparts water repellency and water repellency.
　撥水撥油剤組成物において、撥水撥油剤の有効成分（含フッ素重合体）とサイズ剤の有効成分（例えば、アルキルケテンダイマー）の重量比は、３０：７０～９５：５、５５：４５～９０：１０、６０：４０～８５：１５または６５：３５～８０：２０であってよい In the water and oil repellent composition, the weight ratio of the active ingredient of the water and oil repellent (fluoropolymer) to the active ingredient of the sizing agent (eg, alkylketene dimer) is 30:70 to 95:5, 55:45. may be ~90:10, 60:40-85:15 or 65:35-80:20
（Ａ）含フッ素重合体
　含フッ素重合体は、フルオロアルキル基を有する含フッ素単量体から誘導された繰り返し単位を有する重合体である。
　含フッ素重合体は、
フルオロアルキル基を有する含フッ素単量体から誘導された繰り返し単位を有する単独重合体、あるいは
フルオロアルキル基を有する含フッ素単量体から誘導された繰り返し単位、および共重合可能な他の重合性化合物から誘導された繰り返し単位を有する共重合体であってよい。
　含フッ素重合体は、ランダム重合体であっても、あるいはブロック重合体であってもよい。 (A) Fluoropolymer The fluoropolymer is a polymer having repeating units derived from a fluoromonomer having a fluoroalkyl group.
The fluoropolymer is
A homopolymer having a repeating unit derived from a fluoromonomer having a fluoroalkyl group, or a repeating unit derived from a fluoromonomer having a fluoroalkyl group, and other copolymerizable compounds It may be a copolymer having repeating units derived from.
The fluoropolymer may be a random polymer or a block polymer.
　本開示において、含フッ素重合体（Ａ）は、（Ａ１）フルオロアルキル基を有する含フッ素単量体から誘導された繰り返し単位のみからなってよいが、
繰り返し単位（Ａ１）に加えて、
（Ａ２）長鎖炭化水素基含有単量体から誘導された繰り返し単位、
（Ａ３）非架橋性単量体から誘導された繰り返し単位、および
（Ａ４）架橋性単量体から誘導された繰り返し単位
から選択された少なくも１種の繰り返し単位を有することが好ましい。 In the present disclosure, the fluoropolymer (A) may consist only of repeating units derived from (A1) a fluoromonomer having a fluoroalkyl group,
In addition to the repeating unit (A1),
(A2) a repeating unit derived from a long-chain hydrocarbon group-containing monomer;
It preferably has at least one repeating unit selected from (A3) a repeating unit derived from a non-crosslinkable monomer and (A4) a repeating unit derived from a crosslinkable monomer.
（Ａ１）含フッ素単量体
　含フッ素単量体は、一般に、パーフルオロアルキル基もしくはパーフルオロアルケニル基およびアクリル酸基もしくはメタクリル酸基もしくはα－置換アクリル酸基を有する重合性化合物である。 (A1) Fluorine-Containing Monomer The fluorine- containing monomer is generally a polymerizable compound having a perfluoroalkyl group or perfluoroalkenyl group and an acrylic acid group, a methacrylic acid group or an α-substituted acrylic acid group.
　含フッ素単量体（Ａ１）は式：
ＣＨ２＝Ｃ（－Ｘ１１）－Ｃ（＝Ｏ）－Ｙ１１－Ｚ１１－Ｒｆ
［式中、Ｘ１１は、水素原子、一価の有機基またはハロゲン原子であり、
Ｙ１１は、－Ｏ－または－ＮＨ－であり、
Ｚ１１は、直接結合または二価の有機基であり、
Ｒｆは、炭素数１～２０のフルオロアルキル基である。］
で示される化合物（アクリレートエステルまたはアクリルアミド）であることが好ましい。 The fluorine-containing monomer (A1) has the formula:
CH 2 =C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf
[Wherein, X 11 is a hydrogen atom, a monovalent organic group or a halogen atom;
Y 11 is —O— or —NH—;
Z 11 is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
is preferably a compound represented by (acrylate ester or acrylamide).
　Ｘ１１は、水素原子、炭素数１～２１の直鎖状または分岐状のアルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ1Ｘ2基（但し、Ｘ1およびＸ2は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。）、シアノ基、炭素数１～２１の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基であってよい。Ｘ１１の具体例は、Ｈ、ＣＨ３、Ｃｌ、Ｂｒ、Ｉ、Ｆ、ＣＮ、ＣＦ３である。Ｘ１１は、水素原子、メチル基または塩素原子であることが好ましく、メチル基であることが特に好ましい。 X 11 is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (provided that X 1 and X 2 are hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted It may be a substituted phenyl group. Specific examples of X 11 are H, CH 3 , Cl, Br, I, F, CN, CF 3 . X 11 is preferably a hydrogen atom, a methyl group or a chlorine atom, particularly preferably a methyl group.
　Ｙ１１は、－Ｏ－または－ＮＨ－である。Ｙ１１は、－Ｏ－であることが好ましい。 Y 11 is -O- or -NH-. Y 11 is preferably -O-.
　Ｚ１１は、直接結合、炭素数１～２０の直鎖状または分岐状脂肪族基（特に、アルキレン基）、例えば、式－（ＣＨ２）ｘ－（式中、ｘは１～１０である。）で示される基、あるいは、炭素数６～１８の芳香族基または環状脂肪族基、あるいは、式－Ｒ２（Ｒ１）Ｎ－ＳＯ２－または式－Ｒ２（Ｒ１）Ｎ－ＣＯ－で示される基（式中、Ｒ１は、炭素数１～１０のアルキル基であり、Ｒ２は、炭素数１～１０の直鎖アルキレン基または分枝状アルキレン基である。）、あるいは、式－ＣＨ２ＣＨ（ＯＲ３）ＣＨ２－（Ａｒ－Ｏ）p－（式中、Ｒ３は、水素原子、または、炭素数１～１０のアシル基（例えば、ホルミルまたはアセチルなど）、Ａｒは、置換基を必要により有するアリーレン基、ｐは０または１を表す。）で示される基、あるいは、式－ＣＨ２－Ａｒ－(Ｏ)ｑ－（式中、Ａｒは、置換基を必要により有するアリーレン基、ｑは０または１である。）で示される基、-(CH2)m－SO2－(CH2)n－基または -(CH2)m－S－(CH2)n－基（但し、mは１～１０、nは０～１０、である）であってよい。 Z 11 is a direct bond, a linear or branched aliphatic group (especially an alkylene group) having 1 to 20 carbon atoms, such as the formula —(CH 2 ) x — (wherein x is 1 to 10) ), or an aromatic or cycloaliphatic group having 6 to 18 carbon atoms, or a group of the formula -R 2 (R 1 )N-SO 2 - or the formula -R 2 (R 1 )N- a group represented by CO— (wherein R 1 is an alkyl group having 1 to 10 carbon atoms and R 2 is a linear or branched alkylene group having 1 to 10 carbon atoms), Alternatively, the formula —CH 2 CH(OR 3 )CH 2 —(Ar—O) p — (wherein R 3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (e.g., formyl, acetyl, etc.) , Ar is an arylene group optionally having a substituent, p represents 0 or 1.), or a group represented by the formula —CH 2 —Ar—(O) q — (wherein Ar is a substituent and q is 0 or 1.), -(CH 2 ) m -SO 2 -(CH 2 ) n - group or -(CH 2 ) m -S-(CH 2 ) may be an n -group, where m is from 1 to 10 and n is from 0 to 10;
　あるいは、Ｚ１１は、炭素数１～１０の脂肪族基、炭素数６～１８の芳香族基または環状脂肪族基、-CH2CH2N(R1)SO2－基（但し、R1は炭素数１～４のアルキル基である。）、
-CH2CH(OZ1)CH2-(Ph-O)p-基（但し、Z1は水素原子またはアセチル基、Phはフェニレン基、ｐは０または１である。）、-(CH2)n-Ph-O-基（但し、Phはフェニレン基、ｎは０～１０である。）、-(CH2)m－SO2－(CH2)n－基または  -(CH2)m－S－(CH2)n－基（但し、mは１～１０、nは０～１０、である）であることが好ましい。脂肪族基は、アルキレン基（特に炭素数は１～４、例えば１または２である。）であることが好ましい。芳香族基または環状脂肪族基は、置換または非置換であってよい。S 基または SO2基はRf基に直接に結合していてよい。 Alternatively, Z 11 is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cycloaliphatic group having 6 to 18 carbon atoms, or a —CH 2 CH 2 N(R 1 )SO 2 — group (with the proviso that R 1 is an alkyl group having 1 to 4 carbon atoms.),
-CH2CH ( OZ1 ) CH2- (Ph-O) p- group (where Z1 is a hydrogen atom or an acetyl group, Ph is a phenylene group, and p is 0 or 1), -( CH2 ) n —Ph—O— group (where Ph is a phenylene group and n is 0 to 10), —(CH 2 ) m —SO 2 —(CH 2 ) n — group or —(CH 2 ) m It is preferably a -S-(CH 2 ) n - group (where m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly having 1 to 4, eg 1 or 2, carbon atoms). An aromatic or cycloaliphatic group may be substituted or unsubstituted. The S group or SO2 group may be attached directly to the Rf group.
　Ｒｆ基は、パーフルオロアルキル基であることが好ましい。Ｒｆ基の炭素数は、1～１２、例えば１～６、特に４～６、特別に６であることが好ましい。Ｒｆ基の例は、－ＣＦ3、－ＣＦ2ＣＦ3、－ＣＦ2ＣＦ2ＣＦ3、－ＣＦ(ＣＦ3) 2、－ＣＦ2ＣＦ2ＣＦ2ＣＦ3、－ＣＦ2ＣＦ(ＣＦ3)2、－Ｃ(ＣＦ３)3、－(ＣＦ2)4ＣＦ3、－(ＣＦ2)2ＣＦ(ＣＦ3)2、－ＣＦ2Ｃ(ＣＦ3)3、－ＣＦ(ＣＦ3)ＣＦ2ＣＦ2ＣＦ3、－(ＣＦ2)5ＣＦ3、－(ＣＦ2)3ＣＦ(ＣＦ3)2、－(ＣＦ2)4ＣＦ(ＣＦ3)2、－Ｃ8Ｆ17等である。 The Rf group is preferably a perfluoroalkyl group. The Rf group preferably has 1 to 12 carbon atoms, such as 1 to 6 carbon atoms, especially 4 to 6 carbon atoms, especially 6 carbon atoms. Examples of Rf groups are -CF3 , -CF2CF3 , -CF2CF2CF3 , -CF ( CF3 ) 2 , -CF2CF2CF2CF3 , -CF2CF ( CF3 ) 2 , -C( CF3 ) 3 , -( CF2 ) 4CF3 , -( CF2 ) 2CF ( CF3 ) 2 , -CF2C ( CF3 ) 3 , -CF( CF3 ) CF2 CF 2 CF 3 , -(CF 2 ) 5 CF 3 , -(CF 2 ) 3 CF(CF 3 ) 2 , -(CF 2 ) 4 CF(CF 3 ) 2 , -C 8 F 17 and the like.
　含フッ素単量体の具体例としては、例えば以下のものを例示できるが、これらに限定されるものではない。
　　CH2=C(－H)－C(=O)－O－(CH2)2－Rf
　　CH2=C(－H)－C(=O)－O－C6H4－Rf
　　CH2=C(－Cl)－C(=O)－O－(CH2)2－Rf
　　CH2=C(－H)－C(=O)－O－(CH2)2N(－CH3) SO2－Rf
　　CH2=C(－H)－C(=O)－O－(CH2)2N(－C2H5) SO2－Rf
　　CH2=C(－H)－C(=O)－O－CH2CH(－OH) CH2－Rf Specific examples of the fluorine-containing monomer include, but are not limited to, the following.
CH2 =C(-H)-C(=O)-O-( CH2 ) 2 -Rf
CH2 =C(-H) -C (=O)-O- C6H4 -Rf
CH2 =C(-Cl)-C(=O)-O-( CH2 ) 2 -Rf
CH2 =C(-H)-C(=O)-O-( CH2 ) 2N ( -CH3 )SO2 - Rf
CH2 = C (-H)-C(=O)-O-( CH2 ) 2N ( -C2H5 )SO2 - Rf
CH2 =C(-H)-C(=O)-O- CH2CH (-OH)CH2 - Rf
　　CH2=C(－H)－C(=O)－O－CH2CH(－OCOCH3) CH2－Rf
　　CH2=C(－H)－C(=O)－O－(CH2)2－S－Rf
　　CH2=C(－H)－C(=O)－O－(CH2)2－S－(CH2)2－Rf
　　CH2=C(－H)－C(=O)－O－(CH2)3－SO2－Rf
　　CH2=C(－H)－C(=O)－O－(CH2)2－SO2－(CH2)2－Rf
　　CH2=C(－H)－C(=O)－NH－(CH2)2－Rf
　　CH2=C(－CH3)－C(=O)－O－(CH2)2－S－Rf
　　CH2=C(－CH3)－C(=O)－O－(CH2)2－S－(CH2)2－Rf
　　CH2=C(－CH3)－C(=O)－O－(CH2)3－SO2－Rf
　　CH2=C(－CH3)－C(=O)－O－(CH2)2－SO2－(CH2)2－Rf
　　CH2=C(－CH3)－C(=O)－NH－(CH2)2－Rf CH2 =C(-H)-C(=O)-O- CH2CH ( -OCOCH3 ) CH2 -Rf
CH2 =C(-H)-C(=O)-O-( CH2 ) 2 -S-Rf
CH2 =C(-H)-C(=O)-O-( CH2 ) 2- S-( CH2 ) 2 -Rf
CH2 =C(-H)-C(=O)-O-( CH2 ) 3- SO2 -Rf
CH2 =C(-H)-C(=O)-O-( CH2 ) 2- SO2- ( CH2 ) 2- Rf
CH2 =C(-H)-C(=O)-NH-( CH2 ) 2 -Rf
CH2 =C( -CH3 )-C(=O)-O-( CH2 ) 2- S-Rf
CH2 =C( -CH3 )-C(=O)-O-( CH2 ) 2- S-( CH2 ) 2- Rf
CH2 =C( -CH3 )-C(=O)-O-( CH2 ) 3- SO2 -Rf
CH2 =C( -CH3 )-C(=O)-O-( CH2 ) 2- SO2- ( CH2 ) 2 -Rf
CH2 =C( -CH3 )-C(=O)-NH-( CH2 ) 2- Rf
　　CH2=C(－F)－C(=O)－O－(CH2)2－S－Rf
　　CH2=C(－F)－C(=O)－O－(CH2)2－S－(CH2)2－Rf
　　CH2=C(－F)－C(=O)－O－(CH2)2－SO2－Rf
　　CH2=C(－F)－C(=O)－O－(CH2)2－SO2－(CH2)2－Rf
　　CH2=C(－F)－C(=O)－NH－(CH2)2－Rf
　　CH2=C(－Cl)－C(=O)－O－(CH2)2－S－Rf
　　CH2=C(－Cl)－C(=O)－O－(CH2)2－S－(CH2)2－Rf
　　CH2=C(－Cl)－C(=O)－O－(CH2)2－SO2－Rf
　　CH2=C(－Cl)－C(=O)－O－(CH2)2－SO2－(CH2)2－Rf
　　CH2=C(－Cl)－C(=O)－NH－(CH2)2－Rf CH2 =C(-F)-C(=O)-O-( CH2 ) 2 -S-Rf
CH2 =C(-F)-C(=O)-O-( CH2 ) 2- S-( CH2 ) 2 -Rf
CH2 =C(-F)-C(=O)-O-( CH2 ) 2- SO2 -Rf
CH2 =C(-F)-C(=O)-O-( CH2 ) 2- SO2- ( CH2 ) 2- Rf
CH2 =C(-F)-C(=O)-NH-( CH2 ) 2 -Rf
CH2 =C(-Cl)-C(=O)-O-( CH2 ) 2 -S-Rf
CH2 =C(-Cl)-C(=O)-O-( CH2 ) 2- S-( CH2 ) 2 -Rf
CH2 =C(-Cl)-C(=O)-O-( CH2 ) 2- SO2 -Rf
CH2 =C(-Cl)-C(=O)-O-( CH2 ) 2- SO2- ( CH2 ) 2- Rf
CH2 =C(-Cl)-C(=O)-NH-( CH2 ) 2 -Rf
　　CH2=C(－CF3)－C(=O)－O－(CH2)2－S－Rf
　　CH2=C(－CF3)－C(=O)－O－(CH2)2－S－(CH2)2－Rf
　　CH2=C(－CF3)－C(=O)－O－(CH2)2－SO2－Rf
　　CH2=C(－CF3)－C(=O)－O－(CH2)2－SO2－(CH2)2－Rf
　　CH2=C(－CF3)－C(=O)－NH－(CH2)2－Rf
　　CH2=C(－CF2H)－C(=O)－O－(CH2)2－S－Rf
　　CH2=C(－CF2H)－C(=O)－O－(CH2)2－S－(CH2)2－Rf
　　CH2=C(－CF2H)－C(=O)－O－(CH2)2－SO2－Rf
　　CH2=C(－CF2H)－C(=O)－O－(CH2)2－SO2－(CH2)2－Rf
　　CH2=C(－CF2H)－C(=O)－NH－(CH2)2－Rf
　　CH2=C(－CN)－C(=O)－O－(CH2)2－S－Rf
　　CH2=C(－CN)－C(=O)－O－(CH2)2－S－(CH2)2－Rf
　　CH2=C(－CN)－C(=O)－O－(CH2)2－SO2－Rf
　　CH2=C(－CN)－C(=O)－O－(CH2)2－SO2－(CH2)2－Rf
　　CH2=C(－CN)－C(=O)－NH－(CH2)2－Rf CH2 =C( -CF3 )-C(=O)-O-( CH2 ) 2- S-Rf
CH2 =C( -CF3 )-C(=O)-O-( CH2 ) 2- S-( CH2 ) 2- Rf
CH2 =C( -CF3 )-C(=O)-O-( CH2 ) 2- SO2 -Rf
CH2 =C( -CF3 )-C(=O)-O-( CH2 ) 2- SO2- ( CH2 ) 2 -Rf
CH2 =C( -CF3 )-C(=O)-NH-( CH2 ) 2- Rf
CH2 =C( -CF2H )-C(=O)-O-( CH2 ) 2- S-Rf
CH2 =C( -CF2H )-C(=O)-O-( CH2 ) 2- S-( CH2 ) 2- Rf
CH2 =C( -CF2H )-C(=O)-O-( CH2 ) 2- SO2 -Rf
CH2 =C( -CF2H )-C(=O)-O-( CH2 ) 2- SO2- ( CH2 ) 2 -Rf
CH2 =C( -CF2H )-C(=O)-NH-( CH2 ) 2- Rf
CH2 =C(-CN)-C(=O)-O-( CH2 ) 2 -S-Rf
CH2 =C(-CN)-C(=O)-O-( CH2 ) 2- S-( CH2 ) 2 -Rf
CH2 =C(-CN)-C(=O)-O-( CH2 ) 2- SO2 -Rf
CH2 =C(-CN)-C(=O)-O-( CH2 ) 2- SO2- ( CH2 ) 2- Rf
CH2 =C(-CN)-C(=O)-NH-( CH2 ) 2 -Rf
　　CH2=C(－CF2CF3)－C(=O)－O－(CH2)2－S－Rf
　　CH2=C(－CF2CF3)－C(=O)－O－(CH2)2－S－(CH2)2－Rf
　　CH2=C(－CF2CF3)－C(=O)－O－(CH2)2－SO2－Rf
　　CH2=C(－CF2CF3)－C(=O)－O－(CH2)2－SO2－(CH2)2－Rf
　　CH2=C(－CF2CF3)－C(=O)－NH－(CH2)2－Rf
　　CH2=C(－F)－C(=O)－O－(CH2)3－S－Rf
　　CH2=C(－F)－C(=O)－O－(CH2)3－S－(CH2)2－Rf
　　CH2=C(－F)－C(=O)－O－(CH2)3－SO2－Rf
　　CH2=C(－F)－C(=O)－O－(CH2)3－SO2－(CH2)2－Rf
　　CH2=C(－F)－C(=O)－NH－(CH2)3－Rf CH2 =C( -CF2CF3 )-C(=O)-O-( CH2 ) 2 - S-Rf
CH2 =C( -CF2CF3 )-C(=O)-O-( CH2 ) 2- S- ( CH2 ) 2 -Rf
CH2 =C( -CF2CF3 )-C(=O) -O- ( CH2 ) 2- SO2 -Rf
CH2 =C( -CF2CF3 ) -C (=O)-O-( CH2 ) 2- SO2- ( CH2 ) 2- Rf
CH2 =C( -CF2CF3 )-C(=O)-NH- ( CH2 ) 2 -Rf
CH2 =C(-F)-C(=O)-O-( CH2 ) 3 -S-Rf
