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CN102149738A - Water- and oil-repellent composition - Google Patents

Water- and oil-repellent composition Download PDF

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Publication number
CN102149738A
CN102149738A CN2009801360406A CN200980136040A CN102149738A CN 102149738 A CN102149738 A CN 102149738A CN 2009801360406 A CN2009801360406 A CN 2009801360406A CN 200980136040 A CN200980136040 A CN 200980136040A CN 102149738 A CN102149738 A CN 102149738A
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group
methyl
monomer
atom
water
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CN102149738B (en
Inventor
榎本孝司
山本育男
宫原正弘
薄谷光宏
南里昌史
久保田浩治
坂下浩敏
南晋一
仲村尚子
武内留美
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Daikin Industries Ltd
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Daikin Industries Ltd
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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

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

Refuse water and refuse oil compositions
The cross reference of related application
The application requires the right of priority of No. the 61/096th, 927, the U. S. application submitted on September 15th, 2008, and its disclosure is incorporated herein by reference.
Technical field
The present invention relates to fluoropolymer and treatment compositions, the surface treating composition that particularly contains this polymkeric substance, it gives textiles (for example, carpet), paper, non-woven fabrics, stone-laying, electrostatic filter, dust respirator and fuel cell component refusing water, refuse oil and pollution resistance with excellence.
Background technology
So far, multiple fluorochemicals has been proposed.Fluorochemicals has favourable effect, and it has the excellent properties of aspects such as thermotolerance, anti-oxidant, weathering resistance.By utilizing the low free energy character of fluorochemicals, promptly be difficult to the character of adhering to, fluorochemicals is used as, and for example, refuses water and oil-repellent agent and stain control agent.For example, United States Patent (USP) discloses a kind of finishing compound that is used for textiles, leather, paper and mineral substance No. 5247008, and this compound comprises the water dispersion of polymkeric substance of the aminoalkyl ester of the alkyl ester of perfluoroalkyl ester, acrylic or methacrylic acid of acrylic or methacrylic acid and acrylic or methacrylic acid.
The example that can be used as the fluorochemicals of refusing water and oil-repellent agent comprises the fluoropolymer with the repeating unit that derives from (methyl) acrylate with fluoroalkyl.Recent a plurality of results of study show that in the actual treatment of surface treatment agent to fiber, important surface properties is not a static contact angle, but dynamic contact angle, especially receding contact angle.That is, the advancing contact angle of water does not rely on the carbon number of fluoroalkyl side chain, and is the receding contact angle under at least 8 the situation at carbon number for the receding contact angle of water under 7 the situation at the most significantly is lower than carbon number.Corresponding, x-ray analysis shows when the carbon number of side chain crystallizable side chain at least 7 time.The water repellency of known reality is relevant with the degree of crystallinity of side chain, and the mobility of surfactant molecule is the important factor (for example, MAEKAWA Takashige, FINE CHEMICAL, Vol.23, No.6,12 pages (1994)) that shows actual performance.Owing to reason above-mentioned, think that the acrylic ester polymer of the fluoroalkyl that has the low carbon number that is at most 7 (especially being at most 6) in side chain has low-crystalline, make polymkeric substance can not satisfy actual performance (especially water repellency).
Result of study in recent years, (EPA Report " PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS ", (EPA reports " the preliminary risk assessment of the development toxicity relevant with being exposed to Perfluorocaprylic Acid and salt thereof "), (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)) etc. clear and definite PFOA, (Perfluorocaprylic Acid) has the potential risk of environmental load indefinitely.EPA (USEPA) announces that on April 14th, 2003 EPA has strengthened the science investigation to PFOA.
On the other hand, federal register (Federal Register) (FR Vol.68, No.73/2003 April 16 [FRL-7303-8]) ( Http:// www.epa.gov/opptintr/pfoa/pfoafr.pdf), in April, 2003, the EPA environment news release " EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID " of Monday distribution (EPA strengthens the science investigation to the chemical process auxiliary agent) ( Http:// www.epa.gov/ Opptintr/pfoa/pfoaprs.pdf) and EPA OPPT FACT SHEET (on April 14th, 2003) ( Http:// www.epa.gov/opptintr/pfoa/pfoafacts.pdf) announce that " telomer " may metabolism or be decomposed into PFOA.It announces that also " telomer " is used for a large amount of commercially available prod, comprises the anti-soil on fire foam, care products and cleaning product and carpet, textiles, paper and the leather, anti-spot and anti-oil coating.
Summary of the invention
The problem to be solved in the present invention
The purpose of this invention is to provide a kind of treatment compositions, it can give base material such as textiles refusing water, refuse oil and didirtresistance with excellence.
The scheme that addresses this problem
The invention provides a kind of fluoropolymer, it comprises and derives from following repeating unit:
(A) by the fluorochemical monomer of following general formula:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf
Wherein X is hydrogen atom, unit price organic group or halogen atom,
Y is-O-or-NH-;
Z is direct key or divalent organic group;
Rf is the fluoroalkyl with 1-20 carbon atom; With
(B) has (methyl) acrylate monomer of cyclic hydrocarbon radical.
The effect of invention
The invention provides a kind of agent composition, it gives base material such as textiles refusing water, refuse oil and didirtresistance with excellence.
