WO2016208662A1 - Surface treatment agent composition - Google Patents

Surface treatment agent composition Download PDF

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Publication number
WO2016208662A1
WO2016208662A1 PCT/JP2016/068625 JP2016068625W WO2016208662A1 WO 2016208662 A1 WO2016208662 A1 WO 2016208662A1 JP 2016068625 W JP2016068625 W JP 2016068625W WO 2016208662 A1 WO2016208662 A1 WO 2016208662A1
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WIPO (PCT)
Prior art keywords
group
fluorine
monomer
carbon atoms
agent composition
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PCT/JP2016/068625
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French (fr)
Japanese (ja)
Inventor
晋一 南
福森　正樹
正弘 宮原
正人 井置
育男 山本
孝司 榎本
涛 陳
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ダイキン工業株式会社
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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
Priority to CN201680037178.0A priority Critical patent/CN107683317B/en
Priority to KR1020177036717A priority patent/KR102100174B1/en
Publication of WO2016208662A1 publication Critical patent/WO2016208662A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to a surface treatment composition such as a treatment agent, particularly a water / oil repellent composition containing a fluoropolymer mixture.
  • a surface treatment composition such as a treatment agent, particularly a water / oil repellent composition containing a fluoropolymer mixture.
  • the present invention has excellent water repellency, oil repellency, antifouling properties, particularly fibers, for textile products (for example, carpets), paper, nonwoven fabrics, stones, electrostatic filters, dust masks, and fuel cell components.
  • the present invention relates to a water / oil repellent composition having excellent processing sustainability during continuous water / oil repellent processing.
  • the fluorine-containing compound has an advantage of excellent properties such as heat resistance, oxidation resistance, and weather resistance.
  • the fluorine-containing compound is used as, for example, a water / oil repellent and an antifouling agent by utilizing the characteristic that the free energy of the fluorine-containing compound is low, that is, it is difficult to adhere.
  • Examples of the fluorine-containing compound that can be used as a water / oil repellent include a fluorine-containing polymer having a (meth) acrylate ester having a fluoroalkyl group as a constituent monomer.
  • a fluorine-containing polymer having a (meth) acrylate ester having a fluoroalkyl group as a constituent monomer In practical treatment of fibers with surface treatment agents, various research results so far indicate that dynamic contact angles, particularly receding contact angles, are important as surface characteristics, not static contact angles. That is, the advancing contact angle of water does not depend on the carbon number of the side chain of the fluoroalkyl group, but the receding contact angle of water is significantly smaller at 7 or less than the carbon number of the side chain of 8 or more. .
  • Japanese Patent Laid-Open No. 2001-98257 discloses a polymer (A) containing a polymerization unit of a polymerizable monomer having a polyfluoroalkyl group, a surfactant (B) having a specific Draves wetting time, and an aqueous medium (C ) Is an essential component.
  • JP-A-2004-262970 discloses a water / oil repellent aqueous composition containing a fluorine-based water / oil repellent (A), an emulsion (B) containing paraffin wax and carboxy group-containing polyethylene, and an organic acid (C). Is disclosed. These patents do not mention processing sustainability.
  • One object of the present invention is to provide a surface treating agent composition that is excellent in processing sustainability of water and oil repellent processing such as fibers.
  • the present invention (I) a first fluorine-containing polymer having a repeating unit derived from a fluorine-containing monomer (a) and a repeating unit derived from a halogenated olefin (b), (II) a second fluorine-containing polymer having a repeating unit derived from the fluorine-containing monomer (a) and having no repeating unit derived from a halogenated olefin; and (III) a liquid medium It is related with the surface treating agent composition which consists of.
  • the surface treating agent composition of the present invention is excellent in processing sustainability of water / oil repellent processing. According to the present invention, excellent durability such as excellent water repellency, oil repellency, antifouling property and dirt detachability, for example, water and oil repellency can be obtained.
  • the surface treating agent composition of the present invention can be used as a water / oil repellent composition, an antifouling agent composition and / or a soil release agent composition.
  • the fluoropolymer is a combination of a first fluoropolymer and a second fluoropolymer.
  • a monomer constituting the repeating unit of the fluoropolymer A fluorine-containing monomer (a), a halogenated olefin monomer (b), and a monomer (c) other than the monomers (a) and (b) are used.
  • the first fluorinated polymer and the second fluorinated polymer serve as active ingredients of the water / oil repellent, the antifouling agent and the soil release agent.
  • the fluorinated monomer is generally a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group, a methacrylic acid group, or an ⁇ -substituted acrylic acid group.
  • X are Cl, Br, I, F, CN, CF 3 , preferably Cl.
  • the surface treatment composition is excellent in practical water repellency (particularly spray water repellency).
  • the Rf group is preferably a perfluoroalkyl group.
  • the number of carbon atoms in the Rf group is preferably 1 to 12, for example 1 to 6, particularly 4 to 6, and more preferably 6.
  • Rf groups are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ).
  • Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group, -CH 2 CH 2 N (R 1 ) SO 2 -group (where R 1 is an alkyl group having 1 to 4 carbon atoms), -CH 2 CH (OZ 1 ) CH 2- (Ph-O) p -group (where Z 1 is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1),-(CH 2 ) n -Ph-O- group (where Ph is a phenylene group, 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, for example, 1 or 2 carbon atoms).
  • the aromatic group or cycloaliphatic group may be substituted or unsubstituted.
  • the S group or SO 2 group may be directly bonded to the Rf group.
  • fluorine-containing monomer (a) include, but are not limited to, for example, the following.
  • the halogenated olefin monomer (halogenated olefin) preferably has no fluorine atom.
  • the halogenated olefin is preferably an olefin 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 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. Vinyl chloride and vinylidene chloride are preferred, with vinyl chloride being particularly preferred.
  • Other monomers (c) other than the monomer monomers (a) and (b) preferably do not contain fluorine.
  • examples of the other monomer (c) include a non-fluorine non-crosslinkable monomer (c1) and a non-fluorine crosslinkable monomer (c2).
  • the non-fluorine non-crosslinkable monomer (c1) is a monomer containing no fluorine atom.
  • the non-fluorine non-crosslinkable monomer (c1) does not have a crosslinkable functional group.
  • the non-fluorine noncrosslinkable monomer (c1) is noncrosslinkable.
  • the non-fluorine non-crosslinkable monomer (c1) is preferably a non-fluorine monomer having a carbon-carbon double bond.
  • the non-fluorine non-crosslinkable monomer (c1) is preferably a vinyl monomer containing no fluorine.
  • the non-fluorine non-crosslinkable monomer (c1) is generally a compound having one carbon-carbon double bond.
  • linear or cyclic hydrocarbon group having 1 to 30 carbon atoms examples include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, and 6 to 6 carbon atoms. 30 aromatic hydrocarbon groups, and aromatic aliphatic hydrocarbon groups having 7 to 30 carbon atoms.
  • non-fluorine non-crosslinkable monomer (c1) examples include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, Methoxy polypropylene glycol (meth) acrylate and vinyl alkyl ether are included.
  • the non-fluorine non-crosslinkable monomer (c1) is not limited to these examples.
  • the non-fluorine non-crosslinkable monomer (c1) may be a (meth) acrylate ester having an alkyl group.
  • the number of carbon atoms in the alkyl group may be 1-30, for example, 6-30 (eg 10-30).
  • the non-fluorine non-crosslinkable monomer (c1) may be a (meth) acrylate monomer having a cyclic hydrocarbon group.
  • a 21 represents a hydrogen atom or a methyl group
  • a 22 is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms.
  • the cyclic hydrocarbon group-containing acrylate ester monomer is a monomer whose homopolymer has a high glass transition point (for example, 50 ° C. or higher, particularly 80 ° C. or higher).
  • the cyclic hydrocarbon group-containing acrylate ester monomer does not have a fluoroalkyl group.
  • the cyclic hydrocarbon group-containing acrylate ester monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.
  • a 21 is particularly preferably a methyl group.
  • a 22 is a cyclic hydrocarbon group which may have a chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups. The cyclic hydrocarbon group is preferably saturated.
  • the cyclic hydrocarbon group has 4 to 30 carbon atoms, preferably 6 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an araliphatic group having 7 to 20 carbon atoms.
  • the number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 12 or less.
  • the cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. 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.
  • cyclic hydrocarbon group-containing acrylate ester monomers include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2- And ethyl-2-adamantyl (meth) acrylate.
  • the presence of the cyclic hydrocarbon group-containing acrylate ester monomer increases the water repellency and oil repellency provided by the copolymer.
  • the fluoropolymer of the present invention may have a repeating unit derived from the non-fluorine crosslinkable monomer (c2).
  • the non-fluorine crosslinkable monomer (c2) is a monomer containing no fluorine atom.
  • the non-fluorine crosslinkable monomer (c2) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine.
  • the non-fluorine crosslinkable monomer (c2) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group.
  • the non-fluorine crosslinkable monomer (c2) may be mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group.
  • the non-fluorine crosslinkable monomer (c2) may be di (meth) acrylate.
  • non-fluorine crosslinkable monomer (c2) examples include diacetone (meth) acrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3- Chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di ( Examples include (meth) acrylate
  • non-fluorine non-crosslinkable monomer (c1) and / or the non-fluorine crosslinkable monomer (c2) By copolymerizing the non-fluorine non-crosslinkable monomer (c1) and / or the non-fluorine crosslinkable monomer (c2), water and oil repellency and antifouling properties, and cleaning resistance and washing resistance of these performances Various properties such as solubility, solubility in solvents, hardness, and feel can be improved as necessary.
  • acrylate when simply referred to as “acrylate” or “acrylamide”, not only a compound in which the ⁇ -position is a hydrogen atom, but also the ⁇ -position is another group (for example, a monovalent organic group including a methyl group). Or a compound substituted with a halogen atom).
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acrylamide” means acrylamide or methacrylamide.
  • Each of the monomer (a), the monomer (b), and the monomer (c) (for example, each of the monomers (c1) and (c2)) may be a single type, or Two or more combinations may be used.
  • the amount of each monomer in the first fluoropolymer is as follows.
  • the amount of the fluorine-containing monomer (a) may be 20% by weight to 100% by weight, preferably 30% by weight to 90% by weight with respect to the fluorine-containing polymer.
  • the amount of halogenated olefin monomer (b) is 5 to 300 parts by weight, for example 10 to 200 parts by weight, in particular 20 to 100 parts by weight, especially 30 to 80 parts by weight;
  • the amount of the other monomer (c) is 0 to 800 parts by weight, for example 1 to 300 parts by weight, in particular 2 to 200 parts by weight, in particular 3 to 100 parts by weight.
  • the amount of non-fluorine non-crosslinkable monomer (c1) is 0 to 500 parts by weight, for example 1 to 300 parts by weight, in particular 2 to 200 parts by weight, in particular 3 to 100 parts by weight
  • the amount of non-fluorine crosslinkable monomer (c2) may be 0 to 80 parts by weight, for example 0 to 50 parts by weight, in particular 0.1 to 30 parts by weight, especially 1 to 20 parts by weight.
  • the amount of each monomer in the second fluoropolymer is as follows.
  • the amount of the fluoromonomer (a) may be 20% by weight to 100% by weight, preferably 30% by weight to 90% by weight, based on the fluoropolymer.
  • the second fluoropolymer does not have a repeating unit derived from a halogenated olefin.
  • the amount of the other monomer (c) is 0 to 800 parts by weight, for example 1 to 300 parts by weight, in particular 2 to 200 parts by weight, in particular 3 to 100 parts by weight.
  • the amount of non-fluorine non-crosslinkable monomer (c1) is 0 to 500 parts by weight, for example 1 to 300 parts by weight, in particular 2 to 200 parts by weight, in particular 3 to 100 parts by weight.
  • the amount of non-fluorine crosslinkable monomer (c2) may be 0 to 80 parts by weight, for example 0 to 50 parts by weight, in particular 0.1 to 30 parts by weight, especially 1 to 20 parts by weight.
  • each of the fluorinated monomer (a) and the other monomer (c) in the first fluorinated polymer and the second fluorinated polymer may be the same or different.
  • the weight ratio of the first fluoropolymer to the second fluoropolymer may be 5:95 to 95: 5, for example, 20:80 to 20:80.
  • the molecule of the first fluoropolymer and the molecule of the second fluoropolymer are not chemically bonded.
  • the surfactant contains one or both of a nonionic surfactant and a cationic surfactant. Further, the surfactant may include an amphoteric surfactant. It is preferable that the surfactant does not contain an anionic surfactant.
  • Nonionic surfactant is a nonionic surfactant having an oxyalkylene group.
  • the number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2 to 10. In general, the number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100.
  • Nonionic surfactants are alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, linear and / or branched fatty acids (saturated and / or unsaturated).
  • Polyalkylene glycol ester polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), alkylene oxide adduct of acetylene glycol, and the like.
  • the structures of the alkylene oxide addition moiety and the polyalkylene glycol moiety are polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (random copolymer or block copolymer) Is preferred).
  • the nonionic surfactant preferably has a structure that does not contain an aromatic group because of environmental problems (biodegradability, environmental hormones, etc.).
  • Nonionic surfactants have the formula: R 1 O— (CH 2 CH 2 O) p — (R 2 O) q —R 3 [Wherein R 1 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 is an alkylene group having 3 or more carbon atoms (for example, 3 to 10 carbon atoms), and R 3 Is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is 0 or a number of 1 or more. ] It may be a compound shown by these.
  • R 1 preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms.
  • R 1 include a lauryl group, a tridecyl group, and an oleyl group.
  • R 2 are a propylene group and a butylene group.
  • p may be a number of 3 or more (for example, 5 to 200).
  • q may be a number of 2 or more (for example, 5 to 200). That is, — (R 2 O) q — may form a polyoxyalkylene chain.
  • the nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center.
  • the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and an oxystyrene chain. Of these, an oxypropylene chain is preferable.
  • Preferred nonionic surfactants have the formula: R 1 O— (CH 2 CH 2 O) p —H [Wherein, R 1 and p are as defined above. ] Is a surfactant.
  • nonionic surfactants are: C 10 H 21 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H C 12 H 25 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H C 16 H 31 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H C 16 H 33 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H C 18 H 35 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H C 18 H 37 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H C 12 H 25 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -C 12 H 25 C 16 H 31 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -C 16 H 31 C 16 H 33 O- (CH 2 CH 2 O)
  • nonionic surfactants include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C 7 -C 19 ) or alkyl. Condensation products with (C 12 -C 18 ) amine and the like are included.
  • the proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, in particular 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer).
  • the average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example, 500 to 3,000.
  • Nonionic surfactants can be used alone or in combination of two or more.
  • the nonionic surfactant is preferably a combination of two or more. In a combination of two or more, at least one nonionic surfactant is R 1 O— (CH 2 CH) in which the R 1 group (and / or R 3 group) is a branched alkyl group (eg, an isotridecyl group).
  • the amount of the nonionic surfactant in which R 1 group is a branched alkyl group is 5 to 100 parts by weight, for example, 8 to 50 parts by weight, particularly 10 parts per 100 parts by weight of the nonionic surfactant (B2). It may be up to 40 parts by weight.
  • the remaining nonionic surfactant is an R 1 group (and / or R 3 group) (saturated and / or unsaturated) linear alkyl group (eg, lauryl group (n- R 1 O— (CH 2 CH 2 O) p — (R 2 O) q —R 3 [particularly R 1 O— (CH 2 CH 2 O) p —H], which is a lauryl group)) It may be.
  • R 1 group (and / or R 3 group) (saturated and / or unsaturated) linear alkyl group eg, lauryl group (n- R 1 O— (CH 2 CH 2 O) p — (R 2 O) q —R 3 [particularly R 1 O— (CH 2 CH 2 O) p —H], which is a lauryl group)
  • Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Examples thereof include polyethylene glycol polypropylene glycol block copolymers.
  • the nonionic surfactant may be acetylene alcohol (particularly acetylene glycol) or acetylene alcohol (particularly acetylene). Glycol) oxyethylene adducts are preferred.
  • a preferred nonionic surfactant is an alcohol having an unsaturated triple bond or an alkylene oxide adduct of the alcohol (both the alcohol and the alkylene oxide adduct are referred to as “acetylene alcohol compounds”).
  • Particularly preferred nonionic surfactants are alkylene oxide adducts of monools or polyols having unsaturated triple bonds.
  • An acetylene alcohol compound is a compound containing one or more triple bonds and one or more hydroxyl groups.