CH2 =C(-F)-C(=O)-O-( CH2 ) 3 -S-( CH2 ) 2 -Rf
CH2 =C(-F)-C(=O)-O-( CH2 ) 3- SO2 -Rf
CH2 =C(-F)-C(=O)-O-( CH2 ) 3- SO2- ( CH2 ) 2- Rf
CH2 =C(-F)-C(=O)-NH-( CH2 ) 3 -Rf
　　CH2=C(－Cl)－C(=O)－O－(CH2)3－S－Rf
　　CH2=C(－Cl)－C(=O)－O－(CH2)3－S－(CH2)2－Rf
　　CH2=C(－Cl)－C(=O)－O－(CH2)3－SO2－Rf
　　CH2=C(－Cl)－C(=O)－O－(CH2)3－SO2－(CH2)2－Rf
　　CH2=C(－CF3)－C(=O)－O－(CH2)3－S－Rf
　　CH2=C(－CF3)－C(=O)－O－(CH2)3－S－(CH2)2－Rf
　　CH2=C(－CF3)－C(=O)－O－(CH2)3－SO2－Rf
　　CH2=C(－CF3)－C(=O)－O－(CH2)3－SO2－(CH2)2－Rf
　　CH2=C(－CF2H)－C(=O)－O－(CH2)3－S－Rf
　　CH2=C(－CF2H)－C(=O)－O－(CH2)3－S－(CH2)2－Rf
　　CH2=C(－CF2H)－C(=O)－O－(CH2)3－SO2－Rf
　　CH2=C(－CF2H)－C(=O)－O－(CH2)3－SO2－(CH2)2－Rf CH2 =C(-Cl)-C(=O)-O-( CH2 ) 3 -S-Rf
CH2 =C(-Cl)-C(=O)-O-( CH2 ) 3 -S-( CH2 ) 2 -Rf
CH2 =C(-Cl)-C(=O)-O-( CH2 ) 3- SO2 -Rf
CH2 =C(-Cl)-C(=O)-O-( CH2 ) 3- SO2- ( CH2 ) 2- Rf
CH2 =C( -CF3 )-C(=O)-O-( CH2 ) 3 -S-Rf
CH2 =C( -CF3 )-C(=O)-O-( CH2 ) 3- S-( CH2 ) 2- Rf
CH2 =C( -CF3 )-C(=O)-O-( CH2 ) 3- SO2 -Rf
CH2 =C( -CF3 )-C(=O)-O-( CH2 ) 3- SO2- ( CH2 ) 2 -Rf
CH2 =C( -CF2H )-C(=O)-O-( CH2 ) 3 -S-Rf
CH2 =C( -CF2H )-C(=O)-O-( CH2 ) 3- S-( CH2 ) 2- Rf
CH2 =C( -CF2H )-C(=O)-O-( CH2 ) 3 - SO2 -Rf
CH2 =C( -CF2H )-C(=O)-O-( CH2 ) 3- SO2- ( CH2 ) 2 -Rf
　　CH2=C(－CN)－C(=O)－O－(CH2)3－S－Rf
　　CH2=C(－CN)－C(=O)－O－(CH2)3－S－(CH2)2－Rf
　　CH2=C(－CN)－C(=O)－O－(CH2)3－SO2－Rf
　　CH2=C(－CN)－C(=O)－O－(CH2)3－SO2－(CH2)2－Rf
　　CH2=C(－CF2CF3)－C(=O)－O－(CH2)3－S－Rf
　　CH2=C(－CF2CF3)－C(=O)－O－(CH2)3－S－(CH2)2－Rf
　　CH2=C(－CF2CF3)－C(=O)－O－(CH2)3－SO2－Rf
　　CH2=C(－CF2CF3)－C(=O)－O－(CH2)2－SO2－(CH2)2－Rf
[上記式中、Ｒｆは、炭素数１～２０のフルオロアルキル基である。] CH2 =C(-CN)-C(=O)-O-( CH2 ) 3 -S-Rf
CH2 =C(-CN)-C(=O)-O-( CH2 ) 3 -S-( CH2 ) 2 -Rf
CH2 =C(-CN)-C(=O)-O-( CH2 ) 3- SO2- Rf
CH2 =C(-CN)-C(=O)-O-( CH2 ) 3- SO2- ( CH2 ) 2- Rf
CH2 =C( -CF2CF3 )-C(=O) -O- ( CH2 ) 3 -S-Rf
CH2 =C( -CF2CF3 )-C(=O)-O-( CH2 ) 3 - S-( CH2 ) 2 -Rf
CH2 =C( -CF2CF3 )-C(=O)-O-( CH2 ) 3 - SO2 -Rf
CH2 =C( -CF2CF3 ) -C (=O)-O-( CH2 ) 2- SO2- ( CH2 ) 2- Rf
[In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
　含フッ素単量体は、１種であっても、または２種以上の組み合わせであってもよい。
　２種以上の含フッ素単量体の組み合わせの例として、
Ｘ１１が水素原子である単量体１とＸ１１がメチル基である単量体２の組み合わせ、
Ｘ１１が水素原子である単量体１とＸ１１が塩素原子である単量体２の組み合わせ、
Ｘ１１がメチル基である単量体１とＸ１１がハロゲン原子である単量体２の組み合わせ、
が挙げられる。組み合わせにおいて、単量体１と単量体２のモル比は、１０：９０～９０：１０または３０：７０～７０：３０であってよい。 The fluorine-containing monomer may be used singly or in combination of two or more.
Examples of combinations of two or more fluorine-containing monomers include
a combination of monomer 1 in which X 11 is a hydrogen atom and monomer 2 in which X 11 is a methyl group;
a combination of monomer 1 in which X 11 is a hydrogen atom and monomer 2 in which X 11 is a chlorine atom;
a combination of monomer 1 in which X 11 is a methyl group and monomer 2 in which X 11 is a halogen atom;
is mentioned. In combination, the molar ratio of monomer 1 to monomer 2 may be from 10:90 to 90:10 or from 30:70 to 70:30.
（Ａ２）長鎖炭化水素基含有単量体
　長鎖炭化水素基含有単量体は、フルオロアルキル基を有しない。あるいは、長鎖炭化水素基含有単量体は、フッ素原子を含有しない。
　長鎖炭化水素基は、飽和または不飽和の基である。長鎖炭化水素基は飽和の炭化水素基、特にアルキル基であることが好ましい。 (A2) Long-chain hydrocarbon group-containing monomer The long-chain hydrocarbon group-containing monomer does not have a fluoroalkyl group. Alternatively, the long-chain hydrocarbon group-containing monomer does not contain fluorine atoms.
A long-chain hydrocarbon group is a saturated or unsaturated group. The long-chain hydrocarbon group is preferably a saturated hydrocarbon group, especially an alkyl group.
　長鎖炭化水素基は、炭素数７～４０の直鎖状または分岐状の炭化水素基であることが好ましい。直鎖状または分岐状の炭化水素基の炭素数は、１０～４０または１２～４０または１８～４０であってよい。直鎖状または分岐状の炭化水素基は、炭素数好ましくは１２～４０、より好ましくは１２～３０、特に１８～２８、特別に１８～２２（または１８～２４）であることが好ましく、一般に飽和の脂肪族炭化水素基、特にアルキル基であることが好ましい。長鎖炭化水素基はステアリル基、イコシル基またはベヘニル基であることが特に好ましい。 The long-chain hydrocarbon group is preferably a straight or branched hydrocarbon group having 7 to 40 carbon atoms. The number of carbon atoms in the linear or branched hydrocarbon group may be 10-40 or 12-40 or 18-40. The linear or branched hydrocarbon group preferably has 12 to 40 carbon atoms, more preferably 12 to 30 carbon atoms, particularly 18 to 28 carbon atoms, especially 18 to 22 carbon atoms (or 18 to 24 carbon atoms), and generally A saturated aliphatic hydrocarbon group, particularly an alkyl group is preferred. Particularly preferably, the long-chain hydrocarbon group is stearyl, icosyl or behenyl.
　長鎖炭化水素基含有単量体は、式：
ＣＨ2＝Ｃ(－Ｘ)－Ｃ(＝Ｏ)－Ｙ－Ｒｎ
［式中、Ｘは、水素原子、一価の有機基またはハロゲン原子であり、
Ｙは、－Ｏ－および－ＮＨ－から選択された少なくとも１つの基を有する２価～４価の連結基であり、
Ｒは、炭素数７～４０の炭化水素基であり、
ｎは１～３の整数である。］
で示される単量体であることが好ましい。 The long-chain hydrocarbon group-containing monomer has the formula:
CH 2 =C(-X)-C(=O)-Y-R n
[Wherein, X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is a divalent to tetravalent linking group having at least one group selected from -O- and -NH-,
R is a hydrocarbon group having 7 to 40 carbon atoms,
n is an integer of 1-3. ]
is preferably a monomer represented by
　Ｘは、水素原子、メチル基、フッ素原子を除くハロゲン、置換または非置換のベンジル基、置換または非置換のフェニル基であってよい。Ｘの例は、水素原子、メチル基、塩素原子、臭素原子、ヨウ素原子、シアノ基である。Ｘは、水素原子、メチル基、塩素原子であることが好ましい。 X may be a hydrogen atom, a methyl group, a halogen excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of X are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, cyano group. X is preferably a hydrogen atom, a methyl group or a chlorine atom.
　Ｙは、２価～４価の基である。Ｙは、２価の基であることが好ましい。
　Ｙは、炭素数１の炭化水素基、－Ｃ６Ｈ６－、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ（Ｃ＝Ｏ）２－または－ＮＨ－から選ばれる少なくとも１つ以上によって構成される基（但し、炭化水素基を除く）であることが好ましい。炭素数１の炭化水素基の例として、－ＣＨ２－、－ＣＨ＝または－Ｃ≡が挙げられる。 Y is a divalent to tetravalent group. Y is preferably a divalent group.
Y is at least one or more selected from a hydrocarbon group having 1 carbon atom, -C 6 H 6 -, -O-, -C(=O)-, -S(C=O) 2 - or -NH- It is preferably a group (excluding a hydrocarbon group) constituted by: Examples of C 1 hydrocarbon groups include -CH 2 -, -CH= or -C≡.
　Ｙの例は、－Ｙ’－、－Ｙ’－Ｃ(＝Ｏ)－、－Ｃ(＝Ｏ)－Ｙ’－、－Ｙ’－Ｃ(＝Ｏ)－Ｙ’－、－Ｙ’－Ｃ(＝Ｏ)－Ｙ’－、－Ｙ’－Ｒ’－、－Ｙ’－Ｒ’－Ｙ’－、－Ｙ’－Ｒ’－Ｙ’－Ｃ（＝Ｏ）－、－Ｙ’－Ｒ’－Ｃ（＝Ｏ）－Ｙ’－、－Ｙ’－Ｒ’－Ｙ’－Ｃ（＝Ｏ）－Ｙ’－、または－Ｙ’－Ｒ’－Ｙ’－Ｒ’－
［式中、Ｙ’は、直接結合、－Ｏ－または－ＮＨ－であり、
Ｒ’は－(ＣＨ２）m－（ｍは１～５の整数である）または－Ｃ６Ｈ６－（フェニレン基）である。］
である。 Examples of Y are -Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'- C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'- R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'-
[wherein Y' is a direct bond, -O- or -NH-,
R' is -(CH 2 ) m - (m is an integer of 1 to 5) or -C 6 H 6 - (phenylene group). ]
is.
　Ｙの具体例として、－Ｏ－、－ＮＨ－、－Ｏ－Ｃ(＝Ｏ)－、－Ｃ(＝Ｏ)－ＮＨ－、－ＮＨ－Ｃ(＝Ｏ)－、－Ｏ－Ｃ(＝Ｏ)－ＮＨ－、－ＮＨ－Ｃ(＝Ｏ)－Ｏ－、－ＮＨ－Ｃ(＝Ｏ)－ＮＨ－、－Ｏ－Ｃ６Ｈ６－、－Ｏ－(ＣＨ２）m－Ｏ－、－ＮＨ－(ＣＨ２）m－ＮＨ－、－Ｏ－(ＣＨ２）m－ＮＨ－、－ＮＨ－(ＣＨ２）m－Ｏ－、－Ｏ－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－、－Ｏ－(ＣＨ２）m－Ｃ（＝Ｏ）－Ｏ－、－ＮＨ－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－、－ＮＨ－(ＣＨ２）m－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－ＮＨ－、－Ｏ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－(ＣＨ２）m－Ｃ（＝Ｏ）－ＮＨ－、－Ｏ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－、－Ｏ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－ＮＨ－、－Ｏ－(ＣＨ２）m－Ｏ－Ｃ６Ｈ６－、－ＮＨ－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－ＮＨ－、－ＮＨ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－Ｏ－、－ＮＨ－(ＣＨ２）m－Ｃ（＝Ｏ）－ＮＨ－、－ＮＨ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－、－ＮＨ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－ＮＨ－、－ＮＨ－(ＣＨ２）m－Ｏ－Ｃ６Ｈ６－、－ＮＨ－(ＣＨ２）m－ＮＨ－Ｃ６Ｈ６－
［式中、ｍは１～５の整数、特に２または４である。］
が挙げられる。 Specific examples of Y include -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(= O)—NH—, —NH—C(=O)—O—, —NH—C(=O)—NH—, —O—C 6 H 6 —, —O—(CH 2 ) m —O— , -NH-(CH 2 ) m -NH-, -O-(CH 2 ) m -NH-, -NH-(CH 2 ) m -O-, -O-(CH 2 ) m -OC( =O)-, -O-(CH 2 ) m -C(=O)-O-, -NH-(CH 2 ) m -O-C(=O)-, -NH-(CH 2 ) m - C(=O)-O-, -O-(CH 2 ) m -O-C(=O)-NH-, -O-(CH 2 ) m -NH-C(=O)-O-,- O-(CH 2 ) m -C(=O)-NH-, -O-(CH 2 ) m -NH-C(=O)-, -O-(CH 2 ) m -NH-C(=O )—NH—, —O—(CH 2 ) m —OC 6 H 6 —, —NH—(CH 2 ) m —OC(=O)—NH—, —NH—(CH 2 ) m -NH-C(=O)-O-, -NH-(CH 2 ) m -C(=O)-NH-, -NH-(CH 2 ) m -NH-C(=O)-, -NH -(CH 2 ) m -NH-C(=O)-NH-, -NH-(CH 2 ) m -O-C 6 H 6 -, -NH-(CH 2 ) m -NH-C 6 H 6 -
[wherein m is an integer of 1 to 5, especially 2 or 4; ]
is mentioned.
　Ｙは、－Ｏ－、－ＮＨ－、－Ｏ－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－、－Ｏ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－、－Ｏ－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－ＮＨ－、－Ｏ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－ＮＨ－
［式中、ｍは１～５の整数、特に２または４である。］
であることがさらに好ましい。Ｙは、－Ｏ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－であることが特に好ましい。 Y is -O-, -NH-, -O-(CH 2 ) m -O-C(=O)-, -O-(CH 2 ) m -NH-C(=O)-, -O- (CH 2 ) m —O—C(=O)—NH—, —O—(CH 2 ) m —NH—C(=O)—O—, —O—(CH 2 ) m —NH—C( =O)-NH-
[wherein m is an integer of 1 to 5, especially 2 or 4; ]
is more preferable. Y is particularly preferably -O-(CH 2 ) m -NH-C(=O)-.
　Ｙは、－Ｏ－、－ＮＨ－、－Ｏ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－、－Ｏ－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－ＮＨ－、－Ｏ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－ＮＨ－
［式中、ｍは１～５の整数、特に２または４である。］
であることが特に好ましい。 Y is -O-, -NH-, -O-(CH 2 ) m -NH-C(=O)-, -O-(CH 2 ) m -OC(=O)-NH-, - O-(CH 2 ) m -NH-C(=O)-O-, -O-(CH 2 ) m -NH-C(=O)-NH-
[wherein m is an integer of 1 to 5, especially 2 or 4; ]
is particularly preferred.
　Ｒは、直鎖状または分岐状の炭化水素基であることが好ましい。炭化水素基は、特に直鎖状の炭化水素基であってよい。炭化水素基は、脂肪族炭化水素基、特に飽和の脂肪族炭化水素基、特別にアルキル基であることが好ましい。炭水水素基の炭素数は、１２～３０、例えば１６～２６、特に１８～２２であることが好ましい。 R is preferably a linear or branched hydrocarbon group. The hydrocarbon radicals may in particular be linear hydrocarbon radicals. The hydrocarbon groups are preferably aliphatic hydrocarbon groups, especially saturated aliphatic hydrocarbon groups, especially alkyl groups. The number of carbon atoms in the hydrocarbon group is preferably 12-30, for example 16-26, especially 18-22.
　ｎは１～３の整数、好ましくは１である。
　Ｙが４価の炭素数１の炭化水素基を有する場合、ｎ＝３であることが好ましい。Ｙが３価の炭素数１の炭化水素基を有する場合、ｎ＝２であることが好ましい。Ｙが３価および４価の炭素数１の炭化水素基を有しない場合に、ｎ＝１である。 n is an integer of 1 to 3, preferably 1;
When Y has a tetravalent C 1 hydrocarbon group, n=3 is preferred. When Y has a trivalent C 1 hydrocarbon group, n=2 is preferred. n=1 when Y does not have a trivalent or tetravalent C 1 hydrocarbon group.
　長鎖炭化水素基含有単量体（Ａ２）の例は、
（ａ１）Ｃ(＝Ｏ)－Ｏ－またはＣ(＝Ｏ)－ＮＨ－が炭素数７～４０の炭化水素基に直接に結合しているアクリル単量体、および
（ａ２）Ｃ(＝Ｏ)－Ｏ－またはＣ(＝Ｏ)－ＮＨ－が炭素数７～４０の炭化水素基に直接に結合していないアクリル単量体である。 Examples of the long-chain hydrocarbon group-containing monomer (A2) are
(a1) an acrylic monomer in which C(=O)-O- or C(=O)-NH- is directly bonded to a hydrocarbon group having 7 to 40 carbon atoms, and (a2) C(=O )--O-- or C(=O)--NH-- is an acrylic monomer in which a hydrocarbon group having 7 to 40 carbon atoms is not directly bonded.
　アクリル単量体（ａ２）は、アクリル単量体（ａ１）と異なった化合物である。
　アクリル単量体（ａ２）は、（Ｃ(＝Ｏ)－Ｏ－またはＣ(＝Ｏ)－ＮＨ－に直接に結合しておらず、炭素数７～４０の炭化水素基に直接に結合する）アミド基、ウレタン基またはウレア基を有する（メタ）アクリレートまたは（メタ）アクリルアミドであってよい。含窒素単量体は、Ｃ(＝Ｏ)－Ｏ－またはＣ(＝Ｏ)－ＮＨ－に直接に結合していないアミド基であって、炭素数７～４０の炭化水素基に直接に結合するアミド基を有するアクリレートであることが好ましい。 The acrylic monomer (a2) is a compound different from the acrylic monomer (a1).
