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WO2010030044A2 - Water- and oil-repellent composition - Google Patents

Water- and oil-repellent composition Download PDF

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Publication number
WO2010030044A2
WO2010030044A2 PCT/JP2009/066323 JP2009066323W WO2010030044A2 WO 2010030044 A2 WO2010030044 A2 WO 2010030044A2 JP 2009066323 W JP2009066323 W JP 2009066323W WO 2010030044 A2 WO2010030044 A2 WO 2010030044A2
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WO
WIPO (PCT)
Prior art keywords
group
fluorine
acrylate
monomer
atom
Prior art date
Application number
PCT/JP2009/066323
Other languages
French (fr)
Other versions
WO2010030044A3 (en
Inventor
Takashi Enomoto
Ikuo Yamamoto
Masahiro Miyahara
Mitsuhiro Usugaya
Masashi Nanri
Kouji Kubota
Hirotoshi Sakashita
Shinichi Minami
Hisako Nakamura
Rumi Takeuchi
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 JP2011511918A priority Critical patent/JP6017783B2/en
Priority to CN200980136040.6A priority patent/CN102149738B/en
Publication of WO2010030044A2 publication Critical patent/WO2010030044A2/en
Publication of WO2010030044A3 publication Critical patent/WO2010030044A3/en

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    • 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
    • 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
    • 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
    • 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
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • 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
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/295—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing fluorine
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/11—Halides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • 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
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (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
    • C08F220/1811—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
    • 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 fluorine-containing polymer and a treatment composition, particularly a surface treatment composition containing the polymer, which imparts excellent water repellency, oil repellency and soil resistance to a textile (for example, a carpet) , a paper, a non-woven fabric, masonry, an electrostatic filter, a dust protective mask, and a part of fuel cell.
  • a treatment composition particularly a surface treatment composition containing the polymer, which imparts excellent water repellency, oil repellency and soil resistance to a textile (for example, a carpet) , a paper, a non-woven fabric, masonry, an electrostatic filter, a dust protective mask, and a part of fuel cell.
  • the fluorine-containing compounds have the advantageous effects of having properties excellent in heat resistance, oxidation resistance, weather resistance and the like.
  • the fluorine-containing compounds are used as, for example, a water- and oil-repellent agent and a soil resistant agent by utilizing the properties that the fluorine-containing compounds have low free energy, i.e., difficulty in adherence.
  • 5247008 discloses a finishing compound for textile, leather, paper and mineral substance, which compound comprises an aqueous dispersion of polymers of a perfluoroalkyl ester of an acrylic acid or methacrylic acid, an alkyl ester of an acrylic acid or methacrylic acid and an aminoalkyl ester of an acrylic acid or methacrylic acid.
  • fluorine-containing compounds usable as the water- and oil-repellent agent include a fluorine- containing polymer having repeating units derived from (meth) acrylate ester having a fluoroalkyl group.
  • the important surface property is not a static contact angle, but is a dynamic contact angle, particularly a receding contact angle. That is, the advancing contact angle of water is not dependent on the carbon number of the fluoroalkyl side chain, but the receding contact angle of water in the case of carbon number of at most 7 is remarkably low than that in the case of carbon number of at least 8.
  • an X-ray analysis shows that the side chain crystallizes when the carbon number of side chain is at least 7. It is known that the actual water repellency has correlation with the crystallization of the side chain and that mobility of the surface treatment agent molecules is an important factor for exhibiting actual performances (for example, MAEKAWA Takashige, FINE CHEMICAL, Vol. 23, No. 6, page 12 (1994)) . Due to the reasons mentioned above, it is believed that the acrylate polymer having low carbon number of fluoroalkyl group in the side chain which is at most 7 (particularly at most 6) has low crystallinity so that the polymer cannot satisfy the actual performances (particularly water repellency) .
  • telomer may possibly metabolize or decompose to PFOA.
  • telomer is used in a large number of commercial products including fire fighting foams, care products and cleaning products as well as soil, stain and grease resistant coating on carpets, textiles, paper, and leather.
  • An object of the present invention is to provide a treatment composition which can impart excellent water repellency, oil repellency and stain-proofing properties to a substrate such as a textile.
  • the present invention provides a fluorine-containing polymer comprising repeating units derived from: (A) a fluorine-containing monomer represented by the general formula:
  • Z is a direct bond or divalent organic group
  • Rf is a fluoroalkyl group having 1 to 20 carbon atoms
  • B a (meth) acrylate monomer having a cyclic hydrocarbon group.
  • the present invention provides a treatment agent composition which imparts excellent water repellency, oil repellency and stain-proofing properties to a substrate such as textiles .
  • the fluorine-containing polymer of the present invention comprises:
  • X is a hydrogen atom, a monovalent organic group or a halogen atom
  • Y is -0- or -NH-;
  • Z is a direct bond or divalent organic group;
  • Rf is a fluoroalkyl group having 1 to 20 carbon atoms.
  • Z may be, for example, a linear alkylene group or branched alkylene group having 1 to 20 carbon atoms, such as a group represented by the formula - (CH 2 ) x - [wherein x is from 1 to 10] or a group represented by the formula -SO 2 N (R 1 ) R 2 - or by the formula -CON (R 1 ) R 2 - [wherein R 1 is an alkyl group having 1 to 10 carbon atoms and R 2 is a linear alkylene group or branched alkylene group having 1 to 10 carbon atoms] or by the formula -CH 2 CH (OR 3 ) CH 2 - [wherein R 3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, formyl group or acetyl group) ] or by the formula -Ar-CH 2 - [wherein Ar is an arylene group optionally having a substituent group] , or by the formula - (CH 2 )
  • X may be, for example, H, Me (methyl group) , Cl, Br, I, F, CN or CF 3 .
  • the fluorine-containing monomer (A) is preferably an acrylate ester represented by the formula:
  • X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (where each of X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) , a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group or a substituted or unsubstituted phenyl group; Y is -0- or -NH- group; Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to 18 carbon
  • Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms .
  • the fluorine-containing monomer (A) may be substituted with a halogen atom or the like at the alpha-position (of o
  • X may be a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) , a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or an unsubstituted benzyl group, or a substituted or an unsubstituted phenyl group.
  • the Rf group is preferably a perfluoroalkyl group.
  • the number of the Rf group is preferably from 1 to 12, for example, 1 to 6, particularly from 4 to 6.
  • Examples of the Rf group include -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2, -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ) 2 , -C(CF 3 J 3 , -
  • Z is preferably an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to
  • the aliphatic group is preferably an alkylene group (having particularly 1 to 4, for example, 1 or 2 carbon atoms) .
  • the aromatic group or the cyclic aliphatic group may be substituted or unsubstituted.
  • the S group or the SO 2 group may directly bond to the Rf group.
  • fluorine-containing monomer (A) examples include, but are not limited to, the following:
  • the (meth) acrylate monomer (B) having a cyclic hydrocarbon group is generally a fluorine-free monomer.
  • (meth) acrylate monomer (B) having a cyclic hydrocarbon group is a compound having (preferably monovalent) cyclic hydrocarbon group and monovalent (meth) acrylate group.
  • the monovalent cyclic hydrocarbon group directly bonds to the monovalent (meth) acrylate group.
  • the cyclic hydrocarbon group include a saturated or unsaturated, monocyclic group, polycyclic group or bridged ring group.
  • the cyclic hydrocarbon group is preferably a saturated group.
  • the cyclic hydrocarbon group preferably has from 4 to 20 carbon atoms.
  • Examples of the cyclic hydrocarbon group include a cycloaliphatic 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 carbon number of the cyclic hydrocarbon group is particularly preferably at most 15, for example at most 10.
  • a carbon atom in the cyclic hydrocarbon group preferably directly bonds to an ester group in the
  • the cyclic hydrocarbon group is preferably a saturated cycloaliphatic group. Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butyl cyclohexyl group, an isobornyl group, a dicyclopentanyl group and a dicyclopentenyl group.
  • the (meth) acrylate group is an acrylate group or a methacrylate group, preferably a methacrylate group.
  • the monomer having cyclic hydrocarbon group examples include cyclohexyl methacrylate, t- butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate and dicyclopentenyl acrylate.
  • the fluorine-containing polymer of the present invention may contain repeating units derived from (C) other monomer which is other than the monomers (A) and (B) .
  • the other monomer (C) is preferably free from a fluorine atom.