Embodiment
Fluoropolymer of the present invention comprises:
(A) fluorochemical monomer and
(B) has (methyl) acrylate monomer of cyclic hydrocarbon radical.
Explained later monomer (A) and (B).
(A) fluorochemical monomer
Fluorochemical monomer is expressed from the next:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf
Wherein
X is hydrogen atom, unit price organic group or halogen atom;
Y is-O-or-NH-;
Z is direct key or divalent organic group;
Rf is the fluoroalkyl with 1-20 carbon atom.
Z can be, for example, has the straight chain alkylene or the branched alkylene of 1-20 carbon atom, such as by formula-(CH 2) xThe group of-[wherein x is 1-10] representative or by formula-SO 2N (R 1) R 2-or formula-CON (R 1) R 2-[R wherein 1For having the alkyl of 1-10 carbon atom, and R 2For having the straight chain alkylene or the branched alkylene of 1-10 carbon atom] or by formula-CH 2CH (OR 3) CH 2-[R wherein 3For hydrogen atom or have the acyl group (for example, formyl radical or ethanoyl) of 1-10 carbon atom] or by formula-Ar-CH 2-[wherein Ar randomly has substituent arylidene] or by formula-(CH 2) m-SO 2-(CH 2) n-group or-(CH 2) m-S-(CH 2) nThe group of-group [wherein m is 1-10, and n is 0-10] representative.
X can be, for example, and H, Me (methyl), Cl, Br, I, F, CN or CF 3
The acrylate that fluorochemical monomer (A) is preferably represented by following formula:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf (1)
Wherein
X is hydrogen atom, have the straight or branched alkyl of 1-21 carbon atom, fluorine atom, chlorine atom, bromine atoms, iodine atom, CFX 1X 2Group (X wherein 1And X 2In each be hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom), cyano group, straight or branched fluoroalkyl, replacement or unsubstituted benzyl or replacement or unsubstituted phenyl with 1-21 carbon atom;
Y is-O-or-the NH-group;
Z be the aliphatic group with 1-10 carbon atom, aromatics or cycloaliphatic groups with 6-18 carbon atom ,-CH 2CH 2N (R 1) SO 2-group (R wherein 1For having the alkyl of 1-4 carbon atom) ,-CH 2CH (OZ 1) CH 2-group (Z wherein 1Be hydrogen atom or ethanoyl) ,-(CH 2) m-SO 2-(CH 2) n-group or-(CH 2) m-S-(CH 2) n-group (wherein m is that 1-10 and n are 0-10),
Rf is straight chain or the straight chain fluoroalkyl with 1-20 carbon atom.
Fluorochemical monomer (A) can replace on (acrylate or methacrylic ester) alpha-position with halogen atom etc.Therefore, in formula (1), X can be straight or branched alkyl, fluorine atom, chlorine atom, bromine atoms, iodine atom, the CFX with 2-21 carbon atom 1X 2Group (X wherein 1And X 2Represent hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom), cyano group, straight or branched fluoroalkyl, replacement or unsubstituted benzyl or replacement or unsubstituted phenyl with 1-21 carbon atom.
In formula (1), the Rf group is perfluoroalkyl preferably.The number of Rf group is preferably 1-12, for example 1-6, especially 4-6.The Rf examples of groups comprises-CF 3,-CF 2CF 3,-CF 2CF 2CF 3,-CF (CF 3) 2,-CF 2CF 2CF 2CF 3,-CF 2CF (CF 3) 2,-C (CF 3) 3,-(CF 2) 4CF 3,-(CF 2) 2CF (CF 3) 2,-CF 2C (CF 3) 3,-CF (CF 3) CF 2CF 2CF 3,-(CF 2) 5CF 3,-(CF 2) 3CF (CF 3) 2,-(CF 2) 4CF (CF 3) 2With-C 8F 17
Z preferably have the aliphatic group of 1-10 carbon atom, aromatics or cycloaliphatic groups with 6-18 carbon atom ,-CH 2CH 2N (R 1) SO 2-group (R wherein 1For having the alkyl of 1-4 carbon atom) or-CH 2CH (OZ 1) CH 2-group (Z wherein 1Be hydrogen atom or ethanoyl) or-(CH 2) m-SO 2-(CH 2) n-group or-(CH 2) m-S-(CH 2) n-group (wherein m is 1-10, and n is 0-10).Aliphatic group is preferably alkylene (especially having 1-4, for example 1 or 2 carbon atoms).Aromatic group or cycloaliphatic groups can be that replace or unsubstituted.S group or SO 2Group can be directly and the Rf group bonding.
