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WO2015080026A1 - Agent de traitement de surface - Google Patents

Agent de traitement de surface Download PDF

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Publication number
WO2015080026A1
WO2015080026A1 PCT/JP2014/080815 JP2014080815W WO2015080026A1 WO 2015080026 A1 WO2015080026 A1 WO 2015080026A1 JP 2014080815 W JP2014080815 W JP 2014080815W WO 2015080026 A1 WO2015080026 A1 WO 2015080026A1
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WO
WIPO (PCT)
Prior art keywords
group
monomer
surfactant
acrylate
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/080815
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English (en)
Japanese (ja)
Inventor
福森　正樹
晋一 南
良輔 原
留美 川部
育男 山本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Priority to CN201480063523.9A priority Critical patent/CN105764980B/zh
Priority to KR1020167013365A priority patent/KR101851086B1/ko
Publication of WO2015080026A1 publication Critical patent/WO2015080026A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • 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
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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

Definitions

  • the present invention relates to a surface treatment agent, particularly a water / oil repellent and an antifouling agent.
  • telomers can produce PFOA by degradation or metabolism (telomers mean long chain fluoroalkyl groups).
  • telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather.
  • fluorine-containing compounds There is concern about the accumulation of fluorine-containing compounds in the environment.
  • the fluorine-containing water / oil repellent containing the fluorine-containing polymer is subjected to heat treatment at a high temperature (for example, 100 ° C. or more) after being attached to a substrate such as a textile product in order to exhibit water / oil repellency. Must be given. High energy is required for heat treatment at high temperature.
  • the fluoropolymer is expensive.
  • JP 2006-328624 A is a water repellent comprising a non-fluorine polymer containing a (meth) acrylic acid ester having 12 or more carbon atoms in the ester moiety as a monomer unit, the (meth) acrylic acid ester Discloses a water repellent in which the proportion of is 80 to 100% by mass with respect to the total amount of monomer units constituting the non-fluorine polymer.
  • this water repellent is inferior in water and oil repellency.
  • An object of the present invention is to provide a surface treating agent that gives excellent water and oil repellency and preferably does not use a fluorinated monomer, particularly a fluoroalkyl group-containing monomer.
  • the present invention (1) (i) a polymer having a repeating unit derived from a long-chain (meth) acrylate ester monomer, and (ii) a repeating unit derived from a (meth) acrylate monomer having a cyclic hydrocarbon group ,
  • the present invention relates to (2) a surfactant, and (3) an aqueous emulsion treating agent containing a liquid medium containing water.
  • a surface treatment agent which is an aqueous emulsion containing a surfactant containing one or both of a nonionic surfactant and a cationic surfactant, and (3) a liquid medium containing water.
  • the nonionic surfactant is at least one selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides;
  • Agent [5] The surface treating agent according to any one of [1] to [4] 4, wherein the surfactant includes a surfactant compound having both an amide group and an amino group.
  • a method for treating a textile product comprising treating the textile product with the surface treating agent according to any one of [1] to [8].
  • the surface treatment agent of the present invention does not use a fluoroalkyl group-containing monomer, there is no concern about accumulation of fluorine-containing compounds in the environment.
  • the surface treatment agent of the present invention gives excellent water and oil repellency, particularly strong water repellency, to the substrate. Furthermore, water / oil repellency is exhibited by low temperature treatment without the need for heat treatment at high temperature.
  • the treatment agent of the present invention has good stability (emulsion stability).
  • the treatment agent of the present invention is excellent in strong water repellency represented by heavy rain.
  • Performance equal to or greater than or equal to that of a processing agent containing only a fluoropolymer containing a fluoroalkyl group-containing monomer as an active ingredient by a processing agent containing only a non-fluorine polymer as an active component (especially the initial Water / oil repellency including water / oil repellency).
  • the copolymer (preferably a non-fluorine polymer) is (I) having a repeating unit derived from a long-chain (meth) acrylate ester monomer, and (ii) a repeating unit derived from a (meth) acrylate monomer having a cyclic hydrocarbon group.
