Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
• • 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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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Paints Or Removers (AREA)

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