The acrylic monomer (a2) is not directly bonded to (C(=O)-O- or C(=O)-NH-, but is directly bonded to a hydrocarbon group having 7 to 40 carbon atoms. ) (meth)acrylates or (meth)acrylamides with amide, urethane or urea groups. The nitrogen-containing monomer is an amide group that is not directly bonded to C(=O)-O- or C(=O)-NH- and is directly bonded to a hydrocarbon group having 7 to 40 carbon atoms. It is preferably an acrylate having an amide group that
（ａ１）アクリル単量体
　アクリル単量体（ａ１）は、式：
　ＣＨ2＝Ｃ(－Ｘ１)－Ｃ(＝Ｏ)－Ｙ１－Ｒ１
［式中、Ｘ１は、水素原子、一価の有機基またはハロゲン原子であり、
　Ｙ１は、－Ｏ－または－ＮＨ－であり、
　Ｒ１は、炭素数７～４０の炭化水素基である。］
で示される化合物であることが好ましい。 (a1) Acrylic monomer Acrylic monomer (a1) has the formula:
CH 2 =C(-X 1 )-C(=O)-Y 1 -R 1
[Wherein, X 1 is a hydrogen atom, a monovalent organic group or a halogen atom;
Y 1 is -O- or -NH-,
R 1 is a hydrocarbon group having 7 to 40 carbon atoms. ]
It is preferably a compound represented by.
　アクリル単量体（ａ１）は、Ｙ１が－Ｏ－である長鎖アクリレートエステル単量体、またはＹ１が－ＮＨ－である長鎖アクリルアミド単量体である。 Acrylic monomer (a1) is a long chain acrylate ester monomer in which Y 1 is —O— or a long chain acrylamide monomer in which Y 1 is —NH—.
　Ｘ１は、水素原子、メチル基、フッ素原子を除くハロゲン、置換または非置換のベンジル基、置換または非置換のフェニル基であってよい。Ｘ１の例は、水素原子、メチル基、塩素原子、臭素原子、ヨウ素原子、シアノ基である。Ｘ１は、水素原子、メチル基、塩素原子であることが好ましい。 X 1 may be a hydrogen atom, a methyl group, a halogen excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of X 1 are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, cyano group. X 1 is preferably a hydrogen atom, a methyl group or a chlorine atom.
　Ｙ１は、－Ｏ－または－ＮＨ－である。 Y 1 is -O- or -NH-.
　Ｒは、直鎖状または分岐状の炭化水素基であることが好ましい。炭化水素基は、特に直鎖状の炭化水素基であってよい。炭化水素基は、脂肪族炭化水素基、特に飽和の脂肪族炭化水素基、特別にアルキル基であることが好ましい。炭水水素基の炭素数は、７～３０または１２～３０、例えば１６～２６、特に１８～２２（または１８～２４）であってよい。 R is preferably a linear or branched hydrocarbon group. The hydrocarbon radicals may in particular be linear hydrocarbon radicals. The hydrocarbon groups are preferably aliphatic hydrocarbon groups, especially saturated aliphatic hydrocarbon groups, especially alkyl groups. The carbon number of the hydrocarbon group may be 7-30 or 12-30, eg 16-26, especially 18-22 (or 18-24).
　長鎖アクリレートエステル単量体の具体例は、ノニル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イコシル（メタ）アクリレート、ベヘニル（メタ）アクリレート、ステアリルαクロロアクリレート、イコシルαクロロアクリレート、ベヘニルαクロロアクリレートである。
　長鎖アクリルアミド単量体の具体例は、ノニル（メタ）アクリルアミド、ラウリル（メタ）アクリルアミド、ステアリル（メタ）アクリルアミド、イコシル（メタ）アクリルアミド、ベヘニル（メタ）アクリルアミドである。
　長鎖アクリレートエステル単量体または長鎖アクリルアミド単量体が存在することにより、含フッ素重合体が与える撥水性、撥油性および風合いが高くなる。 Specific examples of long chain acrylate ester monomers are nonyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, icosyl alpha chloro Acrylate, behenyl α-chloroacrylate.
Specific examples of long-chain acrylamide monomers are nonyl (meth)acrylamide, lauryl (meth)acrylamide, stearyl (meth)acrylamide, icosyl (meth)acrylamide, behenyl (meth)acrylamide.
The presence of the long-chain acrylate ester monomer or the long-chain acrylamide monomer enhances the water repellency, oil repellency, and texture provided by the fluoropolymer.
（ａ２）アクリル単量体
　アクリル単量体（ａ２）は、－Ｏ－および－ＮＨ－から選択された少なくとも１つの基を有する２価～４価の連結基を、Ｃ(＝Ｏ)－Ｏ－またはＣ(＝Ｏ)－ＮＨ－と炭素数７～４０の炭化水素基との間に有する（メタ）アクリレートまたは（メタ）アクリルアミドであってよい。
　アクリル単量体（ａ２）は、式：
　ＣＨ2＝Ｃ(－Ｘ２)－Ｃ(＝Ｏ)－Ｙ２－Ｚ１（－Ｚ２－Ｒ２)ｐ
［式中、Ｘ２は、水素原子、一価の有機基またはハロゲン原子であり、
　Ｙ２は、－Ｏ－または－ＮＨ－であり、
　Ｚ１は、直接結合、２価または３価の炭素数１～５の炭化水素基であり、
　Ｚ２は、それぞれ独立的に、直接結合、－Ｏ－および－ＮＨ－から選択された少なくとも１つの基を有する２価～４価の連結基であり、
　Ｒ２は、それぞれ独立的に、炭素数７～４０の炭化水素基であり、
　ｐは、１または２である。］
で示される化合物であることが好ましい。 (a2) Acrylic monomer Acrylic monomer (a2) is a divalent to tetravalent linking group having at least one group selected from -O- and -NH-, C(=O)-O - or C(=O)-NH- and a (meth)acrylate or (meth)acrylamide between a hydrocarbon group having 7 to 40 carbon atoms.
The acrylic monomer (a2) has the formula:
CH 2 =C(-X 2 )-C(=O)-Y 2 -Z 1 (-Z 2 -R 2 ) p
[Wherein, X 2 is a hydrogen atom, a monovalent organic group or a halogen atom;
Y 2 is -O- or -NH-,
Z 1 is a direct bond, a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,
Z 2 is each independently a divalent to tetravalent linking group having at least one group selected from a direct bond, —O— and —NH—;
each R 2 is independently a hydrocarbon group having 7 to 40 carbon atoms,
p is 1 or 2; ]
It is preferably a compound represented by.
　アクリル単量体（ａ２）は、Ｙ２が－Ｏ－である長鎖アクリレートエステル単量体、またはＹ２が－ＮＨ－である長鎖アクリルアミド単量体である。 Acrylic monomer (a2) is a long chain acrylate ester monomer in which Y 2 is —O— or a long chain acrylamide monomer in which Y 2 is —NH—.
　Ｘ２は、水素原子、メチル基、フッ素原子を除くハロゲン、置換または非置換のベンジル基、置換または非置換のフェニル基であってよい。Ｘ２の例は、水素原子、メチル基、塩素原子、臭素原子、ヨウ素原子、シアノ基である。得られる重合体の主鎖が剛直でないほど、側鎖の結晶性を阻害しないので、Ｘ２は、水素原子、メチル基、塩素原子であることが好ましく、水素原子、メチル基であることがより好ましく、水素原子であることが特に好ましい。 X2 may be a hydrogen atom, a methyl group, a halogen excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of X2 are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a cyano group. X2 is preferably a hydrogen atom, a methyl group, or a chlorine atom, more preferably a hydrogen atom or a methyl group, because the less rigid the main chain of the resulting polymer is, the less the crystallinity of the side chain is impaired. A hydrogen atom is preferred, and a hydrogen atom is particularly preferred.
　Ｙ２は、－Ｏ－または－ＮＨ－である。 Y 2 is -O- or -NH-.
　Ｚ１は、直接結合、２価または３価の炭素数１～５の炭化水素基（特にアルキル基）であり、枝分かれ構造を有していてもよい。Ｚ１の炭素数は、２～４、特に２であることが好ましい。Ｚ１の具体例は、直接結合、２価の基として、－ＣＨ２－、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２－、枝分かれ構造を有する（３価の基である）－ＣＨ２ＣＨ＝、－ＣＨ２（ＣＨ－）ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ＝、－ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ＝、－ＣＨ２ＣＨ２（ＣＨ－）ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２ＣＨ＝である。Ｚ１は直接結合でないことが好ましい。 Z 1 is a direct bond, a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms (especially an alkyl group), and may have a branched structure. Z 1 preferably has 2 to 4 carbon atoms, particularly 2 carbon atoms. Specific examples of Z 1 include -CH 2 -, -CH 2 CH 2 - , -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH as a direct bond and a divalent group. 2 CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH= having a branched structure (which is a trivalent group), —CH 2 (CH—)CH 2 —, —CH 2 CH 2 CH=, —CH 2 CH 2 CH 2 CH 2 CH=, -CH 2 CH 2 (CH-)CH 2 -, -CH 2 CH 2 CH 2 CH=. Z 1 is preferably not a direct bond.
　Ｚ２の具体例は、直接結合、－Ｏ－、－ＮＨ－、－（Ｏ）k－Ｃ(＝Ｏ)－、－Ｃ（＝Ｏ）－Ｏ－、－Ｃ(＝Ｏ)－ＮＨ－、－ＮＨ－Ｃ(＝Ｏ)－、－（Ｏ）k－Ｃ(＝Ｏ)－ＮＨ－、－ＮＨ－Ｃ(＝Ｏ)－Ｏ－、－ＮＨ－Ｃ(＝Ｏ)－ＮＨ－、－（Ｏ）k－Ｃ６Ｈ６－、－（Ｏ）k－(ＣＨ２）m－Ｏ－、－ＮＨ－(ＣＨ２）m－ＮＨ－、－（Ｏ）k－(ＣＨ２）m－ＮＨ－、－ＮＨ－(ＣＨ２）m－Ｏ－、－（Ｏ）k－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－、－（Ｏ）k－(ＣＨ２）m－Ｃ（＝Ｏ）－Ｏ－、－ＮＨ－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－、－ＮＨ－(ＣＨ２）m－Ｃ（＝Ｏ）－Ｏ－、－（Ｏ）k－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－ＮＨ－、－（Ｏ）k－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－Ｏ－、－（Ｏ）k－(ＣＨ２）m－Ｃ（＝Ｏ）－ＮＨ－、－（Ｏ）k－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－、－（Ｏ）k－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－ＮＨ－、－（Ｏ）k－(ＣＨ２）m－Ｏ－Ｃ６Ｈ６－、－ＮＨ－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－ＮＨ－、－ＮＨ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－Ｏ－、－ＮＨ－(ＣＨ２）m－Ｃ（＝Ｏ）－ＮＨ－、－ＮＨ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－、－ＮＨ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－ＮＨ－、－ＮＨ－(ＣＨ２）m－Ｏ－Ｃ６Ｈ６－、－ＮＨ－(ＣＨ２）m－ＮＨ－Ｃ６Ｈ６－である［式中、ｋは、０または１であり、ｍは１～５の整数、特に２または４である。］。 Specific examples of Z 2 include a direct bond, -O-, -NH-, -(O) k -C(=O)-, -C(=O)-O-, -C(=O)-NH- , -NH-C(=O)-, -(O) k -C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -(O) k -C 6 H 6 -, -(O) k -(CH 2 ) m -O-, -NH-(CH 2 ) m -NH-, -(O) k -(CH 2 ) m -NH-, -NH-(CH 2 ) m -O-, -(O) k -(CH 2 ) m -O-C(=O)-, -(O) k -(CH 2 ) m -C (=O)-O-, -NH-(CH 2 ) m -O-C(=O)-, -NH-(CH 2 ) m -C(=O)-O-, -(O) k - (CH 2 ) m —O—C(=O)—NH—, —(O) k —(CH 2 ) m —NH—C(=O)—O—, —(O) k —(CH 2 ) m —C(=O)—NH—, —(O) k —(CH 2 ) m —NH—C(=O)—, —(O) k —(CH 2 ) m —NH—C(=O ) —NH—, —(O) k —(CH 2 ) m —OC 6 H 6 —, —NH—(CH 2 ) m —OC(=O)—NH—, —NH—(CH 2 ) m -NH-C(=O)-O-, -NH-(CH 2 ) m -C(=O)-NH-, -NH-(CH 2 ) m -NH-C(=O)- , -NH-(CH 2 ) m -NH-C(=O)-NH-, -NH-(CH 2 ) m -O-C 6 H 6 -, -NH-(CH 2 ) m -NH-C 6 H 6 -, wherein k is 0 or 1 and m is an integer from 1 to 5, especially 2 or 4; ].
　Ｚ２は、－（Ｏ）k－、－ＮＨ－、－（Ｏ）k－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－、－（Ｏ）k－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－、－（Ｏ）k－(ＣＨ２）m－Ｏ－Ｃ（＝Ｏ）－ＮＨ－、－（Ｏ）k－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－Ｏ－、－（Ｏ）k－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－ＮＨ－
［式中、ｋは、０または１であり、ｍは１～５の整数、特に２または４である。］
であることが特に好ましい。 Z 2 is -(O) k -, -NH-, -(O) k -(CH 2 ) m -O-C(=O)-, -(O) k -(CH 2 ) m -NH- C(=O)-, -(O) k- ( CH2 ) m -O-C(=O)-NH-, -(O) k- ( CH2 ) m -NH-C(=O)- O-, -(O) k- ( CH2 ) m -NH-C(=O)-NH-
[wherein k is 0 or 1 and m is an integer from 1 to 5, especially 2 or 4; ]
is particularly preferred.
　Ｚ１およびＺ２は同時に直接結合であることはない。 Z 1 and Z 2 cannot be direct bonds at the same time.
　Ｒ２は、直鎖状または分岐状の炭化水素基であることが好ましい。炭化水素基は、特に直鎖状の炭化水素基であってよい。炭化水素基は、脂肪族炭化水素基、特に飽和の脂肪族炭化水素基、特別にアルキル基であることが好ましい。炭水水素基の炭素数は、１２～３０、例えば１６～２６、特に１８～２２（または１８～２４）であることが好ましい。 R 2 is preferably a linear or branched hydrocarbon group. The hydrocarbon radicals may in particular be linear hydrocarbon radicals. The hydrocarbon groups are preferably aliphatic hydrocarbon groups, especially saturated aliphatic hydrocarbon groups, especially alkyl groups. The number of carbon atoms in the hydrocarbon group is preferably 12-30, for example 16-26, especially 18-22 (or 18-24).
　アクリル単量体（ａ２）は、ＣＨ2＝Ｃ(－Ｘ２)－Ｃ(＝Ｏ)－Ｏ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－Ｒ２、ＣＨ2＝Ｃ(－Ｘ２)－Ｃ(＝Ｏ)－Ｏ－Ｒ２またはこれらの組み合わせであることが好ましい［ここで、Ｘ２、ｍおよびＲ２は上記と同意義である。］。アクリル単量体（ａ２）は、ＣＨ2＝Ｃ(－Ｘ２)－Ｃ(＝Ｏ)－Ｏ－(ＣＨ２）m－ＮＨ－Ｃ（＝Ｏ）－Ｒ２であることが特に好ましい。 The acrylic monomer (a2) is CH 2 =C(-X 2 )-C(=O)-O-(CH 2 ) m -NH-C(=O)-R 2 , CH 2 =C(- X 2 )--C(=O)--OR 2 or a combination thereof [wherein X 2 , m and R 2 have the same meanings as above. ]. It is particularly preferred that the acrylic monomer (a2) is CH 2 ═C(—X 2 )—C(═O)—O—(CH 2 ) m —NH—C(═O)—R 2 .
　アクリル単量体（ａ２）は、ヒドロキシアルキル（メタ）アクリレートまたはヒドロキシアルキル（メタ）アクリルアミドと長鎖アルキルイソシアネートを反応させることによって製造できる。長鎖アルキルイソシアネートとしては例えば、ラウリルイソシアネート、ミリスチルイソシアネート、セチルイソシアネート、ステアリルイソシアネート、オレイルイソシアネート、ベヘニルイソシアネートなどがある。
　あるいは、アクリル単量体（ａ２）は、側鎖にイソシアネート基を有する（メタ）アクリレート、例えば、２－メタクリロイルオキシエチルイソシアネートと長鎖アルキルアミンまたは長鎖アルキルアルコールを反応させることでも製造できる。長鎖アルキルアミンとしては例えば、ラウリルアミン、ミリスチルアミン、セチルアミン、ステアリルアミン、オレイルアミン、ベヘニルアミンなどがある。長鎖アルキルアルコールとしては例えば、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、オレイルアルコール、ベヘニルアルコールなどがある。 The acrylic monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, behenyl isocyanate, and the like.
Alternatively, the acrylic monomer (a2) can also be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl isocyanate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, behenylamine, and the like. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.
　アクリル単量体（ａ２）の具体例は、次のとおりである。下記の化学式の化合物は、α位が水素原子であるアクリレートであるが、具体例は、α位がメチル基であるメタクリレートおよびα位が塩素原子であるアクリレートであってよい。
Figure JPOXMLDOC01-appb-I000001
Specific examples of the acrylic monomer (a2) are as follows. The compounds of the following chemical formulas are acrylates in which the α-position is a hydrogen atom, and specific examples may be methacrylates in which the α-position is a methyl group and acrylates in which the α-position is a chlorine atom.
Figure JPOXMLDOC01-appb-I000001
Figure JPOXMLDOC01-appb-I000002