  • Examples of the other monomer (C) include (C-I) non- crosslinkable monomers and (C-2) crosslinkable monomers.
  • the non-crosslinkable monomer (C-I) unlike the crosslinkable monomer (C-2) , has no crosslinkability .
  • the non-crosslinkable monomer (C-I) is preferably a monomer free from a fluorine atom, and has a carbon-carbon double bond.
  • the non-crosslinkable monomer (C-I) is preferably a vinyl monomer free from a fluorine atom.
  • the non-crosslinkable monomer (C-I) is generally a compound having one carbon- carbon double bond.
  • Preferable examples of the non- crosslinkable monomer include, but not limited to, ethylene, vinyl acetate, vinyl halide such as vinyl chloride, vinylidene halide such as vinylidene chloride, acrylonitrile, styrene, polyethyleneglycol (meth) acrylate, polypropyleneglycol (meth) acrylate, methoxypolyethyleneglycol (meth) acrylate, methoxypolypropyleneglycol (meth) acrylate, and vinylalkylether.
  • the non-crosslinkable monomer (C-I) is not limited to the above examples.
  • the non-crosslinkable monomer (C-I) is preferably at least one of vinyl halide and vinylidene halide.
  • the non-crosslinkable monomer (C-I) may be
  • (meth) acrylate ester having an alkyl group.
  • the alkyl group may have 1 to 30 carbon atoms, for example 6 to 30, such as
  • non-crosslinkable monomer (C-I) may be an acrylate of the general formula:
  • CH 2 CA 1 COOA 2
  • a 1 is a hydrogen atom or a methyl group or a halogen atom other than fluorine atom (e.g. a chlorine atom, a bromine atom and a iodine atom)
  • the fluorine-containing polymer of the present invention may contain repeating units derived from the crosslinkable monomer (C-2) .
  • the crosslinkable monomer (C-2) may be a compound free from a fluorine atom and has at least two reactive groups and/or carbon-carbon double bonds.
  • the crosslinkable monomer (c) may be a compound which has at least two carbon-carbon double bonds or a compound which has at least one carbon-carbon double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group and a carboxyl group,
  • crosslinkable monomer (C-2) examples include, but are not limited to, diacetoneacrylamide, (meth) acrylamide, N-methylolacrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl
  • non-crosslinkable monomer (C-I) and/or the crosslinkable monomer (C-2) are copolymerized, various properties such as water- and oil-repellency, stain-proofing properties, cleaning durability and washing durability of said properties, solubility in solvents, hardness and feeling may be improved depending on the necessity.
  • (meth) acrylate monomer (B) may be from 0.1 to 300 parts by weight, preferably from 1 to 80 parts by weight, and the amount of the other monomer (C) may be at most 150 parts by weight, preferably from 0.1 to 100 parts by weight, based on
  • the amount of the non-crosslinkable monomer (C-I) may be at most 100 parts by weight, for example from 0.1 to 50 parts by weight, and the amount of the crosslinkable monomer (C-2) may be at most 50 parts by weight, for example at most 20 parts by weight, particularly from 0.1 to 15 parts by weight, based on 100 parts by weight of the fluorine- containing monomer (A) .
  • the fluorine-containing monomer (A) , the (meth) acrylate monomer (B) and the optionally used other monomer (C) can be polymerized.
  • Examples of an olefinically unsaturated co- monomer included in the monomer (A) include alkyl acrylate or methacrylate esters having 1 to 30 carbon atoms in the alkyl group such as butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate or butyl methacrylate.
  • the alkyl acrylate or methacrylate can be used to adjust the glass transition temperature (Tg) of the resulting polymeric product; for example, an acrylate having a long chain alkyl group of 4-20, particularly 8-20 carbon atoms such as stearyl acrylate or methacrylate, octyl acrylate, 2-ethylhexyl acrylate or dodecyl acrylate or methacrylate can be used to form a softer polymer of lower Tg.
  • Tg glass transition temperature
  • Copolymers with an alkyl acrylate or methacrylate monomer may improve various properties such as water- and oil-repellency and soil releasability, cleaning durability, washing durability and abrasion resistance of such repellency and releasability, solubility in solvent, hardness and feel (handle) .
  • Other acrylate or methacrylate comonomers which can be o
  • the other usable olefinically unsaturated comonomers include vinyl chloride, vinylidene chloride, styrene, acrylonitrile, methacrylonitrile, ethylene, vinyl alkyl ether, isoprene, or vinyl ester, for example, vinyl acetate or vinyl propionate.
  • An olefinically unsaturated comonomer having a functional group, which does not react with an amine group and which can react with the other functional organic group, may be used in order to impart the properties of increased durability (endurance) to the textiles and other substrates.
  • Examples of such a functional group include hydroxyl, amino and amide groups.
  • Examples of the olefinically unsaturated comonomers containing them are acrylamide, methacrylamide, N- methylolacrylanaide, hydroxyethyl methacrylate, hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate or methacrylate, N, N-dimethylaminoethyl acrylate or methacrylate and diethylaminoethyl acrylate or methacrylate.
  • the fluorine-containing polymer of the present invention can be produced by any of conventional polymerization methods and the polymerization condition can be optionally selected.
  • the polymerization method includes, for example, a solution polymerization, a suspension polymerization and an emulsion polymerization.
  • a method of dissolving the monomer (s) into an organic solvent in the presence of a polymerization initiator replacing the atmosphere by nitrogen, and stirring the mixture with heating at the temperature within the range from 3O 0 C to 12O 0 C for 1 hour to 10 hours.
  • the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert- butyl peroxide, lauryl peroxide, cumene hydroperoxide, t- butyl peroxypivalate and diisopropyl peroxydicarbonate .
  • the polymerization initiator may be used in the amount within the range from 0.01 to 20 parts by weight, for example, from 0.01 to 10 parts by weight, based on 100 parts by weight of total of the monomers.
  • the organic solvent is inert to the monomer (s) and dissolves the monomer (s)
  • examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4- dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1, 1, 2, 2-tetrachloroethane, 1,1,1- trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane and trichlorotrifluoroethane .
  • the organic solvent may be used in the amount within the range from 50 to 2,000 parts by weight, for example
  • emulsion polymerization there can be used a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifying agent, replacing the atmosphere by nitrogen, and polymerizing with stirring, for example, at the temperature within the range from 5O 0 C to 8O 0 C for 1 hour to 10 hours.
  • polymerization initiator for example, water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1- hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutyla ⁇ iidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate and oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate can be used.
  • the polymerization initiator may be used in the amount within the range from 0.01 to 10 parts by weight based on 100 parts by weight of the monomers .
  • the monomers are dispersed in water by using an emulsifying device capable of applying a strong shearing energy (e.g., a high-pressure homogenizer and an ultrasonic homogenizer) and then polymerized with using the oil-soluble polymerization initiator.
  • a strong shearing energy e.g., a high-pressure homogenizer and an ultrasonic homogenizer
  • various emulsifying agents such as an anionic emulsifying agent, a cationic emulsifying agent and a nonionic emulsifying agent can be used in the amount within the range from 0.5 to 20 parts by weight based on 100 parts by weight of the monomers.
  • a compatibilizing agent capable of sufficiently compatibilizing them e.g., a water-soluble organic solvent and a low- molecular weight monomer
  • the emulsifiability and polymerizability can be improved.
  • water-soluble organic solvent examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol and ethanol .
  • the water-soluble organic solvent may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of water.
  • Examples of the low- molecular weight monomer are methyl methacrylate, glycidyl methacrylate, 2, 2, 2-trifluoroethyl methacrylate.
  • the low- molecular weight monomer may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of total of monomers.
  • the fluorine-containing polymer can be applied to fibrous substrates (such as textiles) by any known method to treat textiles in liquid.
  • concentration of the fluorine- containing polymer in the solution applied to the textiles may be within the range from 0.5 to 20% by weight or from 1 to 5% by weight.
  • the textile is a cloth
  • the cloth may be immersed in the solution or the solution may be adhered or sprayed to the cloth.
  • the treated textiles are dried, preferably heated at a temperature between 100 0 C and 200 0 C in order to develop the oil repellency.
  • the fluorine-containing polymer can be applied to a textile via a cleaning process, such as in a laundry application or dry cleaning process.
  • the textile which is treated is typically a fabric, including woven, knitted and nonwoven fabrics, fabrics in garment form and carpet, but may also be a fibre or yarn or intermediate textile product such as a sliver or roving.