  • the copolymer is further One or both of (iii) a repeating unit derived from a short-chain (meth) acrylate ester monomer and (iv) a repeating unit derived from a non-fluorine crosslinkable monomer may be included.
  • the copolymer may have a fluorine atom, but preferably does not have a fluorine atom. That is, the copolymer is preferably a non-fluorine polymer.
  • the long chain (meth) acrylate ester monomer does not have a fluoroalkyl group.
  • the long chain (meth) acrylate ester monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.
  • a 11 is particularly preferably a methyl group.
  • a 12 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 has 18 to 30 carbon atoms.
  • the linear or branched hydrocarbon group preferably has 18 to 28 carbon atoms, particularly 18 or 22, and is generally a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.
  • long-chain (meth) acrylate ester monomer stearyl (meth) acrylate and behenyl (meth) acrylate.
  • Stearyl (meth) acrylate is particularly preferred.
  • the presence of the long chain (meth) acrylate ester monomer increases the water repellency and oil repellency provided by the polymer.
  • 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 cyclohexyl group, t-butylcyclohexyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group and adamantyl.
  • 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 short chain (meth) acrylate ester monomer copolymer may have a repeating unit derived from a short chain (meth) acrylate ester monomer.
  • the short chain (meth) acrylate ester monomer does not have a fluoroalkyl group.
  • the short chain (meth) acrylate ester monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.
  • a 31 is particularly preferably a methyl group.
  • a 32 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 has 1 to 17 carbon atoms.
  • the linear or branched hydrocarbon group preferably has 1 to 14 carbon atoms, and is generally a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.
  • short chain (meth) acrylate ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) ) Acrylate, cetyl (meth) acrylate.
  • Particularly preferred specific examples of the short chain (meth) acrylate ester monomer are lauryl (meth) acrylate and cetyl (meth) acrylate. The presence of the short-chain (meth) acrylate ester monomer improves the water repellency and texture imparted by the polymer.
  • the non-fluorine crosslinkable monomer copolymer may or may not have a repeating unit derived from the 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 (preferably (meth) acrylate groups) and not containing fluorine.
  • the non-fluorine crosslinkable monomer is a compound having at least two olefinic carbon-carbon double bonds (preferably a (meth) acrylate group), or at least one olefinic carbon-carbon double bond and at least one It may be a compound having a reactive group.
  • 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.
  • the presence of the non-fluorine crosslinkable monomer increases the washing durability imparted by the polymer.
  • 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.
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acrylamide means acrylamide or methacrylamide
  • each of the monomers is preferably an acrylate ester.
  • Each of the monomers (i) to (v) may be a single compound or a mixture of two or more.
  • the amount of monomer (i) is 40% by weight or more, preferably 50 parts by weight or more based on the copolymer.
  • the amount of monomer (i) may be 95 parts by weight or less, for example 80 parts by weight or less, alternatively 75 parts by weight or less, or 70 parts by weight or less based on the copolymer.
  • the amount of the repeating unit (ii) is 1 to 150 parts by weight, preferably 1 to 30 parts by weight, The amount of the repeating unit (iii) is 0 to 100 parts by weight, preferably 1 to 30 parts by weight, The amount of the repeating unit (iv) is 0 to 50 parts by weight, preferably 1 to 10 parts by weight, The amount of the repeating unit (v) may be 0 to 100 parts by weight, preferably 1 to 30 parts by weight.
  • the number average molecular weight (Mn) of the copolymer may generally be from 1,000 to 1,000,000, for example from 5,000 to 500,000, in particular from 3,000 to 200,000.
  • the number average molecular weight (Mn) of the copolymer is generally measured by GPC (gel permeation chromatography).
  • the polymer may be one kind of polymer or a combination of two or more kinds of polymers.
  • monomers are copolymerized to obtain a treating agent composition in which the copolymer is dispersed or dissolved in a medium.
  • the monomers used in the present invention are as follows. Monomer (i) + (ii), Monomer (i) + (ii) + (iii), Monomer (i) + (ii) + (iv), or monomer (i) + (ii) + (iii) + (iv). In addition to the above, monomer (v) may be used.
  • Non-fluorine crosslinkable monomer is a combination of monomer (i) + monomer (ii) + monomer (iv) or monomer (i) + monomer (ii) + monomer (iv) + halogen