Figure JPOXMLDOC01-appb-I000003

Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-I000002

Figure JPOXMLDOC01-appb-I000003

Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-I000005

Figure JPOXMLDOC01-appb-I000006

Figure JPOXMLDOC01-appb-I000007
Figure JPOXMLDOC01-appb-I000005

Figure JPOXMLDOC01-appb-I000006

Figure JPOXMLDOC01-appb-I000007
Figure JPOXMLDOC01-appb-I000008

Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-I000008

Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-I000010

［上記式中、ｍは１～５の整数であり、ｎは７～４０の整数である。］、ならびに
上記化学式において、α位がメチル基であるメタクリレートおよびα位が塩素原子であるアクリレート。
Figure JPOXMLDOC01-appb-I000010

[In the above formula, m is an integer of 1 to 5, and n is an integer of 7 to 40. ], and methacrylates in which the α-position is a methyl group and acrylates in which the α-position is a chlorine atom in the above chemical formulas.
　アクリル単量体（ａ２）の代表的な具体例は、パルミチン酸アミドエチル（メタ）アクリレート、ステアリン酸アミドエチル（メタ）アクリレート、ベヘニン酸アミドエチル（メタ）アクリレート、ミリスチン酸アミドエチル（メタ）アクリレートである。 Typical specific examples of the acrylic monomer (a2) are palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth) acrylate, behenic acid amide ethyl (meth) acrylate, and myristate amide ethyl (meth) acrylate.
　アクリル単量体（ａ２）は、式：
　Ｒ２２－Ｃ(＝Ｏ）－ＮＨ－Ｒ２３－Ｏ－Ｒ２１
［式中、Ｒ２１は、エチレン性不飽和重合性基を有する有機残基、
Ｒ２２は、炭素数７～４０の炭化水素基、
Ｒ２３は、炭素数１～５の炭化水素基である。]
で示されるアミド基含有単量体であることが特に好ましい。 The acrylic monomer (a2) has the formula:
R 22 -C(=O)-NH-R 23 -OR 21
[Wherein, R 21 is an organic residue having an ethylenically unsaturated polymerizable group,
R 22 is a hydrocarbon group having 7 to 40 carbon atoms;
R 23 is a hydrocarbon group having 1 to 5 carbon atoms. ]
Particularly preferred is an amide group-containing monomer represented by.
　アミド基含有単量体の例は、カルボン酸アミドアルキル（メタ）アクリレートである。
　アミド基含有単量体の具体例としては、パルミチン酸アミドエチル（メタ）アクリレート、ステアリン酸アミドエチル（メタ）アクリレート、ベヘニン酸アミドエチル（メタ）アクリレート、ミリスチン酸アミドエチル（メタ）アクリレート、ラウリン酸アミドエチル（メタ）アクリレート、イソステアリン酸エチルアミド（メタ）アクリレート、オレイン酸エチルアミド（メタ）アクリレート、ターシャリーブチルシクロヘキシルカプロン酸アミドエチル（メタ）アクリレート、アダマンタンカルボン酸エチルアミド（メタ）アクリレート、ナフタレンカルボン酸アミドエチル（メタ）アクリレート、アントラセンカルボン酸アミドエチル（メタ）アクリレート、パルミチン酸アミドプロピル（メタ）アクリレート、ステアリン酸アミドプロピル（メタ）アクリレート、パルミチン酸アミドエチルビニルエーテル、ステアリン酸アミドエチルビニルエーテル、パルミチン酸アミドエチルアリルエーテル、ステアリン酸アミドエチルアリルエーテル、またはこれらの混合物が挙げられる。 Examples of amide group-containing monomers are carboxylic acid amide alkyl (meth)acrylates.
Specific examples of the amide group-containing monomer include ethyl palmitamide (meth)acrylate, stearamideethyl (meth)acrylate, behenamideethyl (meth)acrylate, myristateamideethyl (meth)acrylate, and laurateamideethyl (meth)acrylate. Acrylates, isostearic acid ethylamide (meth)acrylate, oleic acid ethylamide (meth)acrylate, tert-butylcyclohexylcaproic acid amide ethyl (meth)acrylate, adamantanecarboxylic acid ethylamide (meth)acrylate, naphthalenecarboxylic acid amideethyl (meth)acrylate, anthracenecarboxylic acid Acid amide ethyl (meth) acrylate, palmitamide propyl (meth) acrylate, stearamide propyl (meth) acrylate, palmitamide ethyl vinyl ether, stearamide ethyl vinyl ether, palmitamide ethyl allyl ether, stearamide ethyl allyl ether , or mixtures thereof.
　アミド基含有単量体は、ステアリン酸アミドエチル（メタ）アクリレートであることが好ましい。アミド基含有単量体は、ステアリン酸アミドエチル（メタ）アクリレートを含む混合物であってよい。ステアリン酸アミドエチル（メタ）アクリレートを含む混合物において、ステアリン酸アミドエチル（メタ）アクリレートの量は、アミド基含有単量体全体の重量に対して、例えば５５～９９重量％、好ましくは６０～８５重量％、更に好ましくは６５～８０重量％であってよく、残りの単量体は、例えば、パルミチン酸アミドエチル（メタ）アクリレートであってよい。 The amide group-containing monomer is preferably stearamidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate. In the mixture containing stearamide ethyl (meth)acrylate, the amount of stearamide ethyl (meth)acrylate is, for example, 55 to 99% by weight, preferably 60 to 85% by weight, based on the total weight of the amide group-containing monomer. , more preferably 65 to 80% by weight, and the remaining monomer may be, for example, palmitamide ethyl (meth)acrylate.
（Ａ３）非架橋性単量体
　非架橋性単量体（Ａ３）は、長鎖炭化水素基含有単量体（Ａ２）以外の単量体である。非架橋性単量体（Ａ３）は、フッ素原子を含まない単量体である。非架橋性単量体（Ａ３）は、架橋性官能基を有さない。非架橋性単量体（Ａ３）は、架橋性単量体（Ａ４）とは異なり、非架橋性である。非架橋性単量体（Ａ３）は、好ましくは、エチレン性不飽和炭素－炭素二重結合を有する単量体である。非架橋性単量体（Ａ３）は、好ましくは、フッ素を含まないビニル単量体である。非架橋性単量体（Ａ３）は一般には、１つのエチレン性不飽和炭素－炭素二重結合を有する化合物である。 (A3) Non-crosslinking monomer The non-crosslinking monomer (A3) is a monomer other than the long-chain hydrocarbon group-containing monomer (A2). A non-crosslinkable monomer (A3) is a monomer containing no fluorine atom. A non-crosslinkable monomer (A3) does not have a crosslinkable functional group. The non-crosslinkable monomer (A3) is non-crosslinkable, unlike the crosslinkable monomer (A4). Non-crosslinkable monomer (A3) is preferably a monomer having an ethylenically unsaturated carbon-carbon double bond. The non-crosslinkable monomer (A3) is preferably a fluorine-free vinyl monomer. Non-crosslinking monomers (A3) are generally compounds having one ethylenically unsaturated carbon-carbon double bond.
　好ましい非架橋性単量体（Ａ３）は、式：
　　ＣＨ２＝ＣＡ－Ｔ
［式中、Ａは、水素原子、メチル基、または、フッ素原子以外のハロゲン原子（例えば、塩素原子、臭素原子およびヨウ素原子）であり、
Ｔは、水素原子、鎖状または環状の炭化水素基、またはエステル結合を（場合により、オキシアルキレン基をも）有する鎖状または環状の有機基である。］
で示される化合物である。 A preferred non-crosslinking monomer (A3) has the formula:
CH2 =CA-T
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom and an iodine atom),
T is a hydrogen atom, a chain or cyclic hydrocarbon group, or a chain or cyclic organic group having an ester bond (and optionally an oxyalkylene group). ]
is a compound represented by
　（例えば炭素数１～４０の）鎖状または環状の炭化水素基の例は、炭素数１～４０の直鎖または分岐の脂肪族炭化水素基、炭素数４～４０の環状脂肪族基、炭素数６～４０の芳香族炭化水素基、炭素数７～４０の芳香脂肪族炭化水素基である。 Examples of linear or cyclic hydrocarbon groups (for example, having 1 to 40 carbon atoms) include linear or branched aliphatic hydrocarbon groups having 1 to 40 carbon atoms, cycloaliphatic groups having 4 to 40 carbon atoms, carbon They are an aromatic hydrocarbon group having 6 to 40 carbon atoms and an araliphatic hydrocarbon group having 7 to 40 carbon atoms.
　エステル結合を有する鎖状または環状の（炭素数１～３００または１～４１の）有機基の例は、-C(=O)-O-Q および-O-C(=O)-Q（ここで、Ｑは、炭素数１～４０の直鎖または分岐の脂肪族炭化水素基、炭素数４～４０の環状脂肪族基、炭素数６～４０の芳香族炭化水素基、炭素数７～４０の芳香脂肪族炭化水素基であってよく、あるいは１つまたは複数（例えば、２～３００）のアルキレングリコール基（炭素数２～４、特に２または３）であってよく、あるいは該グリコール基を有してよい）である。 Examples of linear or cyclic organic groups (having 1 to 300 or 1 to 41 carbon atoms) having an ester bond are -C(=O)-O-Q and -O-C(=O)-Q (where Q is , a linear or branched aliphatic hydrocarbon group having 1 to 40 carbon atoms, a cycloaliphatic group having 4 to 40 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an araliphatic group having 7 to 40 carbon atoms It may be a hydrocarbon group, or it may be one or more (for example, 2 to 300) alkylene glycol groups (2 to 4 carbon atoms, especially 2 or 3) or may have said glycol groups. ).
　非架橋性単量体（Ａ３）の好ましい例には、例えば、エチレン、酢酸ビニル、アクリロニトリル、スチレン、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、およびビニルアルキルエーテルが含まれる。非架橋性単量体（Ａ３）はこれらの例に限定されない。 Preferred examples of the non-crosslinkable monomer (A3) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, methoxypolypropylene Included are glycol (meth)acrylates and vinyl alkyl ethers. Non-crosslinking monomers (A3) are not limited to these examples.
　非架橋性単量体（Ａ３）は、アルキル基を有する（メタ）アクリレートエステルであってよい。アルキル基の炭素原子の数は１～１７、１～１０、１～６または１～４であってよい。例えば、非架橋性単量体（Ａ３）は、一般式：
ＣＨ２＝ＣＡ１ＣＯＯＡ２
［式中、Ａ１は、水素原子、メチル基、または、フッ素原子以外のハロゲン原子（例えば、塩素原子、臭素原子およびヨウ素原子）であり、
Ａ２は、ＣｎＨ２ｎ＋１（ｎ＝１～１７または１～６）によって表されるアルキル基である。］
で示されるアクリレートであってよい。
　含フッ素重合体は、炭素原子数１～１７のアルキル基を有する（メタ）アクリレートエステルから誘導された繰り返し単位を有しなくてもよい。 The non-crosslinkable monomer (A3) may be a (meth)acrylate ester having an alkyl group. The number of carbon atoms in the alkyl group may be 1-17, 1-10, 1-6 or 1-4. For example, the non-crosslinkable monomer (A3) has the general formula:
CH2 = CA1COOA2
[In the formula, A 1 is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom and an iodine atom),
A 2 is an alkyl group represented by C n H 2n+1 (n=1-17 or 1-6). ]
It may be an acrylate represented by
The fluoropolymer may not have repeating units derived from a (meth)acrylate ester having an alkyl group of 1 to 17 carbon atoms.
　非架橋性単量体（Ａ３）は、環状炭化水素基を有する（メタ）アクリレート単量体であってよい。環状炭化水素基を有する（メタ）アクリレート単量体は、（好ましくは一価の）環状炭化水素基および一価の（メタ）アクリレート基を有する化合物である。一価の環状炭化水素基と一価の（メタ）アクリレート基は、直接に結合している。環状炭化水素基としては、飽和または不飽和である、単環基、多環基、橋かけ環基などが挙げられる。環状炭化水素基は、飽和であることが好ましい。環状炭化水素基の炭素数は４～２０であることが好ましい。環状炭化水素基としては、炭素数４～２０、特に５～１２の環状脂肪族基、炭素数６～２０の芳香族基、炭素数７～２０の芳香脂肪族基が挙げられる。環状炭化水素基の炭素数は、１５以下、例えば１０以下であることが特に好ましい。環状炭化水素基の環における炭素原子が、（メタ）アクリレート基におけるエステル基に直接に結合することが好ましい。環状炭化水素基は、飽和の環状脂肪族基であることが好ましい。 The non-crosslinkable monomer (A3) may be a (meth)acrylate monomer having a cyclic hydrocarbon group. A (meth)acrylate monomer having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth)acrylate group. The monovalent cyclic hydrocarbon group and the monovalent (meth)acrylate group are directly bonded. Cyclic hydrocarbon groups include saturated or unsaturated monocyclic groups, polycyclic groups, bridged ring groups, and the like. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group preferably has 4 to 20 carbon atoms. Cyclic hydrocarbon groups include cycloaliphatic groups having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, aromatic groups having 6 to 20 carbon atoms, and araliphatic groups having 7 to 20 carbon atoms. The number of carbon atoms in the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. A carbon atom in the ring of the cyclic hydrocarbon group is preferably directly bonded to the ester group in the (meth)acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.
　環状炭化水素基の具体例は、シクロヘキシル基、ｔ－ブチルシクロヘキシル基、イソボルニル基、ジシクロペンタニル基、ジシクロペンテニル基、アダマンチル基である。アクリレート基は、アクリレート基またはメタアクリレート基であることが好ましいが、メタクリレート基が特に好ましい。環状炭化水素基を有する単量体の具体例としては、シクロヘキシル（メタ）アクリレート、ｔ－ブチルシクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニルオキシエチル（メタ）アクリレート、トリシクロペンタニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、２－メチル－２－アダマンチル（メタ）アクリレート、２－エチル－２－アダマンチル（メタ）アクリレート等が挙げられる。 Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group and an adamantyl group. The acrylate groups are preferably acrylate or methacrylate groups, with methacrylate groups being particularly preferred. Specific examples of monomers having a cyclic hydrocarbon group include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. , dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl -2-adamantyl (meth)acrylate and the like.
　非架橋性単量体（Ａ３）はハロゲン化オレフィンであってもよい。ハロゲン化オレフィンは、１～１０の塩素原子、臭素原子またはヨウ素原子で置換されている炭素数２～２０のハロゲン化オレフィンであってよい。ハロゲン化オレフィンは、炭素数２～２０の塩素化オレフィン、特に１～５の塩素原子を有する炭素数２～５のオレフィンであることが好ましい。ハロゲン化オレフィンの好ましい具体例は、ハロゲン化ビニル、例えば塩化ビニル、臭化ビニル、ヨウ化ビニル、ハロゲン化ビニリデン、例えば塩化ビニリデン、臭化ビニリデン、ヨウ化ビニリデンである。 The non-crosslinkable monomer (A3) may be a halogenated olefin. Halogenated olefins may be halogenated olefins having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred examples of halogenated olefins are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide.
（Ａ４）架橋性単量体
　含フッ素重合体は、架橋性単量体（Ａ４）から誘導された繰り返し単位を有していてよい。架橋性単量体（Ａ４）は、フッ素原子を含まない単量体である。架橋性単量体（Ａ４）は、少なくとも２つの反応性基および／またはエチレン性不飽和炭素－炭素二重結合を有し、フッ素を含有しない化合物であってよい。架橋性単量体（Ａ４）は、少なくとも２つのエチレン性不飽和炭素－炭素二重結合を有する化合物、あるいは少なくとも１つのエチレン性不飽和炭素－炭素二重結合および少なくとも１つの反応性基を有する化合物であってよい。反応性基の例は、ヒドロキシル基、エポキシ基、クロロメチル基、ブロックイソシアネート基、アミノ基、カルボキシル基、などである。 (A4) Crosslinkable monomer The fluoropolymer may have repeating units derived from the crosslinkable monomer (A4). A crosslinkable monomer (A4) is a monomer containing no fluorine atom. Crosslinking monomers (A4) may be fluorine-free compounds having at least two reactive groups and/or ethylenically unsaturated carbon-carbon double bonds. Crosslinking monomer (A4) is a compound having at least two ethylenically unsaturated carbon-carbon double bonds, or at least one ethylenically unsaturated carbon-carbon double bond and at least one reactive group It may be a compound. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.
　架橋性単量体（Ａ４）としては、例えば、ジアセトンアクリルアミド、(メタ)アクリルアミド、Ｎ－メチロールアクリルアミド、ヒドロキシメチル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート、３－クロロ－２－ヒドロキシプロピル(メタ)アクリレート、2-アセトアセトキシエチル（メタ）アクリレート、Ｎ,Ｎ－ジメチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ－ジエチルアミノエチル(メタ)アクリレート、ブタジエン、イソプレン、クロロプレン、グリシジル(メタ)アクリレートなどが例示されるが、これらに限定されるものでない。 Examples of the crosslinkable monomer (A4) include diacetone acrylamide, (meth)acrylamide, N-methylolacrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl ( meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butadiene, isoprene, chloroprene, glycidyl (meth)acrylate, etc. Examples include, but are not limited to.
　非架橋性単量体（Ａ３）および／または架橋性単量体（Ａ４）を共重合させることにより、撥水撥油性や防汚性およびこれらの性能の耐クリーニング性、耐洗濯性、溶剤への溶解性、硬さ、感触などの種々の性質を必要に応じて改善することができる。 By copolymerizing the non-crosslinkable monomer (A3) and/or the crosslinkable monomer (A4), water and oil repellency, antifouling properties, cleaning resistance, washing resistance, solvent Various properties such as solubility, hardness and feel can be improved as desired.
　単量体を、ブロックイソシアネート化合物およびオルガノポリシロキサン化合物からなる群から選択された少なくとも１種の化合物の存在下で、重合してよい。ブロックイソシアネート化合物（またはオルガノポリシロキサン化合物）の量は、単量体１００重量部に対して、０～１００重量部、例えば１～５０重量部であってよい。 The monomer may be polymerized in the presence of at least one compound selected from the group consisting of blocked isocyanate compounds and organopolysiloxane compounds. The amount of blocked isocyanate compound (or organopolysiloxane compound) may be 0 to 100 parts by weight, for example 1 to 50 parts by weight, based on 100 parts by weight of the monomer.
　単量体をブロックイソシアネート化合物の存在下で重合することにより、ブロックイソシアネート基を有する重合体が得られる。ブロックイソシアネート化合物は、少なくとも一種のブロック剤によってブロックされているイソシアネートである。ブロック剤の例としては、オキシム類、フェノール類、アルコール類、メルカプタン類、アミド類、イミド類、イミダゾール類、尿素類、アミン類、イミン類、ピラゾール類、および活性メチレン化合物類が挙げられる。ブロック剤の他の例には、ピリジノール類、チオフェノール類、ジケトン類およびエステル類が挙げられる。ブロックイソシアネート化合物は、親水性基を有する化合物によって変性されていてもよい。 A polymer having a blocked isocyanate group is obtained by polymerizing the monomer in the presence of the blocked isocyanate compound. A blocked isocyanate compound is an isocyanate that is blocked with at least one blocking agent. Examples of blocking agents include oximes, phenols, alcohols, mercaptans, amides, imides, imidazoles, ureas, amines, imines, pyrazoles, and 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.
　含フッ素単量体（Ａ１）は、含フッ素重合体に対して、３０～１００重量％、好ましくは３２～９８重量％、例えば３５～９５重量％、特に４０～９０重量％であってよい。
　含フッ素重合体において、含フッ素単量体（Ａ１）１００重量部に対して、
長鎖炭化水素基含有単量体（Ａ２）の量が、１０００重量部以下、例えば０．１～３００重量部、特に１～２００重量部であり、
非架橋性単量体（Ａ３）の量が、１０００重量部以下、例えば０．１～３００重量部、特に１～２００重量部であり、
架橋性単量体（Ａ４）の量が、５０重量部以下、例えば３０重量部以下、特に０．１～２０重量部であってよい。
　あるいは、含フッ素重合体に対して、
含フッ素単量体（Ａ１）の量が、３０～９０重量％、例えば３５～８０重量％、特に４０～７０重量％、
長鎖炭化水素基含有単量体（Ａ２）の量が、１～６０重量％、例えば５～５０重量％、特に１０～４０重量％であり、
非架橋性単量体（Ａ３）の量が、１～６０重量％、例えば５～５０重量％、特に１０～４０重量％であり、
架橋性単量体（Ａ４）の量が、３０重量％以下、例えば０.１～２０重量％、特に１～１０重量％であってよい。 The fluoromonomer (A1) may be 30 to 100% by weight, preferably 32 to 98% by weight, for example 35 to 95% by weight, particularly 40 to 90% by weight, relative to the fluoropolymer.
In the fluoropolymer, per 100 parts by weight of the fluoromonomer (A1),
The amount of the long-chain hydrocarbon group-containing monomer (A2) is 1000 parts by weight or less, for example 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight,
The amount of the non-crosslinkable monomer (A3) is 1000 parts by weight or less, for example 0.1 to 300 parts by weight, especially 1 to 200 parts by weight,
The amount of crosslinkable monomer (A4) may be 50 parts by weight or less, for example 30 parts by weight or less, especially 0.1 to 20 parts by weight.
Alternatively, for a fluoropolymer,
the amount of the fluorine-containing monomer (A1) is 30 to 90% by weight, for example 35 to 80% by weight, particularly 40 to 70% by weight;
the amount of the long-chain hydrocarbon group-containing monomer (A2) is 1 to 60% by weight, for example 5 to 50% by weight, especially 10 to 40% by weight;
the amount of non-crosslinking monomer (A3) is 1 to 60% by weight, for example 5 to 50% by weight, especially 10 to 40% by weight;
The amount of crosslinkable monomers (A4) may be up to 30% by weight, for example 0.1 to 20% by weight, especially 1 to 10% by weight.
　含フッ素重合体の数平均分子量（Ｍｎ）は、一般に１０００～１００００００、例えば２０００～５０００００、特に３０００～２０００００であってよい。含フッ素重合体の数平均分子量（Ｍｎ）は、一般に、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により測定する。
　撥水撥油剤および含フッ素重合体は、単独または２種以上の組み合わせで用いることができる。 The number average molecular weight (Mn) of the fluoropolymer may generally be from 1,000 to 1,000,000, for example from 2,000 to 500,000, especially from 3,000 to 200,000. The number average molecular weight (Mn) of the fluoropolymer is generally measured by GPC (gel permeation chromatography).
The water/oil repellent and the fluoropolymer can be used alone or in combination of two or more.
　撥水撥油剤が水系エマルションである場合に、界面活性剤を含有することが好ましい。界面活性剤は、ノニオン性界面活性剤、カチオン性界面活性剤、アニオン界面活性剤および両性界面活性剤の中から選択された少なくとも１種であってよい。 When the water and oil repellent is an aqueous emulsion, it preferably contains a surfactant. The surfactant may be at least one selected from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants.
　ノニオン性界面活性剤の例としては、エーテル、エステル、エステルエーテル、アルカノールアミド、多価アルコールおよびアミンオキシド、およびこれらのポリオキシアルキレン（特にエチレン）付加化合物が挙げられる。
　カチオン性界面活性剤の例として、アミン、アミン塩、４級アンモニウム塩、イミダゾリンおよびイミダゾリニウム塩が挙げられる。
　アニオン性界面活性剤の例として、脂肪酸塩、スルホン酸塩、硫酸エステル塩が挙げられる。
　両性界面活性剤の例としては、アラニン類、イミダゾリニウムベタイン類、アミドベタイン類、酢酸ベタイン等が挙げられる。 Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides, and their polyoxyalkylene (especially ethylene) adducts.
Examples of cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazolines and imidazolinium salts.