  • the textile material can be a natural fibre such as cotton or wool, a manmade fibre such as viscose rayon or lyocell or a synthetic fibre such as polyester, polyamide or acrylic fibre, or can be a mixture of fibres such as a mixture of natural and synthetic fibres.
  • the polymeric product of the invention is particularly effective in rendering cellulosic fibres such as cotton or rayon oleophobic and oil repellent.
  • the process of the invention generally also renders the textile hydrophobic and water repellent.
  • Fabric treatment with the polymeric product of the invention imparts oil repellency to fabrics whilst at the same time imparting an improvement in feel compared to untreated fabric and also imparting an improvement in feel compared to fabric treated with known fluoropolymer textile treatment agents.
  • the fibrous substrate can alternatively be leather.
  • the polymeric product can be applied to leather from aqueous solution or emulsion at various stages of leather processing, for example during leather wet end processing or during leather finishing, to render the leather hydrophobic and oleophobic.
  • the fibrous substrate can alternatively be paper.
  • the polymeric product can be applied to preformed paper or at various stages of papermaking, for example during drying of the paper.
  • the surface treatment agent of the present invention is preferably in the form of a solution, an emulsion or an aerosol.
  • the surface treatment agent generally comprises the fluorine-containing polymer and a medium (particularly a liquid medium, for example, an organic solvent and/or water) .
  • the concentration of the fluorine-containing polymer in the surface treatment agent may be, for example, from 0.1 to 50 % by weight.
  • the surface treatment agent of the present invention preferably comprises a fluorine-containing polymer and an aqueous medium.
  • aqueous medium means a medium consisting of water alone, as well as a medium comprising, in addition to water, an organic solvent (the amount of the organic solvent is at most 80 parts by weight, for example, 0.1 to 50 parts by weight, particularly 5 to 30 parts by weight based on 100 parts by weight of water) .
  • the fluorine-containing polymer is preferably produced by preparing a dispersion of the fluorine-containing polymer by the emulsion polymerization.
  • the surface treatment agent of the present invention preferably comprises an aqueous dispersion of the particles of a fluorine-containing polymer in an aqueous medium.
  • the particles of the fluorine- containing polymer in the dispersion preferably have an average particle size of from 0.01 to 200 micrometer, for example from 0.1 to 5 micrometer, particularly from 0.05 to 0.2 micrometer.
  • the average particle size may be measured by a dynamic light-scattering device, electron microscope, etc.
  • the surface treatment agent can be applied to a substrate to be treated by a know procedure.
  • the application of the surface treatment agent can be conducted by immersion, spraying and coating.
  • the surface treatment agent is diluted with an organic solvent or water, is adhered to surfaces of the substrate by a well-known procedure such as an immersion coating, a spray coating and a foam coating, and is dried.
  • the treatment liquid is applied together with a suitable crosslinking agent, followed by curing.
  • mothproofing agents, softeners, antimicrobial agents, flame retardants, antistatic agents, paint fixing agents, crease-proofing agents, etc. to the surface treatment agent.
  • the concentration of the fluorine-containing compound in the treatment liquid contacted with the substrate may be from 0.01 to 10% by weight (particularly for immersion coating) , for example, from 0.05 to 10% by weight (particularly for spray coating), based on the treatment liquid.
  • the substrate to be treated with the surface treatment agent (for example, a water- and oil-repellent agent) of the present invention is preferably a textile.
  • the textile includes various examples.
  • the textile include animal- or vegetable-origin natural fibers such as cotton, hemp, wool and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene; semisynthetic fibers such as rayon and acetate; inorganic fibers such as glass fiber, carbon fiber and asbestos fiber; and a mixture of these fibers .
  • the textile may be in any form such as a fiber, a yarn and a fabric.
  • treatment means that the treatment agent is applied to the substrate by immersion, spray, coating or the like.
  • the fluorine-containing polymer which is an active component of the treatment agent can penetrate the internal of the substrate or can adhere on the surface of the substrate by the treatment.
  • a treated fabric is stored in a thermo-hygrostat having a temperature of 21 0 C and a humidity of 65% for at least 4 hours.
  • a test liquid (isopropyl alcohol (IPA), water, and a mixture thereof, as shown in Table 2) which has been also stored at 21 0 C is used.
  • the test is conducted in an air- conditioned room having a temperature of 21 0 C and a humidity of 65%.
  • a droplet of the test liquid in an amount of 0.05 ML is softly dropped by a micropipette on the fabric. If the droplet remains on the fabric after standing for 30 seconds, the test liquid passes the test.
  • the water repellency is expressed by a point corresponding to a maximum content (% by volume) of isopropyl alcohol (IPA) in the test liquid which passes the test.
  • IPA isopropyl alcohol
  • the water repellency is evaluated as twelve levels which are Fail, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 in order of a poor level to an excellent level.
  • the symbol "+” added to the numbers means that the result is superior to the number itself, and the symbol "-" added to the numbers means that the result is inferior to the number itself.
  • each of advancing contact angle, receding contact angle and sliding angle were measured with using an automated contact angle meter DROPMASTER 700 (manufactured by Kyowa Interface Science Co. Ltd. ) .
  • VCM vinyl chloride
  • 2, 2-azobis- (2-amidinopropane) dihydrochloride (0.91 g) was added to conduct a reaction at 6O 0 C for 5 hours, and an aqueous dispersion of a polymer was obtained.
  • VCM vinyl chloride
  • 2, 2-azobis- (2-amidinopropane) dihydrochloride (0.91 g) was added to conduct a reaction at 60 0 C for 5 hours, and an aqueous dispersion of a polymer was obtained.
  • VCM vinyl chloride
  • 2, 2-azobis- (2- amidinopropane) dihydrochloride (0.91 g) was added to conduct a reaction at 6O 0 C for 5 hours, and an aqueous dispersion of a polymer was obtained.
  • VCM vinyl chloride
  • 2, 2-azobis- (2-amidinopropane) dihydrochloride (0.91 g) was added to conduct a reaction at 6O 0 C for 5 hours, and an aqueous dispersion of a polymer was obtained.

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  • Life Sciences & Earth Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
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  • Paints Or Removers (AREA)

Abstract

A fluorine-containing polymer comprising repeating units derived from: (A) a fluorine-containing monomer represented by the general formula: CH2=C(-X)-C(=O)-Y-Z-Rf wherein X is a hydrogen atom, a monovalent organic group or a halogen atom, Y is -O- or -NH-; Z is a direct bond or a divalent organic group; Rf is a fluoroalkyl group having 1 to 20 carbon atoms; and (B) a (meth)acrylate monomer having a cyclic hydrocarbon group provides a water- and oil-repellent agent which imparts excellent water repellency, oil repellency and stain-proofing properties to a substrate.

Description

DESCRIPTION
WATER- AND OIL-REPELLENT COMPOSITION
CROSS REFERENCE TO RELATED APPLICATIONS
This application has priority from US Application No. 61/096,927 filed September 15, 2008, disclosures of which are incorporated herein by reference.
TECHNICAL FIELD
The present invention relates to a fluorine-containing polymer and a treatment composition, particularly a surface treatment composition containing the polymer, which imparts excellent water repellency, oil repellency and soil resistance to a textile (for example, a carpet) , a paper, a non-woven fabric, masonry, an electrostatic filter, a dust protective mask, and a part of fuel cell.
BACKGROUND ART Hitherto, various fluorine-containing compounds have been proposed. The fluorine-containing compounds have the advantageous effects of having properties excellent in heat resistance, oxidation resistance, weather resistance and the like. The fluorine-containing compounds are used as, for example, a water- and oil-repellent agent and a soil resistant agent by utilizing the properties that the fluorine-containing compounds have low free energy, i.e., difficulty in adherence. For example, U.S. Patent No. 5247008 discloses a finishing compound for textile, leather, paper and mineral substance, which compound comprises an aqueous dispersion of polymers of a perfluoroalkyl ester of an acrylic acid or methacrylic acid, an alkyl ester of an acrylic acid or methacrylic acid and an aminoalkyl ester of an acrylic acid or methacrylic acid.