  • the acetylene alcohol compound may be a compound containing a polyoxyalkylene moiety. Examples of the polyoxyalkylene moiety include polyoxyethylene, polyoxypropylene, a random addition structure of polyoxyethylene and polyoxypropylene, and a block addition structure of polyoxyethylene and polyoxypropylene.
  • the acetylene alcohol compound has the formula: HO—CR 11 R 12 —C ⁇ C—CR 13 R 14 —OH, or HO—CR 15 R 16 —C ⁇ C—H [Wherein R 11 , R 12 , R 13 , R 14 , R 15 , R 16 may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ] It may be a compound shown by these.
  • the acetylene alcohol compound may be an alkylene oxide adduct of the compound represented by this chemical formula.
  • the alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and particularly preferably a linear or branched alkyl group having 6 to 12 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group.
  • the alkylene oxide is preferably an alkylene oxide having 1 to 20 carbon atoms (particularly 2 to 5) such as ethylene oxide or propylene oxide, and the addition number of alkylene oxide is preferably 1 to 50.
  • the cationic surfactant is preferably a compound having no amide group.
  • the cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt.
  • Specific examples of the cationic surfactant include, but are not limited to, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, Quaternary ammonium salt type surfactants such as alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like can be mentioned.
  • Preferred examples of the cationic surfactant are: R 21 -N + (-R 22) (- R 23) (- R 24) X - [Wherein R 21 , R 22 , R 23 and R 24 represent a hydrocarbon group having 1 to 30 carbon atoms, X is an anionic group. ] It is a compound of this.
  • R 21 , R 22 , R 23 and —R 24 are alkyl groups (eg, methyl group, butyl group, stearyl group, palmityl group).
  • Specific examples of X are halogen (for example, chlorine) and acid (for example, hydrochloric acid, acetic acid).
  • the cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 30 carbon atoms).
  • the cationic surfactant is preferably an ammonium salt.
  • It may be an ammonium salt represented by R 1 may have 12 to 50 carbon atoms, such as 12 to 30 carbon atom
  • cationic surfactant examples include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl Di (hydropolyoxyethylene) ammonium chloride, benzyldodecyl di (hydropolyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride are included.
  • amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, betaine acetate, and the like. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethylhydroxyethyl imidazolinium betaine, lauryl dimethyl. Examples include aminoacetic acid betaine and fatty acid amidopropyldimethylaminoacetic acid betaine.
  • Each of the nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may be one kind or a combination of two or more.
  • the surfactant only the nonionic surfactant or only the cationic surfactant may be used, but it is preferable to use a combination of the nonionic surfactant and the cationic surfactant.
  • the weight ratio of the nonionic surfactant to the cationic surfactant is preferably 85:15 to 20:80, more preferably 80:20 to 40: It may be 60.
  • the total amount of the surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight with respect to 100 parts by weight of the polymer.
  • the liquid medium surface treating agent composition is preferably a dispersion in which a polymer is dispersed in a liquid medium.
  • the liquid medium may be an organic solvent, but is preferably an aqueous medium.
  • the “aqueous medium” refers to a medium composed of only water and an organic solvent (generally a water-soluble organic solvent) in addition to water (the amount of the organic solvent is 80 parts by weight with respect to 100 parts by weight of water. In the following, for example, the medium also contains 0.1 to 50 parts by weight, in particular 5 to 30 parts by weight.
  • the amount of the aqueous medium may be 20 to 99% by weight, for example 40 to 95% by weight, based on the surface treatment agent composition.
  • the surface treating agent composition may contain a non-fluorine water-repellent compound as a component other than the fluoropolymer and the surfactant.
  • the non-fluorine water repellent compound surface treating agent composition may contain a water repellent compound containing no fluorine atom (non-fluorine water repellent compound).
  • the non-fluorine water repellent compound may be a non-fluorine acrylate polymer, a saturated or unsaturated hydrocarbon compound, or a silicone compound.
  • the non-fluorine acrylate polymer is a homopolymer composed of one type of non-fluorine acrylate monomer, a copolymer composed of at least two types of non-fluorine acrylate monomers, or at least one type of non-fluorine acrylate monomer. It is a copolymer composed of an acrylate monomer and at least one other non-fluorine monomer (ethylenically unsaturated compound such as ethylene or vinyl monomer).
  • A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
  • T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond.
  • linear or cyclic hydrocarbon group having 1 to 30 carbon atoms examples include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, and 6 to 6 carbon atoms. 30 aromatic hydrocarbon groups, and aromatic aliphatic hydrocarbon groups having 7 to 30 carbon atoms.
  • non-fluorinated acrylate monomers include, for example, alkyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate It is.
  • the non-fluorine acrylate monomer is preferably an alkyl (meth) acrylate ester.
  • the number of carbon atoms in the alkyl group may be 1-30, for example, 6-30 (eg 10-30).
  • Specific examples of non-fluorine acrylate monomers are lauryl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate.
  • the non-fluorinated acrylate polymer can be produced by the same polymerization method as that of the fluoropolymer.
  • the saturated or unsaturated hydrocarbon compound is preferably a saturated hydrocarbon.
  • the carbon number may be 15 or more, preferably 20 to 300, for example 25 to 100.
  • Specific examples of the saturated or unsaturated hydrocarbon compound include paraffin.
  • Silicone compounds are generally used as water repellents. The silicone compound is not limited as long as it is a compound exhibiting water repellency.
  • the amount of the non-fluorine water repellent compound is 0 to 500 parts by weight, for example, 5 to 200 parts by weight, particularly 5 to 100 parts by weight based on the total of 100 parts by weight of the first fluoropolymer and the second fluoropolymer. It may be part by weight.
  • the fluorine-containing polymer (first fluorine-containing monomer and second fluorine-containing monomer) in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected.
  • Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.
  • solution polymerization a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, is heated and stirred in the range of 30 to 120 ° C. for 1 to 10 hours.
  • the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. Can be mentioned.
  • the polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
  • the organic solvent is inert to the monomer and dissolves them.
  • an ester for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate
  • a ketone for example, carbon It may be a ketone having a number of 2 to 30, specifically methyl ethyl ketone or diisobutyl ketone, or an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol).
  • organic solvent examples include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, Examples include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like.
  • the organic solvent is used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total
  • Emulsion polymerization employs a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after purging with nitrogen, the mixture is stirred and polymerized in the range of 50 to 80 ° C. for 1 to 10 hours.
  • Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used.
  • the polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
  • the monomer is polymerized by submerging the monomer into water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable.
  • an emulsifier various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers.
  • a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers.
  • water-soluble organic solvent examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water.
  • the low molecular weight monomer examples include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers.
  • it may be used in the range of 10 to 40 parts by weight.
  • a chain transfer agent may be used.
  • the molecular weight of the polymer can be varied.
  • chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol and thioglycerol (especially alkyl mercaptans (for example, having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium bisulfite. Etc.
  • the chain transfer agent may be used in an amount of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomers.
  • the treatment agent composition of the present invention may be in the form of a solution, an emulsion (particularly an aqueous dispersion) or an aerosol, but is preferably an aqueous dispersion.
  • the treating agent composition comprises a polymer (active component of the surface treating agent) and a medium (particularly a liquid medium such as an organic solvent and / or water).
  • the amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the treatment agent composition.
  • the concentration of the polymer may be 0.01 to 95% by weight, such as 5 to 50% by weight.
  • the treating agent composition of the present invention can be applied to an object to be treated by a conventionally known method.
  • the treatment agent composition is dispersed in an organic solvent or water, diluted, and attached to the surface of an object to be treated by a known method such as dip coating, spray coating, foam coating, etc., and then dried. Taken. Further, if necessary, it may be applied together with an appropriate crosslinking agent and cured.
  • an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent and the like can be added to the treatment agent composition of the present invention.
  • the concentration of the polymer in the treatment liquid brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example 0.05 to 10% by weight.
  • Examples of the object to be treated with the treating agent composition (for example, water and oil repellent) of the present invention include textile products, stone materials, filters (for example, electrostatic filters), dust masks, fuel cell components (for example, gas) Diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like.
  • filters for example, electrostatic filters
  • dust masks for example, fuel cell components (for example, gas) Diffusion electrodes and gas diffusion supports
  • glass paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides
  • ceramic products plastics, painted surfaces, plasters and the like.
  • natural animal and vegetable fibers such as cotton, hemp, wool, and silk
  • synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene
  • semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers
  • Inorganic fibers such as asbestos fibers, or mixed fibers thereof.
  • the fiber product may be in the form of a fiber, cloth or the like.
  • the treatment agent composition of the present invention can also be used as an internal release agent or an external release agent.
  • the polymer can be applied to a fibrous substrate (eg, a textile product, etc.) by any of the known methods for treating textile products with a liquid.
  • a fibrous substrate eg, a textile product, etc.
  • the fabric may be immersed in the solution, or the solution may be attached or sprayed onto the fabric.
  • the treated fiber product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.
  • the polymer may be applied to the textile by a cleaning method, for example, it may be applied to the textile by a laundry application or a dry cleaning method.
  • the textile products to be treated are typically fabrics, which include woven, knitted and non-woven fabrics, fabrics and carpets in clothing form, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving yarn).
  • the textile product material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or May be a mixture of fibers, such as a mixture of natural and synthetic fibers.
  • the production polymer of the present invention is particularly effective in making cellulosic fibers (such as cotton or rayon) oleophobic and oleophobic.
  • the method of the present invention also generally makes the textile product hydrophobic and water repellent.
  • the fibrous base material may be leather.
  • aqueous solutions or aqueous emulsifications at various stages of leather processing, for example during the wet processing of leather or during the finishing of leather You may apply it to leather from things.
  • the fibrous substrate may be paper.
  • the production polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.
  • “Processing” means applying a treatment agent to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the polymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.
  • shower water repellency test A shower water repellency test was conducted according to JIS-L-1092. The shower water repellency test was performed (as shown in Table 1 below). Represented by. A glass funnel with a volume of at least 250 ml and a spray nozzle capable of spraying 250 ml of water for 20-30 seconds are used. The specimen frame is a metal frame having a diameter of 15 cm. Three test piece sheets having a size of about 20 cm ⁇ 20 cm are prepared, and the sheet is fixed to the test piece holder frame so that the sheet is not wrinkled. Center the spray on the center of the sheet. Room temperature water (250 mL) is placed in a glass funnel and sprayed onto the specimen sheet (over a time period of 25-30 seconds).
  • Ten test specimen sheets having a water repellent continuous processability size of about 20 cm ⁇ 50 cm are prepared and continuously treated with a water / oil repellent treatment solution diluted to a predetermined concentration. Each sheet is evaluated by performing the above-described shower water repellency test.
  • VCM vinyl chloride
  • VCM vinyl chloride
  • VCM vinyl chloride
  • VCM vinyl chloride
  • Comparative production example 3 A 500 ml reaction flask is charged with 136.6 g of paraffin (melting point: 50 ° C.), 194 g of pure water, 34.1 g of water-soluble glycol solvent, 6.3 g of alkyltrimethylammonium chloride, 7.0 g of polyoxyethylene alkyl ether, and stirred at 60 ° C. for 15 minutes. An aqueous dispersion was obtained by emulsifying and dispersing with ultrasonic waves. The composition of the polymer almost coincided with the composition of the charged monomer.
  • Example 1 The aqueous liquid produced in Production Examples 1 and 2 was diluted with pure water so that the fluoropolymer concentration was 30% solids, mixed at 50:50 and stirred sufficiently, A 2.00% test solution (100 g) was prepared by further diluting with water so that the ratio was 2%. Ten PET cloths (500 mm ⁇ 200 mm) were continuously dipped in this test solution, passed through a mangle, and treated with a pin tenter at 170 ° C. for 1 minute. Thereafter, it was subjected to a water repellency test. The results are shown in Table A. Table A also shows the results of measuring the initial water repellency of the test solutions having concentrations of 1.00%, 1.20% and 1.40%.
  • Example 2 After the aqueous liquid produced in Production Examples 1 and 2 was diluted with pure water so that the fluoropolymer concentration was 30% solids, it was mixed at 30:70 and sufficiently stirred. It processed and evaluated similarly. The results are shown in Table A.
  • Example 3 After the aqueous liquid produced in Production Examples 2 and 3 was diluted with pure water so that the fluoropolymer concentration was 30% solids, it was mixed at 50:50 and sufficiently stirred. It processed and evaluated similarly. The results are shown in Table A.
  • Example 4 After the aqueous liquid produced in Production Examples 2 and 3 was diluted with pure water so that the fluoropolymer concentration was 30% solids, it was mixed at 70:30 and sufficiently stirred. It processed and evaluated similarly. The results are shown in Table A.
  • Example 5 After the aqueous liquid produced in Production Examples 4 and 5 was diluted with pure water so that the fluoropolymer concentration was 30% solids, it was mixed at 50:50 and sufficiently stirred. It processed and evaluated similarly. The results are shown in Table A.
  • Example 6 After the aqueous liquid produced in Production Examples 1, 2, and 6 was diluted with pure water so that the polymer concentration was 30% solids, the mixture was mixed at 50: 17.5: 32.5 and stirred sufficiently, Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
  • Example 7 The aqueous liquids produced in Production Examples 1, 2, and 7 were diluted with pure water so that the polymer concentration was 30% solids, then mixed at 50:25:25 and stirred sufficiently, and then the Examples The same treatment as in Example 1 was performed. The results are shown in Table A.
  • Comparative Example 1 The aqueous liquid produced in Production Example 1 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
  • Comparative Example 2 The aqueous liquid produced in Production Example 2 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
  • Comparative Example 3 The aqueous liquid produced in Production Example 3 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
  • Comparative Example 4 The aqueous liquid produced in Production Example 4 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
  • Comparative Example 5 The aqueous liquid produced in Production Example 5 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
  • Comparative Example 6 The aqueous liquid produced in Comparative Production Example 1 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
  • Comparative Example 7 The aqueous liquid produced in Comparative Production Example 2 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
  • Comparative Example 8 The aqueous liquid produced in Production Example 1 and Comparative Production Example 3 was diluted with pure water so that the concentration became 30% solids, then mixed at 75:25 and stirred sufficiently, and then the ratio of this 30% diluted solution was further diluted with water so as to be 2% to prepare a 2.00% test solution (100 g). Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
  • the surface treating agent composition of the present invention can be used as, for example, a water / oil repellent, an antifouling agent and a soil release agent.

Abstract

Disclosed is a surface treatment agent composition which comprises (I) a first fluoropolymer including repeating units derived from a fluoromonomer (a) and repeating units derived from a halogenated olefin (b), (II) a second fluoropolymer including repeating units derived from a fluoromonomer (a) but including no repeating units derived from any halogenated olefin, and (III) a liquid medium.

Description

表面処理剤組成物Surface treatment composition
　本発明は、処理剤、特に、含フッ素重合体混合物を含む撥水撥油剤組成物などの表面処理剤組成物に関する。具体的には、本発明は、繊維製品（例えば、カーペット）、紙、不織布、石材、静電フィルター、防塵マスク、燃料電池の部品に、優れた撥水性、撥油性、防汚性、特に繊維の連続撥水撥油加工時に高い加工持続性に優れた撥水撥油剤組成物に関する。 The present invention relates to a surface treatment composition such as a treatment agent, particularly a water / oil repellent composition containing a fluoropolymer mixture. Specifically, the present invention has excellent water repellency, oil repellency, antifouling properties, particularly fibers, for textile products (for example, carpets), paper, nonwoven fabrics, stones, electrostatic filters, dust masks, and fuel cell components. The present invention relates to a water / oil repellent composition having excellent processing sustainability during continuous water / oil repellent processing.
　従来、種々の含フッ素化合物が提案されている。含フッ素化合物には、耐熱性、耐酸化性、耐候性などの特性に優れているという利点がある。含フッ素化合物の自由エネルギーが低い、すなわち、付着し難いという特性を利用して、含フッ素化合物は、例えば、撥水撥油剤および防汚剤として使用されている。 Conventionally, various fluorine-containing compounds have been proposed. The fluorine-containing compound has an advantage of excellent properties such as heat resistance, oxidation resistance, and weather resistance. The fluorine-containing compound is used as, for example, a water / oil repellent and an antifouling agent by utilizing the characteristic that the free energy of the fluorine-containing compound is low, that is, it is difficult to adhere.