Examples of anionic surfactants include fatty acid salts, sulfonates, and sulfate ester salts.
Examples of amphoteric surfactants include alanines, imidazolinium betaines, amidobetaines, and betaine acetate.
　界面活性剤の量は、含フッ素重合体（または単量体の合計）１００重量部に対して、０．１～５０重量部、例えば、１～２０重量部であってよい。 The amount of the surfactant may be 0.1 to 50 parts by weight, for example 1 to 20 parts by weight, with respect to 100 parts by weight of the fluoropolymer (or the total amount of monomers).
　含フッ素重合体は通常の重合方法の何れでも製造でき、また重合反応の条件も任意に選択できる。このような重合方法として、溶液重合、懸濁重合、乳化重合が挙げられる。含フッ素重合体を乳化重合法または溶液重合法により製造することが好ましい。
　撥水撥油剤は、乳化重合によって、含フッ素重合体の分散液を形成することが好ましい。撥水撥油剤は、水性分散液であること、より詳細には、含フッ素重合体の粒子が水性媒体に分散する水性分散液であることが好ましい。 The fluorine-containing polymer can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. The fluorine-containing polymer is preferably produced by an emulsion polymerization method or a solution polymerization method.
The water and oil repellent preferably forms a fluoropolymer dispersion by emulsion polymerization. The water and oil repellent is preferably an aqueous dispersion, more specifically, an aqueous dispersion in which fluoropolymer particles are dispersed in an aqueous medium.
　含フッ素重合体を重合により製造した後に、水（または水性媒体）を添加して、含フッ素重合体を水に分散させることが好ましい。
　水（または水性媒体）は、含フッ素重合体を重合により製造した後に、添加してもよい。例えば、単量体を有機溶媒の存在下で重合して、含フッ素重合体を製造した後に、重合体混合物に水を添加して、有機溶媒を留去して、含フッ素重合体を水に分散させてよい。有機溶媒は留去しなくてもよい。界面活性剤は、重合前または重合後に添加してよく、あるいは添加しなくてもよい。界面活性剤を添加しない場合にも、良好な水性分散液が得られる。 It is preferable to add water (or an aqueous medium) to disperse the fluoropolymer in water after producing the fluoropolymer by polymerization.
Water (or an aqueous medium) may be added after the fluoropolymer is produced by polymerization. For example, after the monomers are polymerized in the presence of an organic solvent to produce a fluoropolymer, water is added to the polymer mixture, the organic solvent is distilled off, and the fluoropolymer is dissolved in water. You can disperse it. It is not necessary to distill off the organic solvent. A surfactant may be added before or after polymerization, or may not be added. Good aqueous dispersions are obtained even when no surfactant is added.
＜（２）サイズ剤＞
　サイズ剤は、紙用として一般に使用されているサイズ剤である。サイズ剤は、紙に対してインクなど液体の浸透性を抑え、裏移りや滲みを防ぐ機能を有する。
　サイズ剤は、紙の製造において内添サイズ剤または外添サイズ剤として、例えば外添サイズ剤（すなわち、表面サイズ剤）として、用いられているものであることが好ましい。
　サイズ剤は、サイズ剤の有効成分（液体の浸透性を抑える成分）および水を含むことが好ましい。本明細書において、サイズ剤の有効成分を「サイズ有効成分」と呼ぶことがある。 <(2) Sizing agent>
Sizing agents are commonly used sizing agents for paper. The sizing agent has the function of suppressing the permeability of liquid such as ink to paper and preventing set-off and bleeding.
The sizing agent is preferably one that is used as an internal or external sizing agent in the manufacture of paper, for example, as an external sizing agent (ie, surface sizing agent).
The sizing agent preferably contains an active ingredient of the sizing agent (a component that suppresses liquid permeability) and water. In this specification, the active ingredient of the sizing agent may be referred to as "active sizing ingredient".
　サイズ有効成分は、特に限定されないが、例示すれば、
アルキルケテンダイマー、アルケニルケテンダイマーなどのケテンダイマー；
アルキルコハク酸無水物、アルケニルコハク酸無水物；
ワックス；
ポリビニルアルコールおよび変性ポリビニルアルコールなどのビニルアルコール重合体；
メラミン／ホルマリン重合体；
スチレン／（メタ）アクリル酸共重合体、スチレン／（メタ）アクリル酸エステル共重合体、スチレン／（メタ）アクリル酸／（メタ）アクリル酸エステル共重合体、スチレン／マレイン酸共重合体などのスチレン重合体；
イソブチレン／（メタ）アクリル酸共重合体、ジイソブチレン／マレイン酸共重合体、プロピレン／マレイン酸共重合体、エチレン／マレイン酸共重合体などのオレフィン重合体；
ポリ（メタ）アクリル単独重合体および共重合体、例えば、（メタ）アクリル酸エステル／アクリロニトリル共重合体を挙げることができる。 The size active ingredient is not particularly limited, but for example,
ketene dimers such as alkyl ketene dimers and alkenyl ketene dimers;
Alkyl succinic anhydride, alkenyl succinic anhydride;
wax;
vinyl alcohol polymers such as polyvinyl alcohol and modified polyvinyl alcohol;
melamine/formalin polymers;
Styrene/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid ester copolymer, styrene/(meth)acrylic acid/(meth)acrylic acid ester copolymer, styrene/maleic acid copolymer, etc. styrene polymer;
Olefin polymers such as isobutylene/(meth)acrylic acid copolymer, diisobutylene/maleic acid copolymer, propylene/maleic acid copolymer, ethylene/maleic acid copolymer;
Poly(meth)acrylic homopolymers and copolymers such as (meth)acrylate/acrylonitrile copolymers may be mentioned.
　アルキルケテンダイマーおよびアルケニルケテンダイマーにおいて、アルキル基およびアルケニル基の炭素数は、３～４０、４～３６または４～２４、例えば、１２～２４であってよい。
　ワックスとしては、パラフィンワックス、マイクロクリスタリンワックス、フィッシャートロプシュワックス、ポリエチレンワックス、動植物蝋、および鉱物蝋などが挙げられる。ノルマルアルカンが挙げられる。ワックスの炭素数は、２０～６０、例えば、２５～４５であってよい。ワックスの分子量は、１５０～１０００または３００～７００であってよい。 In the alkyl ketene dimers and alkenyl ketene dimers, the alkyl and alkenyl groups may have 3-40, 4-36 or 4-24, eg 12-24, carbon atoms.
Waxes include paraffin waxes, microcrystalline waxes, Fischer-Tropsch waxes, polyethylene waxes, animal and plant waxes, mineral waxes, and the like. Examples include normal alkanes. The wax may have 20 to 60 carbon atoms, such as 25 to 45 carbon atoms. The wax may have a molecular weight of 150-1000 or 300-700.
　（メタ）アクリル酸エステルは、アルコール残基が炭化水素アルコール（特に、飽和脂肪族炭化水素アルコールおよび飽和脂環式炭化水素アルコールなどの脂肪族炭化水素アルコール）（炭化水素基の炭素数１～４０または３～３０）であることが好ましい。異なるアルキル鎖長の２種以上の（メタ）アクリル酸アルキルエステルの共重合体、あるいは、（メタ）アクリル酸アルキルエステルと架橋基、例えば、－ＯＨ基および／または－ＣＯＯＨ基を含有する（メタ）アクリル酸エステルとの共重合体が好ましい。
　本明細書において、（メタ）アクリル酸は、アクリル酸およびメタクリル酸を意味する。 (Meth) acrylic acid esters, alcohol residues are hydrocarbon alcohols (especially aliphatic hydrocarbon alcohols such as saturated aliphatic hydrocarbon alcohols and saturated alicyclic hydrocarbon alcohols) (hydrocarbon groups with 1 to 40 carbon atoms) or 3 to 30). Copolymers of two or more (meth)acrylic acid alkyl esters with different alkyl chain lengths, or (meth)acrylic acid alkyl esters and cross-linking groups such as —OH and/or —COOH groups (meth) ) copolymers with acrylic acid esters are preferred.
As used herein, (meth)acrylic acid means acrylic acid and methacrylic acid.
　好ましいサイズ剤は、アルキルケテンダイマー、アルケニルケテンダイマー、ワックス、スチレン／（メタ）アクリル酸共重合体、スチレン／アクリル酸エステル共重合体、スチレン／（メタ）アクリル酸／（メタ）アクリル酸エステル共重合体、スチレン／マレイン酸共重合体等のスチレン重合体、イソブチレン／アクリル酸共重合体、ジイソブチレン／マレイン酸共重合体、プロピレン／マレイン酸共重合体、エチレン／マレイン酸共重合体である。
　より好ましいサイズ剤は、アルキルケテンダイマー、アルケニルケテンダイマー、アルキルケテンダイマー、スチレン重合体及びスチレン共重合体、およびそれら混合物である。 Preferred sizing agents are alkyl ketene dimers, alkenyl ketene dimers, waxes, styrene/(meth)acrylic acid copolymers, styrene/acrylic acid ester copolymers, styrene/(meth)acrylic acid/(meth)acrylic acid ester copolymers. polymers, styrene polymers such as styrene/maleic acid copolymers, isobutylene/acrylic acid copolymers, diisobutylene/maleic acid copolymers, propylene/maleic acid copolymers, ethylene/maleic acid copolymers. .
More preferred sizing agents are alkylketene dimers, alkenylketene dimers, alkylketene dimers, styrene polymers and copolymers, and mixtures thereof.
　耐アルコール性がさらに高くなるので、アルキルケテンダイマーおよびアルケニルケテンダイマーが特に好ましい。本明細書において、アルキルケテンダイマーおよびアルケニルケテンダイマーを「ＡＫＤ」と表示することがある。 Alkyl ketene dimers and alkenyl ketene dimers are particularly preferred because they have higher alcohol resistance. In this specification, alkyl ketene dimers and alkenyl ketene dimers are sometimes indicated as "AKD".
　アルキルケテンダイマーおよびアルケニルケテンダイマーは、式：
Figure JPOXMLDOC01-appb-I000011
［式中、Ｒ１及びＲ２は、同一であっても異なっていても良く、それぞれ炭素数４～２４のアルキル基又はアルケニル基を表す。］
で示される化合物であってよい。 Alkyl ketene dimers and alkenyl ketene dimers have the formula:
Figure JPOXMLDOC01-appb-I000011
[In the formula, R 1 and R 2 may be the same or different and each represents an alkyl group or an alkenyl group having 4 to 24 carbon atoms. ]
It may be a compound represented by
　サイズ剤は、単独または２種以上の組み合わせで用いることができる。
　サイズ剤は、アルキルケテンダイマーおよび／またはアルケニルケテンダイマーに加えて、ワックスなどの上記の他の有効成分を含んでいてよい。アルキルケテンダイマーおよび／またはアルケニルケテンダイマーと他の有効成分との組み合わせにおいて、アルキルケテンダイマーおよび／またはアルケニルケテンダイマーと他の有効成分との重量比は１０：９０～９０：１０または３０：７０～７０：３０であってよい。 A sizing agent can be used individually or in combination of 2 or more types.
The sizing agent may contain, in addition to the alkyl ketene dimer and/or the alkenyl ketene dimer, other active ingredients as described above, such as waxes. In the combination of alkyl ketene dimer and/or alkenyl ketene dimer and other active ingredient, the weight ratio of alkyl ketene dimer and/or alkenyl ketene dimer and other active ingredient is 10:90 to 90:10 or 30:70 to It may be 70:30.
　サイズ剤は、水溶液または水性分散液（水系液）であることが好ましい。
　サイズ剤の水性分散液は、例えば、界面活性剤の存在下で、サイズ剤を水に分散させることによって製造できる。
　サイズ剤が水系エマルションである場合に、界面活性剤を含有することが好ましい。界面活性剤は、ノニオン性界面活性剤、カチオン性界面活性剤、アニオン界面活性剤および両性界面活性剤の中から選択された少なくとも１種であってよい。ノニオン性界面活性剤、カチオン性界面活性剤、アニオン界面活性剤および両性界面活性剤の例は、含フッ素重合体において説明したのと同様の例である。界面活性剤の量は、サイズ有効成分１００重量部に対して、０．１～５０重量部、例えば、１～２０重量部であってよい。 The sizing agent is preferably an aqueous solution or aqueous dispersion (aqueous liquid).
Aqueous dispersions of sizing agents can be prepared, for example, by dispersing the sizing agent in water in the presence of a surfactant.
When the sizing agent is an aqueous emulsion, it preferably contains a surfactant. The surfactant may be at least one selected from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants. Examples of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants are the same as those described for the fluorine-containing polymer. The amount of surfactant may be from 0.1 to 50 parts by weight, for example from 1 to 20 parts by weight, based on 100 parts by weight of the size active ingredient.
　サイズ剤をカチオン性または両性（例えば、カチオン性分散液）と呼ぶ場合には、一般に、界面活性剤がカチオン性または両性であってよい。 When the sizing agent is called cationic or amphoteric (eg, cationic dispersion), generally the surfactant may be cationic or amphoteric.
＜撥水撥油剤キット＞
　撥水撥油剤キットは、撥水撥油剤（１）、およびサイズ剤（２）を有する。撥水撥油剤キットは、撥水撥油剤（１）とサイズ剤（２）との組み合わせを意味する。
　撥水撥油剤（１）は、一般に、含フッ素重合体および液状媒体を含んでなる。サイズ剤（２）は、一般に、サイズ有効成分および液状媒体を含んでなる。
　１つの態様において、撥水撥油剤（１）とサイズ剤（２）とを混合して撥水撥油剤組成物を予め形成する必要はない。例えば、撥水撥油剤（１）とサイズ剤（２）とを別個に用意し、処理液に添加してよい。 <Water and Oil Repellent Kit>
The water and oil repellent kit has a water and oil repellent (1) and a sizing agent (2). A water and oil repellent agent kit means a combination of a water and oil repellent agent (1) and a sizing agent (2).
The water/oil repellent (1) generally comprises a fluoropolymer and a liquid medium. Sizing agent (2) generally comprises a sizing active ingredient and a liquid medium.
In one aspect, it is not necessary to pre-form the water and oil repellent composition by mixing the water and oil repellent (1) and the sizing agent (2). For example, the water and oil repellent agent (1) and the sizing agent (2) may be separately prepared and added to the treatment liquid.
＜撥水撥油剤組成物＞
　撥水撥油剤組成物は、分散液、溶液、エマルションまたはエアゾールの形態であることが好ましい。撥水撥油剤組成物は、含フッ素共重合体およびサイズ有効成分に加えて、媒体（特に、液状媒体、例えば、有機溶媒および／または水）を含んでなることが好ましい。撥水撥油剤において、含フッ素重合体およびサイズ有効成分の濃度は、例えば、０．０１～５０重量％であってよい。 <Water and oil repellent composition>
The water and oil repellent composition is preferably in the form of dispersion, solution, emulsion or aerosol. The water and oil repellent composition preferably contains a medium (especially a liquid medium such as an organic solvent and/or water) in addition to the fluorine-containing copolymer and the sizing active ingredient. In the water and oil repellent, the concentration of the fluoropolymer and the sizing active ingredient may be, for example, 0.01 to 50% by weight.
　撥水撥油剤組成物（あるいは撥水撥油剤またはサイズ剤）が含む液状媒体は、水性媒体であることが好ましい。本明細書において、「水性媒体」とは、水のみからなる媒体、および水に加えて有機溶剤（有機溶剤の量は、水１００重量部に対して、８０重量部以下、例えば０．１～５０重量部、特に５～３０重量部である。）をも含有する媒体を意味する。 The liquid medium contained in the water and oil repellent composition (or water and oil repellent or sizing agent) is preferably an aqueous medium. As used herein, the term "aqueous medium" refers to a medium consisting only of water, and an organic solvent in addition to water (the amount of the organic solvent is 80 parts by weight or less, for example, 0.1 to 100 parts by weight per 100 parts by weight of water). 50 parts by weight, especially 5 to 30 parts by weight).
　撥水撥油剤組成物は、任意の適切な方法より被処理物（基材）に適用すること、例えば撥水撥油剤組成物で基材を処理することができる。換言すれば、撥水撥油剤組成物で処理することからなる、基材を処理する方法が提供される。本開示において「処理」とは、撥水撥油剤またはこれを含む処理剤を、浸漬、噴霧、塗布などにより被処理物に適用することを意味する。処理により、処理剤の活性成分である含フッ素重合体が被処理物の内部に浸透するおよび／または被処理物の表面に付着する。本開示の処理方法は一般に、被処理物を撥水撥油性（あるいは撥水性／疎水性かつ撥油性／疎油性）ならびに撥アルコール性にし得る。 The water and oil repellent composition can be applied to the object to be treated (substrate) by any appropriate method, for example, the substrate can be treated with the water and oil repellent composition. In other words, there is provided a method of treating a substrate comprising treating it with the repellent composition. In the present disclosure, “treatment” means applying a water and oil repellent agent or a treatment agent containing the same to an object to be treated by immersion, spraying, coating, or the like. Due to the treatment, the fluorine-containing polymer, which is the active ingredient of the treatment agent, permeates into the material to be treated and/or adheres to the surface of the material to be treated. The treatment methods of the present disclosure are generally capable of rendering treated objects water- and oil-repellent (or water-repellent/hydrophobic and oil-repellent/oleophobic) as well as alcohol-repellent.
　代表的には、撥水撥油剤組成物（または撥水撥油剤およびサイズ剤）を水に分散して希釈して処理液とし、これを浸漬塗布、スプレー塗布、泡塗布などのような既知の方法により被処理物に付着させ、乾燥する方法が採られ得る。また、必要ならば、撥水撥油剤組成物を適当な架橋剤と共に使用して被処理物に適用し、キュアリングを行ってもよい。さらに、撥水撥油剤組成物を、帯電防止剤、浸透剤、防虫剤、柔軟剤、抗菌剤、難燃剤、塗料定着剤、防シワ剤などと併用することも可能である。被処理物と接触させる際の処理液における含フッ素重合体およびサイズ有効成分の濃度は０.０１～１０重量％（特に、浸漬塗布の場合）、例えば０.０５～１０重量％であってよい。 Typically, the water and oil repellent composition (or the water and oil repellent and the sizing agent) is dispersed in water and diluted to form a treatment liquid, which is applied to known methods such as dip coating, spray coating and foam coating. A method of adhering to an object to be treated and drying can be adopted. If necessary, the water and oil repellent composition may be used together with a suitable cross-linking agent, applied to the object to be treated, and cured. Furthermore, the water and oil repellent composition can be used in combination with antistatic agents, penetrants, insect repellents, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, and the like. The concentration of the fluoropolymer and sizing active ingredient in the treatment liquid when brought into contact with the object to be treated may be 0.01 to 10% by weight (especially in the case of dip coating), for example 0.05 to 10% by weight. .
　撥水撥油剤組成物が、帯電防止剤および／または浸透剤を含んでなるか、あるいは撥水撥油剤組成物を帯電防止剤および／または浸透剤と併用することが好ましい。 It is preferable that the water and oil repellent composition contains an antistatic agent and/or a penetrating agent, or that the water and oil repellent composition is used in combination with an antistatic agent and/or a penetrating agent.
　本開示は、帯電防止剤を使用する場合に、顕著な効果を与える。すなわち、良好な撥アルコール性および耐水圧性を保ちながら、良好な帯電防止性が得られる。
　帯電防止剤としては、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤が挙げられる。具体的には、アニオン性界面活性剤としては、リン酸エステル系化合物、たとえば、ブチルリン酸金属塩としての、ＺＥＬＥＣ　ＴＹ（Ｓｔｅｐａｎ社製）が挙げられる。ノニオン性界面活性剤の例は、ポリオキシエチレン系化合物が、カチオン性界面活性剤としては、アルキルアンモニウムクロリドが、両性界面活性剤としては、アミドアルキルベタイン系化合物が挙げられる。帯電防止剤は、１種を単独でまたは２種以上の組み合わせで用いてもよい。
　帯電防止剤の量は、疎水性基材処理剤組成物（１００重量％）中、０．０１～１．０重量％または０．１～．５重量％であってよい。あるいは、帯電防止剤の量は、含フッ素重合体１００重量部に対して、１～１０００重量部または１０～５００重量部であってよい。 The present disclosure provides significant advantages when using antistatic agents. That is, good antistatic properties can be obtained while maintaining good alcohol repellency and water pressure resistance.
Antistatic agents include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Specifically, the anionic surfactant includes a phosphate compound such as ZELEC TY (manufactured by Stepan) as a butyl phosphate metal salt. Examples of nonionic surfactants include polyoxyethylene compounds, cationic surfactants include alkylammonium chloride, and amphoteric surfactants include amidoalkylbetaine compounds. You may use an antistatic agent individually by 1 type or in combination of 2 or more types.
The amount of the antistatic agent is 0.01-1.0% by weight or 0.1-. It may be 5% by weight. Alternatively, the amount of the antistatic agent may be 1 to 1000 parts by weight or 10 to 500 parts by weight with respect to 100 parts by weight of the fluoropolymer.
　浸透剤は、撥水撥油剤組成物を疎水性基材に浸透させることができる。浸透剤としては、アルコール、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤等が挙げられる。浸透剤の具体例には、炭素数が１～１０のアルキル基を有するアルコール、ポリオキシエチレンアルキルエーテル、n-ヘキサノールもしくはn-デカノールのノニオン乳化剤乳化分散液が挙げられる。浸透剤は、１種を単独でまたは２種以上の組み合わせで用いてもよい。
　浸透剤の量は、疎水性基材処理剤組成物（１００重量％）中、０．０１～１．０重量％または０．１～．５重量％であってよい。あるいは、浸透剤の量は、含フッ素重合体１００重量部に対して、１～１０００重量部または１０～５００重量部であってよい。 The penetrant allows the water and oil repellent composition to penetrate into the hydrophobic substrate. Penetrants include alcohols, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like. Specific examples of penetrants include nonionic emulsifier emulsified dispersions of alcohols having alkyl groups of 1 to 10 carbon atoms, polyoxyethylene alkyl ethers, n-hexanol or n-decanol. Penetrants may be used singly or in combination of two or more.
The amount of the penetrant is 0.01 to 1.0% by weight or 0.1 to . It may be 5% by weight. Alternatively, the amount of penetrant may be 1 to 1000 parts by weight or 10 to 500 parts by weight with respect to 100 parts by weight of the fluoropolymer.
　撥水撥油剤組成物で処理される被処理物（基材）としては、繊維基材が好ましい。繊維基材を撥水撥油剤組成物で処理することによって繊維製品を得ることができる。 A fibrous base material is preferable as the object (base material) to be treated with the water and oil repellent composition. A textile product can be obtained by treating a textile substrate with the water and oil repellent composition.