  • a combination of olefins is preferred. In this combination, the water-repellent washing durability is high.
  • the surfactant includes a nonionic surfactant and a cationic surfactant.
  • the surfactant may consist solely of nonionic surfactants and cationic surfactants, or may contain other surfactants (other than nonionic surfactants and cationic surfactants). Examples of other surfactants are amphoteric surfactants. It is preferable that the surfactant does not contain an anionic surfactant.
  • Nonionic surfactant examples include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.
  • examples of the ether are compounds having an oxyalkylene group (preferably a polyoxyethylene group).
  • esters are alcohol and fatty acid esters.
  • examples of the alcohol are monovalent to hexavalent (especially divalent to pentavalent) alcohol having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohol).
  • fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.
  • ester ether is a compound obtained by adding an alkylene oxide (particularly, ethylene oxide) to an ester of an alcohol and a fatty acid.
  • the alcohol are monovalent to hexavalent (especially divalent to pentavalent) alcohol having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohol).
  • fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.
  • alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or dialkanolamino.
  • fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.
  • the alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.
  • the polyhydric alcohol may be a divalent to pentavalent alcohol having 3 to 30 carbon atoms.
  • the amine oxide may be an oxide of an amine (secondary amine or preferably a tertiary amine) (eg 5 to 50 carbon atoms).
  • the nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene 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.
  • the nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.
  • 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).
  • 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, an alkenyl group having 2 to 22 carbon atoms, or an acyl group, Each of R 2 is independently the same or different and is an alkylene group having 3 or more carbon atoms (eg, 3 to 10); 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, 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 a styrene chain, among which 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, each of R 11 , R 12 , R 13 , R 14 , R 15 , R 16 is independently the same or different and is 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.
  • acetylene alcohol compound examples include acetylene diol, propargyl alcohol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4 , 7,9-Tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1- Examples include pentyne-3-ol, 3-hexyne-2,5-diol, and 2-butyne-1,4-diol. Polyethoxylates and ethylene oxide adducts of these specific examples are also included.
  • the nonionic surfactant may not have a triple bond, or may have a triple bond.
  • the nonionic surfactant may be only one of a nonionic surfactant having no triple bond or a nonionic surfactant having a triple bond, but a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond It may be a combination of active agents.
  • a combination of a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond has a triple bond with a nonionic surfactant having no triple bond (eg, a nonionic surfactant having an oxyalkylene group).
  • the weight ratio of nonionic surfactant (for example, acetylene alcohol compound) may be 10:90 to 90:10, for example 20:80 to 80:20.
  • the cationic surfactant is preferably a compound having no amide group.
  • cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazolines and imidazolinium salts.
  • the cationic surfactant is preferably an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt.
  • cationic surfactant examples 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.
  • cationic surfactants are: R 21 -N + (-R 22) (- R 23) (- R 24) X - [In the formula, each of R 21 , R 22 , R 23 and R 24 is independently the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms; X is an anionic group. ] It is a compound of this.
  • the hydrocarbon group may have an oxygen atom, and may be, for example, an oxyalkylene such as a polyoxyalkylene group (the alkylene has 2 to 5 carbon atoms, for example).
  • R 21 , R 22 , R 23 and R 24 are preferably hydrocarbon groups having 1 to 30 carbon atoms (for example, aliphatic hydrocarbons, aromatic hydrocarbons or araliphatic hydrocarbons).
  • R 21 , R 22 , R 23 and R 24 include an alkyl group (for example, methyl group, butyl group, stearyl group, palmityl group), aryl group (for example, phenyl group), aralkyl group (for example, benzyl group) (Phenylmethyl group), phenethyl group (phenylethyl group)).
  • X are halogen (for example, chlorine), acid (for example, inorganic acid such as hydrochloric acid, organic acid such as acetic acid (particularly fatty 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, particularly a quaternary ammonium salt.