　撥水撥油剤として使用できる含フッ素化合物として、フルオロアルキル基を有する（メタ）アクリレートエステルを構成モノマーとする含フッ素重合体が挙げられる。表面処理剤の繊維への実用処理では、これまでの種々の研究結果からその表面特性として静的な接触角ではなく、動的接触角、特に後退接触角が重要であることを示している。すなわち、水の前進接触角はフルオロアルキル基の側鎖炭素数に依存しないが、水の後退接触角は、側鎖の炭素数8以上に比較して7以下では著しく小さくなることを示している。これと対応してX線解析は側鎖の炭素数が７以上では側鎖の結晶化が起こることを示している。実用的な撥水性が側鎖の結晶性と相関関係を有していること、および表面処理剤分子の運動性が実用性能発現の重要な要因であることが知られている（例えば、前川隆茂、ファインケミカル、Vol23, No.6, P12(1994)）。上記理由により、側鎖の炭素数が７（特に６以下）以下と短いフルオロアルキル基をもつ（メタ）アクリレート系ポリマーでは側鎖の結晶性が低いためそのままでは実用性能を満足しない問題があった。また、撥水撥油加工では連続加工が一般的であり、排水・生産性の面から高い加工持続性を有する撥水撥油剤が求められてきた。 Examples of the fluorine-containing compound that can be used as a water / oil repellent include a fluorine-containing polymer having a (meth) acrylate ester having a fluoroalkyl group as a constituent monomer. In practical treatment of fibers with surface treatment agents, various research results so far indicate that dynamic contact angles, particularly receding contact angles, are important as surface characteristics, not static contact angles. That is, the advancing contact angle of water does not depend on the carbon number of the side chain of the fluoroalkyl group, but the receding contact angle of water is significantly smaller at 7 or less than the carbon number of the side chain of 8 or more. . Correspondingly, X-ray analysis shows that side chain crystallization occurs when the side chain has 7 or more carbon atoms. It is known that practical water repellency correlates with the side chain crystallinity, and the mobility of surface treatment agent molecules is an important factor in the development of practical performance (for example, Takashi Maekawa , Fine Chemical, Vol23, No.6, P12 (1994)). For the above reason, the (meth) acrylate polymer having a short fluoroalkyl group with a side chain having 7 or less carbon atoms (especially 6 or less) has a problem of not satisfying the practical performance as it is because the side chain has low crystallinity. . In addition, continuous processing is common in water and oil repellent processing, and water and oil repellent agents having high processing sustainability have been demanded from the viewpoint of drainage and productivity.
　特開2001-98257号公報は、ポリフルオロアルキル基を有する重合性単量体の重合単位を含む重合体（Ａ）、特定のドレーブス濡れ時間を有する界面活性剤（Ｂ）、および水系媒体（Ｃ）を必須成分とする組成物を開示している。特開2004-262970号公報は、フッ素系撥水撥油剤（Ａ）、パラフィンワックスとカルボキシ基含有ポリエチレンとを含む乳化物（Ｂ）および有機酸（Ｃ）を含有する撥水撥油剤水性組成物を開示している。
　これらの特許においては加工持続性については述べられていない。 Japanese Patent Laid-Open No. 2001-98257 discloses a polymer (A) containing a polymerization unit of a polymerizable monomer having a polyfluoroalkyl group, a surfactant (B) having a specific Draves wetting time, and an aqueous medium (C ) Is an essential component. JP-A-2004-262970 discloses a water / oil repellent aqueous composition containing a fluorine-based water / oil repellent (A), an emulsion (B) containing paraffin wax and carboxy group-containing polyethylene, and an organic acid (C). Is disclosed.
These patents do not mention processing sustainability.
特開2001-98257号公報JP 2001-98257 A 特開2004-262970号公報JP 2004-262970 A
　本発明の１つの目的は繊維などの撥水撥油加工の加工持続性に優れる表面処理剤組成物を提供することにある。 One object of the present invention is to provide a surface treating agent composition that is excellent in processing sustainability of water and oil repellent processing such as fibers.
　本発明は、
　（I）含フッ素単量体（ａ）から誘導された繰り返し単位およびハロゲン化オレフィン（ｂ）から誘導された繰り返し単位を有する第１含フッ素重合体、
　（II）含フッ素単量体（ａ）から誘導された繰り返し単位を有しており、ハロゲン化オレフィンから誘導された繰り返し単位を有しない第２含フッ素重合体、ならびに
　（III）液状媒体
を含んでなる表面処理剤組成物に関する。 The present invention
(I) a first fluorine-containing polymer having a repeating unit derived from a fluorine-containing monomer (a) and a repeating unit derived from a halogenated olefin (b),
(II) a second fluorine-containing polymer having a repeating unit derived from the fluorine-containing monomer (a) and having no repeating unit derived from a halogenated olefin; and (III) a liquid medium It is related with the surface treating agent composition which consists of.
　本発明の表面処理剤組成物は、撥水撥油加工の加工持続性に優れる。
　本発明によれば、優れた撥水性、撥油性、防汚性および汚れ脱離性、例えば、撥水撥油性の優れた耐久性が得られる。
　本発明の表面処理剤組成物は、撥水撥油剤組成物、防汚剤組成物および／または汚れ脱離剤組成物として使用できる。 The surface treating agent composition of the present invention is excellent in processing sustainability of water / oil repellent processing.
According to the present invention, excellent durability such as excellent water repellency, oil repellency, antifouling property and dirt detachability, for example, water and oil repellency can be obtained.
The surface treating agent composition of the present invention can be used as a water / oil repellent composition, an antifouling agent composition and / or a soil release agent composition.
（１）含フッ素重合体
　本発明において、含フッ素重合体は、第１含フッ素重合体と第２含フッ素重合体の組み合わせである。
　含フッ素重合体の繰り返し単位を構成する単量体として、
含フッ素単量体（ａ）と、ハロゲン化オレフィン単量体（ｂ）と、単量体（ａ）および（ｂ）以外の他の単量体（ｃ）とを使用する。 (1) Fluoropolymer In the present invention, the fluoropolymer is a combination of a first fluoropolymer and a second fluoropolymer.
As a monomer constituting the repeating unit of the fluoropolymer,
A fluorine-containing monomer (a), a halogenated olefin monomer (b), and a monomer (c) other than the monomers (a) and (b) are used.
　本発明において、第１含フッ素重合体および第２含フッ素重合体は、撥水撥油剤、防汚剤および汚れ脱離剤の有効成分として働く。 In the present invention, the first fluorinated polymer and the second fluorinated polymer serve as active ingredients of the water / oil repellent, the antifouling agent and the soil release agent.
（ａ）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。 (A) Fluorinated monomer The fluorinated monomer is generally a polymerizable compound having a perfluoroalkyl group or a 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（ａ）は、例えば、一般式：
　　CH2=C(－X)－C(=O)－Y－Z－Rf            （Ｉ）
［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- または -NH-であり、 
Ｚ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。］
で示される化合物であってよい。 The fluorine-containing monomer (a) is, for example, a general formula:
CH 2 = C (-X) -C (= O) -Y-Z-Rf (I)
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-,
Z is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
It may be a compound shown by these.
　含フッ素単量体（ａ）は、一般式：
　　CH2=C(－X)－C(=O)－Y－Z－Rf            （Ｉ）
［式中、Ｘ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り；
Ｙは、－Ｏ－または－ＮＨ－であり；
Ｚは、直接結合、あるいは
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６～３０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、あるいは
-(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。）であり；
Ｒｆは、炭素数１～２０の直鎖状または分岐状のフルオロアルキル基である。] 
で示される化合物であることが好ましい。 The fluorine-containing monomer (a) has the general formula:
CH 2 = C (-X) -C (= O) -Y-Z-Rf (I)
[Wherein, X 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 (where X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, A substituted or unsubstituted phenyl group;
Y is —O— or —NH—;
Z is a direct bond or a linear or branched aliphatic group (particularly an alkylene group) having 1 to 20 carbon atoms, for example, the formula — (CH 2 ) x — (wherein x is 1 to 10). .), An aromatic group having 6 to 30 carbon atoms or a cyclic aliphatic group, or
A group represented by the formula —R 2 (R 1 ) N—SO 2 — or a formula —R 2 (R 1 ) N—CO— (wherein R 1 is an alkyl group having 1 to 10 carbon atoms; 2 is a straight-chain alkylene group or branched alkylene group having 1 to 10 carbon atoms), or
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 (eg, formyl or acetyl), Ar Is an arylene group optionally having a substituent, p represents 0 or 1, or a group represented by:
A group represented by the formula —CH 2 —Ar— (O) q — (wherein Ar is an arylene group optionally having a substituent, q is 0 or 1), or
— (CH 2 ) m —SO 2 — (CH 2 ) n — group or — (CH 2 ) m —S— (CH 2 ) n — group (where m is 1 to 10 and n is 0 to 10) .);
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
It is preferable that it is a compound shown by these.
　Ｘの代表的な具体例は、Ｃｌ、Ｂｒ、Ｉ、Ｆ、ＣＮ、ＣＦ３、好ましくはＣｌである。特に、α位が塩素原子である場合に、表面処理剤組成物は実用的な撥水性（特に、スプレー撥水性）に優れている。 Representative examples of X are Cl, Br, I, F, CN, CF 3 , preferably Cl. In particular, when the α-position is a chlorine atom, the surface treatment composition is excellent in practical water repellency (particularly spray water repellency).
　含フッ素単量体において、Ｒｆ基が、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、特別には４～６、更に好ましくは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。 In the fluorine-containing monomer, the Rf group is preferably a perfluoroalkyl group. The number of carbon atoms in the Rf group is preferably 1 to 12, for example 1 to 6, particularly 4 to 6, and more preferably 6. Examples of Rf groups are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ). 2 , -C (CF 3 ) 3 ,-(CF 2 ) 4 CF 3 ,-(CF 2 ) 2 CF (CF 3 ) 2 , -CF 2 C (CF 3 ) 3 , -CF (CF 3 ) CF 2 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.
　Ｚ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。 Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group,
-CH 2 CH 2 N (R 1 ) SO 2 -group (where R 1 is an alkyl group having 1 to 4 carbon atoms),
-CH 2 CH (OZ 1 ) CH 2- (Ph-O) p -group (where Z 1 is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1),-(CH 2 ) n -Ph-O- group (where Ph is a phenylene group, 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, for example, 1 or 2 carbon atoms). The aromatic group or cycloaliphatic group may be substituted or unsubstituted. The S group or SO 2 group may be directly bonded to the Rf group.
　含フッ素単量体（ａ）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 (a) include, but are not limited to, for example, the following.
CH 2 = C (-H) -C (= O) -O- (CH 2 ) 2 -Rf
CH 2 = C (-H) -C (= O) -O-C 6 H 4 -Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -Rf
CH 2 = C (-H) -C (= O) -O- (CH 2 ) 2 N (-CH 3 ) SO 2 -Rf
CH 2 = C (-H) -C (= O) -O- (CH 2 ) 2 N (-C 2 H 5 ) SO 2 -Rf
CH 2 = C (-H) -C (= O) -O-CH 2 CH (-OH) CH 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 CH 2 = C (-H) -C (= O) -O-CH 2 CH (-OCOCH 3 ) CH 2 -Rf
CH 2 = C (-H) -C (= O) -O- (CH 2 ) 2 -S-Rf
CH 2 = C (-H) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf
CH 2 = C (-H) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf
CH 2 = C (-H) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-H) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (-CH 3 ) -C (= O) -O- (CH 2 ) 2 -S-Rf
CH 2 = C (-CH 3 ) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf
CH 2 = C (-CH 3 ) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf
CH 2 = C (-CH 3 ) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-CH 3 ) -C (= O) -NH- (CH 2 ) 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 CH 2 = C (-F) -C (= O) -O- (CH 2 ) 2 -S-Rf
CH 2 = C (-F) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf
CH 2 = C (-F) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf
CH 2 = C (-F) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-F) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -S-Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-Cl) -C (= O) -NH- (CH 2 ) 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 CH 2 = C (-CF 3 ) -C (= O) -O- (CH 2 ) 2 -S-Rf
CH 2 = C (-CF 3 ) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf
CH 2 = C (-CF 3 ) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf
CH 2 = C (-CF 3 ) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-CF 3 ) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 2 -S-Rf
CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf
CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf
CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-CF 2 H) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 2 -S-Rf
CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf
CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf
CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-CN) -C (= O) -NH- (CH 2 ) 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 CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 2 -S-Rf
CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf
CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf
CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-CF 2 CF 3 ) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (-F) -C (= O) -O- (CH 2 ) 3 -S-Rf
CH 2 = C (-F) -C (= O) -O- (CH 2 ) 3 -S- (CH 2 ) 2 -Rf
CH 2 = C (-F) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf
CH 2 = C (-F) -C (= O) -O- (CH 2 ) 3 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-F) -C (= O) -NH- (CH 2 ) 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 CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 3 -S-Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 3 -S- (CH 2 ) 2 -Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 3 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-CF 3 ) -C (= O) -O- (CH 2 ) 3 -S-Rf
CH 2 = C (-CF 3 ) -C (= O) -O- (CH 2 ) 3 -S- (CH 2 ) 2 -Rf
CH 2 = C (-CF 3 ) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf
CH 2 = C (-CF 3 ) -C (= O) -O- (CH 2 ) 3 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 3 -S-Rf
CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 3 -S- (CH 2 ) 2 -Rf
CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf
CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 3 -SO 2- (CH 2 ) 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。] CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 3 -S-Rf
CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 3 -S- (CH 2 ) 2 -Rf
CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf
CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 3 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 3 -S-Rf
CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 3 -S- (CH 2 ) 2 -Rf
CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf
CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf
[In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
（ｂ）ハロゲン化オレフィン単量体
　ハロゲン化オレフィン単量体（ハロゲン化オレフィン）は、フッ素原子を有しないことが好ましい。
　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。塩化ビニルおよび塩化ビニリデンが好ましく、塩化ビニルが特に好ましい。 (B) Halogenated olefin monomer The halogenated olefin monomer (halogenated olefin) preferably has no fluorine atom.
The halogenated olefin is preferably an olefin 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 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. Vinyl chloride and vinylidene chloride are preferred, with vinyl chloride being particularly preferred.
（ｃ）他の単量体
　単量体（ａ）および（ｂ）以外の他の単量体（ｃ）は、フッ素を含有しないことが好ましい。他の単量体（ｃ）として、非フッ素非架橋性単量体（ｃ１）および非フッ素架橋性単量体（ｃ２）が挙げられる。 (C) Other monomers (c) other than the monomer monomers (a) and (b) preferably do not contain fluorine. Examples of the other monomer (c) include a non-fluorine non-crosslinkable monomer (c1) and a non-fluorine crosslinkable monomer (c2).
（ｃ１）非フッ素非架橋性単量体
　非フッ素非架橋性単量体（ｃ１）は、フッ素原子を含まない単量体である。非フッ素非架橋性単量体（ｃ１）は、架橋性官能基を有さない。非フッ素非架橋性単量体（ｃ１）は、架橋性単量体（ｃ２）とは異なり、非架橋性である。非フッ素非架橋性単量体（ｃ１）は、好ましくは、炭素－炭素二重結合を有する非フッ素単量体である。非フッ素非架橋性単量体（ｃ１）は、好ましくは、フッ素を含まないビニル単量体である。非フッ素非架橋性単量体（ｃ１）は一般には、１つの炭素－炭素二重結合を有する化合物である。 (C1) Non-fluorine non-crosslinkable monomer The non-fluorine non-crosslinkable monomer (c1) is a monomer containing no fluorine atom. The non-fluorine non-crosslinkable monomer (c1) does not have a crosslinkable functional group. Unlike the crosslinkable monomer (c2), the non-fluorine noncrosslinkable monomer (c1) is noncrosslinkable. The non-fluorine non-crosslinkable monomer (c1) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (c1) is preferably a vinyl monomer containing no fluorine. The non-fluorine non-crosslinkable monomer (c1) is generally a compound having one carbon-carbon double bond.
　好ましい非フッ素非架橋性単量体（ｃ１）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、炭素数１～３０の鎖状または環状の炭化水素基、またはエステル結合を有する鎖状または環状の炭素数１～３１の有機基である。］
で示される化合物である。 Preferred non-fluorine non-crosslinkable monomers (c1) have the formula:
CH 2 = CA-T
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond. ]
It is a compound shown by these.
　炭素数１～３０の鎖状または環状の炭化水素基の例は、炭素数１～３０の直鎖または分岐の脂肪族炭化水素基、炭素数４～３０の環状脂肪族基、炭素数６～３０の芳香族炭化水素基、炭素数７～３０の芳香脂肪族炭化水素基である。 Examples of the linear or cyclic hydrocarbon group having 1 to 30 carbon atoms include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, and 6 to 6 carbon atoms. 30 aromatic hydrocarbon groups, and aromatic aliphatic hydrocarbon groups having 7 to 30 carbon atoms.