The specific examples of fluorochemical monomer (A) includes, but are not limited to following:
CH 2＝C(-H)-C(＝O)-O-(CH 2) 2-Rf
CH 2＝C(-H)-C(＝O)-O-C 6H 4-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 2-Rf
CH 2＝C(-H)-C(＝O)-O-(CH 2) 2N(-CH 3)SO 2-Rf
CH 2＝C(-H)-C(＝O)-O-(CH 2) 2N(-C 2H 5)SO 2-Rf
CH 2＝C(-H)-C(＝O)-O-CH 2CH(-OH)CH 2-Rf
CH 2＝C(-H)-C(＝O)-O-CH 2CH(-OCOCH 3)CH 2-Rf
CH 2＝C(-H)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-H)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-H)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-H)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-H)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-CH 3)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-CH 3)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-CH 3)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-CH 3)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-CH 3)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 2-SO 2-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-F)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 2-SO 2-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-Cl)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 2-SO 2-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-CF 3)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 2-SO 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 2-SO 2-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-CN)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 2-S-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 2-S-(CH 2) 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 2-SO 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-NH-(CH 2) 2-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 3-S-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 3-S-(CH 2) 2-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-F)-C(＝O)-O-(CH 2) 3-SO 2-(CH 2) 2-Rf
CH 2＝C(-F)-C(＝O)-NH-(CH 2) 3-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 3-S-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 3-S-(CH 2) 2-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-Cl)-C(＝O)-O-(CH 2) 3-SO 2-(CH 2) 2-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 3-S-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 3-S-(CH 2) 2-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-CF 3)-C(＝O)-O-(CH 2) 3-SO 2-(CH 2) 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 3-S-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 3-S-(CH 2) 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-CF 2H)-C(＝O)-O-(CH 2) 3-SO 2-(CH 2) 2-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 3-S-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 3-S-(CH 2) 2-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-CN)-C(＝O)-O-(CH 2) 3-SO 2-(CH 2) 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 3-S-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 3-S-(CH 2) 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 3-SO 2-Rf
CH 2＝C(-CF 2CF 3)-C(＝O)-O-(CH 2) 2-SO 2-(CH 2) 2-Rf
Wherein Rf is the fluoroalkyl with 1-20 carbon atom.
(B) has (methyl) acrylate monomer of cyclic hydrocarbon radical
(methyl) acrylate monomer (B) with cyclic hydrocarbon radical is generally not fluorine-containing monomer.(methyl) acrylate monomer (B) with cyclic hydrocarbon radical is for having the compound of (preferably monovalent) cyclic hydrocarbon radical and unit price (methyl) acrylate group.Monovalent cyclic hydrocarbon base and unit price (methyl) acrylate group Direct Bonding.The example of cyclic hydrocarbon radical comprises saturated or undersaturated monocyclic groups, many cyclic groups or bridged ring group.Cyclic hydrocarbon radical is preferably saturated group.Cyclic hydrocarbon radical preferably has the 4-20 carbon atom.The example of cyclic hydrocarbon radical comprises the cycloaliphatic groups with 4-20 carbon atom, especially 5-12 carbon atom, has the aromatic group of 6-20 carbon atom and has the araliphatic group of 7-20 carbon atom.The carbon number of cyclic hydrocarbon radical is preferably at the most 15 especially, and for example at the most 10.Carbon atom in the cyclic hydrocarbon radical preferably with (methyl) acrylate group in the ester group Direct Bonding.Cyclic hydrocarbon radical is preferably saturated cycloaliphatic groups.The specific examples of cyclic hydrocarbon radical comprises cyclohexyl, tert-butylcyclohexyl, isobornyl, two cyclopentyl and dicyclopentenyl.(methyl) acrylate group is acrylate group or methacrylate based group, the preferred methacrylate group.
Monomeric specific examples with cyclic hydrocarbon radical comprises cyclohexyl methacrylate, methacrylic acid tertiary butyl cyclohexyl, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, methacrylic acid two ring pentyl esters, vinylformic acid two ring pentyl ester, methacrylic acid two cyclopentenes esters and vinylformic acid two cyclopentenes esters.
(C) other monomers
Fluoropolymer of the present invention can contain and derives from the repeating unit that is different from monomer (A) and other monomers (C) (B).Other monomers (C) preferably do not contain fluorine atom.The example of other monomers (C) comprises (C-1) not monomer and (C-2) crosslinkable monomer of crosslinkable.
(C-1) monomer of crosslinkable not
Do not resemble crosslinkable monomer (C-2), the monomer of crosslinkable (C-1) does not have crosslinkable.The monomer of crosslinkable (C-1) is not preferably the not monomer of contain fluorine atoms, and has carbon-to-carbon double bond.The monomer of crosslinkable (C-1) is not preferably the not vinyl monomer of contain fluorine atoms.The monomer of crosslinkable (C-1) is not generally the compound with carbon-to-carbon double bond.The monomeric preferred embodiment of crosslinkable does not comprise, but be not limited to ethene, vinyl-acetic ester, vinyl halide such as vinylchlorid, vinylidene halide such as vinylidene chloride, vinyl cyanide, vinylbenzene, polyoxyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate and vinyl alkyl ethers.The monomer of crosslinkable (C-1) is not limited to top example.The monomer of crosslinkable (C-1) is not preferably at least a in vinyl halide and the vinylidene halide.
The monomer of crosslinkable (C-1) can not be (methyl) acrylate with alkyl.Alkyl can have 1-30 carbon atom, and for example 6-30, such as 10-30 carbon atom.For example, the monomer of crosslinkable (C-1) can not be the acrylate of following general formula:
CH 2＝CA 1COOA 2
A wherein 1Be the halogen atom (for example, chlorine atom, bromine atoms and iodine atom) beyond hydrogen atom or methyl or the fluorine atom, and A 2For by C nH 2n+1(n=1-30) Biao Shi alkyl.