  • the cationic surfactant has the formula: R 31 p - N + R 32 q X - Wherein each R 31 is independently the same or different and is a C12 or higher (eg C 12 -C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) group.
  • R 32 is independently the same or different, and is an H or C1-4 alkyl group, benzyl group, polyoxyethylene group (number of oxyethylene groups such as 1 (particularly 2, particularly 3) to 50) (CH 3 and C 2 H 5 are particularly preferred),
  • It may be an ammonium salt represented by R 31 may have 12 to 50 carbon atoms, such as 12 to 30 carbon atoms.
  • cationic surfactant examples include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl Di (hydropolyoxyethylene) ammonium chloride and benzyldodecyl di (hydropolyoxyethylene) ammonium chloride 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.
  • the surfactant may or may not contain a surfactant compound having an amide group and an amino group, that is, an amidoamine surfactant.
  • R 11 is preferably an alkyl group or an alkenyl group.
  • R 11 may have 8 to 30 carbon atoms, such as 12 to 24 carbon atoms.
  • R 12 , R 13 and R 14 are preferably a hydrogen atom or an alkyl group.
  • R 12 , R 13 and R 14 preferably have 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
  • n is 0 to 10, for example 1 to 10, in particular 2 to 5.
  • amidoamine surfactants include isostearic acid diethylaminoethylamide, oleic acid dimethylaminoethylamide, oleic acid dimethylaminopropylamide, oleic acid diethylaminoethylamide, oleic acid diethylaminopropylamide, stearic acid diethylaminoethylamide, stearic acid Diethylaminopropylamide, stearic acid dibutylaminoethylamide, stearic acid dibutylaminopropylamide, stearic acid dipropylaminopropylamide, stearic acid dipropylaminoethylamide, stearic acid dimethylaminoethylamide, stearic acid dimethylaminopropylamide, palmitic acid Diethylaminoethylamide, palmitic acid diethylaminopropylamide, palmitic acid
  • the amidoamine surfactant may be a salt, for example, an acid salt or a quaternary ammonium salt.
  • the cationic group is the nitrogen atom of the amino group, and the anionic group varies.
  • the anionic group include a halogen ion, a sulfate ion, a carboxylate ion having 1 to 4 carbon atoms which may be substituted with a hydroxyl group, and an alkyl sulfate ion having 1 to 4 carbon atoms.
  • Acid salts are obtained by neutralizing amidoamines with acids, such as inorganic acids and / or organic acids.
  • inorganic acids include hydrochloric acid, sulfuric acid, and phosphoric acid.
  • Organic acids include short-chain monocarboxylic acids such as acetic acid and propionic acid; long-chain monocarboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and erucic acid; malonic acid and succinic acid Dicarboxylic acids such as glutaric acid, adipic acid, maleic acid, fumaric acid, and phthalic acid; hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, and citric acid; poly such as polyglutamic acid Carboxylic acids; acidic amino acids such as glutamic acid and aspartic acid; alkyl sulfates, alkyl
  • inorganic acids short-chain monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, acidic amino acids are generally used, and hydrochloric acid, sulfuric acid, acetic acid, succinic acid, glycolic acid, lactic acid, malic acid, citric acid Glutamic acid is particularly used.
  • Quaternary ammonium salts can be obtained by quaternizing amidoamines.
  • the amidoamine surfactant may be nonionic or ionic (cationic), but is preferably nonionic. In the case of nonionic, it is preferable to add an ionic compound such as an acid to ionize it.
  • Each of the nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may be one kind or a combination of two or more.
  • the amount of the cationic surfactant is preferably 15% by weight or more, more preferably 20% by weight or more, particularly preferably 22% by weight or more, based on the total amount of the nonionic surfactant and the cationic surfactant. For example 25% or more, in particular 30% or more, especially 35% or more.
  • the upper limit of the amount of cationic surfactant can be, for example, 60% by weight, in particular 50% by weight.
  • the weight ratio of the nonionic surfactant to the cationic surfactant is preferably 85:15 to 20:80, more preferably 80:20 to 40:60.
  • the amount of the surfactant other than the nonionic surfactant and the cationic surfactant may be 50% by weight or less, for example, 20% by weight or less based on the total amount of the surfactant. It may be 1% by weight or more.
  • the amount of the cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight with respect to 100 parts by weight of the polymer.
  • 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 amount of amidoamine surfactant may be up to 80% by weight, for example 5 to 70% by weight, in particular 10 to 60% by weight, based on the total amount of surfactant.
  • the liquid medium may be water alone or a mixture of water and a (water-miscible) organic solvent.