　エステル結合を有する鎖状または環状の炭素数１～３１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１～３０の直鎖または分岐の脂肪族炭化水素基、炭素数４～３０の環状脂肪族基、炭素数６～３０の芳香族炭化水素基、炭素数７～３０の芳香脂肪族炭化水素基）である。 Examples of the linear or cyclic organic group having 1 to 31 carbon atoms having an ester bond are -C (= O) -OQ and -OC (= O) -Q (where Q is 1-30 carbon atoms). Straight chain or branched aliphatic hydrocarbon groups, cyclic aliphatic groups having 4 to 30 carbon atoms, aromatic hydrocarbon groups having 6 to 30 carbon atoms, and araliphatic hydrocarbon groups having 7 to 30 carbon atoms). .
　非フッ素非架橋性単量体（ｃ１）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。非フッ素非架橋性単量体（ｃ１）はこれらの例に限定されない。 Preferred examples of the non-fluorine non-crosslinkable monomer (c1) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, Methoxy polypropylene glycol (meth) acrylate and vinyl alkyl ether are included. The non-fluorine non-crosslinkable monomer (c1) is not limited to these examples.
　非フッ素非架橋性単量体（ｃ１）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１～３０であってよく、例えば、６～３０（例えば、１０～３０）であってよい。例えば、非フッ素非架橋性単量体（ｃ１）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＝１～３０）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。
　Ａ２の好ましい具体例は、ラウリル、ステアリル、ベヘニルである。 The non-fluorine non-crosslinkable monomer (c1) may be a (meth) acrylate ester having an alkyl group. The number of carbon atoms in the alkyl group may be 1-30, for example, 6-30 (eg 10-30). For example, the non-fluorine non-crosslinkable monomer (c1) has the general formula:
CH 2 = CA 1 COOA 2
[Wherein, A 1 is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, 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 to 30). ]
An acrylate represented by
Preferred examples of A 2 are lauryl, stearyl and behenyl.
　非フッ素非架橋性単量体（ｃ１）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。 The non-fluorine non-crosslinkable monomer (c1) may be a (meth) acrylate monomer having a cyclic hydrocarbon group.
　環状炭化水素基含有アクリレートエステル単量体は、
式：
　　ＣＨ２＝ＣＡ２１－Ｃ(＝Ｏ)－Ｏ－Ａ２２
［式中、Ａ２１は、水素原子またはメチル基であり、
Ａ２２は、炭素数４～３０の環状炭化水素含有基である。]
で示される化合物であることが好ましい。
　環状炭化水素基含有アクリレートエステル単量体は、そのホモポリマーのガラス転移点が高い（例えば、５０℃以上、特に８０℃以上）単量体である。 Cyclic hydrocarbon group-containing acrylate ester monomer
formula:
CH 2 = CA 21 -C (= O) -OA 22
[In the formula, A 21 represents a hydrogen atom or a methyl group;
A 22 is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms. ]
It is preferable that it is a compound shown by these.
The cyclic hydrocarbon group-containing acrylate ester monomer is a monomer whose homopolymer has a high glass transition point (for example, 50 ° C. or higher, particularly 80 ° C. or higher).
　環状炭化水素基含有アクリレートエステル単量体は、フルオロアルキル基を有しない。環状炭化水素基含有アクリレートエステル単量体は、フッ素原子を含有してもよいが、フッ素原子を含有しないことが好ましい。 The cyclic hydrocarbon group-containing acrylate ester monomer does not have a fluoroalkyl group. The cyclic hydrocarbon group-containing acrylate ester monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.
　Ａ２１は、メチル基であることが特に好ましい。
　Ａ２２は、鎖状基（例えば、直鎖状または分岐状の炭化水素基）を有していてよい環状炭化水素基である。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、４～３０であり、６～２０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１２以下であることが特に好ましい。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。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。 A 21 is particularly preferably a methyl group.
A 22 is a cyclic hydrocarbon group which may have a chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group has 4 to 30 carbon atoms, preferably 6 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an araliphatic group having 7 to 20 carbon atoms. The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 12 or less. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. 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.
　環状炭化水素基含有アクリレートエステル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。
　環状炭化水素基含有アクリレートエステル単量体が存在することにより、共重合体が与える撥水性および撥油性が高くなる。 Specific examples of cyclic hydrocarbon group-containing acrylate ester monomers include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2- And ethyl-2-adamantyl (meth) acrylate.
The presence of the cyclic hydrocarbon group-containing acrylate ester monomer increases the water repellency and oil repellency provided by the copolymer.
（ｃ２）非フッ素架橋性単量体
　本発明の含フッ素重合体は、非フッ素架橋性単量体（ｃ２）から誘導された繰り返し単位を有していてよい。非フッ素架橋性単量体（ｃ２）は、フッ素原子を含まない単量体である。非フッ素架橋性単量体（ｃ２）は、少なくとも２つの反応性基および／または炭素－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。非フッ素架橋性単量体（ｃ２）は、少なくとも２つの炭素－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。非フッ素架橋性単量体（ｃ２）は、反応性基を有するモノ（メタ）アクリレート、ジ（メタ）アクリレートまたはモノ（メタ）アクリルアミドであってよい。あるいは、非フッ素架橋性単量体（ｃ２）は、ジ（メタ）アクリレートであってよい。 (C2) Non-fluorine crosslinkable monomer The fluoropolymer of the present invention may have a repeating unit derived from the non-fluorine crosslinkable monomer (c2). The non-fluorine crosslinkable monomer (c2) is a monomer containing no fluorine atom. The non-fluorine crosslinkable monomer (c2) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. The non-fluorine crosslinkable monomer (c2) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups and the like. The non-fluorine crosslinkable monomer (c2) may be mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer (c2) may be di (meth) acrylate.
　非フッ素架橋性単量体（ｃ２）としては、例えば、ジアセトン(メタ)アクリルアミド、(メタ)アクリルアミド、Ｎ－メチロール(メタ)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、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、１，６－ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレートなどが例示 Examples of the non-fluorine crosslinkable monomer (c2) include diacetone (meth) acrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3- Chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di ( Examples include (meth) acrylate
　非フッ素非架橋性単量体（ｃ１）および／または非フッ素架橋性単量体（ｃ２）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-fluorine non-crosslinkable monomer (c1) and / or the non-fluorine crosslinkable monomer (c2), water and oil repellency and antifouling properties, and cleaning resistance and washing resistance of these performances Various properties such as solubility, solubility in solvents, hardness, and feel can be improved as necessary.
　本明細書において、単に「アクリレート」または「アクリルアミド」と呼ぶ場合には、α位が水素原子である化合物のみならず、α位が他の基（例えば、メチル基を含めた一価の有機基またはハロゲン原子）で置換されている化合物も含む。本明細書において、「（メタ）アクリレート」とは、アクリレートまたはメタクリレートを意味し、「（メタ）アクリルアミド」とは、アクリルアミドまたはメタクリルアミドを意味する。
　単量体（ａ）、単量体（ｂ）、単量体（ｃ）（例えば、単量体（ｃ１）および（ｃ２）のそれぞれ）のそれぞれは、１種の単独であっても、または２種以上の組み合わせであってもよい。 In the present specification, when simply referred to as “acrylate” or “acrylamide”, not only a compound in which the α-position is a hydrogen atom, but also the α-position is another group (for example, a monovalent organic group including a methyl group). Or a compound substituted with a halogen atom). In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylamide” means acrylamide or methacrylamide.
Each of the monomer (a), the monomer (b), and the monomer (c) (for example, each of the monomers (c1) and (c2)) may be a single type, or Two or more combinations may be used.
　第１含フッ素重合体におけるそれぞれの単量体の量は次のとおりである。
　第１含フッ素重合体において、含フッ素単量体（ａ）の量は、含フッ素重合体に対して２０重量％～１００重量％、好ましくは３０重量％～９０重量％であってよい。
　第１含フッ素重合体において、含フッ素単量体（ａ）１００重量部に対して、
ハロゲン化オレフィン単量体（ｂ）の量が５～３００重量部、例えば１０～２００重量部、特に２０～１００重量部、特別に３０～８０重量部であり、
他の単量体（ｃ）の量が０～８００重量部、例えば１～３００重量部、特に２～２００重量部であり、特別に３～１００重量部であってよい。
　第１含フッ素重合体において、含フッ素単量体（ａ）１００重量部に対して、
非フッ素非架橋性単量体（ｃ１）の量が０～５００重量部、例えば１～３００重量部、特に２～２００重量部であり、特別に３～１００重量部であってよく、
非フッ素架橋性単量体（ｃ２）の量が０～８０重量部、例えば０～５０重量部、特に０．１～３０重量部、特別に１～２０重量部であってよい。 The amount of each monomer in the first fluoropolymer is as follows.
In the first fluorine-containing polymer, the amount of the fluorine-containing monomer (a) may be 20% by weight to 100% by weight, preferably 30% by weight to 90% by weight with respect to the fluorine-containing polymer.
In the first fluoropolymer, with respect to 100 parts by weight of the fluoromonomer (a),
The amount of halogenated olefin monomer (b) is 5 to 300 parts by weight, for example 10 to 200 parts by weight, in particular 20 to 100 parts by weight, especially 30 to 80 parts by weight;
The amount of the other monomer (c) is 0 to 800 parts by weight, for example 1 to 300 parts by weight, in particular 2 to 200 parts by weight, in particular 3 to 100 parts by weight.
In the first fluoropolymer, with respect to 100 parts by weight of the fluoromonomer (a),
The amount of non-fluorine non-crosslinkable monomer (c1) is 0 to 500 parts by weight, for example 1 to 300 parts by weight, in particular 2 to 200 parts by weight, in particular 3 to 100 parts by weight,
The amount of non-fluorine crosslinkable monomer (c2) may be 0 to 80 parts by weight, for example 0 to 50 parts by weight, in particular 0.1 to 30 parts by weight, especially 1 to 20 parts by weight.
　第２含フッ素重合体におけるそれぞれの単量体の量は次のとおりである。
　第２含フッ素重合体において、含フッ素単量体（ａ）の量は、含フッ素重合体に対して２０重量％～１００重量％、好ましくは３０重量％～９０重量％であってよい。
　第２含フッ素重合体は、ハロゲン化オレフィンから誘導された繰り返し単位を有しない。
　第２含フッ素重合体において、単量体（ａ）１００重量部に対して、
他の単量体（ｃ）の量が０～８００重量部、例えば１～３００重量部、特に２～２００重量部であり、特別に３～１００重量部であってよい。
　第２含フッ素重合体において、含フッ素単量体（ａ）１００重量部に対して、
非フッ素非架橋性単量体（ｃ１）の量が０～５００重量部、例えば１～３００重量部、特に２～２００重量部であり、特別に３～１００重量部であってよい。
非フッ素架橋性単量体（ｃ２）の量が０～８０重量部、例えば０～５０重量部、特に０．１～３０重量部、特別に１～２０重量部であってよい。 The amount of each monomer in the second fluoropolymer is as follows.
In the second fluoropolymer, the amount of the fluoromonomer (a) may be 20% by weight to 100% by weight, preferably 30% by weight to 90% by weight, based on the fluoropolymer.
The second fluoropolymer does not have a repeating unit derived from a halogenated olefin.
In the second fluoropolymer, with respect to 100 parts by weight of the monomer (a),
The amount of the other monomer (c) is 0 to 800 parts by weight, for example 1 to 300 parts by weight, in particular 2 to 200 parts by weight, in particular 3 to 100 parts by weight.
In the second fluoropolymer, with respect to 100 parts by weight of the fluoromonomer (a),
The amount of non-fluorine non-crosslinkable monomer (c1) is 0 to 500 parts by weight, for example 1 to 300 parts by weight, in particular 2 to 200 parts by weight, in particular 3 to 100 parts by weight.
The amount of non-fluorine crosslinkable monomer (c2) may be 0 to 80 parts by weight, for example 0 to 50 parts by weight, in particular 0.1 to 30 parts by weight, especially 1 to 20 parts by weight.
　第１含フッ素重合体および第２含フッ素重合体における含フッ素単量体（ａ）および他の単量体（ｃ）のそれぞれは、同一または異なっていてよい。
　表面処理剤組成物において、第１含フッ素重合体と第２含フッ素重合体の重量比は、５：９５～９５：５、例えば２０：８０～２０：８０であってよい。
　第１含フッ素重合体および第２含フッ素重合体の混合物において、一般に、第１含フッ素重合体の分子と第２含フッ素重合体の分子は化学的に結合していない。 Each of the fluorinated monomer (a) and the other monomer (c) in the first fluorinated polymer and the second fluorinated polymer may be the same or different.
In the surface treating agent composition, the weight ratio of the first fluoropolymer to the second fluoropolymer may be 5:95 to 95: 5, for example, 20:80 to 20:80.
In the mixture of the first fluoropolymer and the second fluoropolymer, generally, the molecule of the first fluoropolymer and the molecule of the second fluoropolymer are not chemically bonded.
（２）界面活性剤
　本発明の処理剤において、界面活性剤は、ノニオン性界面活性剤およびカチオン性界面活性剤の一方または両方を含む。さらに、界面活性剤は、両性界面活性剤を含んでもよい。界面活性剤はアニオン性界面活性剤を含まないことが好ましい。 (2) Surfactant In the treatment agent of the present invention, the surfactant contains one or both of a nonionic surfactant and a cationic surfactant. Further, the surfactant may include an amphoteric surfactant. It is preferable that the surfactant does not contain an anionic surfactant.
（２－１）ノニオン性界面活性剤
　ノニオン性界面活性剤は、オキシアルキレン基を有するノニオン性界面活性剤である。オキシアルキレン基におけるアルキレン基の炭素数は、２～１０であることが好ましい。ノニオン性界面活性剤の分子におけるオキシアルキレン基の数は、一般に、２～１００であることが好ましい。
　ノニオン性界面活性剤は、直鎖状および／または分岐状の脂肪族（飽和および／または不飽和）基のアルキレンオキシド付加物、直鎖状および／または分岐状脂肪酸（飽和および／または不飽和）のポリアルキレングリコールエステル、ポリオキシエチレン（POE）／ポリオキシプロピレン（POP）共重合体（ランダム共重合体またはブロック共重合体）、アセチレングリコールのアルキレンオキシド付加物等であってよい。これらの中で、アルキレンオキシド付加部分およびポリアルキレングリコール部分の構造がポリオキシエチレン（POE）またはポリオキシプロピレン（POP）またはPOE/POP共重合体（ランダム共重合体であってもブロック共重合体であってよい）であるものが好ましい。
　また、ノニオン性界面活性剤は、環境上の問題（生分解性、環境ホルモンなど）から芳香族基を含まない構造が好ましい。 (2-1) Nonionic surfactant The nonionic surfactant is a nonionic surfactant having an oxyalkylene group. The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2 to 10. In general, the number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100.
Nonionic surfactants are alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, linear and / or branched fatty acids (saturated and / or unsaturated). Polyalkylene glycol ester, polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), alkylene oxide adduct of acetylene glycol, and the like. Among these, the structures of the alkylene oxide addition moiety and the polyalkylene glycol moiety are polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (random copolymer or block copolymer) Is preferred).
The nonionic surfactant preferably has a structure that does not contain an aromatic group because of environmental problems (biodegradability, environmental hormones, etc.).
　ノニオン性界面活性剤は、式：
　　　Ｒ1Ｏ－(ＣＨ２ＣＨ２Ｏ)p－(Ｒ2Ｏ)q－Ｒ3
[式中、Ｒ1は炭素数１～２２のアルキル基または炭素数２～２２のアルケニル基またはアシル基、Ｒ2は炭素数３以上（例えば、３～１０）のアルキレン基であり、Ｒ3は水素原子、炭素数１～２２のアルキル基または炭素数２～２２のアルケニル基、ｐは２以上の数、ｑは0または１以上の数である。]
で示される化合物であってよい。 Nonionic surfactants have the formula:
R 1 O— (CH 2 CH 2 O) p — (R 2 O) q —R 3
[Wherein R 1 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 is an alkylene group having 3 or more carbon atoms (for example, 3 to 10 carbon atoms), and R 3 Is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is 0 or a number of 1 or more. ]
It may be a compound shown by these.