Examples of the fluorine-containing compounds usable as the water- and oil-repellent agent include a fluorine- containing polymer having repeating units derived from (meth) acrylate ester having a fluoroalkyl group. Various recent research results indicate that, in the practical treatment of fibers with the surface treatment agent, the important surface property is not a static contact angle, but is a dynamic contact angle, particularly a receding contact angle. That is, the advancing contact angle of water is not dependent on the carbon number of the fluoroalkyl side chain, but the receding contact angle of water in the case of carbon number of at most 7 is remarkably low than that in the case of carbon number of at least 8. In correspondence to this, an X-ray analysis shows that the side chain crystallizes when the carbon number of side chain is at least 7. It is known that the actual water repellency has correlation with the crystallization of the side chain and that mobility of the surface treatment agent molecules is an important factor for exhibiting actual performances (for example, MAEKAWA Takashige, FINE CHEMICAL, Vol. 23, No. 6, page 12 (1994)) . Due to the reasons mentioned above, it is believed that the acrylate polymer having low carbon number of fluoroalkyl group in the side chain which is at most 7 (particularly at most 6) has low crystallinity so that the polymer cannot satisfy the actual performances (particularly water repellency) .
Recent study results (EPA Report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS"
(http://www.epa.gov/opptintr/pfoa/pfoara.pdf)) and the like clarify that a PFOA (perfluorooctanoic acid) doubtfully has a potential risk of environmental load. EPA (Environmental
Protection Agency of USA) announced on April 14, 2003 that the EPA intensifies the scientific investigation on PFOA.
On the other hand, Federal Register (FR Vol. 68, No. 73/April 16, 2003 [FRL-7303-8] )
(http://www.epa.gov/opptintr/pfoa/pfoafr.pdf) , EPA Environmental News for release Monday April, 2003 "EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING
AID" (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf), and EPA
OPPT FACT SHEET April 14, 2003
(http: //www. epa.gov/opptintr/pfoa/pfoafacts.pdf) announced that a "telomer" may possibly metabolize or decompose to PFOA.
It is also announced that the "telomer" is used in a large number of commercial products including fire fighting foams, care products and cleaning products as well as soil, stain and grease resistant coating on carpets, textiles, paper, and leather.
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
An object of the present invention is to provide a treatment composition which can impart excellent water repellency, oil repellency and stain-proofing properties to a substrate such as a textile.
Means for Solving the Problems The present invention provides a fluorine-containing polymer comprising repeating units derived from: (A) a fluorine-containing monomer represented by the general formula:
CH2=C (-X) -C (=0) -Y-Z-Rf wherein X is a hydrogen atom, a monovalent organic group or a halogen atom, Y is -0- or -NH-;
Z is a direct bond or divalent organic group; Rf is a fluoroalkyl group having 1 to 20 carbon atoms; and (B) a (meth) acrylate monomer having a cyclic hydrocarbon group.
EFFECTS OF THE INVENTION
The present invention provides a treatment agent composition which imparts excellent water repellency, oil repellency and stain-proofing properties to a substrate such as textiles .
MODES OF CARRYING OUT THE INVENTION The fluorine-containing polymer of the present invention comprises:
(A) a fluorine-containing monomer, and
(B) a (meth) acrylate monomer having a cyclic hydrocarbon group.
The monomers (A) and (B) are explained hereinafter. (A) Fluorine-Containing Monomer
The fluorine-containing monomer is represented by the formula: CH2=C (-X) -C (=0) -Y-Z-Rf wherein
X is a hydrogen atom, a monovalent organic group or a halogen atom;
Y is -0- or -NH-; Z is a direct bond or divalent organic group;
Rf is a fluoroalkyl group having 1 to 20 carbon atoms.
Z may be, for example, a linear alkylene group or branched alkylene group having 1 to 20 carbon atoms, such as a group represented by the formula - (CH2) x- [wherein x is from 1 to 10] or a group represented by the formula -SO2N (R1) R2- or by the formula -CON (R1) R2- [wherein R1 is an alkyl group having 1 to 10 carbon atoms and R2 is a linear alkylene group or branched alkylene group having 1 to 10 carbon atoms] or by the formula -CH2CH (OR3) CH2- [wherein R3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, formyl group or acetyl group) ] or by the formula -Ar-CH2- [wherein Ar is an arylene group optionally having a substituent group] , or by the formula - (CH2) m-S02- (CH2) n- group or - (CH2) m-S- (CH2) n- group [wherein m is 1-10, n is 0-10] .
X may be, for example, H, Me (methyl group) , Cl, Br, I, F, CN or CF3. The fluorine-containing monomer (A) is preferably an acrylate ester represented by the formula:
CH2=C (-X) -C (=0) -Y-Z-Rf (1) wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX1X2 group (where each of X1 and X2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) , a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group or a substituted or unsubstituted phenyl group; Y is -0- or -NH- group; Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to 18 carbon atoms, a -CH2CH2N (R1) SO2- group (wherein R1 is an alkyl group having 1 to 4 carbon atoms), a -CH2CH(OZ1) CH2- group (wherein Z1 is a hydrogen atom or an acetyl group), a - (CH2)m~SO2- (CH2) n~ group or a - (CH2) m~S- (CH2) n- group (wherein m is 1 to 10 and n is 0 to 10) ,
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms .
The fluorine-containing monomer (A) may be substituted with a halogen atom or the like at the alpha-position (of o
acrylate or methacrylate) . Therefore, in the formula (1), X may be a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX1X2 group (wherein X1 and X2 represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) , a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or an unsubstituted benzyl group, or a substituted or an unsubstituted phenyl group.
In the formula (1) , the Rf group is preferably a perfluoroalkyl group. The number of the Rf group is preferably from 1 to 12, for example, 1 to 6, particularly from 4 to 6. Examples of the Rf group include -CF3, -CF2CF3, -CF2CF2CF3, -CF (CF3) 2, -CF2CF2CF2CF3, -CF2CF (CF3) 2, -C(CF3J3, -
(CFz)4CF3, -(CF2) 2CF(CF3) 2, -CF2C(CFs)3, -CF(CF3)CF2CF2CF3, -
(CF2)5CF3, -(CF2) 3CF(CF3) 2, -(CF2) 4CF(CF3) 2 and -C8F17.
Z is preferably an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to
18 carbon atoms, -CH2CH2N (R1) SO2- group (wherein R1 is an alkyl group having 1 to 4 carbon atoms) or -CH2CH (OZ1) CH2- group (wherein Z1 is a hydrogen atom or an acetyl group) or -
(CH2) H1-SO2- (CH2) n- group or - (CH2) m-S- (CH2) n- group (wherein m is 1 to 10, n is 0 to 10) . The aliphatic group is preferably an alkylene group (having particularly 1 to 4, for example, 1 or 2 carbon atoms) . The aromatic group or the cyclic aliphatic group may be substituted or unsubstituted. The S group or the SO2 group may directly bond to the Rf group.