(C-2) crosslinkable monomer
Fluoropolymer of the present invention can contain the repeating unit that derives from crosslinkable monomer (C-2).Crosslinkable monomer (C-2) can be a contain fluorine atoms and have the compound of at least two reactive groups and/or carbon-to-carbon double bond not.Crosslinkable monomer (C) can be to have the compound of at least two carbon-to-carbon double bonds or have at least one carbon-to-carbon double bond and the compound of at least one reactive group.The example of reactive group comprises hydroxyl, epoxy group(ing), chloromethyl, blocked isocyanate base, amino and carboxyl.
The example of crosslinkable monomer (C-2) comprises, but be not limited to, diacetone-acryloamide(DAA), (methyl) acrylamide, N hydroxymethyl acrylamide, (methyl) vinylformic acid hydroxyl methyl esters, (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid 3-chloro-2-hydroxypropyl acrylate, 2-acetoacetyl (methyl) ethyl propenoate, (methyl) vinylformic acid N, N-dimethylaminoethyl, (methyl) vinylformic acid N, N-lignocaine ethyl ester, divinyl, isoprene, chloroprene and (methyl) glycidyl acrylate.
When not monomer of crosslinkable (C-1) and/or crosslinkable monomer (C-2) copolymerization, can improve various character as required, such as solvability, hardness and the sense of touch in the anti-spatter property of refusing water and oil repellent, didirtresistance, described character and washing fastness, the solvent.
In fluoropolymer, based on the fluorochemical monomer (A) of 100 weight parts, the amount of (methyl) acrylate monomer (B) can be the 0.1-300 weight part, preferred 1-80 weight part, and the amount of other monomers (C) can be 150 weight parts at the most, preferred 0.1-100 weight part.
Fluorochemical monomer (A) based on 100 weight parts, the amount of the monomer of crosslinkable (C-1) can not be 100 weight parts at the most, and the amount of for example 0.1-50 weight part, and crosslinkable monomer (C-2) can be 50 weight parts at the most, for example 20 weight parts, especially 0.1-15 weight part at the most.
Fluorochemical monomer (A), (methyl) acrylate monomer (B) and optional other monomers (C) that use can be aggregated.The example that is included in the olefinic unsaturated comonomer in the monomer (A) comprises alkyl acrylate or the alkyl methacrylate that has 1-30 carbon atom in the alkyl, such as butyl acrylate, ethyl propenoate, methyl acrylate, methyl methacrylate or butyl methacrylate.Alkyl acrylate or alkyl methacrylate can be used for adjusting the second-order transition temperature (Tg) of the polymerisate that obtains; For example, have 4-20, the especially acrylate of the chain alkyl of 8-20 carbon atom, such as octadecyl acrylate or stearyl methacrylate, Octyl acrylate, 2-EHA or dodecyl acrylate or methacrylic acid 2-ethylhexyl or methacrylic dodecyl gallate, can be used for forming low Tg than flexible polymer.Can improve multiple character with the multipolymer of alkyl acrylate or alkyl methacrylate monomer, such as anti-spatter property, washing fastness and the wear resistance of refusing water and oil repellent and soil release characteristics (soil releasability), described water and oil repellant and soil release characteristics, solvability, hardness and sense of touch (feel) in the solvent.
Operable other acrylate or methacrylate co-monomers comprise (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid 3-methyl butyl ester, (methyl) vinylformic acid 2-ethyl-just own ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid ring ten diester, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) CA, (methyl) vinylformic acid two ring pentyl esters, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid diamantane ester, (methyl) isobornyl acrylate, polyethylene glycol acrylate or polyethylene glycol methacrylate-styrene polymer, propylene glycol acrylate or propylene glycol methacrylic ester, methoxy poly (ethylene glycol) acrylate or methoxy polyethylene glycol methacrylate-styrene polymer and methoxyl group polypropylene glycol acrylate or MPEG methacrylic ester.Other available olefinic unsaturated comonomers comprise vinylchlorid, vinylidene chloride, vinylbenzene, vinyl cyanide, methacrylonitrile, ethene, vinyl alkyl ethers, isoprene or vinyl ester, for example, and vinyl-acetic ester or propionate.
Can use have not with the amine groups reaction and can with the olefinic unsaturated comonomer of the functional group of other organo-functional groups reactions so that give the character of textiles and other base materials weather resistance (wearing quality) to increase.The example of this functional group comprises hydroxyl, amino and amide group.The example that contains their olefinic unsaturated comonomer is acrylamide, Methacrylamide, N hydroxymethyl acrylamide, hydroxyethyl methylacrylate, Hydroxyethyl acrylate, vinylformic acid 3-chloro-2-hydroxypropyl acrylate or methacrylic acid 3-chloro-2-hydroxypropyl acrylate, vinylformic acid N, N-dimethylamino ethyl ester or methacrylic acid N, N-dimethylamino ethyl ester and vinylformic acid diethylamino ethyl ester or diethyl aminoethyl methacrylate.
Fluoropolymer of the present invention can pass through conventional arbitrarily polymerization process and produce, and polymerizing condition can randomly be selected.Polymerization process comprises, for example, and solution polymerization, suspension polymerization and letex polymerization.
