WO2014208422A1 - Agent de traitement de surface et polymère contenant du fluor - Google Patents

Agent de traitement de surface et polymère contenant du fluor Download PDF

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Publication number
WO2014208422A1
WO2014208422A1 PCT/JP2014/066179 JP2014066179W WO2014208422A1 WO 2014208422 A1 WO2014208422 A1 WO 2014208422A1 JP 2014066179 W JP2014066179 W JP 2014066179W WO 2014208422 A1 WO2014208422 A1 WO 2014208422A1
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Prior art keywords
group
fluorine
carbon atoms
monomer
atom
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PCT/JP2014/066179
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English (en)
Japanese (ja)
Inventor
徹也 上原
正弘 宮原
育男 山本
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ダイキン工業株式会社
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Publication of WO2014208422A1 publication Critical patent/WO2014208422A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to a surface treatment agent, particularly a water- and oil-repellent agent, and a fluorine-containing polymer which is an active component of the surface treatment agent.
  • 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. .
  • WO2004 / 096939 A1 discloses a surface treatment agent comprising a fluorinated monomer, a monomer that does not contain a fluorine atom, and a fluorinated polymer formed from a crosslinkable monomer that is present if necessary. ing.
  • WO2008 / 143093 A1 includes a fluorine-containing acrylate monomer and a fluorine-containing polymer formed from one or both of a monomer having a cyclic hydrocarbon group or a monomer having a short-chain hydrocarbon group.
  • a masonry treatment agent is disclosed.
  • WO2006 / 121171 A1 discloses a surface treating agent comprising a fluorosilicone reaction product comprising a mercapto functional organopolysiloxane and a fluorinated monomer.
  • WO2004 / 108855 A1 is a surface treatment agent comprising a fluoropolymer formed from a fluoromonomer, wherein (a) the fluoropolymer has a silicon atom, and / or (B) A silicon-containing polymer in which the surface treatment agent comprises a fluorine-containing polymer (first polymer) and a second polymer different from the first polymer, and the second polymer has a silicon atom.
  • a surface treatment agent is disclosed.
  • the treatment agents proposed in these prior art documents may not give excellent water and oil repellency.
  • An object of the present invention is to provide a surface treatment agent having excellent water and oil repellency.
  • the present invention also provides (1) a surface treatment agent comprising the above fluoropolymer, and (2) a liquid medium.
  • the surface treating agent of the present invention gives excellent water and oil repellency to a substrate. Also gives excellent antifouling properties. Excellent water and oil repellency and antifouling durability.
  • the fluoropolymer of the present invention has good copolymerizability.
  • the fluorine-containing polymer is (I) a repeating unit derived from a fluorine-containing monomer, (Ii) having a repeating unit derived from a cyclic hydrocarbon group-containing monomer, and (iii) a repeating unit derived from a linear or branched hydrocarbon group-containing monomer.
  • the polymer and treatment agent of the present invention preferably do not contain a silicon-containing monomer or a silicon-containing chain transfer agent. In the presence of a silicon-containing compound, the oil repellency may deteriorate.
  • Z is, for example, a linear alkylene group having 1 to 20 carbon atoms or a branched alkylene group, such as a group represented by the formula — (CH 2 ) x — (wherein x is 1 to 10), Alternatively, a group represented by the formula —SO 2 N (R 1 ) R 2 — or a formula —CON (R 1 ) R 2 (wherein R 1 is an alkyl group having 1 to 10 carbon atoms, and R 2 is , A straight-chain alkylene group or a branched alkylene group having 1 to 10 carbon atoms), or a formula —CH 2 CH (OR 3 ) CH 2 — (wherein R 3 is a hydrogen atom or carbon A group represented by an acyl group of 1 to 10 (for example, formyl or acetyl), or a formula —Ar—CH 2 — (wherein Ar is an arylene group optionally having a substituent) .) a group represented by, - (
  • the Rf group is preferably a perfluoroalkyl group.
  • the number of carbon atoms in the Rf group is preferably 1-20, such as 1-6, especially 4-6, especially 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) or -CH 2 CH (OZ 1 ) CH 2 -group (where Z 1 is a hydrogen atom or an acetyl group) 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, n is 0 to 10, Preferably).
  • 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 (i) include the following, but are not limited thereto.
  • the cyclic hydrocarbon group-containing acrylate ester monomer (ii) does not have a fluoroalkyl group.