　被処理物が繊維基材である場合、繊維基材を液体で処理するための任意の適切な方法に従って、撥水撥油剤組成物を含んでなる処理液を用いて、撥水撥油剤組成物を繊維基材に適用することができる。
　基材の内部に撥水撥油剤組成物（撥水撥油剤およびサイズ剤）を適用してもよいが、基材の表面に撥水撥油剤組成物を適用することが好ましい。基材表面への含フッ素重合体およびサイズ有効成分のそれぞれの付着量は、（１つの面で）０.００１ｇ／ｍ２～１０ｇ／ｍ２または０．０１ｇ／ｍ２～１ｇ／ｍ２（固形分量）であってよい。 When the object to be treated is a fiber base material, the water and oil repellent composition is treated with a treatment liquid containing the water and oil repellent composition according to any suitable method for treating a fiber base material with a liquid. can be applied to the fibrous substrate.
Although the water and oil repellent composition (water and oil repellent and sizing agent) may be applied to the interior of the substrate, it is preferred to apply the water and oil repellent composition to the surface of the substrate. The amount of each of the fluorine-containing polymer and the sizing active ingredient attached to the substrate surface is 0.001 g/m 2 to 10 g/m 2 (on one side) or 0.01 g/m 2 to 1 g/m 2 ( solid content).
　繊維基材は、繊維、糸、布等の任意の形態であり得、典型的には布であり得る。代表的には、撥水撥油剤組成物を水性媒体に分散希釈して調合される処理液に繊維基材を浸漬し、その後、処理液から繊維基材（例えば布）を取り出して、ロール等（例えばロール間）で押圧することにより余分な処理液を除去し、乾燥させて、撥水撥油剤組成物の活性成分を繊維基材に残すことによって、撥水撥油性および撥アルコール性が付与された繊維製品を得ることができる。撥水撥油剤組成物は、高い加工安定性を有し、かかる処理の際、繊維基材が処理液に入ることにより機械的衝撃（またはせん断力）が処理液に加わっても、エマルション粒子が安定的に維持され得、ポリマー（含フッ素重合体）の塊状物がロール等に付着したり、繊維基材に付着したりすることを効果的に防止できる。かかる効果は、含フッ素重合体のフルオロアルキル基の炭素数が６以下である場合に特に顕著である。 The fibrous base material can be in any form such as fiber, thread, cloth, etc., and typically can be cloth. Typically, the fiber base material is immersed in a treatment liquid prepared by dispersing and diluting the water and oil repellent composition in an aqueous medium, and then the fiber base material (for example, cloth) is taken out from the treatment liquid and rolled or the like. Excess treatment liquid is removed by pressing (for example, between rolls) and dried to leave the active ingredient of the water and oil repellent composition on the fiber substrate, thereby imparting water and oil repellency and alcohol repellency. You can get a finished textile product. The water and oil repellent composition has high processing stability, and even if mechanical impact (or shear force) is applied to the treatment liquid when the fiber base material enters the treatment liquid during such treatment, the emulsion particles It can be stably maintained, and can effectively prevent polymer (fluoropolymer) lumps from adhering to a roll or the like or adhering to a fiber base material. Such an effect is particularly remarkable when the fluoroalkyl group of the fluoropolymer has 6 or less carbon atoms.
　あるいは、撥水撥油剤組成物はクリーニング法によって繊維基材に適用してよく、例えば、洗濯適用またはドライクリーニング法などにおいて繊維基材に適用してよい。 Alternatively, the water and oil repellent composition may be applied to the fibrous substrate by a cleaning method, for example, it may be applied to the fibrous substrate in a laundering application or dry cleaning method.
　繊維基材は、典型的には、布（生地とも呼ばれ得る）の形態であり、これには、織物、編物および不織布（例えば医療用不織布）、衣料品形態の布およびカーペットが含まれる。繊維基材は、他の形態、例えば、繊維、糸または中間繊維製品（例えば、スライバーまたは粗糸など）であってもよい。繊維基材は、不織布、特に医療用不織布であることが好ましい。 The fibrous substrate is typically in the form of cloth (which may also be referred to as fabric), which includes woven, knitted and nonwoven fabrics (eg medical nonwoven fabrics), clothing form fabrics and carpets. The fibrous substrate may be in other forms, such as fibers, yarns or intermediate textile products such as sliver or roving. The fibrous substrate is preferably a nonwoven fabric, especially a medical nonwoven fabric.
　繊維基材の材料としては種々の例を挙げることができ、天然繊維および化学繊維を含む任意の繊維材料であってよい。天然繊維には、例えば、綿、麻などの植物性繊維、羊毛、絹などの動物性繊維、アスベストなどの鉱物性繊維が含まれ、動植物性天然繊維が好ましく使用され得る。化学繊維には、リヨセルなどの精製繊維、レーヨン（ビスコースレーヨン等を含む）などの再生繊維、アセテートなどの半合成繊維、ポリアミド系（ナイロン、アラミド等を含む）、ポリビニルアルコール系、ポリ塩化ビニル系、ポリエステル系、ポリアクリロニトリル系、ポリオレフィン系（ポリエチレン、ポリプロピレン等を含む）、ポリエーテルエステル系、ポリウレタン系などの合成繊維、ガラス繊維、炭素繊維などの無機繊維が含まれ、精製繊維、半合成繊維、合成繊維が好ましく使用される。繊維基材の材料は、これらで例示される繊維材料からなる群より選択される２つまたはそれ以上の材料の混合物（例えば任意の天然繊維と任意の合成繊維との混合物などであってよく、混合繊維、複合繊維、混紡糸、混織糸などの形態であってもよい）であってもよい。 Various examples can be cited as the material of the fiber base material, and any fiber material including natural fibers and chemical fibers may be used. Natural fibers include, for example, vegetable fibers such as cotton and hemp, animal fibers such as wool and silk, and mineral fibers such as asbestos, and animal and plant natural fibers are preferably used. Chemical fibers include refined fibers such as lyocell, regenerated fibers such as rayon (including viscose rayon, etc.), semi-synthetic fibers such as acetate, polyamide (including nylon, aramid, etc.), polyvinyl alcohol, and polyvinyl chloride. Synthetic fibers such as polyester, polyacrylonitrile, polyolefin (including polyethylene, polypropylene, etc.), polyether ester, polyurethane, etc., inorganic fibers such as glass fiber, carbon fiber, refined fiber, semi-synthetic Fibers and synthetic fibers are preferably used. The material of the fiber base material may be a mixture of two or more materials selected from the group consisting of the fiber materials exemplified above (for example, a mixture of any natural fiber and any synthetic fiber, etc.) It may be in the form of mixed fiber, composite fiber, mixed yarn, mixed woven yarn, etc.).
　撥水撥油剤組成物は、親水性の繊維材料および疎水性の繊維材料のいずれに対しても、撥水撥油性ならびに撥アルコール性を付与することができる。親水性の繊維材料の例としては、セルロース系（綿またはレーヨンなど）が挙げられる。疎水性の繊維材料の例としては、ポリオレフィン系（ポリエチレン、ポリプロピレン、ポリエチレン混紡物など）、ポリ塩化ビニル系、ポリアミド系（ナイロンなど）、ポリエステル系、ポリスチレン系が挙げられる。 The water and oil repellent composition can impart water and oil repellency and alcohol repellency to both hydrophilic and hydrophobic textile materials. Examples of hydrophilic fibrous materials include cellulosics (such as cotton or rayon). Examples of hydrophobic fiber materials include polyolefins (polyethylene, polypropylene, polyethylene blends, etc.), polyvinyl chlorides, polyamides (nylon, etc.), polyesters, and polystyrenes.
　とりわけ、撥水撥油剤組成物は、高い撥アルコール性が求められる繊維製品、例えば医療用ガウンや手術着などに利用され得る医療用不織布などの不織布製品を製造するために、不織布の繊維基材に適用され得るが、これに限定されない。医療用不織布は、代表的には、疎水性の繊維材料から構成される不織布であってよく、例えばポリプロピレン（ＰＰ）不織布、ポリエチレンテレフタレート（ＰＥＴ）不織布、ポリプロピレンとポリエチレンとの複合不織布、ポリエチレン不織布などであってよい。 In particular, the water and oil repellent composition is used as a fiber base material for nonwoven fabrics in order to produce nonwoven fabric products such as medical nonwoven fabrics that can be used for textile products that require high alcohol repellency, such as medical gowns and surgical gowns. can be applied to, but not limited to, Nonwoven fabrics for medical use may typically be nonwoven fabrics composed of hydrophobic fibrous materials, such as polypropylene (PP) nonwoven fabrics, polyethylene terephthalate (PET) nonwoven fabrics, composite nonwoven fabrics of polypropylene and polyethylene, polyethylene nonwoven fabrics, and the like. can be
　あるいは、繊維基材は皮革であってよい。撥水撥油剤組成物を、皮革を疎水性および疎油性にするために、皮革加工の様々な段階で、例えば、皮革の湿潤加工の期間中に、または、皮革の仕上げの期間中に、水溶液または水性乳化物から皮革に適用してよい。 Alternatively, the fiber base material may be leather. The water and oil repellent composition is added in aqueous solution at various stages of leather processing, for example during wet processing of leather or during finishing of leather, in order to render the leather hydrophobic and oleophobic. Or it may be applied to leather from an aqueous emulsion.
　あるいは、繊維基材は紙であってもよい。撥水撥油剤組成物を、予め形成した紙に適用してよく、または、製紙の様々な段階で、例えば、紙の乾燥期間中に適用してもよい。 Alternatively, the fiber base material may be paper. The repellent composition may be applied to preformed paper or may be applied at various stages of papermaking, such as during drying of the paper.
　以上、実施形態について説明したが、特許請求の範囲の趣旨および範囲から逸脱することなく、形態や詳細の多様な変更が可能なことが理解されるであろう。 Although the embodiments have been described above, it will be understood that various changes in form and detail are possible without departing from the spirit and scope of the claims.
　以下、実施例を示して本開示を具体的に説明するが、これら実施例に限定されるものではない。「部」および「％」は、特記しなければ、「重量部」および「重量％」である。 The present disclosure will be specifically described below with reference to Examples, but the present disclosure is not limited to these Examples. "Parts" and "%" are "parts by weight" and "% by weight" unless otherwise specified.
　以下において使用した試験方法は次のとおりである。 The test methods used below are as follows.
［撥アルコール性］
　撥水撥油剤を純水により希釈し、サイズ剤などの薬剤を添加して、処理液（１０００ｇ）を調製した。本試験において、処理すべき布（繊維基材）として、ポリプロピレン不織布（４５ｇ／ｍ２）を使用した。１枚のポリプロピレン不織布（４５ｇ／ｍ２）（５１０ｍｍ ｘ ２０５ｍｍ）をこの処理液に浸し、マングルロール間に通し、１２０℃で２分間、ピンテンターで処理した。得られた試験布（処理済み布）について、撥アルコール性を評価した。具体的には、ＡＡＴＣＣ試験法１９３－２００７に準拠して下記の通り試験して評価した。
　処理済み布を温度２１℃、湿度５０％の恒温恒湿機に４時間以上保管する。試験液（イソプロピルアルコール（ＩＰＡ）、水、およびその混合液、表１に示す。）も温度２１℃で保存したものを使用する。試験は温度２１℃、湿度５０％の恒温恒湿室で行う。試験液を試験布上にマイクロピペットで一滴５０μＬの５滴を静かに滴下し、３０秒間放置後、４または５滴の液滴が試験布上に残っていれば、その試験液をパスしたものとする。撥アルコール性は、パスした試験液のイソプロピルアルコール（ＩＰＡ）含量（体積％）の最大なものをその点数とし、撥水性不良なものから良好なレベルまでＦａｉｌ、０、１、２、３、４、５、６、７、８、９、及び１０の１２級で評価する。級数が大きいほうが、撥アルコール性が高い。 [Alcohol Repellency]
A treatment liquid (1000 g) was prepared by diluting the water and oil repellent with pure water and adding chemicals such as a sizing agent. In this test, a polypropylene non-woven fabric (45 g/m 2 ) was used as the fabric (fiber substrate) to be treated. A sheet of polypropylene non-woven fabric (45 g/m 2 ) (510 mm x 205 mm) was immersed in this treatment solution, passed between mangle rolls, and treated with a pin tenter at 120°C for 2 minutes. The obtained test cloth (treated cloth) was evaluated for alcohol repellency. Specifically, it was tested and evaluated as follows in accordance with AATCC test method 193-2007.
The treated cloth is stored in a thermo-hygrostat at a temperature of 21° C. and a humidity of 50% for 4 hours or more. Test liquids (isopropyl alcohol (IPA), water, and mixtures thereof, shown in Table 1) are also stored at a temperature of 21°C and used. The test is performed in a constant temperature and humidity room with a temperature of 21° C. and a humidity of 50%. Gently drop 5 drops of 50 μL of the test liquid onto the test cloth with a micropipette and leave it for 30 seconds. If 4 or 5 drops remain on the test cloth, the test liquid has passed. and The alcohol repellency is scored based on the maximum isopropyl alcohol (IPA) content (% by volume) of the test solution that passes, and the water repellency ranges from poor water repellency to good level Fail, 0, 1, 2, 3, 4. , 5, 6, 7, 8, 9, and 10. The larger the series, the higher the alcohol repellency.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
[耐水圧性］
　Worldwide　Strategic　Partners(以下、WSPと記す。)80.1に従って、昇圧速度：60mbar/分の条件で、三点水滴が通過した圧力、または評価用サンプルが破断した圧力を耐水圧性とした。 [Water pressure resistance]
According to Worldwide Strategic Partners (hereinafter referred to as WSP) 80.1, the pressure at which a three-point water droplet passed or the pressure at which the sample for evaluation was broken was taken as water pressure resistance under the condition of pressure increase rate of 60 mbar/min.
［表面抵抗率］
　WSP40.1に従って、評価用サンプルに荷電圧(IOOV)を印加し、30秒後の表面電気抵抗率を測定した。 [Surface resistivity]
A charging voltage (IOOV) was applied to the evaluation sample according to WSP40.1, and the surface electrical resistivity was measured after 30 seconds.
　実施例および比較例で使用した物質は次のとおりである。
含フッ素撥水撥油剤Ａ：　製造例１
含フッ素撥水撥油剤Ｂ：　製造例２
PERGLUTIN K 175 EP：　BK Giulini GmbH社　Polymer solution with high cationic charge density, acrylate copolymer
PERGLUTIN K 485：　BK Giulini GmbH社　Cationic polymer dispersion, styrene-acrylate copolymer
AD1602：　星光PMC社　カチオン性、アルキルケテンダイマー
AD1606：　星光PMC社　弱カチオン性、アルキルケテンダイマー
Basoplast 265D：　BASF社　Cationic dispersion, Styrene-Butylacrylate copolymer
Basoplast 2023LC：　BASF社　Standard dispersion, AKD
FennoSize S A466：　Kemira社　Amphoteric surface sizing agent
Hydrores 166M：　Kemira社　Alkylketendimer wax aqueous dispersion Substances used in Examples and Comparative Examples are as follows.
Fluorine-containing water and oil repellent agent A: Production example 1
Fluorine-Containing Water and Oil Repellent B: Production Example 2
PERGLUTIN K 175 EP: Polymer solution with high cationic charge density, acrylate copolymer from BK Giulini GmbH
PERGLUTIN K 485: Cationic polymer dispersion, styrene-acrylate copolymer from BK Giulini GmbH
AD1602: Seiko PMC cationic, alkyl ketene dimer
AD1606: Seiko PMC weak cationic, alkyl ketene dimer
Basoplast 265D: BASF Cationic dispersion, Styrene-Butylacrylate copolymer
Basoplast 2023LC: BASF Standard dispersion, AKD
FennoSize S A466: Amphoteric surface sizing agent from Kemira
Hydrores 166M: Kemira Alkylketendimer wax aqueous dispersion
製造例１
　500mLオートクレーブにF(CF2)6CH2CH2OCOC(CH3)=CH261ｇ、イソノニルメタクリレート11ｇ、ラウリルアクリレート1ｇ、純水160ｇ、水溶性グリコール系溶剤25ｇ、ポリオキシエチレンアルキルエーテル9.5gを入れ、攪拌下に６０℃で１５分間、超音波で乳化分散させた。フラスコ内を窒素置換後、塩化ビニル25ｇを圧入充填し、アゾ基含有水溶性開始剤0.4ｇを添加し、６０℃で２０時間反応させ、重合体の水性分散液（含フッ素撥水撥油剤Ａ）を得た。重合体における単量体組成は、単量体の仕込組成にほぼ一致した。 Production example 1
In a 500 mL autoclave, add F(CF 2 ) 6 CH 2 CH 2 OCOC(CH 3 )=CH 2 61 g, isononyl methacrylate 11 g, lauryl acrylate 1 g, pure water 160 g, water-soluble glycol solvent 25 g, polyoxyethylene alkyl ether 9.5 g. was added and emulsified and dispersed with ultrasonic waves at 60° C. for 15 minutes while stirring. After purging the inside of the flask with nitrogen, 25 g of vinyl chloride was press-fitted, 0.4 g of an azo group-containing water-soluble initiator was added, and the mixture was reacted at 60°C for 20 hours to give an aqueous polymer dispersion (fluorine-containing water and oil repellent agent A ). The monomer composition in the polymer almost matched the charged composition of the monomers.
製造例２
　1000mLオートクレーブにCF3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)=CH2　(n=2.0)　65.1ｇ、CF3CF2-(CF2CF2)n-CH2CH2OCOCＨ=CH2　(n=2.0)　65.1ｇ、ステアリルアクリレート30.9ｇ、純水400ｇ、水溶性グリコール系溶剤56g、塩化アルキルジメチルアンモニウム1.56g、ポリオキシエチレンアルキルエーテル16.1g、を入れ、攪拌下に６０℃で１５分間、超音波で乳化分散させた。フラスコ内を窒素置換後、塩化ビニル61.2gを圧入充填し、アゾ基含有水溶性開始剤0.4ｇを添加し、６０℃で２０時間反応させ、重合体の水性分散液（含フッ素撥水撥油剤Ｂ）を得た。重合体における単量体組成は、単量体の仕込組成にほぼ一致した。 Production example 2
CF3CF2- ( CF2CF2 ) n- CH2CH2OCOC ( Cl )= CH2 (n=2.0) 65.1g, CF3CF2- ( CF2CF2 ) n - CH2 in a 1000mL autoclave Add 65.1 g of CH 2 OCOCH=CH 2 (n=2.0), 30.9 g of stearyl acrylate, 400 g of pure water, 56 g of water-soluble glycol solvent, 1.56 g of alkyldimethylammonium chloride, and 16.1 g of polyoxyethylene alkyl ether, and stir. It was emulsified and dispersed with ultrasonic waves at 60° C. for 15 minutes. After purging the inside of the flask with nitrogen, 61.2 g of vinyl chloride was press-fitted and filled, 0.4 g of an azo group-containing water-soluble initiator was added, and the mixture was reacted at 60°C for 20 hours. B) was obtained. The monomer composition in the polymer almost matched the charged composition of the monomers.
実施例１
　含フッ素撥水撥油剤Ａを純水により希釈した後に、サイズ剤、帯電防止剤および浸透剤を添加して、含フッ素撥水撥油剤Ａを０．８％、サイズ剤を０．３３％、帯電防止剤を０．３％および浸透剤を０．６％含む処理液（１０００ｇ）を調製した。処理すべき布（繊維基材）として、ポリプロピレン不織布（４５ｇ／ｍ２）を使用した。１枚のポリプロピレン不織布（４５ｇ／ｍ２）（５１０ｍｍ ｘ ２０５ｍｍ）をこの処理液に浸し、マングルロール間に通し、１２０℃で２分間、ピンテンターで処理した。撥アルコール性、耐水圧性および表面抵抗率を測定した。結果を表２に示す。 Example 1
After diluting the fluorine-containing water and oil repellent agent A with pure water, a sizing agent, an antistatic agent and a penetrating agent are added to obtain 0.8% of the fluorine-containing water and oil repellent agent A, 0.33% of the sizing agent, A treatment solution (1000 g) containing 0.3% antistatic agent and 0.6% penetrant was prepared. A polypropylene non-woven fabric (45 g/m 2 ) was used as the fabric to be treated (fiber substrate). A sheet of polypropylene non-woven fabric (45 g/m 2 ) (510 mm x 205 mm) was immersed in this treatment solution, passed between mangle rolls, and treated with a pin tenter at 120°C for 2 minutes. Alcohol repellency, water pressure resistance and surface resistivity were measured. Table 2 shows the results.
実施例２～１８
　表２に示す薬剤を使用する以外は、実施例１と同様の手順を繰り返した。結果を表２に示す。 Examples 2-18
The same procedure as in Example 1 was repeated except that the agents shown in Table 2 were used. Table 2 shows the results.
比較例１～４
　表２に示す薬剤を使用する以外は、実施例１と同様の手順を繰り返した。結果を表２に示す。 Comparative Examples 1-4
The same procedure as in Example 1 was repeated except that the agents shown in Table 2 were used. Table 2 shows the results.
［結果の考察］
　サイズ剤を添加した実施例１－１８と、サイズ剤を添加していない比較例１、２を比べると、サイズ剤添加により耐水圧が向上している。一方、実施例１にカルボジイミドを添加した比較例３では、耐水圧向上効果が弱まっている。また、アルケニル無水コハク酸を添加した比較例４では、耐水圧は向上しなかった。理論に結びつけることを意図しないが、サイズ剤でも親水性の高い組成では耐水圧を向上させる効果が低いと推定される。 [Discussion of results]
Comparing Examples 1-18 in which a sizing agent was added and Comparative Examples 1 and 2 in which no sizing agent was added, the water pressure resistance was improved by the addition of the sizing agent. On the other hand, in Comparative Example 3 in which carbodiimide was added to Example 1, the effect of improving water pressure resistance was weakened. Moreover, in Comparative Example 4 in which alkenyl succinic anhydride was added, the water pressure resistance was not improved. Although it is not intended to be bound by theory, it is presumed that even a sizing agent with a highly hydrophilic composition has a low effect of improving water pressure resistance.
　本開示の撥水撥油剤組成物は、繊維基材、特に、医療用不織布などの不織布において有用である。 The water and oil repellent composition of the present disclosure is useful for fiber substrates, particularly nonwoven fabrics such as medical nonwoven fabrics.