  • the amount of the organic solvent may be 30% by weight or less, for example, 10% by weight or less (preferably 0.1% or more) with respect to the liquid medium.
  • the liquid medium is preferably water alone.
  • the water / oil repellent composition of the present invention may contain only the non-fluorine polymer as a polymer (active ingredient), but contains a fluorine-containing polymer in addition to the non-fluorine polymer. Also good.
  • a water / oil repellent composition particularly, an aqueous emulsion
  • particles formed of a non-fluorine polymer and particles formed of a fluoropolymer exist separately. That is, it is preferable to mix the non-fluorine polymer and the fluoropolymer after separately producing the non-fluoropolymer and the fluoropolymer.
  • a non-fluoropolymer emulsion especially an aqueous emulsion
  • a fluoropolymer emulsion especially an aqueous emulsion
  • the non-fluoropolymer emulsion and the fluoropolymer emulsion are mixed. It is preferable.
  • the fluorine-containing polymer is a polymer having a repeating unit derived from a fluorine-containing monomer.
  • the fluorine-containing polymer is a repeating polymer derived from at least one non-fluorine monomer selected from the group consisting of halogenated olefin monomers, non-fluorine non-crosslinkable monomers and non-fluorine crosslinkable monomers. You may have a unit.
  • the halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine or iodine atoms.
  • halogenated olefin monomers are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide.
  • 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 linear or cyclic hydrocarbon group having 1 to 20 carbon atoms, or a linear or cyclic organic group having 1 to 20 carbon atoms having an ester bond.
  • non-fluorine non-crosslinkable monomers include alkyl (meth) acrylate esters, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Acrylate, methoxypolypropylene glycol (meth) acrylate, and vinyl alkyl ether are included.
  • the non-fluorine crosslinkable monomer has a compound having at least two carbon-carbon double bonds (for example, (meth) acrylic group), or has at least one carbon-carbon double bond and at least one reactive group. It may be a compound.
  • the weight ratio of the non-fluorine polymer to the fluoropolymer in the water / oil repellent composition is 100: 0 to 10:90, for example 90:10 to 20:80, preferably 80:20 to 30:70. Good.
  • Each of the non-fluorine polymer and the fluorine-containing polymer may be a single polymer, or may be a combination of two or more polymers. When using a combination of a non-fluorinated polymer and a fluorinated polymer, performance (particularly, water / oil repellency) equivalent to or better than when only a fluorinated polymer is used is obtained.
  • the polymer (non-fluorine polymer and 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. Emulsion polymerization is preferred. If the processing agent of this invention is a water-system emulsion, the manufacturing method of a polymer will not be limited. For example, a water-based emulsion can be obtained by producing a polymer by solution polymerization and then removing the solvent and adding a surfactant and water.
  • 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 nitrogen substitution, is stirred and copolymerized 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 in water using an emulsifier that can impart powerful crushing energy such as a high-pressure homogenizer or ultrasonic homogenizer. It is desirable to do.
  • an emulsifier that can impart powerful crushing energy such as a high-pressure homogenizer or ultrasonic homogenizer.
  • 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.
  • 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 copolymer 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 copolymer (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 copolymer 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. If necessary, curing may be carried out by applying together with a suitable crosslinking agent (for example, blocked isocyanate).
  • a suitable crosslinking agent for example, blocked isocyanate
  • 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 copolymer 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 copolymer 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 copolymer 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 copolymer 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 zeta potential of the aqueous emulsion treating agent is preferably +30 mV or more.
  • the zeta potential is measured by a laser Doppler method (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.).
  • the dynamic surface tension of the aqueous emulsion treatment agent is preferably 55 mN / m or less.
  • the dynamic surface tension is measured by the maximum bubble pressure method (BP-D5 manufactured by Kyowa Interface Science Co., Ltd.).
  • EO polyoxyethylene
  • C12-14 secondary alkyl