Specific examples of the fluorine-containing monomer (A) include, but are not limited to, the following:
CH2=C(-H)-C(=O)-O-(CH2 )2 ~Rf
CH2=C (-H) -C (=0) -0-C6H4 -Rf CH2=C (-Cl) -C (=0) -O- (CH2 )2 -Rf
CH2=C(-H)-C(=O)-O-(CH2 )2N(-CH3 ) SO2 -Rf
CH2=C (-H) -C(=0)-0- (CH2 )2N(-C2H5 ) SO2-Rf
CH2 =C (-H) -C (=0) -0-CH2 CH (-0H) CH2 -Rf
CH2=C (-H) -C (=0) -0-CH2 CH (-OCOCH3 ) CH2 -Rf
CH2=C(-H)-C(=O)-O-(CH2 ) 2 -S-Rf
CH2=C(-H)-C(=O)-O-(CH2 ) 2 -S- (CH2 ) 2 -Rf
CH2=C(-H)-C(=O)-O-(CH2 J3-SO2-Rf
CH2=C(-H)-C(=O)-O-(CH2 J2-SO2-(CH2 J2-Rf CH2 =C (-H) -C (=0) -NH- (CH2 ) 2 -Rf
CH2=C (-CH3 )-C(=0)-0- (CH2 J2-S-Rf
CH2 =C (-CH3 J -C (=0) -0- (CH2 J 2 -S- (CH2 J 2 -Rf
CH2=C (-CH3 )-C(=O)-O-(CH2 ) 3 -SO2 -Rf
CH2 =C (-CH3 ) -C (=0) -0- (CH2 ) 2 -SO2 - (CH2 ) 2 -Rf CH2=C (-CH3 ) -C (=0) -NH- (CH2 ) 2 -Rf CH2 =C (-F) -C (=0) -O- (CH2 ) 2 -S-Rf
CH2=C (-F) -C (=0) -O- (CH2 ) 2 -S- (CH2 ) 2 -Rf
CH2=C (-F) -C (=0) -O- (CH2 J2-SO2-Rf
CH2 =C (-F) -C (=0) -0- (CH2 ) 2 -SO2 - (CH2 ) 2 -Rf
CH2 =C (-F) -C (=0) -NH- (CH2 ) 2 -Rf
CH2=C (-Cl) -C(=0) -0-(CH2 )2-S-Rf
CH2=C (-Cl) -C (=0) -0- (CH2 )2 -S- (CH2 ) 2 -Rf
CH2 =C (-Cl) -C (=0) -0- (CH2 ) 2 -SO2 -Rf
CH2=C (-Cl) -C(=0) -0- (CH2 )2 -SO2 -(CH2 ) 2 -Rf
CH2=C (-Cl) -C (=0) -NH- (CH2 J2-Rf
CH2=C (-CF3 ) -C (=0) -0- (CH2 J2-S-Rf
CH2=C (-CF3 ) -C(=0) -0-(CH2 J2-S- (CH2 J2-Rf
CH2 =C (-CF3 ) -C (=0) -0- (CH2 ) 2 -SO2 -Rf
CH2=C (-CF3 ) -C(=O) -O-(CH2 )2-SO2- (CH2 J2-Rf
CH2 =C ( -CF3 J -C (=0) -NH- (CH2 ) 2 -Rf
CH2 =C (-CF2 H) -C (=0) -0- (CH2 ) 2 -S-Rf
CH2=C(-CF2H) -C(=O)-O-(CH2 )2 -S- (CH2 J2-Rf
CH2=C (-CF2 H) -C (=0) -0- (CH2 ) 2 -SO2 -Rf
CH2 =C (-CF2 H) -C (=0) -0- (CH2 ) 2 -SO2 - (CH2 ) 2 -Rf
CH2=C (-CF2H) -C (=0) -NH- (CH2 J2-Rf
CH2=C (-CN) -C (=0) -0- (CH2 ) 2 -S-Rf
CH2=C (-CN) -C (=0)-0- (CH2 ) 2 -S- (CH2 J2-Rf
CH2 =C (-CN) -C (=0) -0- (CH2 ) 2 -SO2 -Rf CH2=C (-CN) -C (=0) -O- (CH2 ) 2 -SO2 -(CH2 J2-Rf CH2=C (-CN) -C (=0) -NH- (CH2 ) 2 -Rf
CH2=C (-CF2 CF3 ) -C (=0) -O- (CH2 )2-S-Rf
CH2=C (-CF2 CF3 ) -C (=0) -O- (CH2 )2 -S- (CH2 ) 2 -Rf
CH2=C (-CF2 CF3 )-C(=0)-0- (CH2 )2-SO2-Rf
CH2=C (-CF2 CF3 ) -C(=O) -O-(CH2 )2-SO2- (CH2 J2-Rf
CH2=C (-CF2 CF3 ) -C (=0) -NH- (CH2 J2-Rf
CH2=C (-F) -C (=0) -O- (CH2 J3-S-Rf
CH2 =C (-F) -C (=0) -0- (CH2 ) 3 -S- (CH2 ) 2 -Rf
CH2=C (-F) -C (=0) -0- (CH2 J3-SO2-Rf
CH2=C(-F) -C (=O)-O-(CH2 J3-SO2- (CH2 J2-Rf
CH2 =C (-F) -C (=0) -NH- (CH2 J3-Rf
CH2=C (-Cl) -C(=0)-0-(CH2 J3-S-Rf
CH2 =C ( -Cl J -C (=0) -0- (CH2 J 3 -S- (CH2 J 2 -Rf
CH2 =C (-Cl) -C (=0) -0- (CH2 J 3 -SO2 -Rf
CH2=C (-Cl) -C (=0)-0- (CH2 ) 3 -SO2 -(CH2 ) 2 -Rf
CH2=C (-CF3 ) -C (=0) -0- (CH2 ) 3 -S-Rf
CH2 =C (-CF3 ) -C (=0) -0- (CH2 ) 3 -S- (CH2 ) 2 -Rf
CH2=C (-CF3 ) -C(=0) -0-(CH2 J3-SO2-Rf
CH2 =C (-CF3 ) -C (=0) -0- (CH2 ) 3 -SO2 - (CH2 ) 2 -Rf
CH2 =C (-CF2 H) -C (=0) -0- (CH2 ) 3 -S-Rf
CH2=C (-CF2H) -C (=0)-0- (CH2 J3-S-(CH2 J2-Rf
CH2=C (-CF2 H) -C (=0) -0- (CH2 ) 3 -SO2 -Rf CH2=C (-CF2H) -C (=0) -O- (CH2 )3 -SO2 -(CH2 ) 2 -Rf
CH2 =C (-CN) -C (=0) -O- (CH2 ) 3 -S-Rf CH2=C(-CN)-C(=O)-O-(CH2 ) 3 -S- (CH2 J2-Rf CH2 =C (-CN) -C (=0) -O- (CH2 J3-SO2-Rf
CH2=C (-CN) -C (=0) -O- (CH2 ) 3 -SO2 -(CH2 J2-Rf CH2=C (-CF2 CF3 )-C(=0)-0-(CH2 J3-S-Rf CH2=C (-CF2 CF3 )-C(=0)-0-(CH2 J3-S-(CH2J2-Rf CH2=C (-CF2 CF3 )-C(=0)-0-(CH2 J3-SO2-Rf CH2=C (-CF2 CF3 )-C(=0)-0-(CH2 J2 -SO2 -(CH2 J2-Rf wherein Rf is a fluoroalkyl group having 1. to 20 carbon atoms.
(B) (Meth) acrylate Monomer Having a Cyclic Hydrocarbon Group
The (meth) acrylate monomer (B) having a cyclic hydrocarbon group is generally a fluorine-free monomer. The
(meth) acrylate monomer (B) having a cyclic hydrocarbon group is a compound having (preferably monovalent) cyclic hydrocarbon group and monovalent (meth) acrylate group. The monovalent cyclic hydrocarbon group directly bonds to the monovalent (meth) acrylate group. Examples of the cyclic hydrocarbon group include a saturated or unsaturated, monocyclic group, polycyclic group or bridged ring group.
The cyclic hydrocarbon group is preferably a saturated group.
The cyclic hydrocarbon group preferably has from 4 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include a cycloaliphatic 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 carbon number of the cyclic hydrocarbon group is particularly preferably at most 15, for example at most 10. A carbon atom in the cyclic hydrocarbon group preferably directly bonds to an ester group in the
(meth) acrylate group. The cyclic hydrocarbon group is preferably a saturated cycloaliphatic group. Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butyl cyclohexyl group, an isobornyl group, a dicyclopentanyl group and a dicyclopentenyl group. The (meth) acrylate group is an acrylate group or a methacrylate group, preferably a methacrylate group.
Specific examples of the monomer having cyclic hydrocarbon group include cyclohexyl methacrylate, t- butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate and dicyclopentenyl acrylate.
(C) Other Monomer
The fluorine-containing polymer of the present invention may contain repeating units derived from (C) other monomer which is other than the monomers (A) and (B) . The other monomer (C) is preferably free from a fluorine atom. Examples of the other monomer (C) include (C-I) non- crosslinkable monomers and (C-2) crosslinkable monomers.
(C-I) Non-Crosslinkable Monomer
The non-crosslinkable monomer (C-I) , unlike the crosslinkable monomer (C-2) , has no crosslinkability . The non-crosslinkable monomer (C-I) is preferably a monomer free from a fluorine atom, and has a carbon-carbon double bond.
The non-crosslinkable monomer (C-I) is preferably a vinyl monomer free from a fluorine atom. The non-crosslinkable monomer (C-I) is generally a compound having one carbon- carbon double bond. Preferable examples of the non- crosslinkable monomer include, but not limited to, ethylene, vinyl acetate, vinyl halide such as vinyl chloride, vinylidene halide such as vinylidene chloride, acrylonitrile, styrene, polyethyleneglycol (meth) acrylate, polypropyleneglycol (meth) acrylate, methoxypolyethyleneglycol (meth) acrylate, methoxypolypropyleneglycol (meth) acrylate, and vinylalkylether. The non-crosslinkable monomer (C-I) is not limited to the above examples. The non-crosslinkable monomer (C-I) is preferably at least one of vinyl halide and vinylidene halide. The non-crosslinkable monomer (C-I) may be
(meth) acrylate ester having an alkyl group. The alkyl group may have 1 to 30 carbon atoms, for example 6 to 30, such as
10 to 30 carbon atoms. For example, the non-crosslinkable monomer (C-I) may be an acrylate of the general formula:
CH2=CA1COOA2 wherein A1 is a hydrogen atom or a methyl group or a halogen atom other than fluorine atom (e.g. a chlorine atom, a bromine atom and a iodine atom) , and A2 is an alkyl group represented by CnH2n+i (n = 1 to 30) .