  • the cyclic hydrocarbon group-containing acrylate ester monomer (ii) may contain a fluorine atom, but preferably does not contain a fluorine atom.
  • Q 11 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Q 11 is particularly preferably a methyl group.
  • Q 12 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 unsaturated.
  • the cyclic hydrocarbon group has 4 to 30 carbon atoms, preferably 6 to 20 carbon atoms.
  • cyclic hydrocarbon group examples 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 an unsaturated cyclic aliphatic group.
  • cyclic hydrocarbon group examples include a cyclohexyl group, a t-butylcyclohexyl group, a benzyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group.
  • cyclic hydrocarbon group-containing acrylate ester monomer Cyclohexyl acrylate, t-butyl cyclohexyl acrylate, benzyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate; and cyclohexyl methacrylate, t-butyl cyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, dicyclopentanyl And methacrylate and dicyclopentenyl methacrylate.
  • the presence of the cyclic hydrocarbon group-containing acrylate ester monomer increases the water repellency and oil repellency provided by the fluoropolymer.
  • the linear or branched hydrocarbon group-containing monomer (iii) does not have a fluoroalkyl group.
  • the linear or branched hydrocarbon group-containing monomer (iii) may contain a fluorine atom, but preferably does not contain a fluorine atom.
  • Q 21 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogen atom. Q 21 is particularly preferably a methyl group.
  • Q 22 is a linear or branched hydrocarbon group.
  • the linear or branched hydrocarbon group may in particular be a linear hydrocarbon group.
  • the linear or branched hydrocarbon group may have 8 to 30 carbon atoms, for example, 12 to 28, particularly 18 to 26.
  • the linear or branched hydrocarbon group is generally preferably a saturated aliphatic hydrocarbon group, particularly an alkyl group.
  • the monomer (iii) may be a (meth) acrylate ester having an alkyl group, particularly an alkyl (meth) acrylate ester.
  • the number of carbon atoms in the alkyl group may be 8-30, for example 12-28, in particular 18-26.
  • the monomer (iii) are lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.
  • the presence of the linear or branched hydrocarbon group-containing monomer increases the solubility of the fluoropolymer, and increases the water repellency and oil repellency provided by the fluoropolymer.
  • one or both of the monomers (ii) and (iii) are preferably methacrylate esters in which Q 11 and Q 21 are methyl groups. It is particularly preferred that both monomers (ii) and (iii) are methacrylate esters.
  • (iv) amino group-containing monomer or carboxylic acid group-containing monomer monomer one or both of (iv) an amino group-containing monomer and a carboxylic acid group-containing monomer may be used.
  • Examples of amino group-containing monomers have the formula: [Wherein R 11 , R 12 and R 21 are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y 11 is an oxygen atom or NH, and Z is 1 to 4 carbon atoms] 10 branched or straight chain alkylene groups. R 11 and R 12 may be bonded to each other to form a ring together with the adjacent nitrogen atom. ] It is shown by. Since the polymer contains an amino group, for example, when a salt is formed with a protonic acid, the polymer dissociates when dissolved in water and becomes cationic.
  • R 11 , R 12 and R 21 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, butyl, etc.).
  • R 21 is preferably a hydrogen atom or a methyl group.
  • R 11 and R 12 When R 11 and R 12 are bonded to each other to form a ring with an adjacent nitrogen atom, R 11 and R 12 may be bonded through a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom.
  • Examples of the ring formed by combining R 11 and R 12 together with the adjacent nitrogen atom include an aziridine ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.
  • Examples of the alkylene group represented by Z include linear or branched alkylene groups having 1 to 21 carbon atoms (preferably 1 to 4 carbon atoms) such as methylene, ethylene, propylene, trimethylene, tetramethylene and hexamethylene groups. Can be mentioned.
  • amino group-containing monomer examples include Y 11 in the chemical formula (II) such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate.
  • Y 11 is NH in the chemical formula (II) such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide.
  • a carboxylic acid group-containing monomer may be used as a monomer.
  • Examples of carboxylic acid group-containing monomers are acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and tetraconic acid. Since water and oil repellency increases, if the treated substrate contains cotton fibers, use one or both of amino group-containing monomers and carboxylic acid group-containing monomers, especially carboxylic acid group-containing monomers. It is preferable to do.