Claims (10)

  1. 　（１）含フッ素撥水撥油剤および（２）サイズ剤を含み、水系である不織布用撥水撥油剤組成物。 (1) a fluorine-containing water and oil repellent agent and (2) a sizing agent, and a water-based water and oil repellent composition for nonwoven fabrics.
  2. 　カルボジイミド化合物を含まず、撥水撥油剤組成物が撥水撥油剤組成物に対して２０重量％以上の水を含む請求項１に記載の不織布用撥水撥油剤組成物。 The water and oil repellent composition for non-woven fabric according to claim 1, which does not contain a carbodiimide compound and contains 20% by weight or more of water relative to the water and oil repellent composition.
  3. 　含フッ素撥水撥油剤が、式：
    ＣＨ２＝Ｃ（－Ｘ１１）－Ｃ（＝Ｏ）－Ｙ１１－Ｚ１１－Ｒｆ
    ［式中、Ｘ１１は、水素原子、一価の有機基またはハロゲン原子であり、
    Ｙ１１は、－Ｏ－または－ＮＨ－であり、
    Ｚ１１は、直接結合または二価の有機基であり、
    Ｒｆは、炭素数１～２０のフルオロアルキル基である。］
    で示される単量体から形成されている繰り返し単位を有する含フッ素重合体を含んでなる請求項１または２に記載の不織布用撥水撥油剤組成物。     The fluorine-containing water and oil repellent has the formula:
    CH 2 =C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf
    [Wherein, X 11 is a hydrogen atom, a monovalent organic group or a halogen atom;
    Y 11 is —O— or —NH—;
    Z 11 is a direct bond or a divalent organic group,
    Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
    3. The water and oil repellent composition for nonwoven fabric according to claim 1, comprising a fluoropolymer having a repeating unit formed from the monomer represented by:
  4. 　サイズ剤におけるサイズ有効成分が、アルキルケテンダイマー、アルケニルケテンダイマー、ワックス、ビニルアルコール重合体、メラミン／ホルマリン重合体、スチレン／（メタ）アクリル酸共重合体、スチレン／（メタ）アクリル酸エステル共重合体、スチレン／（メタ）アクリル酸／（メタ）アクリル酸エステル共重合体、スチレン／マレイン酸共重合体、イソブチレン／（メタ）アクリル酸共重合体、ジイソブチレン／マレイン酸共重合体、プロピレン／マレイン酸共重合体、エチレン／マレイン酸共重合体、ポリ（メタ）アクリル単独重合体および共重合体、ならびに（メタ）アクリル酸エステル／アクリロニトリル共重合体からなる群から選択された少なくとも１種である請求項１～３のいずれかに記載の不織布用撥水撥油剤組成物。 The effective sizing component in the sizing agent is alkyl ketene dimer, alkenyl ketene dimer, wax, vinyl alcohol polymer, melamine/formalin polymer, styrene/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid ester copolymer. coalescence, styrene/(meth)acrylic acid/(meth)acrylic acid ester copolymer, styrene/maleic acid copolymer, isobutylene/(meth)acrylic acid copolymer, diisobutylene/maleic acid copolymer, propylene/ At least one selected from the group consisting of maleic acid copolymers, ethylene/maleic acid copolymers, poly(meth)acrylic homopolymers and copolymers, and (meth)acrylate/acrylonitrile copolymers The water and oil repellent composition for nonwoven fabric according to any one of claims 1 to 3.
  5. 　サイズ剤におけるサイズ有効成分が、アルキルケテンダイマーおよび／またはアルケニルケテンダイマーを含む請求項１～４のいずれかに記載の不織布用撥水撥油剤組成物。 The water and oil repellent composition for nonwoven fabric according to any one of claims 1 to 4, wherein the sizing active ingredient in the sizing agent contains an alkyl ketene dimer and/or an alkenyl ketene dimer.
  6. サイズ剤におけるサイズ有効成分が、
    アルキルケテンダイマーおよび／またはアルケニルケテンダイマーに加えて、
    ワックス、ビニルアルコール重合体、メラミン／ホルマリン重合体、スチレン／（メタ）アクリル酸共重合体、スチレン／（メタ）アクリル酸エステル共重合体、スチレン／（メタ）アクリル酸／（メタ）アクリル酸エステル共重合体、スチレン／マレイン酸共重合体、イソブチレン／（メタ）アクリル酸共重合体、ジイソブチレン／マレイン酸共重合体、プロピレン／マレイン酸共重合体、エチレン／マレイン酸共重合体、ポリ（メタ）アクリル単独重合体および共重合体、ならびに（メタ）アクリル酸エステル／アクリロニトリル共重合体からなる群から選択された少なくとも１種をも含む請求項１～５のいずれかに記載の不織布用撥水撥油剤組成物。     The sizing active ingredient in the sizing agent is
    In addition to alkylketene dimers and/or alkenylketene dimers,
    Wax, vinyl alcohol polymer, melamine/formalin polymer, styrene/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid ester copolymer, styrene/(meth)acrylic acid/(meth)acrylic acid ester copolymer, styrene/maleic acid copolymer, isobutylene/(meth)acrylic acid copolymer, diisobutylene/maleic acid copolymer, propylene/maleic acid copolymer, ethylene/maleic acid copolymer, poly( The nonwoven fabric repellent according to any one of claims 1 to 5, further comprising at least one selected from the group consisting of meth)acrylic homopolymers and copolymers, and (meth)acrylate/acrylonitrile copolymers. Water and oil repellent composition.
  7. 　撥水撥油剤組成物が、帯電防止剤および浸透剤から選択された少なくとも１種を含んでなるか、あるいは撥水撥油剤組成物を帯電防止剤および浸透剤から選択された少なくとも１種と併用する請求項１～６のいずれかに記載の不織布用撥水撥油剤組成物。 The water and oil repellent composition contains at least one selected from antistatic agents and penetrating agents, or the water and oil repellent composition is used in combination with at least one selected from antistatic agents and penetrating agents. The water and oil repellent composition for nonwoven fabric according to any one of claims 1 to 6.
  8. （１）撥水撥油剤、および
    （２）サイズ剤
    を有する不織布用撥水撥油剤キット。     A nonwoven fabric water and oil repellent kit comprising (1) a water and oil repellent and (2) a sizing agent.
  9. 　不織布を請求項１～７のいずれかに記載の不織布用撥水撥油剤組成物または請求項８に記載の不織布用撥水撥油剤キットで処理する不織布の処理方法。 A method for treating a nonwoven fabric, comprising treating the nonwoven fabric with the water and oil repellent composition for nonwoven fabric according to any one of claims 1 to 7 or the water and oil repellent agent kit for nonwoven fabric according to claim 8.
  10. 　請求項１～７のいずれかに記載の不織布用撥水撥油剤組成物または請求項８に記載の不織布用撥水撥油剤キットにおける撥水撥油重合体およびサイズ有効成分が付着している不織布製品。 Nonwoven fabric to which the water and oil repellent polymer and size active ingredient in the water and oil repellent composition for nonwoven fabric according to any one of claims 1 to 7 or the water and oil repellent agent kit for nonwoven fabric according to claim 8 are attached. product.
PCT/JP2023/004006 2022-02-09 2023-02-07 Water- and oil-repellent composition for nonwoven fabric, and nonwoven fabric product WO2023153403A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210121185.6A CN116607324A (en) 2022-02-09 2022-02-09 Water-repellent and oil-repellent composition for nonwoven fabric and nonwoven fabric product
CN202210121185.6 2022-02-09