In solution polymerization, can make with the following method: in the presence of polymerization starter, monomer is dissolved in the organic solvent, replaces atmosphere, and stirred this mixture 1 hour-10 hours at 30 ℃-120 ℃ temperature range internal heating with nitrogen.The example of polymerization starter comprises Diisopropyl azodicarboxylate, benzoyl peroxide, ditertiary butyl peroxide, lauryl peroxide, cumene hydroperoxide hydrogen, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester and di-isopropyl peroxydicarbonate.The consumption of polymerization starter can be 0.01-20 weight part, for example 0.01-10 weight part based on all monomers of 100 weight parts.
Organic solvent is an inert to monomer, and dissolve described monomer, and the example of organic solvent comprises acetone, chloroform, HCHC225, Virahol, pentane, hexane, heptane, octane, hexanaphthene, benzene,toluene,xylene, sherwood oil, tetrahydrofuran (THF), 1,4-diox, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl acetate, butylacetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trieline, tetrachloroethylene, C2Cl4F2 and Refrigerant R 113.The consumption of organic solvent can be 50-2 based on all monomers of 100 weight parts, 000 weight part, 50-1 for example, 000 weight part.
In letex polymerization, can make with the following method: in the presence of polymerization starter and emulsifying agent in water emulsified monomer, replace atmosphere and for example in 50 ℃-80 ℃ temperature range, stir polymerization 1 hour-10 hours with nitrogen.As polymerization starter, for example, can use water soluble starter, such as benzoyl peroxide, lauroyl peroxide, t-butylperoxyl benzoate, 1-hydroxy-cyclohexyl hydrogen peroxide, 3-carboxylic propionyl superoxide, acetyl peroxide, azo two NSC 18620 dihydrochlorides, Diisopropyl azodicarboxylate, sodium peroxide, Potassium Persulphate and ammonium persulphate; And oil-soluble initiator, such as Diisopropyl azodicarboxylate, benzoyl peroxide, ditertiary butyl peroxide, lauryl peroxide, cumene hydroperoxide hydrogen, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester and di-isopropyl peroxydicarbonate.The consumption of polymerization starter can be the 0.01-10 weight part based on 100 weight parts monomers.
In order to obtain the polymeric dispersions in the water preferable aspect storage stability, it is desirable to by use can apply strong shearing can emulsifier unit (for example, high pressure homogenizer and ultrasonic clarifixator) monomer is dispersed in the water, and use oil-soluble polymerization initiator to carry out polymerization then.As emulsifying agent, various emulsifying agents such as anionic emulsifier, cationic emulsifier and nonionic emulsifying agent can use with the amount based on the 0.5-20 weight part of 100 weight parts monomers.Incomplete when compatible when monomer, preferably can make their fully compatible compatibilizing agent (for example, water-miscible organic solvent and low molecular weight monomers) be added in these monomers.By adding compatibilizing agent, can improve emulsifying property and polymerizability.
The example of water-miscible organic solvent comprises acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol and ethanol.The consumption of water-miscible organic solvent can be 1-50 weight part, for example 10-40 weight part based on 100 weight parts waters.The example of low molecular weight monomers is methyl methacrylate, glycidyl methacrylate, methacrylic acid 2,2, the 2-trifluoro ethyl ester.The consumption of low molecular weight monomers can be 1-50 weight part, for example 10-40 weight part based on all monomers of 100 weight parts.
Fluoropolymer can be applied to fiber base material (such as textiles) by any known method thereby handle textiles in liquid.The concentration that is applied to fluoropolymer in the solution of textiles can be in the scope of 0.5-20 weight % or 1-5 weight %.When textiles was cloth, this cloth may be dipped in the solution or solution can adhere to or be sprayed on this cloth.Treated textiles carries out drying, preferably heats under 100 ℃ to 200 ℃ temperature, so that form oil repellent.
Perhaps, fluoropolymer can be applied to textiles through cleaning process, such as in laundry applications or dry-cleaning process.
Processed textiles is generally fabric, comprises the fabric in braiding, knitting and nonwoven fabric, clothes form and the carpet, but also can be fiber or yarn or middle textile product such as particle or rove.Textile materials can be natural fiber such as cotton or wool, regenerated fiber such as viscose rayon or Lasail (lyocell) or synthon such as polyester, polymeric amide or acrylic fiber maybe can be that fibre blend is such as natural and mixtures synthon.Polymerisate of the present invention makes become oleophobic and refuse oil of cellulosic fibre such as cotton or artificial silk especially effectively.Method of the present invention also makes textiles hydrophobic and refuse water usually.Handle fabric with polymerisate of the present invention and compare with untreated fabric and give fabric and give the improvement of sense of touch simultaneously with oil repellent, and with compare the improvement of also having given sense of touch with the fabric of known fluoropolymer textile treating agent processing.
Fiber base material can be leather in addition.Polymerisate can be in each stage of leather processing from the aqueous solution or emulsion applications in leather, for example during processing of leather wet end or leather finish, thereby make leather become hydrophobic and oleophobic.
Fiber base material can be paper in addition.Polymerisate can be applied to premolding paper or use in each stage of papermaking, for example between the dry epoch of paper.
Surface treatment agent of the present invention is preferably solution, emulsion or aerocolloidal form.Surface treatment agent generally includes fluoropolymer and medium (particularly liquid medium, for example organic solvent and/or water).The concentration of fluoropolymer can be, 0.1-50 weight % for example in the surface treatment agent.