　Ｒ1は、炭素数８～２０、特に１０～１８であることが好ましい。Ｒ1の好ましい具体例としては、ラウリル基、トリデシル基、オレイル基が挙げられる。
　Ｒ2の例は、プロピレン基、ブチレン基である。
　ノニオン性界面活性剤において、ｐは３以上の数（例えば、５～２００）であってよい。ｑは、２以上の数（例えば５～２００）であってよい。すなわち、－(Ｒ2Ｏ)q－がポリオキシアルキレン鎖を形成してもよい。
　ノニオン性界面活性剤は、中央に親水性のポリオキシエチレン鎖と疎水性のオキシアルキレン鎖（特に、ポリオキシアルキレン鎖）を含有したポリオキシエチレンアルキレンアルキルエーテルであってよい。疎水性のオキシアルキレン鎖としては、オキシプロピレン鎖、オキシブチレン鎖、オキシスチレン鎖等が挙げられるが、中でも、オキシプロピレン鎖が好ましい。
　好ましいノニオン性界面活性剤は、式：
　Ｒ1Ｏ－(ＣＨ２ＣＨ２Ｏ)p－Ｈ
[式中、Ｒ1およびｐは上記と同意義である。]
で示される界面活性剤である。 R 1 preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. Preferable specific examples of R 1 include a lauryl group, a tridecyl group, and an oleyl group.
Examples of R 2 are a propylene group and a butylene group.
In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, — (R 2 O) q — may form a polyoxyalkylene chain.
The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and an oxystyrene chain. Of these, an oxypropylene chain is preferable.
Preferred nonionic surfactants have the formula:
R 1 O— (CH 2 CH 2 O) p —H
[Wherein, R 1 and p are as defined above. ]
Is a surfactant.
　ノニオン性界面活性剤の具体例は、
　　C10H21O-(CH2CH2O)ｐ-(C3H6O)ｑ-H
　　C12H25O-(CH2CH2O)ｐ-(C3H6O)ｑ-H
　　C16H31O-(CH2CH2O)ｐ-(C3H6O)ｑ-H
　　C16H33O-(CH2CH2O)ｐ-(C3H6O)ｑ-H
　　C18H35O-(CH2CH2O)ｐ-(C3H6O)ｑ-H
　　C18H37O-(CH2CH2O)ｐ-(C3H6O)ｑ-H
　　C12H25O-(CH2CH2O)ｐ-(C3H6O)ｑ-C12H25
　　C16H31O-(CH2CH2O)ｐ-(C3H6O)ｑ-C16H31
　　C16H33O-(CH2CH2O)ｐ-(C3H6O)ｑ-C12H25
　　iso-C13H27O-(CH2CH2O)ｐ-(C3H6O)ｑ-H
　　C10H21COO-(CH2CH2O)ｐ-(C3H6O)ｑ-H
　　C16H33COO-(CH2CH2O)ｐ-(C3H6O)ｑ-C12H25
 [式中、ｐおよびｑは上記と同意義である。]
などである。 Specific examples of nonionic surfactants are:
C 10 H 21 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H
C 12 H 25 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H
C 16 H 31 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H
C 16 H 33 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H
C 18 H 35 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H
C 18 H 37 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H
C 12 H 25 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -C 12 H 25
C 16 H 31 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -C 16 H 31
C 16 H 33 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -C 12 H 25
iso-C 13 H 27 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H
C 10 H 21 COO- (CH 2 CH 2 O) p- (C 3 H 6 O) q -H
C 16 H 33 COO- (CH 2 CH 2 O) p- (C 3 H 6 O) q -C 12 H 25
[Wherein, p and q are as defined above. ]
Etc.
　ノニオン性界面活性剤の具体例には、エチレンオキシドとヘキシルフェノール、イソオクタチルフェノール、ヘキサデカノール、オレイン酸、アルカン（Ｃ１２－Ｃ１６）チオール、ソルビタンモノ脂肪酸（Ｃ７－Ｃ１９）またはアルキル（Ｃ１２－Ｃ１８）アミンなどとの縮合生成物が包含される。 Specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C 7 -C 19 ) or alkyl. Condensation products with (C 12 -C 18 ) amine and the like are included.
　ポリオキシエチレンブロックの割合がノニオン性界面活性剤（コポリマー）の分子量に対して５～８０重量％、例えば３０～７５重量％、特に４０～７０重量％であることができる。
　ノニオン性界面活性剤の平均分子量は、一般に３００～５,０００、例えば、５００～３,０００である。
　ノニオン性界面活性剤は１種単独でも２種以上を併用することもできる。
　ノニオン性界面活性剤は２種以上の組み合わせであることが好ましい。2種以上の組み合わせにおいて、少なくとも1種のノニオン性界面活性剤は、Ｒ１基（および／またはＲ3基）が分岐のアルキル基（例えば、イソトリデシル基）であるＲ1Ｏ－(ＣＨ２ＣＨ２Ｏ)p－(Ｒ2Ｏ)q－Ｒ3［特に、Ｒ1Ｏ－(ＣＨ２ＣＨ２Ｏ)p－Ｈ］で示される化合物であってよい。Ｒ１基が分岐のアルキル基であるノニオン性界面活性剤の量は、ノニオン性界面活性剤（Ｂ２）合計１００重量部に対して、５～１００重量部、例えば８～５０重量部、特に１０～４０重量部であってよい。2種以上の組み合わせにおいて、残りのノニオン性界面活性剤は、Ｒ１基（および／またはＲ3基）が（飽和および／または不飽和の）直鎖のアルキル基（例えば、ラウリル基（n-ラウリル基））であるＲ1Ｏ－(ＣＨ２ＣＨ２Ｏ)p－(Ｒ2Ｏ)q－Ｒ3［特に、Ｒ1Ｏ－(ＣＨ２ＣＨ２Ｏ)p－Ｈ］で示される化合物であってよい。 The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, in particular 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer).
The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example, 500 to 3,000.
Nonionic surfactants can be used alone or in combination of two or more.
The nonionic surfactant is preferably a combination of two or more. In a combination of two or more, at least one nonionic surfactant is R 1 O— (CH 2 CH) in which the R 1 group (and / or R 3 group) is a branched alkyl group (eg, an isotridecyl group). 2 O) p — (R 2 O) q —R 3 [particularly R 1 O— (CH 2 CH 2 O) p —H]. The amount of the nonionic surfactant in which R 1 group is a branched alkyl group is 5 to 100 parts by weight, for example, 8 to 50 parts by weight, particularly 10 parts per 100 parts by weight of the nonionic surfactant (B2). It may be up to 40 parts by weight. In a combination of two or more, the remaining nonionic surfactant is an R 1 group (and / or R 3 group) (saturated and / or unsaturated) linear alkyl group (eg, lauryl group (n- R 1 O— (CH 2 CH 2 O) p — (R 2 O) q —R 3 [particularly R 1 O— (CH 2 CH 2 O) p —H], which is a lauryl group)) It may be.
　ノニオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ショ糖脂肪酸エステル、ポリオキシエチレンアルキルアミン、ポリオキシエチレン脂肪酸アミド、脂肪酸アルキロールアミド、アルキルアルカノールアミド、アセチレングリコール、アセチレングリコールのオキシエチレン付加物、ポリエチレングリコールポリプロピレングリコールブロックコポリマー等を挙げることができる。 Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Examples thereof include polyethylene glycol polypropylene glycol block copolymers.
　水系エマルションの動的表面張力が低くなる（すなわち、水性エマルションが基材に浸透しやすくなる）ので、ノニオン性界面活性剤としては、アセチレンアルコール（特に、アセチレングリコール）、またはアセチレンアルコール（特に、アセチレングリコール）のオキシエチレン付加物が好ましい。 Since the dynamic surface tension of the water-based emulsion becomes low (that is, the aqueous emulsion easily penetrates into the substrate), the nonionic surfactant may be acetylene alcohol (particularly acetylene glycol) or acetylene alcohol (particularly acetylene). Glycol) oxyethylene adducts are preferred.
　好ましいノニオン性界面活性剤は、不飽和三重結合を有するアルコールまたはこのアルコールのアルキレンオキサイド付加物（このアルコールとこのアルキレンオキサイド付加物の両方を「アセチレンアルコール化合物」という。）である。特に好ましいノニオン性界面活性剤は、不飽和三重結合を有するモノオールまたはポリオールのアルキレンオキサイド付加物である。
　アセチレンアルコール化合物は１つ以上の三重結合と１つ以上の水酸基とを含む化合物である。アセチレンアルコール化合物は、ポリオキシアルキレン部分を含む化合物であってよい。ポリオキシアルキレン部分の例としてポリオキシエチレン、ポリオキシプロピレン、ポリオキシエチレンとポリオキシプロピレンとのランダム付加構造、ポリオキシエチレンとポリオキシプロピレンとのブロック付加構造が挙げられる。 A preferred nonionic surfactant is an alcohol having an unsaturated triple bond or an alkylene oxide adduct of the alcohol (both the alcohol and the alkylene oxide adduct are referred to as “acetylene alcohol compounds”). Particularly preferred nonionic surfactants are alkylene oxide adducts of monools or polyols having unsaturated triple bonds.
An acetylene alcohol compound is a compound containing one or more triple bonds and one or more hydroxyl groups. The acetylene alcohol compound may be a compound containing a polyoxyalkylene moiety. Examples of the polyoxyalkylene moiety include polyoxyethylene, polyoxypropylene, a random addition structure of polyoxyethylene and polyoxypropylene, and a block addition structure of polyoxyethylene and polyoxypropylene.
　アセチレンアルコール化合物は、式：
ＨＯ－ＣＲ１１ Ｒ１２ －Ｃ≡Ｃ－ＣＲ１３ Ｒ１４ －ＯＨ、　　または
ＨＯ－ＣＲ１５ Ｒ１６ －Ｃ≡Ｃ－Ｈ
［式中、Ｒ１１ 、Ｒ１２ 、Ｒ１３ 、Ｒ１４ 、Ｒ１５ 、Ｒ１６ はそれぞれ同一であっても異なっていてもよく、水素原子または炭素数１～３０のアルキル基である。］
で示される化合物であってよい。アセチレンアルコール化合物は、この化学式で示される化合物のアルキレンオキシド付加物であってよい。アルキル基は炭素数１～１２の直鎖状または分岐状のアルキル基が好ましく、特に炭素数６～１２の直鎖状または分岐状のアルキル基が好ましい。例えば、メチル基、エチル基、プロピル基、ブチル基、イソブチル基などが挙げられる。また、アルキレンオキシドとしては、エチレンオキシド、プロピレンオキシドなどの炭素数１～２０（特に２～５）のアルキレンオキシドが好ましく、アルキレンオキシドの付加数は１～５０が好ましい。 The acetylene alcohol compound has the formula:
HO—CR 11 R 12 —C≡C—CR 13 R 14 —OH, or HO—CR 15 R 16 —C≡C—H
[Wherein R 11 , R 12 , R 13 , R 14 , R 15 , R 16 may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]
It may be a compound shown by these. The acetylene alcohol compound may be an alkylene oxide adduct of the compound represented by this chemical formula. The alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and particularly preferably a linear or branched alkyl group having 6 to 12 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group. The alkylene oxide is preferably an alkylene oxide having 1 to 20 carbon atoms (particularly 2 to 5) such as ethylene oxide or propylene oxide, and the addition number of alkylene oxide is preferably 1 to 50.
（２－２）カチオン性界面活性剤
　カチオン性界面活性剤は、アミド基を有しない化合物であることが好ましい。 (2-2) Cationic surfactant The cationic surfactant is preferably a compound having no amide group.
　カチオン性界面活性剤は、アミン塩、４級アンモニウム塩、オキシエチレン付加型アンモニウム塩であってよい。カチオン性界面活性剤の具体例としては、特に限定されないが、アルキルアミン塩、アミノアルコール脂肪酸誘導体、ポリアミン脂肪酸誘導体、イミダゾリン等のアミン塩型界面活性剤、アルキルトリメチルアンモニム塩、ジアルキルジメチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩、ピリジニウム塩、アルキルイソキノリニウム塩、塩化ベンゼトニウム等の４級アンモニウム塩型界面活性剤等が挙げられる。 The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt. Specific examples of the cationic surfactant include, but are not limited to, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, Quaternary ammonium salt type surfactants such as alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like can be mentioned.
　カチオン性界面活性剤の好ましい例は、
　R21-N+(-R22)(-R23)(-R24) X-
［式中、R21、R22、R23およびR24は炭素数１～３０の炭化水素基、
Xはアニオン性基である。］
の化合物である。
　R21、R22、R23および-R24の具体例は、アルキル基（例えば、メチル基、ブチル基、ステアリル基、パルミチル基）である。Xの具体例は、ハロゲン（例えば、塩素）、酸（例えば、塩酸、酢酸）である。
　カチオン性界面活性剤は、モノアルキルトリメチルアンモニウム塩（アルキルの炭素数４～３０）であることが特に好ましい。 Preferred examples of the cationic surfactant are:
R 21 -N + (-R 22) (- R 23) (- R 24) X -
[Wherein R 21 , R 22 , R 23 and R 24 represent a hydrocarbon group having 1 to 30 carbon atoms,
X is an anionic group. ]
It is a compound of this.
Specific examples of R 21 , R 22 , R 23 and —R 24 are alkyl groups (eg, methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogen (for example, chlorine) and acid (for example, hydrochloric acid, acetic acid).
The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 30 carbon atoms).
　カチオン性界面活性剤は、アンモニウム塩であることが好ましい。カチオン性界面活性剤は、式：
　　R1 p - N+R2 qX－
［式中、R1はC12以上（例えばＣ１２～Ｃ５０）の直鎖状および／または分岐状の脂肪族（飽和および／または不飽和）基、
R2はHまたはC1～4のアルキル基、ベンジル基、ポリオキシエチレン基（オキシエチレン基の数例えば１（特に２、特別には３）～５０）
（CH3、C2H5が特に好ましい）、
Xはハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子など）、Ｃ1～Ｃ4の脂肪酸塩基、
pは1または2、qは2または3で、p+q=4である。］
で示されるアンモニウム塩であってよい。Ｒ１の炭素数は、１２～５０、例えば１２～３０であってよい。 The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula:
R 1 p - N + R 2 q X -
[Wherein R 1 is a linear and / or branched aliphatic (saturated and / or unsaturated) group of C12 or more (eg, C 12 to C 50 ),
R 2 is H or an alkyl group of C1 to C4, benzyl group, polyoxyethylene group (number of oxyethylene groups, for example, 1 (particularly 2, particularly 3) to 50)
(CH 3 and C 2 H 5 are particularly preferred),
X is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), C 1 -C 4 fatty acid base,
p is 1 or 2, q is 2 or 3, and p + q = 4. ]
It may be an ammonium salt represented by R 1 may have 12 to 50 carbon atoms, such as 12 to 30 carbon atoms.
　カチオン性界面活性剤の具体例には、ドデシルトリメチルアンモニウムアセテート、トリメチルテトラデシルアンモニウムクロライド、ヘキサデシルトリメチルアンモニウムブロマイド、トリメチルオクタデシルアンモニウムクロライド、（ドデシルメチルベンジル）トリメチルアンモニウムクロライド、ベンジルドデシルジメチルアンモニウムクロライド、メチルドデシルジ（ヒドロポリオキシエチレン）アンモニウムクロライド、ベンジルドデシルジ（ヒドロポリオキシエチレン）アンモニウムクロライド、Ｎ－［２－（ジエチルアミノ）エチル］オレアミド塩酸塩が包含される。 Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl Di (hydropolyoxyethylene) ammonium chloride, benzyldodecyl di (hydropolyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride are included.
　両性界面活性剤としては、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、具体的には、ラウリルベタイン、ステアリルベタイン、ラウリルカルボキシメチルヒドロキシエチルイミダゾリニウムベタイン、ラウリルジメチルアミノ酢酸ベタイン、脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン等が挙げられる。
　ノニオン性界面活性剤、カチオン性界面活性剤、および両性界面活性剤のそれぞれが１種または２以上の組み合わせであってよい。
　界面活性剤として、ノニオン性界面活性剤のみまたはカチオン性界面活性剤のみを使用してもよいが、ノニオン性界面活性剤とカチオン性界面活性剤の組み合わせを使用することが好ましい。ノニオン性界面活性剤とカチオン性界面活性剤の組み合わせにおいて、ノニオン性界面活性剤とカチオン性界面活性剤の重量比は、好ましくは８５：１５～２０：８０、より好ましくは８０：２０～４０：６０であってよい。
　界面活性剤の合計量は、重合体１００重量部に対して、０．１～２０重量部、例えば、０．２～１０重量部であってよい。 Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, betaine acetate, and the like. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethylhydroxyethyl imidazolinium betaine, lauryl dimethyl. Examples include aminoacetic acid betaine and fatty acid amidopropyldimethylaminoacetic acid betaine.
Each of the nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may be one kind or a combination of two or more.