(C-2) Crosslinkable Monomer
The fluorine-containing polymer of the present invention may contain repeating units derived from the crosslinkable monomer (C-2) . The crosslinkable monomer (C-2) may be a compound free from a fluorine atom and has at least two reactive groups and/or carbon-carbon double bonds. The crosslinkable monomer (c) may be a compound which has at least two carbon-carbon double bonds or a compound which has at least one carbon-carbon double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group and a carboxyl group,
Examples of the crosslinkable monomer (C-2) include, but are not limited to, diacetoneacrylamide, (meth) acrylamide, N-methylolacrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl
(meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, N, N- dimethylaminoethyl (meth) acrylate, N,N-diethylaminoethyl
(meth) acrylate, butadiene, isoprene, chloroprene and glycidyl
(meth) acrylate .
When the non-crosslinkable monomer (C-I) and/or the crosslinkable monomer (C-2) are copolymerized, various properties such as water- and oil-repellency, stain-proofing properties, cleaning durability and washing durability of said properties, solubility in solvents, hardness and feeling may be improved depending on the necessity.
In the fluorine-containing polymer, the amount of the
(meth) acrylate monomer (B) may be from 0.1 to 300 parts by weight, preferably from 1 to 80 parts by weight, and the amount of the other monomer (C) may be at most 150 parts by weight, preferably from 0.1 to 100 parts by weight, based on
100 parts by weight of the fluorine-containing monomer (A) .
The amount of the non-crosslinkable monomer (C-I) may be at most 100 parts by weight, for example from 0.1 to 50 parts by weight, and the amount of the crosslinkable monomer (C-2) may be at most 50 parts by weight, for example at most 20 parts by weight, particularly from 0.1 to 15 parts by weight, based on 100 parts by weight of the fluorine- containing monomer (A) .
The fluorine-containing monomer (A) , the (meth) acrylate monomer (B) and the optionally used other monomer (C) can be polymerized. Examples of an olefinically unsaturated co- monomer included in the monomer (A) include alkyl acrylate or methacrylate esters having 1 to 30 carbon atoms in the alkyl group such as butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate or butyl methacrylate. The alkyl acrylate or methacrylate can be used to adjust the glass transition temperature (Tg) of the resulting polymeric product; for example, an acrylate having a long chain alkyl group of 4-20, particularly 8-20 carbon atoms such as stearyl acrylate or methacrylate, octyl acrylate, 2-ethylhexyl acrylate or dodecyl acrylate or methacrylate can be used to form a softer polymer of lower Tg. Copolymers with an alkyl acrylate or methacrylate monomer may improve various properties such as water- and oil-repellency and soil releasability, cleaning durability, washing durability and abrasion resistance of such repellency and releasability, solubility in solvent, hardness and feel (handle) . Other acrylate or methacrylate comonomers which can be o
used include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 3-methybutyl (meth) acrylate, 2-ethyl-n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, polyethyleneglycol acrylate or polyethyleneglycol methacrylate, propyleneglycol acrylate or propyleneglycol methacrylate, methoxy polyethyleneglycol acrylate or methoxy polyethyleneglycol methacrylate and methoxy polypropyleneglycol acrylate or methoxy propyleneglycol methacrylate. The other usable olefinically unsaturated comonomers include vinyl chloride, vinylidene chloride, styrene, acrylonitrile, methacrylonitrile, ethylene, vinyl alkyl ether, isoprene, or vinyl ester, for example, vinyl acetate or vinyl propionate.
An olefinically unsaturated comonomer having a functional group, which does not react with an amine group and which can react with the other functional organic group, may be used in order to impart the properties of increased durability (endurance) to the textiles and other substrates.
Examples of such a functional group include hydroxyl, amino and amide groups. Examples of the olefinically unsaturated comonomers containing them are acrylamide, methacrylamide, N- methylolacrylanaide, hydroxyethyl methacrylate, hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate or methacrylate, N, N-dimethylaminoethyl acrylate or methacrylate and diethylaminoethyl acrylate or methacrylate.
The fluorine-containing polymer of the present invention can be produced by any of conventional polymerization methods and the polymerization condition can be optionally selected. The polymerization method includes, for example, a solution polymerization, a suspension polymerization and an emulsion polymerization.
In a solution polymerization, there can be used a method of dissolving the monomer (s) into an organic solvent in the presence of a polymerization initiator, replacing the atmosphere by nitrogen, and stirring the mixture with heating at the temperature within the range from 3O0C to 12O0C for 1 hour to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert- butyl peroxide, lauryl peroxide, cumene hydroperoxide, t- butyl peroxypivalate and diisopropyl peroxydicarbonate . The polymerization initiator may be used in the amount within the range from 0.01 to 20 parts by weight, for example, from 0.01 to 10 parts by weight, based on 100 parts by weight of total of the monomers.
The organic solvent is inert to the monomer (s) and dissolves the monomer (s) , and examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4- dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1, 1, 2, 2-tetrachloroethane, 1,1,1- trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane and trichlorotrifluoroethane . The organic solvent may be used in the amount within the range from 50 to 2,000 parts by weight, for example, from 50 to 1,000 parts by weight, based on 100 parts by weight of total of the monomers.
In the emulsion polymerization, there can be used a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifying agent, replacing the atmosphere by nitrogen, and polymerizing with stirring, for example, at the temperature within the range from 5O0C to 8O0C for 1 hour to 10 hours. As the polymerization initiator, for example, water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1- hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylaπiidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate and oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate can be used. The polymerization initiator may be used in the amount within the range from 0.01 to 10 parts by weight based on 100 parts by weight of the monomers .
In order to obtain a polymer dispersion in water, which is superior in storage stability, it is desirable that the monomers are dispersed in water by using an emulsifying device capable of applying a strong shearing energy (e.g., a high-pressure homogenizer and an ultrasonic homogenizer) and then polymerized with using the oil-soluble polymerization initiator. As the emulsifying agent, various emulsifying agents such as an anionic emulsifying agent, a cationic emulsifying agent and a nonionic emulsifying agent can be used in the amount within the range from 0.5 to 20 parts by weight based on 100 parts by weight of the monomers. When the monomers are not completely compatibilized, a compatibilizing agent capable of sufficiently compatibilizing them (e.g., a water-soluble organic solvent and a low- molecular weight monomer) is preferably added to these monomers. By the addition of the compatibilizing agent, the emulsifiability and polymerizability can be improved.
Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol and ethanol . The water-soluble organic solvent may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of water. Examples of the low- molecular weight monomer are methyl methacrylate, glycidyl methacrylate, 2, 2, 2-trifluoroethyl methacrylate. The low- molecular weight monomer may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of total of monomers.
The fluorine-containing polymer can be applied to fibrous substrates (such as textiles) by any known method to treat textiles in liquid. The concentration of the fluorine- containing polymer in the solution applied to the textiles may be within the range from 0.5 to 20% by weight or from 1 to 5% by weight. When the textile is a cloth, the cloth may be immersed in the solution or the solution may be adhered or sprayed to the cloth. The treated textiles are dried, preferably heated at a temperature between 1000C and 2000C in order to develop the oil repellency.
Alternatively, the fluorine-containing polymer can be applied to a textile via a cleaning process, such as in a laundry application or dry cleaning process.