Surface treatment agent of the present invention preferably includes fluoropolymer and aqueous medium.As used herein, term " aqueous medium " is meant the medium of only being made up of water, and (based on 100 weight parts waters, the amount of organic solvent is 80 weight parts at the most also to comprise organic solvent beyond dewatering, for example 0.1-50 weight part, particularly 5-30 weight part) medium.Fluoropolymer preferably produces by the dispersion of emulsion polymerization prepared fluoropolymer.Surface treatment agent of the present invention preferably includes the water dispersion of fluoropolymer particles in aqueous medium.Fluoropolymer particles in the dispersion preferably has 0.01-200 micron, for example 0.1-5 micron, the especially mean particle size of 0.05-0.2 micron.Mean particle size can wait by dynamic light scattering device, electron microscope and measure.
Surface treatment agent can be applied to pending base material by known steps.The application of surface treatment agent can be undertaken by dipping, spraying and coating.Usually, surface treatment agent is coated with the surface that is attached to base material with organic solvent or water dilution by known steps such as dip coated, spraying and foam, and dry.If desired, treatment liq is used with suitable crosslinking agent, solidifies then.Also mothproofing agent, tenderizer, biocide, fire retardant, static inhibitor, pigment fixing agent, anti-creasing agent etc. may be added in the surface treatment agent.With the concentration of fluorochemicals in the treatment liq that base material contacts based on treatment liq, can be 0.01-10 weight % (especially for dip coated), for example 0.05-10 weight % (especially for spraying).
To be preferably textiles with the base material that surface treatment agent of the present invention (for example, refusing water and oil-repellent agent) is handled.Textiles comprises various examples.The example of textiles comprises natural fiber such as cotton, hemp, wool and the silk in animal or plant source; Synthon such as polymeric amide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene; Semi-synthetic fibre such as artificial silk and acetic ester; Inorganic fibre such as glass fibre, carbon fiber and fibrous magnesium silicate; Mixture with these fibers.
Textiles can be any form such as fiber, yarn and fabric.
Term " processing " is meant that treatment agent is applied to base material by dipping, spraying, coating etc.As the fluoropolymer of the active ingredient of treatment agent by handle the inside that can penetrate base material or can surface attached to base material on.
Embodiment
Explain the present invention by embodiment, comparative example and test case now.Yet, the invention is not restricted to these.
In embodiment below, comparative example and the test case, except as otherwise noted, umber and percentages.
Test procedure carries out as follows.
The water repellency test
It is that 21 ℃ and humidity are in 65% the controlled thermohygrostat at least 4 hours that the fabric of handling is kept at temperature.Use at 21 ℃ of test liquids (Virahol (IPA), water and its mixture, as shown in table 2) of preserving down.In temperature is that 21 ℃ and humidity are to test in 65% the air-conditioned room.A 0.05ML test liquid drops on the fabric lightly by micropipet.Drop is retained on the fabric after 30 seconds if leave standstill, then the test liquid test passes.Water repellency is expressed as the corresponding point of maximum level (volume %) of Virahol (IPA) in the test liquid with test passes.Water repellency is evaluated as 12 levels, for defective, 0,1,2,3,4,5,6,7,8,9 and 10, it is that relatively poor level is to excellent level in proper order.The symbol "+" that adds to numeral is meant that the result is better than this numeral itself, and adds to digital symbol "-" and be meant that the result is inferior to this numeral itself.
Table 1. water repellency test liquid
Figure BPA00001330040400141
Contact angle
When water droplet drips to base material, use each of automatic contact angle meter DROPMASTER 700 (making) measurement advancing contact angle, receding contact angle and slip angle by Kyowa Interface Science Co.Ltd..
Preparation example 1
In 1 liter of autoclave, CF packs into 3CF 2-(CF 2CF 2) n-CH 2CH 2OCOC (CH 3)=CH 2(n=2.0) (13FMA) (78.4g), isobornyl methacrylate (IBMA) (26.0g), pure water (250g), tripropylene glycol (35.1g), polyoxyethylene oleyl ether (5.4g) and polyoxyethylene isotridecyl ether (5.4g) and under 60 ℃ of temperature, stirred 15 minutes, then with ultrasonic emulsification and disperse.After with the atmosphere in the nitrogen displacement autoclave, pack vinylchlorid (VCM) into (30g) by injection.In addition, add 2, the 2-azo is two-(2-amidine propane) dihydrochloride (0.91g) thus reacted 5 hours at 60 ℃, and obtain the water dispersion of polymkeric substance.Monomeric composition (weight ratio) is 13FMA/IBMA/VCM=60/20/20 in the polymkeric substance that obtains.
Preparation example 2
In 1 liter of autoclave, CF packs into 3CF 2-(CF 2CF 2) n-CH 2CH 2OCOC (CH 3)=CH 2(n=2.0) (13FMA) (78.4g), cyclohexyl methacrylate (CHMA) (26.0g), pure water (250g), tripropylene glycol (35.1g), polyoxyethylene oleyl ether (5.4g) and polyoxyethylene isotridecyl ether (5.4g) and under 60 ℃ of temperature, stirred 15 minutes, then with ultrasonic emulsification and disperse.After with the atmosphere in the nitrogen displacement autoclave, pack vinylchlorid (VCM) into (30g) by injection.In addition, add 2, the 2-azo is two-(2-amidine propane) dihydrochloride (0.91g) thus reacted 5 hours at 60 ℃, and obtain the water dispersion of polymkeric substance.Monomeric composition (weight ratio) is 13FMA/CHMA/VCM=60/20/20 in the polymkeric substance that obtains.