  • Table 1 shows the raw materials used in the production examples and comparative production examples.
  • Example 1 A test liquid (1000 g) was prepared by diluting 50 g of the aqueous liquid produced in Production Example 1 with tap water.
  • a cloth (510 mm ⁇ 205 mm) was immersed in this test solution, passed through a mangle, and treated with a pin tenter at 160 ° C. for 2 minutes.
  • the test fabric was subjected to a water repellency test. The same procedure as above was repeated for PET taffeta cloth and nylon taffeta cloth. Thereafter, a Bundesman test was conducted. The results are shown in Table 2.
  • the treatment agent of the present invention can be suitably used for substrates such as textiles and masonry, and imparts excellent water and oil repellency to the substrate.
  • Another aspect of the present invention is as follows.
  • the aqueous emulsion treating agent according to ⁇ 1> which is a compound represented by the formula: ⁇ 3>
  • a 21 represents a hydrogen atom or a methyl group
  • a 32 is a linear or branched aliphatic hydrocarbon group having less than 18 carbon atoms.
  • ⁇ 4> The aqueous emulsion treating agent according to any one of ⁇ 1> to ⁇ 3>, wherein the polymer (1) further has (iv) a repeating unit derived from a non-fluorine crosslinkable monomer.
  • the non-fluorine crosslinkable monomer (iv) is a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group ⁇ 4>
  • ⁇ 6> The polymer (1) is (V) The aqueous emulsion treating agent according to any one of ⁇ 1> to ⁇ 5>, having a repeating unit derived from a halogenated olefin monomer.
  • halogenated olefin monomer (v) is at least one selected from the group consisting of vinyl chloride and vinylidene chloride.
  • the amount of the repeating unit (ii) is 1 to 150 parts by weight, The amount of the repeating unit (iii) is 0 to 100 parts by weight, The amount of the repeating unit (iv) is 0 to 100 parts by weight,
  • Nonionic surfactant has 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, and each R 2 is independently the same or different and has 3 or more carbon atoms (for example, 3 To 10), 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 a number of 0 or 1 or more. . ] The aqueous emulsion treating agent according to any one of ⁇ 1> to ⁇ 10>,
  • aqueous emulsion treating agent wherein the nonionic surfactant is an acetylene alcohol compound selected from the group consisting of acetylene alcohol and an oxyethylene adduct of acetylene alcohol.
  • 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, each of R 11 , R 12 , R 13 , R 14 , R 15 , R 16 is independently the same or different and is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]
  • the aqueous emulsion treating agent according to ⁇ 12> which is a compound represented by the formula:
  • the cationic surfactant has the formula: R 21 -N + (-R 22) (- R 23) (- R 24) X - [In the formula, each of R 21 , R 22 , R 23 and R 24 is independently the same or different and is a hydrocarbon group having 1 to 30 carbon atoms, X is an anionic group. ]
  • ⁇ 16> The aqueous emulsion treating agent according to any one of ⁇ 1> to ⁇ 15>, wherein the aqueous emulsion has a zeta potential of +30 mV or more.
  • ⁇ 17> The aqueous emulsion treating agent according to any one of ⁇ 1> to ⁇ 16>, wherein the dynamic surface tension of the aqueous emulsion is 55 mN / m or less.
  • ⁇ 18> The aqueous emulsion treating agent according to any one of ⁇ 1> to ⁇ 17>, which is a fiber treating agent.
  • aqueous emulsion treating agent according to any one of ⁇ 1> to ⁇ 18>, which is a water / oil repellent or an antifouling agent.
  • a method for treating a textile product comprising treating the textile product with the aqueous emulsion treating agent according to any one of ⁇ 1> to ⁇ 19>.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Textile Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un agent de traitement de surface qui ne fait pas appel à un monomère fluoré et plus particulièrement à un monomère contenant un groupe fluoro-alkyle. L'invention concerne plus spécifiquement un agent de traitement de surface, lequel est une émulsion aqueuse, contenant: (1) un polymère non fluoré qui présente (i) des unités récurrentes dérivées d'un monomère d'ester de (méth)acrylate à longue chaîne représenté par la formule générale (a): CH2=CA11− C(=O) − O − A12, dans laquelle A11 représente un atome d'hydrogène ou un groupe méthyle et A12 représente un groupe hydrocarbures aliphatiques linéaire ou ramifié de 18 à 30 atomes de carbone, ainsi que (ii) des unités récurrentes dérivées d'un monomère de (méth)acrylate possédant un groupe hydrocarbures cycliques; (2) un surfactant contenant un surfactant non ionique et/ou un surfactant cationique; et (3) un milieu fluide contenant de l'eau.
PCT/JP2014/080815 2013-11-22 2014-11-20 Agent de traitement de surface Ceased WO2015080026A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201480063523.9A CN105764980B (zh) 2013-11-22 2014-11-20 表面处理剂
KR1020167013365A KR101851086B1 (ko) 2013-11-22 2014-11-20 표면 처리제