The textile which is treated is typically a fabric, including woven, knitted and nonwoven fabrics, fabrics in garment form and carpet, but may also be a fibre or yarn or intermediate textile product such as a sliver or roving. The textile material can be a natural fibre such as cotton or wool, a manmade fibre such as viscose rayon or lyocell or a synthetic fibre such as polyester, polyamide or acrylic fibre, or can be a mixture of fibres such as a mixture of natural and synthetic fibres. The polymeric product of the invention is particularly effective in rendering cellulosic fibres such as cotton or rayon oleophobic and oil repellent. The process of the invention generally also renders the textile hydrophobic and water repellent. Fabric treatment with the polymeric product of the invention imparts oil repellency to fabrics whilst at the same time imparting an improvement in feel compared to untreated fabric and also imparting an improvement in feel compared to fabric treated with known fluoropolymer textile treatment agents. The fibrous substrate can alternatively be leather. The polymeric product can be applied to leather from aqueous solution or emulsion at various stages of leather processing, for example during leather wet end processing or during leather finishing, to render the leather hydrophobic and oleophobic.
The fibrous substrate can alternatively be paper. The polymeric product can be applied to preformed paper or at various stages of papermaking, for example during drying of the paper.
The surface treatment agent of the present invention is preferably in the form of a solution, an emulsion or an aerosol. The surface treatment agent generally comprises the fluorine-containing polymer and a medium (particularly a liquid medium, for example, an organic solvent and/or water) . The concentration of the fluorine-containing polymer in the surface treatment agent may be, for example, from 0.1 to 50 % by weight.
The surface treatment agent of the present invention preferably comprises a fluorine-containing polymer and an aqueous medium. As used herein, the term "aqueous medium" means a medium consisting of water alone, as well as a medium comprising, in addition to water, an organic solvent (the amount of the organic solvent is at most 80 parts by weight, for example, 0.1 to 50 parts by weight, particularly 5 to 30 parts by weight based on 100 parts by weight of water) . The fluorine-containing polymer is preferably produced by preparing a dispersion of the fluorine-containing polymer by the emulsion polymerization. The surface treatment agent of the present invention preferably comprises an aqueous dispersion of the particles of a fluorine-containing polymer in an aqueous medium. The particles of the fluorine- containing polymer in the dispersion preferably have an average particle size of from 0.01 to 200 micrometer, for example from 0.1 to 5 micrometer, particularly from 0.05 to 0.2 micrometer. The average particle size may be measured by a dynamic light-scattering device, electron microscope, etc.
The surface treatment agent can be applied to a substrate to be treated by a know procedure. The application of the surface treatment agent can be conducted by immersion, spraying and coating. Usually, the surface treatment agent is diluted with an organic solvent or water, is adhered to surfaces of the substrate by a well-known procedure such as an immersion coating, a spray coating and a foam coating, and is dried. If necessary, the treatment liquid is applied together with a suitable crosslinking agent, followed by curing. It is also possible to add mothproofing agents, softeners, antimicrobial agents, flame retardants, antistatic agents, paint fixing agents, crease-proofing agents, etc. to the surface treatment agent. The concentration of the fluorine-containing compound in the treatment liquid contacted with the substrate may be from 0.01 to 10% by weight (particularly for immersion coating) , for example, from 0.05 to 10% by weight (particularly for spray coating), based on the treatment liquid.
The substrate to be treated with the surface treatment agent (for example, a water- and oil-repellent agent) of the present invention is preferably a textile. The textile includes various examples. Examples of the textile include animal- or vegetable-origin natural fibers such as cotton, hemp, wool and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene; semisynthetic fibers such as rayon and acetate; inorganic fibers such as glass fiber, carbon fiber and asbestos fiber; and a mixture of these fibers .
The textile may be in any form such as a fiber, a yarn and a fabric. The term "treatment" means that the treatment agent is applied to the substrate by immersion, spray, coating or the like. The fluorine-containing polymer which is an active component of the treatment agent can penetrate the internal of the substrate or can adhere on the surface of the substrate by the treatment.
EXAMPLES
The present invention is now described in detail by way of Examples, Comparative Examples and Test Examples. However, the present invention is not limited to these.
In the following Examples, Comparative Examples and Test Examples, parts and percentages are by weight unless otherwise specified. The procedures of the tests were performed in the following manner.
Water repellency test
A treated fabric is stored in a thermo-hygrostat having a temperature of 210C and a humidity of 65% for at least 4 hours. A test liquid (isopropyl alcohol (IPA), water, and a mixture thereof, as shown in Table 2) which has been also stored at 210C is used. The test is conducted in an air- conditioned room having a temperature of 210C and a humidity of 65%. A droplet of the test liquid in an amount of 0.05 ML is softly dropped by a micropipette on the fabric. If the droplet remains on the fabric after standing for 30 seconds, the test liquid passes the test. The water repellency is expressed by a point corresponding to a maximum content (% by volume) of isopropyl alcohol (IPA) in the test liquid which passes the test. The water repellency is evaluated as twelve levels which are Fail, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 in order of a poor level to an excellent level. The symbol "+" added to the numbers means that the result is superior to the number itself, and the symbol "-" added to the numbers means that the result is inferior to the number itself.
Table 1 Water repellency test liquid
Figure imgf000029_0001
Contact angle
When water droplets are dropped onto the substrate, each of advancing contact angle, receding contact angle and sliding angle were measured with using an automated contact angle meter DROPMASTER 700 (manufactured by Kyowa Interface Science Co. Ltd. ) .
Preparative Example 1
In a 1 Liter autoclave, CF3CF2- (CF2CF2) n- CH2CH2OCOC (CH3) =CH2 (n=2.0) (13FMA) (78.4 g) , isobornyl methacrylate (IBMA) (26.0 g) , pure water (250 g) , tripropyleneglycol (35.1 g) , polyoxyethylene oleyl ether (5.4 g) and polyoxyethylene isotridecyl ether (5.4 g) were charged and stirred at a temperature of 6O0C for 15 minutes and then emulsified and dispersed with supersonic wave. After the atmosphere in the autoclave was replaced with nitrogen, vinyl chloride (VCM) (30 g) was charged by injection. Further, 2, 2-azobis- (2-amidinopropane) dihydrochloride (0.91 g) was added to conduct a reaction at 6O0C for 5 hours, and an aqueous dispersion of a polymer was obtained. The composition (weight ratio) of the monomers in the obtained polymer was 13FMA/IBMA/VCM=60/20/20.
Preparative Example 2
In a 1 Liter autoclave, CF3CF2- (CF2CF2) n- CH2CH2OCOC (CH3)=CH2 (n=2.0) (13FMA) (78.4 g) , cyclohexyl methacrylate (CHMA) (26.0 g) , pure water (250 g) , tripropyleneglycol (35.1 g) , polyoxyethylene oleyl ether (5.4 g) and polyoxyethylene isotridecyl ether (5.4 g) were charged and stirred at a temperature of 6O0C for 15 minutes and then emulsified and dispersed with supersonic wave. After the atmosphere in the autoclave was replaced with nitrogen, vinyl chloride (VCM) (30 g) was charged by injection. Further, 2, 2-azobis- (2-amidinopropane) dihydrochloride (0.91 g) was added to conduct a reaction at 600C for 5 hours, and an aqueous dispersion of a polymer was obtained. The composition (weight ratio) of the monomers in the obtained polymer was 13FMA/CHMA/VCM=60/20/20.
Preparative Example 3
In a 1 Liter autoclave, CF3CF2- (CF2CF2) n- CH2CH2OCOC (CHs)=CH2 (n=2.0) (13FMA) (78.4 g) , isobornyl methacrylate (IBMA) (13.0 g) , stearyl acrylate (StA) (13.0 g) , pure water (250 g) , tripropyleneglycol (34.3 g) , polyoxyethylene oleyl ether (5.4 g) and polyoxyethylene isotridecyl ether (5.4 g) were charged and stirred at a temperature of 600C for 15 minutes and then emulsified and dispersed with supersonic wave. After the atmosphere in the autoclave was replaced with nitrogen, vinyl chloride (VCM) (30 g) was charged by injection. Further, 2, 2-azobis- (2- amidinopropane) dihydrochloride (0.91 g) was added to conduct a reaction at 6O0C for 5 hours, and an aqueous dispersion of a polymer was obtained. The composition (weight ratio) of the monomers in the obtained polymer was 13FMA/StA/IBMA/VCM=60/10/10/20.