Preparation example 3
In 1 liter of autoclave, CF packs into 3CF 2-(CF 2CF 2) n-CH 2CH 2OCOC (CH 3)=CH 2(n=2.0) (13FMA) (78.4g), isobornyl methacrylate (IBMA) (13.0g), octadecyl acrylate (StA) (13.0g), pure water (250g), tripropylene glycol (34.3g), polyoxyethylene oleyl ether (5.4g) and polyoxyethylene isotridecyl ether (5.4g) and under 60 ℃ of temperature, stirred 15 minutes, then with ultrasonic emulsification and disperse.After with the atmosphere in the nitrogen displacement autoclave, pack vinylchlorid (VCM) into (30g) by injection.In addition, add 2, the 2-azo is two-(2-amidine propane) dihydrochloride (0.91g) thus reacted 5 hours at 60 ℃, and obtain the water dispersion of polymkeric substance.Monomeric composition (weight ratio) is 13FMA/StA/IBMA/VCM=60/10/10/20 in the polymkeric substance that obtains.
Comparative preparation example 1
In 1 liter of autoclave, CF packs into 3CF 2-(CF 2CF 2) n-CH 2CH 2OCOC (CH 3)=CH 2(n=2.0) (13FMA) (78.4g), stearyl methacrylate (StA) (26.0g), pure water (250g), tripropylene glycol (35.1g), polyoxyethylene oleyl ether (5.4g) and polyoxyethylene isotridecyl ether (5.4g) and under 60 ℃ of temperature, stirred 15 minutes, then with ultrasonic emulsification and disperse.After with the atmosphere in the nitrogen displacement autoclave, pack vinylchlorid (VCM) into (30g) by injection.In addition, add 2, the 2-azo is two-(2-amidine propane) dihydrochloride (0.91g) thus reacted 5 hours at 60 ℃, and obtain the water dispersion of polymkeric substance.Monomeric composition (weight ratio) is 13FMA/StA/VCM=60/20/20 in the polymkeric substance that obtains.
Embodiment 1
Each (each 2g and 4g) of two kinds of waterborne liquids that obtain in the preparation example 1 dilutes with preparation test soln (1000g) with pure water.(510mm X 205mm) is immersed in the test soln with a nylon taffeta cloth, handles 2 minutes down at 160 ℃ by ironing machine and with pin tenter.Test cloth carries out the water repellency test.Repeat above-mentioned steps for nylon calico (510mm X 205mm), PET taffeta cloth (510mm X 205mm) and PET tropical cloth (510mm X 205mm).The result is presented in the Table A.
Embodiment 2-3 and comparative example 1
Preparation example 2 with 3 and each of comparative preparation example 1 in the polymkeric substance for preparing be used for handling in the mode identical with embodiment 1, and carry out the water repellency test.The result is presented in the Table A.
Table A
Figure BPA00001330040400161
Table A (continuing)
Figure BPA00001330040400162
Preparation example 4
In the removable glass flask of 500mL, CF packs into 3CF 2-(CF 2CF 2) n-CH 2CH 2OCOC (CH 3)=CH 2(n=2.0) (13FMA) (36.2g), isobornyl methacrylate (IBMA) (24.0g), pure water (115g), tripropylene glycol (16.2g), polyoxyethylene oleyl ether (2.5g) and polyoxyethylene isotridecyl ether (2.5g) and under 60 ℃ of temperature, stirred 15 minutes, then with ultrasonic emulsification and disperse.After with the atmosphere in the nitrogen displacement flask, add 2, the 2-azo is two-(2-amidine propane) dihydrochloride (0.42g) thus reacted 5 hours at 60 ℃, and obtain the water dispersion of polymkeric substance.Monomeric composition (weight ratio) is 13FMA/IBMA=60/40 in the polymkeric substance that obtains.
Preparation example 5
In the removable glass flask of 500mL, CF packs into 3CF 2-(CF 2CF 2) n-CH 2CH 2OCOC (CH 3)=CH 2(n=2.0) (13FMA) (36.2g), cyclohexyl methacrylate (24.0g), pure water (115g), tripropylene glycol (16.2g), polyoxyethylene oleyl ether (2.5g) and polyoxyethylene isotridecyl ether (2.5g) and stirred under 60 ℃ of temperature 15 minutes are then with ultrasonic emulsification and disperse.After with the atmosphere in the nitrogen displacement flask, add 2, the 2-azo is two-(2-amidine propane) dihydrochloride (0.42g) thus reacted 5 hours at 60 ℃, and obtain the water dispersion of polymkeric substance.Monomeric composition (weight ratio) is 13FMA/CHMA=60/40 in the polymkeric substance that obtains.