As the surfactant, only the nonionic surfactant or only the cationic surfactant may be used, but it is preferable to use a combination of the nonionic surfactant and the cationic surfactant. In the combination of the nonionic surfactant and the cationic surfactant, the weight ratio of the nonionic surfactant to the cationic surfactant is preferably 85:15 to 20:80, more preferably 80:20 to 40: It may be 60.
The total amount of the surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight with respect to 100 parts by weight of the polymer.
（３）液状媒体
　表面処理剤組成物は、重合体が液状媒体に分散した分散物であることが好ましい。
　液状媒体は、有機溶媒であってよいが、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（一般に水溶性有機溶剤）（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。
　水性媒体の量は、表面処理剤組成物に対して、２０～９９重量％、例えば４０～９５重量％であってよい。 (3) The liquid medium surface treating agent composition is preferably a dispersion in which a polymer is dispersed in a liquid medium.
The liquid medium may be an organic solvent, but is preferably an aqueous medium. In the present specification, the “aqueous medium” refers to a medium composed of only water and an organic solvent (generally a water-soluble organic solvent) in addition to water (the amount of the organic solvent is 80 parts by weight with respect to 100 parts by weight of water. In the following, for example, the medium also contains 0.1 to 50 parts by weight, in particular 5 to 30 parts by weight.
The amount of the aqueous medium may be 20 to 99% by weight, for example 40 to 95% by weight, based on the surface treatment agent composition.
（４）他の成分
　表面処理剤組成物は、含フッ素重合体および界面活性剤以外の他の成分として、非フッ素撥水性化合物を含有してもよい。
非フッ素撥水性化合物
　表面処理剤組成物は、フッ素原子を含まない撥水性化合物（非フッ素撥水性化合物）を含有することがある。
　非フッ素撥水性化合物は、非フッ素アクリレート重合体、飽和または不飽和の炭化水素化合物、またはシリコーン系化合物であってよい。 (4) Other component The surface treating agent composition may contain a non-fluorine water-repellent compound as a component other than the fluoropolymer and the surfactant.
The non-fluorine water repellent compound surface treating agent composition may contain a water repellent compound containing no fluorine atom (non-fluorine water repellent compound).
The non-fluorine water repellent compound may be a non-fluorine acrylate polymer, a saturated or unsaturated hydrocarbon compound, or a silicone compound.
　非フッ素アクリレート重合体は、１種類の非フッ素アクリレート単量体によって構成される単独重合体、あるいは少なくとも２種類の非フッ素アクリレート単量体によって構成される共重合体、あるいは少なくとも１種類の非フッ素アクリレート単量体および少なくとも１種類の他の非フッ素単量体（エチレン性不飽和化合物、例えば、エチレン、ビニル系単量体）によって構成される共重合体である。
　非フッ素アクリレート重合体を構成する非フッ素アクリレート単量体は、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、炭素数１～３０の鎖状または環状の炭化水素基、またはエステル結合を有する鎖状または環状の炭素数１～３１の有機基である。］
で示される化合物である。 The non-fluorine acrylate polymer is a homopolymer composed of one type of non-fluorine acrylate monomer, a copolymer composed of at least two types of non-fluorine acrylate monomers, or at least one type of non-fluorine acrylate monomer. It is a copolymer composed of an acrylate monomer and at least one other non-fluorine monomer (ethylenically unsaturated compound such as ethylene or vinyl monomer).
The non-fluorine acrylate monomer constituting the non-fluorine acrylate polymer has the formula:
CH 2 = CA-T
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond. ]
It is a compound shown by these.
　炭素数１～３０の鎖状または環状の炭化水素基の例は、炭素数１～３０の直鎖または分岐の脂肪族炭化水素基、炭素数４～３０の環状脂肪族基、炭素数６～３０の芳香族炭化水素基、炭素数７～３０の芳香脂肪族炭化水素基である。 Examples of the linear or cyclic hydrocarbon group having 1 to 30 carbon atoms include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, and 6 to 6 carbon atoms. 30 aromatic hydrocarbon groups, and aromatic aliphatic hydrocarbon groups having 7 to 30 carbon atoms.
　エステル結合を有する鎖状または環状の炭素数１～３１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１～３０の直鎖または分岐の脂肪族炭化水素基、炭素数４～３０の環状脂肪族基、炭素数６～３０の芳香族炭化水素基、炭素数７～３０の芳香脂肪族炭化水素基）である。 Examples of the linear or cyclic organic group having 1 to 31 carbon atoms having an ester bond are -C (= O) -OQ and -OC (= O) -Q (where Q is 1-30 carbon atoms). Straight chain or branched aliphatic hydrocarbon groups, cyclic aliphatic groups having 4 to 30 carbon atoms, aromatic hydrocarbon groups having 6 to 30 carbon atoms, and araliphatic hydrocarbon groups having 7 to 30 carbon atoms). .
　非フッ素アクリレート単量体の例には、例えば、アルキル（メタ）アクリレート、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）アクリレートが含まれる。 Examples of non-fluorinated acrylate monomers include, for example, alkyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate It is.
　非フッ素アクリレート単量体は、アルキル（メタ）アクリレートエステルであることが好ましい。アルキル基の炭素原子の数は１～３０であってよく、例えば、６～３０（例えば、１０～３０）であってよい。非フッ素アクリレート単量体の具体例は、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレートおよびベヘニル（メタ）アクリレートである。
　非フッ素アクリレート重合体は、含フッ素重合体と同様の重合方法で製造できる。 The non-fluorine acrylate monomer is preferably an alkyl (meth) acrylate ester. The number of carbon atoms in the alkyl group may be 1-30, for example, 6-30 (eg 10-30). Specific examples of non-fluorine acrylate monomers are lauryl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate.
The non-fluorinated acrylate polymer can be produced by the same polymerization method as that of the fluoropolymer.
　飽和または不飽和の炭化水素系化合物は飽和の炭化水素であることが好ましい。飽和または不飽和の炭化水素系化合物において、炭素数は、１５以上、好ましくは２０～３００、例えば２５～１００であってよい。飽和または不飽和の炭化水素系化合物の具体例は、パラフィンなどである。
　シリコーン系化合物は、一般に、撥水剤として使用されているものである。シリコーン系化合物は、撥水性を示す化合物であれば、限定されない。
　非フッ素撥水性化合物の量は、第１含フッ素重合体および第２含フッ素重合体の合計１００重量部に対して、０～５００重量部、例えば、５～２００重量部、特に、５～１００重量部であってよい。 The saturated or unsaturated hydrocarbon compound is preferably a saturated hydrocarbon. In a saturated or unsaturated hydrocarbon compound, the carbon number may be 15 or more, preferably 20 to 300, for example 25 to 100. Specific examples of the saturated or unsaturated hydrocarbon compound include paraffin.
Silicone compounds are generally used as water repellents. The silicone compound is not limited as long as it is a compound exhibiting water repellency.
The amount of the non-fluorine water repellent compound is 0 to 500 parts by weight, for example, 5 to 200 parts by weight, particularly 5 to 100 parts by weight based on the total of 100 parts by weight of the first fluoropolymer and the second fluoropolymer. It may be part by weight.
　本発明における含フッ素重合体（第１含フッ素単量体および第２含フッ素単量体）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。 The fluorine-containing polymer (first fluorine-containing monomer and second fluorine-containing monomer) in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.
　溶液重合では、重合開始剤の存在下で、単量体を有機溶媒に溶解させ、窒素置換後、３０～１２０℃の範囲で１～１０時間、加熱撹拌する方法が採用される。重合開始剤としては、例えばアゾビスイソブチロニトリル、ベンゾイルパーオキシド、ジ－ｔ－ブチルパーオキシド、ラウリルパーオキシド、クメンヒドロパーオキシド、t－ブチルパーオキシピバレート、ジイソプロピルパーオキシジカーボネートなどが挙げられる。重合開始剤は単量体１００重量部に対して、０.０１～２０重量部、例えば０.０１～１０重量部の範囲で用いられる。 In solution polymerization, a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, is heated and stirred in the range of 30 to 120 ° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. Can be mentioned. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
　有機溶媒は、単量体に不活性でこれらを溶解するものであり、例えば、エステル（例えば、炭素数２～３０のエステル、具体的には、酢酸エチル、酢酸ブチル）、ケトン（例えば、炭素数２～３０のケトン、具体的には、メチルエチルケトン、ジイソブチルケトン）、アルコール（例えば、炭素数１～３０のアルコール、具体的には、イソプロピルアルコール）であってよい。有機溶媒の具体例としては、アセトン、クロロホルム、ＨＣＨＣ２２５、イソプロピルアルコール、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、ベンゼン、トルエン、キシレン、石油エーテル、テトラヒドロフラン、１,４－ジオキサン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、酢酸エチル、酢酸ブチル、１,１,２,２－テトラクロロエタン、１,１,１－トリクロロエタン、トリクロロエチレン、パークロロエチレン、テトラクロロジフルオロエタン、トリクロロトリフルオロエタンなどが挙げられる。有機溶媒は単量体の合計１００重量部に対して、１０～２０００重量部、例えば、５０～１０００重量部の範囲で用いられる。 The organic solvent is inert to the monomer and dissolves them. For example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate), a ketone (for example, carbon It may be a ketone having a number of 2 to 30, specifically methyl ethyl ketone or diisobutyl ketone, or an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, Examples include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total amount of monomers.
　乳化重合では、重合開始剤および乳化剤の存在下で、単量体を水中に乳化させ、窒素置換後、５０～８０℃の範囲で１～１０時間、撹拌して重合させる方法が採用される。重合開始剤は、過酸化ベンゾイル、過酸化ラウロイル、ｔ－ブチルパーベンゾエート、１－ヒドロキシシクロヘキシルヒドロ過酸化物、３－カルボキシプロピオニル過酸化物、過酸化アセチル、アゾビスイソブチルアミジン－二塩酸塩、アゾビスイソブチロニトリル、過酸化ナトリウム、過硫酸カリウム、過硫酸アンモニウムなどの水溶性のものやアゾビスイソブチロニトリル、ベンゾイルパーオキシド、ジ－ｔ－ブチルパーオキシド、ラウリルパーオキシド、クメンヒドロパーオキシド、t－ブチルパーオキシピバレート、ジイソプロピルパーオキシジカーボネートなどの油溶性のものが用いられる。重合開始剤は単量体１００重量部に対して、０.０１～１０重量部の範囲で用いられる。 Emulsion polymerization employs a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after purging with nitrogen, the mixture is stirred and polymerized in the range of 50 to 80 ° C. for 1 to 10 hours. Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
　放置安定性の優れた重合体水分散液を得るためには、高圧ホモジナイザーや超音波ホモジナイザーのような強力な破砕エネルギーを付与できる乳化装置を用いて、単量体を水中に微粒子化して重合することが望ましい。また、乳化剤としてはアニオン性、カチオン性あるいはノニオン性の各種乳化剤を用いることができ、単量体１００重量部に対して、０.５～２０重量部の範囲で用いられる。アニオン性および／またはノニオン性および／またはカチオン性の乳化剤を使用することが好ましい。単量体が完全に相溶しない場合は、これら単量体に充分に相溶させるような相溶化剤、例えば、水溶性有機溶媒や低分子量の単量体を添加することが好ましい。相溶化剤の添加により、乳化性および共重合性を向上させることが可能である。 In order to obtain a polymer aqueous dispersion with excellent storage stability, the monomer is polymerized by submerging the monomer into water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers. By adding a compatibilizing agent, it is possible to improve emulsifying properties and copolymerization properties.
　水溶性有機溶媒としては、アセトン、メチルエチルケトン、酢酸エチル、プロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコール、トリプロピレングリコール、エタノールなどが挙げられ、水１００重量部に対して、１～５０重量部、例えば１０～４０重量部の範囲で用いてよい。また、低分子量の単量体としては、メチルメタクリレート、グリシジルメタクリレート、２,２,２－トリフルオロエチルメタクリレートなどが挙げられ、単量体の総量１００重量部に対して、１～５０重量部、例えば１０～４０重量部の範囲で用いてよい。 Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water. For example, it may be used in the range of 10 to 40 parts by weight. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers. For example, it may be used in the range of 10 to 40 parts by weight.
　重合においては、連鎖移動剤を使用してもよい。連鎖移動剤の使用量に応じて、重合体の分子量を変化させることができる。連鎖移動剤の例は、ラウリルメルカプタン、チオグリコール、チオグリセロールなどのメルカプタン基含有化合物（特に、（例えば炭素数１～３０の）アルキルメルカプタン）、次亜リン酸ナトリウム、亜硫酸水素ナトリウムなどの無機塩などである。連鎖移動剤の使用量は、単量体の総量１００重量部に対して、０．０１～１０重量部、例えば０．１～５重量部の範囲で用いてよい。 In the polymerization, a chain transfer agent may be used. Depending on the amount of chain transfer agent used, the molecular weight of the polymer can be varied. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol and thioglycerol (especially alkyl mercaptans (for example, having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium bisulfite. Etc. The chain transfer agent may be used in an amount of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomers.
　本発明の処理剤組成物は、溶液、エマルション（特に、水性分散液）またはエアゾールの形態であってよいが、水性分散液であることが好ましい。処理剤組成物は、重合体（表面処理剤の活性成分）および媒体（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。媒体の量は、例えば、処理剤組成物に対して、５～９９．９重量％、特に１０～８０重量％であってよい。
　処理剤組成物において、重合体の濃度は、０．０１～９５重量％、例えば５～５０重量％であってよい。 The treatment agent composition of the present invention may be in the form of a solution, an emulsion (particularly an aqueous dispersion) or an aerosol, but is preferably an aqueous dispersion. The treating agent composition comprises a polymer (active component of the surface treating agent) and a medium (particularly a liquid medium such as an organic solvent and / or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the treatment agent composition.
In the treating agent composition, the concentration of the polymer may be 0.01 to 95% by weight, such as 5 to 50% by weight.
　本発明の処理剤組成物は、従来既知の方法により被処理物に適用することができる。通常、該処理剤組成物を有機溶媒または水に分散して希釈して、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、被処理物の表面に付着させ、乾燥する方法が採られる。また、必要ならば、適当な架橋剤と共に適用し、キュアリングを行ってもよい。さらに、本発明の処理剤組成物に、防虫剤、柔軟剤、抗菌剤、難燃剤、帯電防止剤、塗料定着剤、防シワ剤などを添加して併用することも可能である。基材と接触させる処理液における重合体の濃度は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。 The treating agent composition of the present invention can be applied to an object to be treated by a conventionally known method. Usually, the treatment agent composition is dispersed in an organic solvent or water, diluted, and attached to the surface of an object to be treated by a known method such as dip coating, spray coating, foam coating, etc., and then dried. Taken. Further, if necessary, it may be applied together with an appropriate crosslinking agent and cured. Furthermore, an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent and the like can be added to the treatment agent composition of the present invention. The concentration of the polymer in the treatment liquid brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example 0.05 to 10% by weight.
　本発明の処理剤組成物（例えば、撥水撥油剤）で処理される被処理物としては、繊維製品、石材、フィルター（例えば、静電フィルター）、防塵マスク、燃料電池の部品（例えば、ガス拡散電極およびガス拡散支持体）、ガラス、紙、木、皮革、毛皮、石綿、レンガ、セメント、金属および酸化物、窯業製品、プラスチック、塗面、およびプラスターなどを挙げることができる。繊維製品としては種々の例を挙げることができる。例えば、綿、麻、羊毛、絹などの動植物性天然繊維、ポリアミド、ポリエステル、ポリビニルアルコール、ポリアクリロニトリル、ポリ塩化ビニル、ポリプロピレンなどの合成繊維、レーヨン、アセテートなどの半合成繊維、ガラス繊維、炭素繊維、アスベスト繊維などの無機繊維、あるいはこれらの混合繊維が挙げられる。 Examples of the object to be treated with the treating agent composition (for example, water and oil repellent) of the present invention include textile products, stone materials, filters (for example, electrostatic filters), dust masks, fuel cell components (for example, gas) Diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like. Various examples can be given as textile products. For example, natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.
　繊維製品は、繊維、布等の形態のいずれであってもよい。
　本発明の処理剤組成物は、内部離型剤あるいは外部離型剤としても使用できる。 The fiber product may be in the form of a fiber, cloth or the like.
The treatment agent composition of the present invention can also be used as an internal release agent or an external release agent.