Comparative Preparative Example 1 In a 1 Liter autoclave, CF3CF2- (CF2CF2) n~ CH2CH2OCOC (CH3) =CH2 (n=2.0) (13FMA) (78.4 g) , stearyl methacrylate (StA) (26.0 g) , pure water (250 g) , tripropyleneglycol (35.1 g) , polyoxyethylene oleyl ether (5.4 g) and polyoxyethylene isotridecyl ether (5.4 g) were charged and stirred at a temperature of 6O0C for 15 minutes and then emulsified and dispersed with supersonic wave. After the atmosphere in the autoclave was replaced with nitrogen, vinyl chloride (VCM) (30 g) was charged by injection. Further, 2, 2-azobis- (2-amidinopropane) dihydrochloride (0.91 g) was added to conduct a reaction at 6O0C for 5 hours, and an aqueous dispersion of a polymer was obtained. The composition (weight ratio) of the monomers in the obtained polymer was 13FMA/StA/VCM=60/20/20.
Example 1
Each of two aqueous liquids (each of 2 g and 4 g) obtained in Preparative Example 1 was diluted with pure water to prepare a test solution (1000 g) . A nylon taffeta cloth
(510 mm X 205 mm) was immersed into the test solution, passed through a mangle and treated with a pin tenter at 1600C for 2 minutes. The test cloth was subjected to a water repellency test. The above procedure was repeated for a nylon white cloth (510mm X 205mm), a PET taffeta cloth (510 mm X 205 mm) and a PET tropical cloth (510 mm X 205 mm) . The results are shown in Table A.
Examples 2-3 and Comparative Example 1
The polymer produced in each of Preparative Examples 2 and 3 and Comparative Preparative Example 1 was applied for treatment in the same manner as in Example 1, and the water repellency test was conducted. The results are shown in
Table A.
Table A
Figure imgf000034_0001
Table A (continued)
Figure imgf000034_0002
Preparative Example 4
In a 500 mL separable glass flask, CF3CF2- (CF2CF2) n- CH2CH2OCOC(CHa)=CH2 (n=2.0) (13FMA) (36.2 g) , isobornyl methacrylate (IBMA) (24.0 g) , pure water (115 g) , tripropyleneglycol (16.2 g) , polyoxyethylene oleyl ether (2.5 g) and polyoxyethylene isotridecyl ether (2.5 g) were charged and stirred at a temperature of 6O0C for 15 minutes and then emulsified and dispersed with supersonic wave. After the atmosphere in the flask was replaced with nitrogen, 2,2- azobis- (2-amidinopropane) dihydrochloride (0.42 g) was added to conduct a reaction at 6O0C for 5 hours, and an aqueous dispersion of a polymer was obtained. The composition (weight ratio) of the monomers in the obtained polymer was 13FMA/IBMA=60/40.
Preparative Example 5 In a 500 mL separable glass flask, CF3CF2- (CF2CF2) n~
CH2CH2OCOC (CH3) =CH2 (n=2.0) (13FMA) (36.2 g) , cyclohexyl methacrylate (24.0 g) , pure water (115 g) , tripropyleneglycol
(16.2 g) , polyoxyethylene oleyl ether (2.5 g) and polyoxyethylene isotridecyl ether (2.5 g) were charged and stirred at a temperature of 6O0C for 15 minutes and then emulsified and dispersed with supersonic wave. After the atmosphere in the flask was replaced with nitrogen, 2,2- azobis- (2-amidinopropane) dihydrochloride (0.42 g) was added to conduct a reaction at 6O0C for 5 hours, and an aqueous dispersion of a polymer was obtained. The composition (weight ratio) of the monomers in the obtained polymer was 13FMA/CHMA=60/40.
Comparative Preparative Example 2 In a 500 mL separable glass flask, CF3CF2- (CF2CF2) n- CH2CH2OCOC (CHs)=CH2 (n=2.0) (13FMA) (40.20 g) , pure water (75 g) , tripropyleneglycol (10.8 g) , polyoxyethylene oleyl ether (1.65 g) and polyoxyethylene isotridecyl ether (1.65 g) were charged and stirred at a temperature of 6O0C for 15 minutes and then emulsified and dispersed with supersonic wave. After the atmosphere in the flask was replaced with nitrogen, 2 , 2-azobis- (2-amidinopropane) dihydrochloride (0.28 g) was added to conduct a reaction at 600C for 5 hours, and an aqueous dispersion of a polymer was obtained. The composition (weight ratio) of the monomers in the obtained polymer was 13FMA=IOO.
Comparative Preparative Example 3
In a 500 mL separable glass flask, CF3CF2- (CF2CF2) n- CH2CH2OCOC (CH3) =CH2 (n=2.0) (13FMA) (36.2 g) , stearyl acrylate
(StA) (24.0 g) , pure water (115 g) , tripropyleneglycol
(16.2g), polyoxyethylene oleyl ether (2.5 g) and polyoxyethylene isotridecyl ether (2.5 g) were charged and stirred at a temperature of 6O0C for 15 minutes and then emulsified and dispersed with supersonic wave. After the atmosphere in the flask was replaced with nitrogen, 2,2- azobis- (2-amidinopropane) dihydrochloride (0.42 g) was added to conduct a reaction at 6O0C for 5 hours, and an aqueous dispersion of a polymer was obtained. The composition (weight ratio) of the monomers in the obtained polymer was 13FMA/StA=60/40.
Test Example 1
Using the fluorine-containing polymer obtained from each of Preparative Examples 4 and 5 and Comparative Examples 2 and 3, a film of the polymer was formed on a polyester film by casting and the contact angle on the film was measured. The results are shown in Table B.
Table B
Figure imgf000037_0001

Claims

1. A fluorine-containing polymer comprising repeating units derived from: (A) a fluorine-containing monomer represented by the general formula:
CH2=C (-X) -C (=0) -Y-Z-Rf wherein
X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-;
Z is a direct bond or a divalent organic group; Rf is a fluoroalkyl group having 1 to 20 carbon atoms; and (B) a (meth) acrylate monomer having a cyclic hydrocarbon group.
2. The fluorine-containing polymer according to claim 1, wherein the fluorine-containing monomer (A) is represented by the formula: CH2=C (-X) -C (=0) -Y-Z-Rf wherein
X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX1X2 group (wherein each of X1 and X2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) , a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group or a substituted or unsubstituted phenyl group; Y is -0- or -NH- group;
Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic or a cycloaliphatic group having 6 to 18 carbon atoms, -CH2CH2N (R1) SO2- group (wherein R1 is an alkyl group having 1 to 4 carbon atoms), -CH2CH (OZ1) CH2- group (wherein Z1 is a hydrogen atom or an acetyl group), - (CH2) m-S02- (CH2) n- group, or a - (CH2) m-S- (CH2) n- group (wherein m is 1 to 10 and n is 0 to 10) ,
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms .
3. The fluorine-containing polymer according to claim 1, wherein the (meth) acrylate monomer (B) is a monomer having a saturated cyclic hydrocarbon group.
4. The fluorine-containing polymer according to claim 1, wherein the cyclic hydrocarbon group in the (meth) acrylate monomer (B) has 4 to 20 carbon atoms.
5. The fluorine-containing polymer according to claim 1, wherein, in the (meth) acrylate monomer (B), a carbon atom in the cyclic hydrocarbon group directly bonds to the ester group in the (meth) acrylate group.
6. The fluorine-containing polymer according to claim 1, wherein the cyclic hydrocarbon group in the (meth) acrylate monomer (B) is at least one selected from the group consisting of a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group and a dicyclopentenyl group.
7. The fluorine-containing polymer according to claim 1, wherein the (meth) acrylate monomer (B) is at least one selected from the group consisting of cyclohexyl rαethacrylate, t-butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate and dicyclopentenyl acrylate.
8. The fluorine-containing polymer according to claim 1, wherein the fluorine-containing polymer further comprises (C) an other monomer which is other than the monomers (A) and (B) .
9. The fluorine-containing (monomer) polymer according to claim 8, wherein the other monomer (C) is free from a fluorine atom.
10. The fluorine-containing polymer according to claim 8, wherein the other monomer (C) is at least one selected from the group consisting of vinyl halide and vinylidene halide.
11. A water- and oil-repellent agent comprising the fluorine-containing polymer according to anyone of claims 1 to 10.
12. The water- and oil-repellent agent according to claim 11, which further contains an aqueous medium.
13. The water- and oil-repellent agent according to claim 11, which is an aqueous dispersion.
14. A method for treating a substrate, comprising treating the substrate with the water- and oil-repellent agent according to anyone of claims 11 to 13.
15. A textile treated with the water- and oil-repellent agent according to anyone of claims 11 to 13.
PCT/JP2009/066323 2008-09-15 2009-09-11 Water- and oil-repellent composition WO2010030044A2 (en)

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CN102149738B (en) 2016-02-10
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