  • Other monomers (v) other than the monomer monomers (i) to (iv), for example, non-fluorine non-crosslinkable monomers may be used.
  • examples of other monomers include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate , And vinyl alkyl ethers.
  • Other monomers are not limited to these examples.
  • the other monomer may be a halogenated olefin (preferably having 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 halides such as vinyl chloride, vinyl bromide, vinyl iodide
  • vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide.
  • the other monomer may be a non-fluorine crosslinkable monomer.
  • a non-fluorine crosslinkable monomer is a monomer which does not contain a fluorine atom.
  • the non-fluorine crosslinkable monomer may be a compound having at least two reactive groups and / or olefinic carbon-carbon double bonds and not containing fluorine.
  • the non-fluorine crosslinkable monomer may be a compound having at least two olefinic carbon-carbon double bonds, or a compound having at least one olefinic 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 may be mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group.
  • the non-fluorine crosslinkable monomer may be di (meth) acrylate.
  • One example of a non-fluorine crosslinkable monomer is a vinyl monomer having a hydroxyl group.
  • Non-fluorine crosslinkable monomers include, for example, diacetone (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, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di ( Examples include, but are not limited to, (meth) acrylate.
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acrylamide means acrylamide or methacrylamide
  • Each of the monomers (i) to (v) may be a single monomer or a mixture of two or more thereof.
  • the fluoromonomer (i) is 100 parts by weight.
  • the amount of cyclic hydrocarbon group-containing acrylate ester monomer (ii) is 1 to 1000 parts by weight, for example 10 to 500 parts by weight, in particular 15 to 300 parts by weight, especially 20 to 100 parts by weight.
  • the amount of the aliphatic hydrocarbon group-containing acrylate ester monomer (iii) is 1 to 1000 parts by weight, for example 10 to 500 parts by weight, in particular 15 to 300 parts by weight, especially 20 to 100 parts by weight,
  • the amount of amino group-containing monomer and carboxylic acid group-containing monomer (iv) is 0 to 500 parts by weight, for example 1 to 100 parts by weight, in particular 2 to 50 parts by weight, especially 3 to 30 parts by weight,
  • the amount of other monomers (v) may be 0 to 800 parts by weight, for example 1 to 500 parts by
  • the number average molecular weight (Mn) of the fluoropolymer may generally be from 1,000 to 1,000,000, for example from 3,000 to 500,000, in particular from 5,000 to 200,000.
  • the number average molecular weight (Mn) of the fluoropolymer is generally measured by GPC (gel permeation chromatography).
  • monomers are polymerized to obtain a fluorine-containing composition in which a fluorine-containing polymer is dispersed or dissolved in a medium.
  • monomers (i) to (iii) are used.
  • One or both of monomers (iv) and (v) may be used.
  • the fluorine-containing polymer has repeating units derived from (i) to (iii) and, if necessary, repeating units derived from at least one of the monomers (iv) and (v).
  • the fluoropolymer may consist only of repeating units derived from (i) to (iii).
  • Monomer (i) is mainly used to improve water and oil repellency
  • Monomer (ii) is mainly used to improve water repellency
  • the monomer (iii) is mainly used for improving oil repellency
  • Monomer (iv) is mainly used to improve water repellency
  • the monomer (v) is mainly used for improving the water / oil repellency.
  • the fluoropolymer 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 is preferred.
  • the method for obtaining the organic solvent solution of the fluoropolymer is not limited. For example, after producing a fluoropolymer by emulsion polymerization in water, water is removed and an organic solvent is added to obtain an organic solvent solution of the fluoropolymer.
  • 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, 0.1 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 (a chain transfer agent other than the silicon-containing compound) may be used.
  • chain transfer agent a chain transfer agent other than the silicon-containing compound
  • the molecular weight of the fluoropolymer 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.
  • 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 fluorine-containing composition of the present invention is preferably in the form of a solution, an emulsion (particularly an aqueous dispersion) or an aerosol.
  • the fluorine-containing composition comprises a fluorine-containing polymer (active component of the surface treatment agent) and a medium (in particular, 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 fluorine-containing composition.
  • the concentration of the fluorine-containing polymer may be 0.01 to 95% by weight, for example, 5 to 50% by weight.
  • the fluorine-containing composition of the present invention can be applied to an object to be processed by a conventionally known method.
  • the fluorine-containing 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 or foam coating, and then dried. Taken. Further, if necessary, it may be applied together with an appropriate crosslinking agent and cured.