　重合体は、繊維製品を液体で処理するために知られている方法のいずれかによって繊維状基材（例えば、繊維製品など）に適用することができる。繊維製品が布であるときには、布を溶液に浸してよく、あるいは、布に溶液を付着または噴霧してよい。処理された繊維製品は、撥油性を発現させるために、乾燥され、好ましくは、例えば、１００℃～２００℃で加熱される。 The polymer can be applied to a fibrous substrate (eg, a textile product, etc.) by any of the known methods for treating textile products with a liquid. When the textile product is a fabric, the fabric may be immersed in the solution, or the solution may be attached or sprayed onto the fabric. The treated fiber product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.
　あるいは、重合体はクリーニング法によって繊維製品に適用してよく、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製品に適用してよい。 Alternatively, the polymer may be applied to the textile by a cleaning method, for example, it may be applied to the textile by a laundry application or a dry cleaning method.
　処理される繊維製品は、典型的には、布であり、これには、織物、編物および不織布、衣料品形態の布およびカーペットが含まれるが、繊維または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。繊維製品材料は、天然繊維（例えば、綿または羊毛など）、化学繊維（例えば、ビスコースレーヨンまたはレオセルなど）、または、合成繊維（例えば、ポリエステル、ポリアミドまたはアクリル繊維など）であってよく、あるいは、繊維の混合物（例えば、天然繊維および合成繊維の混合物など）であってよい。本発明の製造重合体は、セルロース系繊維（例えば、綿またはレーヨンなど）を疎油性および撥油性にすることにおいて特に効果的である。また、本発明の方法は一般に、繊維製品を疎水性および撥水性にする。 The textile products to be treated are typically fabrics, which include woven, knitted and non-woven fabrics, fabrics and carpets in clothing form, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving yarn). The textile product material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or May be a mixture of fibers, such as a mixture of natural and synthetic fibers. The production polymer of the present invention is particularly effective in making cellulosic fibers (such as cotton or rayon) oleophobic and oleophobic. The method of the present invention also generally makes the textile product hydrophobic and water repellent.
　あるいは、繊維状基材は皮革であってよい。製造重合体を、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。
　あるいは、繊維状基材は紙であってもよい。製造重合体を、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 fibrous base material may be leather. In order to make the production polymer hydrophobic and oleophobic, aqueous solutions or aqueous emulsifications at various stages of leather processing, for example during the wet processing of leather or during the finishing of leather You may apply it to leather from things.
Alternatively, the fibrous substrate may be paper. The production polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.
　「処理」とは、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、処理剤の有効成分である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。 “Processing” means applying a treatment agent to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the polymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.
　以下、実施例を挙げて本発明を詳しく説明するが、本発明はこれらの実施例に限定されるものではない。
　以下において、部または％または比は、特記しない限り、重量部または重量％または重量比を表す。
　試験の手順は次のとおりである。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.
In the following, parts or% or ratio represents parts by weight or weight% or weight ratio unless otherwise specified.
The test procedure is as follows.
シャワー撥水性試験
　シャワー撥水性試験をＪＩＳ－Ｌ－１０９２に従って行った。シャワー撥水性試験は（下記に記載されている表１に示されるように）撥水性Ｎｏ．によって表された。
　体積が少なくとも２５０ｍｌであるガラス漏斗、および、２５０ｍｌの水を２０秒間～３０秒間にわたって噴霧することができるスプレーノズルを使用する。試験片フレームは、直径が１５ｃｍの金属フレームである。サイズが約２０ｃｍｘ２０ｃｍである３枚の試験片シートを準備し、シートを試験片ホルダーフレームに固定し、シートにしわがないようにする。噴霧の中心をシートの中心に置く。室温の水（２５０ｍＬ）をガラス漏斗に入れ、試験片シートに（２５秒～３０秒の時間にわたって）噴霧する。保持フレームを台から取り外し、保持フレームの一方の端をつかんで、前方表面を下側にし、反対側の端を堅い物質で軽くたたく。保持フレームを１８０°さらに回転させ、同じ手順を繰り返して、過剰な水滴を落とす。湿った試験片を、撥水性が不良から優れた順で、０、５０、７０、８０、９０および１００の評点をつけるために、湿潤比較標準物と比較する。結果を３回の測定の平均から得る。 Shower water repellency test A shower water repellency test was conducted according to JIS-L-1092. The shower water repellency test was performed (as shown in Table 1 below). Represented by.
A glass funnel with a volume of at least 250 ml and a spray nozzle capable of spraying 250 ml of water for 20-30 seconds are used. The specimen frame is a metal frame having a diameter of 15 cm. Three test piece sheets having a size of about 20 cm × 20 cm are prepared, and the sheet is fixed to the test piece holder frame so that the sheet is not wrinkled. Center the spray on the center of the sheet. Room temperature water (250 mL) is placed in a glass funnel and sprayed onto the specimen sheet (over a time period of 25-30 seconds). Remove the holding frame from the base, grab one end of the holding frame, tap the front surface down and dab the opposite end with a hard substance. Rotate the holding frame 180 ° further and repeat the same procedure to drop excess water drops. Wet specimens are compared to wet reference standards to score 0, 50, 70, 80, 90 and 100 in order of poor water repellency. Results are obtained from the average of three measurements.
撥水の連続加工性
　サイズが約２０ｃｍｘ５０ｃｍである１０枚の試験片シートを準備し、所定の濃度に希釈した撥水撥油剤処理液にて連続で処理する。各シートについて前述のシャワー撥水性試験を行い評価する。 Ten test specimen sheets having a water repellent continuous processability size of about 20 cm × 50 cm are prepared and continuously treated with a water / oil repellent treatment solution diluted to a predetermined concentration. Each sheet is evaluated by performing the above-described shower water repellency test.
製造例１
　1000mLオートクレーブにCF3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)=CH2　(n=2.0)（13FClA）　108ｇ、ラウリルアクリレート（LA）24.0ｇ、イソボルニルメタクリレート（IBMA）57.7.g、純水565ｇ、水溶性グリコール系溶剤47g、ポリオキシエチレンオレイルエーテル2.5g、ポリオキシエチレンアルキルエーテル27.8g、を入れ、攪拌下に６０℃で１５分間、超音波で乳化分散させた。オートクレーブ内を窒素置換後、塩化ビニル（VCM）62g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を得た。重合体の組成は、仕込みモノマーの組成にほぼ一致した。 Production Example 1
1000mL autoclave CF 3 CF 2 - (CF 2 CF 2) n -CH 2 CH 2 OCOC (Cl) = CH 2 (n = 2.0) (13FClA) 108g, lauryl acrylate (LA) 24.0 g, isobornyl methacrylate ( IBMA) 57.7.g, pure water 565g, water-soluble glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, polyoxyethylene alkyl ether 27.8g, emulsified and dispersed at 60 ° C for 15 minutes with stirring I let you. After the atmosphere in the autoclave was replaced with nitrogen, 62 g of vinyl chloride (VCM) was press-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 to obtain an aqueous dispersion of polymer. The composition of the polymer almost coincided with the composition of the charged monomer.
製造例２
　５００ｍｌ反応フラスコにＣＦ３ＣＦ２－（ＣＦ２ＣＦ２）ｎ－ＣＨ２ＣＨ２ＯＣＯＣ（Ｃｌ）＝ＣＨ２　（ｎ＝２．０）（13FClA）　51.2ｇ、ステアリルアクリレート(StA)85．4ｇ、純水194ｇ水溶性グリコール系溶剤34.1ｇ、塩化アルキルトリメチルアンモニウム6.3g、ポリオキシエチレンアルキルエーテル7.0gを入れ、攪拌下に６０℃で１５分間、超音波で乳化分散させた。反応フラスコ内を窒素置換後、アゾ基含有水溶性開始剤0.4ｇ及び水９ｇの溶液を添加し、６０℃で２０時間反応させ、重合体の水性分散液を得た。重合体の組成は、仕込みモノマーの組成にほぼ一致した。 Production Example 2
In a 500 ml reaction flask, CF 3 CF 2 — (CF 2 CF 2 ) n —CH 2 CH 2 OCOC (Cl) ═CH 2 (n = 2.0) (13FClA) 51.2 g, stearyl acrylate (StA) 85.4 g, 194 g of pure water, 34.1 g of a water-soluble glycol solvent, 6.3 g of alkyltrimethylammonium chloride, and 7.0 g of polyoxyethylene alkyl ether were added and emulsified and dispersed with ultrasound at 60 ° C. for 15 minutes with stirring. After the atmosphere in the reaction flask was replaced with nitrogen, a solution of 0.4 g of an azo group-containing water-soluble initiator and 9 g of water was added and reacted at 60 ° C. for 20 hours to obtain an aqueous dispersion of polymer. The composition of the polymer almost coincided with the composition of the charged monomer.
製造例３
　1000mLオートクレーブにCF3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)=CH2　(n=2.0)（13FClA）　108ｇ、ラウリルアクリレート（LA）24.0ｇ、イソボルニルメタクリレート（IBMA）57.7.g、純水565ｇ、水溶性グリコール系溶剤47g、ポリオキシエチレンオレイルエーテル2.5g、塩化アルキルトリメチルアンモニウム3.9g、ポリオキシエチレンアルキルエーテル27.8g、を入れ、攪拌下に６０℃で１５分間、超音波で乳化分散させた。オートクレーブ内を窒素置換後、塩化ビニル（VCM）62g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を得た。重合体の組成は、仕込みモノマーの組成にほぼ一致した。 Production Example 3
1000mL autoclave CF 3 CF 2 - (CF 2 CF 2) n -CH 2 CH 2 OCOC (Cl) = CH 2 (n = 2.0) (13FClA) 108g, lauryl acrylate (LA) 24.0 g, isobornyl methacrylate ( IBMA) 57.7.g, pure water 565g, water-soluble glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, alkyltrimethylammonium chloride 3.9g, polyoxyethylene alkyl ether 27.8g, put under stirring at 60 ° C 15 The mixture was emulsified and dispersed with ultrasound for a minute. After the atmosphere in the autoclave was replaced with nitrogen, 62 g of vinyl chloride (VCM) was press-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 to obtain an aqueous dispersion of polymer. The composition of the polymer almost coincided with the composition of the charged monomer.
製造例４
　５００ｍｌ反応フラスコにＣＦ３ＣＦ２－（ＣＦ２ＣＦ２）ｎ－ＣＨ２ＣＨ２ＯＣＯＣ（ＣＨ３）＝ＣＨ２　（ｎ＝２．０）（13FMA）　51.2ｇ、ステアリルアクリレート(StA)85．4ｇ、純水194ｇ水溶性グリコール系溶剤34.1ｇ、塩化アルキルトリメチルアンモニウム6.3g、ポリオキシエチレンアルキルエーテル7.0gを入れ、攪拌下に６０℃で１５分間、超音波で乳化分散させた。反応フラスコ内を窒素置換後、アゾ基含有水溶性開始剤0.4ｇ及び水９ｇの溶液を添加し、６０℃で２０時間反応させ、重合体の水性分散液を得た。重合体の組成は、仕込みモノマーの組成にほぼ一致した。 Production Example 4
In a 500 ml reaction flask, 51.2 g of CF 3 CF 2 — (CF 2 CF 2 ) n —CH 2 CH 2 OCOC (CH 3 ) ═CH 2 (n = 2.0) (13FMA), 85.4 g of stearyl acrylate (StA) 194 g of pure water, 34.1 g of a water-soluble glycol solvent, 6.3 g of alkyltrimethylammonium chloride, and 7.0 g of polyoxyethylene alkyl ether were added, and the mixture was emulsified and dispersed at 60 ° C. for 15 minutes with stirring. After the atmosphere in the reaction flask was replaced with nitrogen, a solution of 0.4 g of an azo group-containing water-soluble initiator and 9 g of water was added and reacted at 60 ° C. for 20 hours to obtain an aqueous dispersion of polymer. The composition of the polymer almost coincided with the composition of the charged monomer.
製造例５
　1000mLオートクレーブにCF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2　(n=2.0)（13FMA）　108ｇ、ラウリルアクリレート（LA）24.0ｇ、イソボルニルメタクリレート（IBMA）57.7.g、純水565ｇ、水溶性グリコール系溶剤47g、ポリオキシエチレンオレイルエーテル2.5g、ポリオキシエチレンアルキルエーテル27.8g、を入れ、攪拌下に６０℃で１５分間、超音波で乳化分散させた。オートクレーブ内を窒素置換後、塩化ビニル（VCM）62g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を得た。重合体の組成は、仕込みモノマーの組成にほぼ一致した。 Production Example 5
CF 3 CF 2- (CF 2 CF 2 ) n -CH 2 CH 2 OCOC (CH 3 ) = CH 2 (n = 2.0) (13FMA) 108 g, lauryl acrylate (LA) 24.0 g, isobornyl methacrylate (IBMA) Put 57.7.g, pure water 565g, water-soluble glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, polyoxyethylene alkyl ether 27.8g, and emulsify ultrasonically at 60 ° C for 15 minutes with stirring. Dispersed. After the atmosphere in the autoclave was replaced with nitrogen, 62 g of vinyl chloride (VCM) was press-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 to obtain an aqueous dispersion of polymer. The composition of the polymer almost coincided with the composition of the charged monomer.
製造例６
　５００mL反応フラスコにステアリルアクリレート(StA) 47.5g、純水=145g、水溶性グリコール系溶剤 15g、ソルビタンモノアルキルエステル 1.5g、ポリオキシエチレンアルキルエーテル　2g、塩化アルキルジメチルアンモニウム 1.5gを入れ、攪拌下に60℃で15分間、超音波で乳化分散させた。反応フラスコ内を窒素置換後、アゾ基含有水溶性開始剤0.5ｇを添加し、60℃で3時間反応させ、重合体の水性分散液を得た。更に純水で固形分濃度を30%に調整した。 Production Example 6
In a 500 mL reaction flask, add 47.5 g of stearyl acrylate (StA), pure water = 145 g, water-soluble glycol solvent 15 g, sorbitan monoalkyl ester 1.5 g, polyoxyethylene alkyl ether 2 g, and alkyldimethylammonium chloride 1.5 g. The mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes. After substituting the inside of the reaction flask with nitrogen, 0.5 g of an azo group-containing water-soluble initiator was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water.
製造例７
　５００mLオートクレーブにステアリルアクリレート(StA)　35g、純水 145g、水溶性グリコール系溶剤15g、ソルビタンモノアルキルエステル　1g、ポリオキシエチレンアルキルエーテル　2g、塩化アルキルジメチルアンモニウム　2gを入れ、攪拌下に60℃で15分間、超音波で乳化分散させた。オートクレーブ内を窒素置換後、塩化ビニルを12.5g圧入で仕込み、2,2-アゾビス（2-アミジノプロパン）2塩酸塩　0.5ｇを添加し、60℃で3時間反応させ、重合体の水性分散液を得た。更に純水で固形分濃度を30%に調整した。 Production Example 7
Into a 500 mL autoclave is added 35 g of stearyl acrylate (StA), 145 g of pure water, 15 g of a water-soluble glycol solvent, 1 g of sorbitan monoalkyl ester, 2 g of polyoxyethylene alkyl ether, and 2 g of alkyldimethylammonium chloride. Then, it was emulsified and dispersed with ultrasonic waves. After replacing the inside of the autoclave with nitrogen, 12.5 g of vinyl chloride was charged by press-fitting, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added, and the mixture was reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of polymer. Got. Further, the solid content concentration was adjusted to 30% with pure water.
比較製造例１
　５００ｍｌ反応フラスコにＣＦ３ＣＦ２－（ＣＦ２ＣＦ２）ｎ－ＣＨ２ＣＨ２ＯＣＯＣＨ＝ＣＨ２　（ｎ＝３．２）（NSFA）　51.2ｇ、ステアリルアクリレート(StA)85．4ｇ、純水194ｇ水溶性グリコール系溶剤34.1ｇ、塩化アルキルトリメチルアンモニウム6.3g、ポリオキシエチレンアルキルエーテル7.0gを入れ、攪拌下に６０℃で１５分間、超音波で乳化分散させた。反応フラスコ内を窒素置換後、アゾ基含有水溶性開始剤0.4ｇ及び水９ｇの溶液を添加し、６０℃で２０時間反応させ、重合体の水性分散液を得た。重合体の組成は、仕込みモノマーの組成にほぼ一致した。 Comparative production example 1
In a 500 ml reaction flask, CF 3 CF 2 — (CF 2 CF 2 ) n —CH 2 CH 2 OCOCH═CH 2 (n = 3.2) (NSFA) 51.2 g, stearyl acrylate (StA) 85.4 g, pure water 194 g 34.1 g of a water-soluble glycol solvent, 6.3 g of alkyltrimethylammonium chloride, and 7.0 g of polyoxyethylene alkyl ether were added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the reaction flask was replaced with nitrogen, a solution of 0.4 g of an azo group-containing water-soluble initiator and 9 g of water was added and reacted at 60 ° C. for 20 hours to obtain an aqueous dispersion of polymer. The composition of the polymer almost coincided with the composition of the charged monomer.