Comparative preparation example 2
In the removable glass flask of 500mL, CF packs into 3CF 2-(CF 2CF 2) n-CH 2CH 2OCOC (CH 3)=CH 2(n=2.0) (13FMA) (40.20g), pure water (75g), tripropylene glycol (10.8g), polyoxyethylene oleyl ether (1.65g) and polyoxyethylene isotridecyl ether (1.65g) and stirred under 60 ℃ of temperature 15 minutes are then with ultrasonic emulsification and disperse.After with the atmosphere in the nitrogen displacement flask, add 2, the 2-azo is two-(2-amidine propane) dihydrochloride (0.28g) thus reacted 5 hours at 60 ℃, and obtain the water dispersion of polymkeric substance.Monomeric composition (weight ratio) is 13FMA=100 in the polymkeric substance that obtains.
Comparative preparation example 3
In the removable glass flask of 500mL, CF packs into 3CF 2-(CF 2CF 2) n-CH 2CH 2OCOC (CH 3)=CH 2(n=2.0) (13FMA) (36.2g), octadecyl acrylate (StA) (24.0g), pure water (115g), tripropylene glycol (16.2g), polyoxyethylene oleyl ether (2.5g) and polyoxyethylene isotridecyl ether (2.5g) and under 60 ℃ of temperature, stirred 15 minutes, then with ultrasonic emulsification and disperse.After with the atmosphere in the nitrogen displacement flask, add 2, the 2-azo is two-(2-amidine propane) dihydrochloride (0.42g) thus reacted 5 hours at 60 ℃, and obtain the water dispersion of polymkeric substance.Monomeric composition (weight ratio) is 13FMA/StA=60/40 in the polymkeric substance that obtains.
Test case 1
Use available from preparation example 4 and 5 and comparative example 2 and 3 in each fluoropolymer, form polymeric film on the polyester film and measure contact angle on the film by casting in.The result is presented among the table B.
Table B
Table B (continuing)
Figure BPA00001330040400182

Claims (15)

1. fluoropolymer comprises deriving from following repeating unit:
(A) by the fluorochemical monomer of following general formula:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf
Wherein
X is hydrogen atom, unit price organic group or halogen atom,
Y is-O-or-NH-;
Z is direct key or divalent organic group;
Rf is the fluoroalkyl with 1-20 carbon atom; With
(B) has (methyl) acrylate monomer of cyclic hydrocarbon radical.
2. fluoropolymer according to claim 1, wherein said fluorochemical monomer (A) is expressed from the next:
CH 2＝C(-X)-C(＝O)-Y-Z-Rf
Wherein
X is a hydrogen atom; Straight or branched alkyl with 1-21 carbon atom; Fluorine atom; The chlorine atom; Bromine atoms; The iodine atom; CFX 1X 2Group, wherein X 1And X 2In each be hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom; Cyano group; Straight or branched fluoroalkyl with 1-21 carbon atom; Replace or unsubstituted benzyl; Or replacement or unsubstituted phenyl;
Y is-O-or-the NH-group;
Z is the aliphatic group with 1-10 carbon atom; Aromatics or cycloaliphatic groups with 6-18 carbon atom;-CH 2CH 2N (R 1) SO 2-group, wherein R 1For having the alkyl of 1-4 carbon atom;-CH 2CH (OZ 1) CH 2-group, wherein Z 1Be hydrogen atom or ethanoyl;-(CH 2) m-SO 2-(CH 2) n-group or-(CH 2) m-S-(CH 2) n-group, wherein m is that 1-10 and n are 0-10;
Rf is the straight or branched fluoroalkyl with 1-20 carbon atom.
3. fluoropolymer according to claim 1, the monomer of wherein said (methyl) acrylate monomer (B) for having saturated cyclic hydrocarbon radical.
4. fluoropolymer according to claim 1, the cyclic hydrocarbon radical in wherein said (methyl) acrylate monomer (B) has 4-20 carbon atom.
5. fluoropolymer according to claim 1, wherein in described (methyl) acrylate monomer (B), the carbon atom in the described cyclic hydrocarbon radical directly with described (methyl) acrylate group in the ester group bonding.
6. fluoropolymer according to claim 1, the cyclic hydrocarbon radical in wherein said (methyl) acrylate monomer (B) are to be selected from least a in cyclohexyl, tert-butylcyclohexyl, isobornyl, two cyclopentyl and the dicyclopentenyl.
7. fluoropolymer according to claim 1, wherein said (methyl) acrylate monomer (B) is for being selected from least a in cyclohexyl methacrylate, methacrylic acid tertiary butyl cyclohexyl, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, methacrylic acid two ring pentyl esters, vinylformic acid two ring pentyl ester, methacrylic acid two cyclopentenes esters and the vinylformic acid two cyclopentenes esters.
8. fluoropolymer according to claim 1, wherein said fluoropolymer also comprise monomer (A) and (B) in addition other monomers (C).
9. fluorine-containing (monomer) according to claim 8 polymkeric substance, wherein said other monomers (C) are contain fluorine atoms not.
10. fluoropolymer according to claim 8, wherein said other monomers (C) are for being selected from least a in vinyl halide and the vinylidene halide.
11. refuse water and oil-repellent agent for one kind, comprise according to each described fluoropolymer among the claim 1-10.
12. water and the oil-repellent agent refused according to claim 11, it also contains water medium.
13. water and the oil-repellent agent refused according to claim 11, it is a water dispersion.
14. a method of handling base material comprises and using according to each describedly refuses water and oil-repellent agent is handled described base material among the claim 11-13.
15. one kind with according to each describedly refuses textiles that water and oil-repellent agent are handled among the claim 11-13.
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