  • insecticides, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixing agents, anti-wrinkle agents, and the like can be added to the fluorine-containing composition of the present invention.
  • the concentration of the fluoropolymer 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 objects to be treated with the fluorine-containing composition (for example, water and oil repellent) of the present invention include textile products, stone materials, filters (for example, electrostatic filters), dust masks, and 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.
  • natural animal and vegetable fibers such as cotton, hemp, wool, silk
  • synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, 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 fluorine-containing composition of the present invention can also be used as an internal release agent or an external release agent.
  • the fluoropolymer can be applied to a fibrous substrate (eg, a fiber product, etc.) by any of the known methods for treating a fiber product with a liquid.
  • a fibrous substrate eg, a fiber 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 fluoropolymer may be applied to the fiber product by a cleaning method, and may be applied to the fiber product in, for example, 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 fluoropolymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.
  • the treatment agent (treatment agent composition) of the present invention may be a dispersion, but is preferably a solution.
  • a solution in which the fluoropolymer is dissolved in a solvent (particularly an organic solvent) is preferable.
  • the solvent is an organic solvent, particularly an organic solvent (one organic solvent or a mixture of two or more organic solvents) having a flash point of 0 to 200 ° C. (especially 21 ° C. or higher and lower than 70 ° C.) at 1 atm. It's okay.
  • the organic solvent is an ester (for example, an ester having 2 to 30 carbon atoms, specifically ethyl acetate or butyl acetate), a ketone (for example, a ketone having 2 to 30 carbon atoms, specifically methyl ethyl ketone or diisobutyl ketone).
  • An alcohol for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol
  • the treatment agent of the present invention can be suitably used for textile products, stone materials, and leather products, and imparts water and oil repellency.
  • the treatment agent can be applied to the substrate as, for example, a spray.
  • 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 25-30 seconds are used. The frame for fixing the test cloth is made of metal having a diameter of 15 cm. Three test cloths having a size of about 20 cm ⁇ 20 cm are prepared, and the test cloth is fixed to the frame so that the test cloth is not wrinkled. Center spray on center of test cloth. Room temperature water (250 mL) is placed in a glass funnel and sprayed onto the test cloth (over a period of 25-30 seconds).
  • Oil repellency test Oil repellency is determined by applying a test solution shown in Table 2 below to AATCC-TM118 on a test cloth in several places at two locations, observing the permeation state after 30 seconds, and giving the test solution that does not exhibit immersion. The highest point of the oil is oil repellency. When the evaluation result was 4 or more, it was evaluated as ⁇ when 2 or 3, and ⁇ when 1 or less.
  • the weight average molecular weight of the fluorine-containing copolymer is determined by GPC (gel permeation chromatography) (polystyrene conversion).
  • GPC gel permeation chromatography
  • Shodex GPC-104 manufactured by SHOWA DENKO KK
  • As the column a column in which two Shodex LF-604, two Shodex KF-601, two Shodex KF-600RL, and two Shodex KF-600RH were connected was used.
  • As the detector a UV (Shodex UV-41,254 nm) detector was used. Standard polystyrene (Shodex STANDARD S series) was used as a standard substance.
  • the analysis sample was prepared by dissolving a fluorine-containing copolymer in tetrahydrofuran to form a 0.5 wt% solution and passing it through a 0.5 ⁇ m filter.
  • the column was kept at 40 ° C., tetrahydrofuran was used as the eluent, the flow rate was 0.6 mL / min, and 50 ⁇ L of an analytical sample was injected.
  • Synthesis example 1 A reactor having a volume of 1 L equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet and a heating device was prepared, and 233 parts of the solvent butyl acetate was added.
  • BzMA benzyl methacrylate
  • StMA stearyl methacrylate
  • MA maleic anhydride
  • a copolymer and a post-treatment were carried out in the same manner as in Synthesis Example 1 except that 3 parts of perpivalic acid-t-butyl initiator was added in this order to (total 100 parts of monomer), and a fluorine-containing copolymer solution ( S3) was obtained.
  • the monomer composition of the fluorinated copolymer almost coincided with the charged monomer composition.