比較製造例２
　1000mLオートクレーブにCF3CF2-(CF2CF2)n-CH2CH2OCOCH=CH2　(n=3.2) （NSFA） 108ｇ、ステアリルアクリレート(StA)81.7g、純水565ｇ、水溶性グリコール系溶剤47g、ポリオキシエチレンオレイルエーテル2.5g、ポリオキシエチレンアルキルエーテル27.8g、を入れ、攪拌下に６０℃で１５分間、超音波で乳化分散させた。オートクレーブ内を窒素置換後、塩化ビニル（VCM）62g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を得た。重合体の組成は、仕込みモノマーの組成にほぼ一致した。 Comparative production example 2
CF 3 CF 2- (CF 2 CF 2 ) n -CH 2 CH 2 OCOCH = CH 2 (n = 3.2) (NSFA) 108 g, stearyl acrylate (StA) 81.7 g, pure water 565 g, water-soluble glycol system 47 g of solvent, 2.5 g of polyoxyethylene oleyl ether, and 27.8 g of polyoxyethylene alkyl ether were added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 62 g of vinyl chloride (VCM) was press-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 to obtain an aqueous dispersion of polymer. The composition of the polymer almost coincided with the composition of the charged monomer.
比較製造例３
　５００ｍｌ反応フラスコにパラフィン(融点50℃)136.6g 純水194ｇ、水溶性グリコール系溶剤34.1ｇ、塩化アルキルトリメチルアンモニウム6.3g、ポリオキシエチレンアルキルエーテル7.0gを入れ、攪拌下に６０℃で１５分間、超音波で乳化分散させ、水性分散液を得た。重合体の組成は、仕込みモノマーの組成にほぼ一致した。 Comparative production example 3
A 500 ml reaction flask is charged with 136.6 g of paraffin (melting point: 50 ° C.), 194 g of pure water, 34.1 g of water-soluble glycol solvent, 6.3 g of alkyltrimethylammonium chloride, 7.0 g of polyoxyethylene alkyl ether, and stirred at 60 ° C. for 15 minutes. An aqueous dispersion was obtained by emulsifying and dispersing with ultrasonic waves. The composition of the polymer almost coincided with the composition of the charged monomer.
実施例１
　製造例１、２において製造した水性液体を純水により含フッ素重合体濃度が３０％固形分となるように希釈した後、５０：５０で混合し十分に攪拌したのち、この３０％希釈液の割合が２％になるように水でさらに希釈して２．００％の試験液（１００ｇ）を調製した。１０枚のＰＥＴ布（５００ｍｍ ｘ ２００ｍｍ）をこの試験液に連続的に浸し、マングルに通し、１７０℃で１分間、ピンテンターで処理した。その後撥水性試験に付した。結果を表Ａに示す。濃度1.00%、1.20%および1.40%の試験液について、初期の撥水性をも測定した結果をも表Ａに示す。 Example 1
The aqueous liquid produced in Production Examples 1 and 2 was diluted with pure water so that the fluoropolymer concentration was 30% solids, mixed at 50:50 and stirred sufficiently, A 2.00% test solution (100 g) was prepared by further diluting with water so that the ratio was 2%. Ten PET cloths (500 mm × 200 mm) were continuously dipped in this test solution, passed through a mangle, and treated with a pin tenter at 170 ° C. for 1 minute. Thereafter, it was subjected to a water repellency test. The results are shown in Table A. Table A also shows the results of measuring the initial water repellency of the test solutions having concentrations of 1.00%, 1.20% and 1.40%.
実施例２
　製造例１、２において製造した水性液体を純水により含フッ素重合体濃度が３０％固形分となるように希釈した後、３０：７０で混合し十分に攪拌したのち、以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Example 2
After the aqueous liquid produced in Production Examples 1 and 2 was diluted with pure water so that the fluoropolymer concentration was 30% solids, it was mixed at 30:70 and sufficiently stirred. It processed and evaluated similarly. The results are shown in Table A.
実施例３
　製造例２、３において製造した水性液体を純水により含フッ素重合体濃度が３０％固形分となるように希釈した後、５０：５０で混合し十分に攪拌したのち、以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Example 3
After the aqueous liquid produced in Production Examples 2 and 3 was diluted with pure water so that the fluoropolymer concentration was 30% solids, it was mixed at 50:50 and sufficiently stirred. It processed and evaluated similarly. The results are shown in Table A.
実施例４
　製造例２、３において製造した水性液体を純水により含フッ素重合体濃度が３０％固形分となるように希釈した後、７０：３０で混合し十分に攪拌したのち、以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Example 4
After the aqueous liquid produced in Production Examples 2 and 3 was diluted with pure water so that the fluoropolymer concentration was 30% solids, it was mixed at 70:30 and sufficiently stirred. It processed and evaluated similarly. The results are shown in Table A.
実施例５
　製造例４、５において製造した水性液体を純水により含フッ素重合体濃度が３０％固形分となるように希釈した後、５０：５０で混合し十分に攪拌したのち、以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Example 5
After the aqueous liquid produced in Production Examples 4 and 5 was diluted with pure water so that the fluoropolymer concentration was 30% solids, it was mixed at 50:50 and sufficiently stirred. It processed and evaluated similarly. The results are shown in Table A.
実施例６
　製造例１、２および６において製造した水性液体を純水により重合体濃度が３０％固形分となるように希釈した後、５０：１７．５：３２．５で混合し十分に攪拌したのち、以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Example 6
After the aqueous liquid produced in Production Examples 1, 2, and 6 was diluted with pure water so that the polymer concentration was 30% solids, the mixture was mixed at 50: 17.5: 32.5 and stirred sufficiently, Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
実施例７
　製造例１、２および７において製造した水性液体を純水により重合体濃度が３０％固形分となるように希釈した後、５０：２５：２５で混合し十分に攪拌したのち、以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Example 7
The aqueous liquids produced in Production Examples 1, 2, and 7 were diluted with pure water so that the polymer concentration was 30% solids, then mixed at 50:25:25 and stirred sufficiently, and then the Examples The same treatment as in Example 1 was performed. The results are shown in Table A.
比較実施例１
　製造例１において製造した水性液体を純水により含フッ素重合体濃度が３０％固形分となるように希釈した後、この３０％希釈液の割合が２％になるように水でさらに希釈して２．００％の試験液（１００ｇ）を調製した。以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Comparative Example 1
The aqueous liquid produced in Production Example 1 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
比較実施例２
　製造例２において製造した水性液体を純水により含フッ素重合体濃度が３０％固形分となるように希釈した後、この３０％希釈液の割合が２％になるように水でさらに希釈して２．００％の試験液（１００ｇ）を調製した。以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Comparative Example 2
The aqueous liquid produced in Production Example 2 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
比較実施例３
　製造例３において製造した水性液体を純水により含フッ素重合体濃度が３０％固形分となるように希釈した後、この３０％希釈液の割合が２％になるように水でさらに希釈して２．００％の試験液（１００ｇ）を調製した。以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Comparative Example 3
The aqueous liquid produced in Production Example 3 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
比較実施例４
　製造例４において製造した水性液体を純水により含フッ素重合体濃度が３０％固形分となるように希釈した後、この３０％希釈液の割合が２％になるように水でさらに希釈して２．００％の試験液（１００ｇ）を調製した。以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Comparative Example 4
The aqueous liquid produced in Production Example 4 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
比較実施例５
　製造例５において製造した水性液体を純水により含フッ素重合体濃度が３０％固形分となるように希釈した後、この３０％希釈液の割合が２％になるように水でさらに希釈して２．００％の試験液（１００ｇ）を調製した。以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Comparative Example 5
The aqueous liquid produced in Production Example 5 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
比較実施例６
　比較製造例１において製造した水性液体を純水により含フッ素重合体濃度が３０％固形分となるように希釈した後、この３０％希釈液の割合が２％になるように水でさらに希釈して２．００％の試験液（１００ｇ）を調製した。以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Comparative Example 6
The aqueous liquid produced in Comparative Production Example 1 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
比較実施例７
　比較製造例２において製造した水性液体を純水により含フッ素重合体濃度が３０％固形分となるように希釈した後、この３０％希釈液の割合が２％になるように水でさらに希釈して２．００％の試験液（１００ｇ）を調製した。以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Comparative Example 7
The aqueous liquid produced in Comparative Production Example 2 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of this 30% diluted solution was 2%. A 2.00% test solution (100 g) was prepared. Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
比較実施例８
　製造例１および比較製造例３において製造した水性液体を純水により濃度が３０％固形分となるように希釈した後、７５：２５で混合し十分に攪拌したのち、この３０％希釈液の割合が２％になるように水でさらに希釈して２．００％の試験液（１００ｇ）を調製した。以降は実施例１と同様に処理し評価した。結果を表Ａに示す。 Comparative Example 8
The aqueous liquid produced in Production Example 1 and Comparative Production Example 3 was diluted with pure water so that the concentration became 30% solids, then mixed at 75:25 and stirred sufficiently, and then the ratio of this 30% diluted solution Was further diluted with water so as to be 2% to prepare a 2.00% test solution (100 g). Thereafter, processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table A.
　略号の意味は次のとおりである。
Figure JPOXMLDOC01-appb-I000001
The meanings of the abbreviations are as follows.
Figure JPOXMLDOC01-appb-I000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明の表面処理剤組成物は、例えば、撥水撥油剤、防汚剤および汚れ脱離剤として使用できる。 The surface treating agent composition of the present invention can be used as, for example, a water / oil repellent, an antifouling agent and a soil release agent.

Claims (13)

  1. 　（I）含フッ素単量体（ａ）から誘導された繰り返し単位およびハロゲン化オレフィン（ｂ）から誘導された繰り返し単位を有する第１含フッ素重合体、
    　（II）含フッ素単量体（ａ）から誘導された繰り返し単位を有しており、ハロゲン化オレフィンから誘導された繰り返し単位を有しない第２含フッ素重合体、ならびに
    　（III）液状媒体
    を含んでなる表面処理剤組成物。     (I) a first fluorine-containing polymer having a repeating unit derived from a fluorine-containing monomer (a) and a repeating unit derived from a halogenated olefin (b),
    (II) a second fluorine-containing polymer having a repeating unit derived from the fluorine-containing monomer (a) and having no repeating unit derived from a halogenated olefin; and (III) a liquid medium A surface treating agent composition comprising:
  2. 　含フッ素単量体（ａ）が、式：
    　　CH2=C(－X)－C(=O)－Y－Z－Rf            （Ｉ）
    ［式中、Ｘ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り；
    Ｙは、－Ｏ－または－ＮＨ－であり；
    Ｚは、直接結合、
    炭素数１～２０の直鎖状または分岐状脂肪族基、
    炭素数６～３０の芳香族基または環状脂肪族基、
    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。）、
    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、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、
    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、あるいは
    -(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。）であり；
    Ｒｆは、炭素数１～２０の直鎖状または分岐状のフルオロアルキル基である。] 
    で示される化合物である請求項１に記載の表面処理剤組成物。     The fluorine-containing monomer (a) has the formula:
    CH 2 = C (-X) -C (= O) -Y-Z-Rf (I)
    [Wherein, X 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 (where X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, A substituted or unsubstituted phenyl group;
    Y is —O— or —NH—;
    Z is a direct bond,
    A linear or branched aliphatic group having 1 to 20 carbon atoms,
    An aromatic group or cycloaliphatic group having 6 to 30 carbon atoms,
    A group represented by the formula —R 2 (R 1 ) N—SO 2 — or a formula —R 2 (R 1 ) N—CO— (wherein R 1 is an alkyl group having 1 to 10 carbon atoms; 2 is a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group).
    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, Ar optionally has a substituent) An arylene group, p represents 0 or 1),
    A group represented by the formula —CH 2 —Ar— (O) q — (wherein Ar is an arylene group optionally having a substituent, q is 0 or 1), or
    — (CH 2 ) m —SO 2 — (CH 2 ) n — group or — (CH 2 ) m —S— (CH 2 ) n — group (where m is 1 to 10 and n is 0 to 10) .);
    Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
    The surface treating agent composition of Claim 1 which is a compound shown by these.
  3. 　含フッ素単量体（ａ）が、α位が塩素原子で置換されているアクリレートである請求項１または２に記載の表面処理剤組成物。 The surface treating agent composition according to claim 1 or 2, wherein the fluorine-containing monomer (a) is an acrylate substituted at the α-position with a chlorine atom.
  4. 　含フッ素単量体（ａ）において、Rfの炭素数が１～６である請求項２に記載の表面処理剤組成物。 The surface treating agent composition according to claim 2, wherein in the fluorine-containing monomer (a), Rf has 1 to 6 carbon atoms.
  5. 　ハロゲン化オレフィン単量体（ｂ）が、塩化ビニルである請求項１に記載の表面処理剤組成物。 The surface treating agent composition according to claim 1, wherein the halogenated olefin monomer (b) is vinyl chloride.
  6. 　第１含フッ素重合体および第２含フッ素重合体の少なくとも一方は、他の単量体（ｃ）から誘導された繰り返し単位を有しており、
    他の単量体（ｃ）が非フッ素非架橋性単量体（ｃ１）であり、
    非フッ素非架橋性単量体（ｃ１）が、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であり、
    Ｔは、水素原子、炭素数１～３０の鎖状または環状の炭化水素基、またはエステル結合を有する鎖状または環状の炭素数１～３１の有機基である。］
    で示される化合物である請求項１～５のいずれかに記載の表面処理剤組成物。     At least one of the first fluoropolymer and the second fluoropolymer has a repeating unit derived from the other monomer (c),
    The other monomer (c) is a non-fluorine non-crosslinkable monomer (c1),
    The non-fluorine non-crosslinkable monomer (c1) has the formula:
    CH 2 = CA-T
    [In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom;
    T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond. ]
    The surface treating agent composition according to any one of claims 1 to 5, which is a compound represented by the formula:
  7. 　第１含フッ素重合体において、含フッ素単量体（ａ）１００重量部に対して、ハロゲン化オレフィン単量体（ｂ）の量が５～３００重量部であり、必要により存在する他の単量体（ｃ）の量が０～８００重量部であり、
    　第２含フッ素重合体において、含フッ素単量体（ａ）１００重量部に対して、必要により存在する他の単量体（ｃ）の量が０～８００重量部である請求項１～６のいずれかに記載の表面処理剤組成物。     In the first fluorine-containing polymer, the amount of the halogenated olefin monomer (b) is 5 to 300 parts by weight with respect to 100 parts by weight of the fluorine-containing monomer (a). The amount of the monomer (c) is 0 to 800 parts by weight,
    In the second fluoropolymer, the amount of the other monomer (c) present if necessary is 0 to 800 parts by weight per 100 parts by weight of the fluoromonomer (a). The surface treating agent composition in any one of.
  8. 　第１含フッ素重合体と第２含フッ素重合体の重量比が５：９５～９５：５である請求項１～７のいずれかに記載の表面処理剤組成物。 The surface treating agent composition according to any one of claims 1 to 7, wherein the weight ratio of the first fluoropolymer to the second fluoropolymer is 5:95 to 95: 5.
  9. 　液状媒体（III）が、水、または水と水溶性有機溶剤の混合物である請求項１～８のいずれかに記載の表面処理剤組成物。 The surface treating agent composition according to any one of claims 1 to 8, wherein the liquid medium (III) is water or a mixture of water and a water-soluble organic solvent.
  10. 　ノニオン性界面活性剤とカチオン性界面活性剤を含む水性分散液である請求項１～９のいずれかに記載の表面処理剤組成物。 The surface treating agent composition according to any one of claims 1 to 9, which is an aqueous dispersion containing a nonionic surfactant and a cationic surfactant.
  11. 　フッ素原子を含まない撥水性化合物を含有する請求項１～１０のいずれかに記載の表面処理剤組成物。 The surface treating agent composition according to any one of claims 1 to 10, comprising a water repellent compound containing no fluorine atom.
  12. 　表面処理剤組成物が、撥水撥油剤組成物、防汚剤組成物または汚れ脱離剤組成物である請求項１～１１のいずれかに記載の表面処理剤組成物。 The surface treating agent composition according to any one of claims 1 to 11, wherein the surface treating agent composition is a water / oil repellent composition, an antifouling agent composition, or a soil release agent composition.
  13. 　請求項１～１２のいずれかに記載の表面処理剤組成物によって処理された基材。 A base material treated with the surface treating agent composition according to any one of claims 1 to 12.
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