Publications (1)

Publication Number Publication Date
WO2023153403A1 true WO2023153403A1 (en) 2023-08-17

Family

ID=87564434

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/004006 WO2023153403A1 (en) 2022-02-09 2023-02-07 Water- and oil-repellent composition for nonwoven fabric, and nonwoven fabric product

Country Status (2)

Country Link
CN (1) CN116607324A (en)
WO (1) WO2023153403A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0657659A (en) * 1992-07-17 1994-03-01 Bayer Kk Method for deeply coloring processing of fiber product
JPH07292573A (en) * 1994-04-19 1995-11-07 Higashi Kagaku:Kk Cloth and its finishing method
JP2005288282A (en) * 2004-03-31 2005-10-20 Powdertech Co Ltd Deoxidizer package
JP2014221456A (en) * 2013-05-13 2014-11-27 北越紀州製紙株式会社 Filter medium for air filter, and method of manufacturing the same
JP2020153057A (en) * 2019-03-13 2020-09-24 ユニチカトレーディング株式会社 Woven or knitted fabric and method for producing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0657659A (en) * 1992-07-17 1994-03-01 Bayer Kk Method for deeply coloring processing of fiber product
JPH07292573A (en) * 1994-04-19 1995-11-07 Higashi Kagaku:Kk Cloth and its finishing method
JP2005288282A (en) * 2004-03-31 2005-10-20 Powdertech Co Ltd Deoxidizer package
JP2014221456A (en) * 2013-05-13 2014-11-27 北越紀州製紙株式会社 Filter medium for air filter, and method of manufacturing the same
JP2020153057A (en) * 2019-03-13 2020-09-24 ユニチカトレーディング株式会社 Woven or knitted fabric and method for producing the same

Also Published As

Publication number Publication date
CN116607324A (en) 2023-08-18

Similar Documents

Publication Publication Date Title
JP5971376B2 (en) Water-based surface treatment agent
JP5915641B2 (en) Water and oil repellent composition
JP5971375B2 (en) Surface treatment agent for water-based emulsion
KR102513179B1 (en) surface treatment agent
JP3864610B2 (en) Water-dispersed water / oil repellent composition and method for producing the same
JP6673462B2 (en) Surface treatment agent
EP2762504A1 (en) Water-repellent and oil-repellent composition
EP2799458B1 (en) Fluorine-containing composition and fluorine-containing polymer
KR101635306B1 (en) Method for manufacturing fluorine-containing polymer
JP2013136687A (en) Surface treating agent, and method for producing the same
JP6866699B2 (en) Surface treatment agent composition
JP7157307B2 (en) Water and oil repellents and textile products
KR102262233B1 (en) Fluorine-containing polymer and surface treatment agent composition
JP3744035B2 (en) Water-dispersed water / oil repellent composition with excellent stability
WO2020158191A1 (en) Water-repellent softening agent
JP6280298B2 (en) Surface treatment agent
JP6249048B2 (en) Surface treatment agent and method for producing the same
JP2002220539A (en) Water-dispersed fluorocopolymer composition
WO2023153403A1 (en) Water- and oil-repellent composition for nonwoven fabric, and nonwoven fabric product
TWI656207B (en) Surface treatment composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23752867

Country of ref document: EP

Kind code of ref document: A1