  • Synthesis example 4 From 60 parts of F (CF 2 ) 6 CH 2 CH 2 OCOC (Cl) ⁇ CH 2 (C6FC1A), 22 parts of isobornyl methacrylate (IBMA), 16 parts of stearyl methacrylate (StMA) and 2 parts of maleic anhydride (MA) Fluorine-containing copolymer by copolymerization and post-treatment as in Synthesis Example 1 except that 3 parts of perpivalic acid-t-butyl initiator is added in this order to the resulting monomer (monomer total 100 parts). A solution (S4) was obtained. The monomer composition of the fluorinated copolymer almost coincided with the charged monomer composition.
  • a copolymer and a post-treatment were carried out in the same manner as in Synthesis Example 1 except that 3 parts of perpivalic acid-t-butyl initiator was added in this order to (total 100 parts of monomer), and a fluorine-containing copolymer solution ( S5) was obtained.
  • the monomer composition of the fluorinated copolymer almost coincided with the charged monomer composition.
  • Synthesis example 8 A reactor having a volume of 1 L equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet and a heating apparatus was prepared, and 233 parts of butyl acetate as a solvent was added.
  • F (CF 2 ) 6 CH 2 CH 2 OCOC (CH 3 ) CH 2 (referred to as “C6SFMA”) 60 parts, isobornyl methacrylate (IBMA) 25 parts and stearyl methacrylate (StMA)
  • IBMA isobornyl methacrylate
  • StMA stearyl methacrylate
  • monomer 100 parts in total
  • initiator 3 parts of perpivalic acid-t-butyl was added in this order, and this mixture was mixed and stirred for 12 hours under a nitrogen atmosphere at 60 ° C. for copolymerization. I did it.
  • this reaction mixture was cooled to room temperature to obtain a fluorinated copolymer solution (R1). The solid concentration of this solution was 30% by weight.
  • the monomer composition of the fluorinated copolymer almost coincided with the charged monomer composition.
  • the weight average molecular weight of the fluorine-containing copolymer was 36000.
  • Example 1 Test cloths were prepared using the solvent dispersions obtained in Preparation Examples 1 to 7 (Synthesis Examples 1 to 7) and Comparative Preparation Examples 1 to 4 (Synthesis Examples 8 to 11), and water repellency and oil repellency were evaluated. .
  • a polyester cloth or cotton cloth is put into a polybin containing 300 g of solvent dispersion (SD1) and sealed, and then the polybin is shaken up and down for 10 seconds to sufficiently immerse the solvent dispersion in the cloth.
  • the cloth removed from the polybin is treated at 1000 rpm for 1 minute using a centrifugal dehydrator to remove excess solvent. Thereafter, it was dried in a draft at room temperature for 24 hours to prepare a test cloth.
  • the test cloth was subjected to a water repellency test and an oil repellency test. Table 3 shows the performance evaluation results.
  • Examples 2-7 Similar to Example 1, except that the fluorine-containing copolymer solvent dispersions SD2 to SD7 obtained in Preparation Examples 2 to 7 were used in place of SD1 of the fluorine-containing copolymer solvent dispersion in Example 1, respectively. The experiment was conducted. The performance evaluation results of the obtained test cloth are shown in Table 3.
  • Example 1 is the same as Example 1 except that each of the fluorine-containing copolymer solvent dispersions RD1 to RD4 obtained in Comparative Preparation Examples 1 to 4 is used instead of SD1 of the fluorine-containing copolymer solvent dispersion in Example 1. The experiment was conducted. The performance evaluation results of the obtained test cloth are shown in Table 3.
  • the treatment agent of the present invention can be suitably used for substrates such as textile products, and imparts excellent water and oil repellency to the substrate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un polymère contenant du fluor comprenant (i) un motif répété dérivé d'un monomère contenant du fluor représenté par la formule CH2=C(-X)-C(=O)-Y-Z-Rf, (ii) un motif répété dérivé d'un monomère d'ester d'acrylate contenant un groupe hydrocarboné cyclique représenté par la formule CH2=CQ11-C(=O)-O-Q12, et (iii) un motif répété dérivé d'un monomère d'ester d'acrylate contenant un groupe hydrocarboné aliphatique représenté par la formule CH2=CQ21-C(=O)-O-Q22. Le polymère contenant du fluor consiste en un agent de traitement de surface présentant une hydrophobie et une oléofugation supérieures.
PCT/JP2014/066179 2013-06-28 2014-06-18 Agent de traitement de surface et polymère contenant du fluor WO2014208422A1 (fr)

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