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Application Number Priority Date Filing Date Title
JP2013241980 2013-11-22
JP2013-241980 2013-11-22

Publications (1)

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WO2015080026A1 true WO2015080026A1 (fr) 2015-06-04

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PCT/JP2014/080815 Ceased WO2015080026A1 (fr) 2013-11-22 2014-11-20 Agent de traitement de surface

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JP (2) JP5811258B2 (fr)
KR (1) KR101851086B1 (fr)
CN (1) CN105764980B (fr)
TW (1) TWI612131B (fr)
WO (1) WO2015080026A1 (fr)

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JP2017186703A (ja) * 2016-04-07 2017-10-12 明成化学工業株式会社 繊維処理用組成物及び当該組成物で処理された繊維製品
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CN108884189A (zh) * 2016-03-16 2018-11-23 大金工业株式会社 共聚物和表面处理剂
WO2019026593A1 (fr) 2017-07-31 2019-02-07 ダイキン工業株式会社 Composition hydrofuge
WO2019163570A1 (fr) * 2018-02-20 2019-08-29 ダイキン工業株式会社 Agent de traitement de surface
WO2020162547A1 (fr) 2019-02-08 2020-08-13 ダイキン工業株式会社 Composition déperlante
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JP6657730B2 (ja) * 2015-10-01 2020-03-04 ダイキン工業株式会社 表面処理剤
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US12351674B2 (en) 2019-12-24 2025-07-08 Mitsui Chemicals, Inc. Polyurethane resin composition, repellent, water repellent for fibers, and stain-proof coating agent
JP7054010B2 (ja) 2019-12-25 2022-04-13 ダイキン工業株式会社 しみ評価方法、水滴評価方法、撥剤評価方法及び撥剤評価装置
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KR102691683B1 (ko) * 2021-06-22 2024-08-08 다이킨 고교 가부시키가이샤 내유제
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JP2025509434A (ja) 2022-03-10 2025-04-11 北京馬普新材料有限公司 共重合体、処理剤及びその製造方法並びに適用

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Publication number Priority date Publication date Assignee Title
JP2015221952A (ja) * 2014-05-23 2015-12-10 明成化学工業株式会社 フッ素を含まないはっ水剤組成物及びはっ水加工方法
WO2017126358A1 (fr) * 2016-01-20 2017-07-27 東レ株式会社 Structure de fibres
CN108884189B (zh) * 2016-03-16 2020-11-27 大金工业株式会社 共聚物和表面处理剂
CN108884189A (zh) * 2016-03-16 2018-11-23 大金工业株式会社 共聚物和表面处理剂
JP2017186703A (ja) * 2016-04-07 2017-10-12 明成化学工業株式会社 繊維処理用組成物及び当該組成物で処理された繊維製品
JPWO2017179589A1 (ja) * 2016-04-15 2019-02-28 Ａｇｃ株式会社 撥水剤組成物、及び透湿防水膜付き物品の製造方法
WO2017179589A1 (fr) * 2016-04-15 2017-10-19 旭硝子株式会社 Composition hydrofuge et procédé servant à la production d'un article doté d'un film imperméable à l'eau et perméable à l'humidité
US11746268B2 (en) 2016-12-28 2023-09-05 Daikin Industries, Ltd. Surface treatment agent
EP3564335A4 (fr) * 2016-12-28 2020-09-09 Daikin Industries, Ltd. Agent de traitement de surface
KR20200023436A (ko) 2017-07-31 2020-03-04 다이킨 고교 가부시키가이샤 발수제 조성물
WO2019026593A1 (fr) 2017-07-31 2019-02-07 ダイキン工業株式会社 Composition hydrofuge
US11041038B2 (en) 2017-07-31 2021-06-22 Daikin Industries, Ltd. Water repellent composition
JP2022111181A (ja) * 2018-02-20 2022-07-29 ダイキン工業株式会社 表面処理剤
WO2019163570A1 (fr) * 2018-02-20 2019-08-29 ダイキン工業株式会社 Agent de traitement de surface
JPWO2019163570A1 (ja) * 2018-02-20 2020-12-17 ダイキン工業株式会社 表面処理剤
JP2020128529A (ja) * 2019-02-08 2020-08-27 ダイキン工業株式会社 撥水剤組成物
KR20210110373A (ko) 2019-02-08 2021-09-07 다이킨 고교 가부시키가이샤 발수제 조성물
WO2020162547A1 (fr) 2019-02-08 2020-08-13 ダイキン工業株式会社 Composition déperlante
KR20240144449A (ko) 2019-02-08 2024-10-02 다이킨 고교 가부시키가이샤 발수제 조성물
US12247093B2 (en) 2019-02-08 2025-03-11 Daikin Industries, Ltd. Water-repellent composition

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JP2015120894A (ja) 2015-07-02
JP2015166465A (ja) 2015-09-24
KR101851086B1 (ko) 2018-04-20
JP5811258B2 (ja) 2015-11-11
TWI612131B (zh) 2018-01-21
JP5971376B2 (ja) 2016-08-17
CN105764980B (zh) 2017-08-08
KR20160076526A (ko) 2016-06-30
CN105764980A (zh) 2016-07-13
TW201529824A (zh) 2015-08-01

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