CN103788288B - Water repellent and refuse fluid composition - Google Patents

Water repellent and refuse fluid composition Download PDF

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Publication number
CN103788288B
CN103788288B CN201410001414.6A CN201410001414A CN103788288B CN 103788288 B CN103788288 B CN 103788288B CN 201410001414 A CN201410001414 A CN 201410001414A CN 103788288 B CN103788288 B CN 103788288B
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monomer
oil
methyl
water repellent
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CN103788288A (en
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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
南晋一
仲村尚子
武内留美
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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

The present invention relates to a kind of fluoropolymer, including deriving from following repetitive: (A) is by formula CH2The fluorochemical monomer that=C (-X)-C (=O)-Y-Z-Rf represents, wherein X is hydrogen atom, monovalent organic groups or halogen atom, and Y is-O-or-NH-；Z is direct key or divalent organic group；Rf is the fluoroalkyl with 1-20 carbon atom；(B) having (methyl) acrylate monomer of cyclic hydrocarbon radical, it provides and gives water repellent, the water repellent refusing oily and antifouling character and the oil-repellent agent that base material is excellent.

Description

Water repellent and refuse fluid composition
The application be JIUYUE in 2009 within 11st, submit to Application No. the 200980136040.6th, The divisional application of the application for a patent for invention of entitled " water repellent and refuse fluid composition ".
Cross-Reference to Related Applications
This application claims in the U. S. application the 61/096,927th of JIUYUE in 2008 submission on the 15th Priority, the disclosure of which is incorporated herein by reference.
Technical field
The present invention relates to fluoropolymer and treatment compositions, especially with the table of this polymer Face treatment compositions, its give textile (such as, carpet), paper, non-woven fabrics, stone-laying, Electrostatic filter, dust mask and fuel cell component with excellent water repellent, refuse oil and pollution resistance.
Background technology
So far, it has been proposed that multiple fluorochemical.Fluorochemical has favourable effect, It has the excellent properties of the aspects such as thermostability, antioxidation, weatherability.By utilizing containing fluorination The low free energy character of compound, is i.e. difficult to the character adhered to, and fluorochemical is used as, such as, Water repellent and oil-repellent agent and anti-fouling agent.Such as, U.S. Patent No. 5247008 discloses a kind of use In the finishing compound of textile, leather, paper and mineral, this compound includes acrylic acid Or the perfluoroalkyl ester of methacrylic acid, acrylic or methacrylic acid Arrcostab and propylene The aqueous dispersion of the polymer of the aminoalkyl ester of acid or methacrylic acid.
The example of the fluorochemical that can be used as water repellent and oil-repellent agent includes having deriving from and has fluorine The fluoropolymer of the repetitive of (methyl) acrylate of alkyl.Recent multiple researchs Result shows, with in the surface conditioning agent actual treatment to fiber, important surface nature is not It is static contact angle, but dynamic contact angle, especially receding contact angle.That is, the advance of water Contact angle does not relies on the carbon number of fluoroalkyl side chains, and water in the case of carbon number is at most 7 Receding contact angle substantially less than carbon number is the receding contact angle in the case of at least 8.On the other hand Should, x-ray analysis shows the crystallizable side chain when the carbon number of side chain is at least 7.Known reality Water repellency is relevant to the degree of crystallinity of side chain, and the mobility of surfactant molecule is that display is real The key factor of border performance (such as, MAEKAWA Takashige, FINE CHEMICAL, Vol.23, No.6,12 page (1994)).Due to reason above-mentioned, it is believed that have in side chain Have that to be at most 7(be especially up to 6) the acrylate polymer tool of fluoroalkyl of low carbon number There is low-crystalline so that polymer can not meet the performance (especially water repellency) of reality.
Result of study (EPA Report " PRELIMINARY RISK in recent years ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS " (EPA report is " preliminary to be exposed to perfluoro caprylic acid and the relevant development toxicity of salt thereof for SALTS Risk assessment ") (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)) etc. clear and definite PFOA (perfluoro caprylic acid) has the potential risk of environmental load indefinitely.EPA(U.S. environment protection Office) announce that EPA strengthens the investigation of the science to PFOA on April 14th, 2003.
On the other hand, federal register (Federal Register) (FR Vol.68, No.73/2003 On April 16, in [FRL-7303-8]) (http://www.epa.gov/opptintr/pfoa/pfoafr.pdf), In April, 2003, EPA Environmental News original text " the EPA INTENSIFIES of Monday distribution SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID" (EPA strengthens the science to chemical process agents and investigates) (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) and EPA OPPT FACT SHEET(2003 April 14) (http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf) announce that " telomer " may Understand metabolism or be decomposed into PFOA.It also announces that " telomer " is used in substantial amounts of commercially available prod, Including fire foam, care product and cleaning product and carpet, textile, paper and leather On anti-soil, stain resistant and oil resistant coating.
Summary of the invention
The problem to be solved in the present invention
It is an object of the invention to provide a kind for the treatment of compositions, it can give base material and such as weave Product with excellent water repellent, refuse oil and soil resistance.
Solve the scheme of this problem
The present invention provides a kind of fluoropolymer, and it includes deriving from following repetitive:
(A) by the fluorochemical monomer of following general formula:
CH2=C(-X)-C(=O)-Y-Z-Rf
Wherein X is hydrogen atom, monovalent organic groups 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) there is (methyl) acrylate monomer of cyclic hydrocarbon radical.
The effect of invention
The present invention provides a kind of agent composition, and it gives base material such as textile with excellence Water repellent, refuse oil and soil resistance.
Detailed description of the invention
The fluoropolymer of the present invention includes:
(A) fluorochemical monomer, and
(B) there is (methyl) acrylate monomer of cyclic hydrocarbon radical.
Explained later monomer (A) and (B).
(A) fluorochemical monomer
Fluorochemical monomer is expressed from the next:
CH2=C(-X)-C(=O)-Y-Z-Rf
Wherein
X is hydrogen atom, monovalent organic groups 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 it may be that such as, has straight chain alkylene group or the branched alkylene of 1-20 carbon atom, Such as by formula-(CH2)xGroup that-[wherein x is 1-10] represents or by formula-SO2N(R1)R2-or formula -CON(R1)R2-[wherein R1For having the alkyl of 1-10 carbon atom, and R2For having 1-10 The straight chain alkylene group of individual carbon atom or branched alkylene] or by formula-CH2CH(OR3)CH2-[wherein R3For hydrogen atom or the acyl group (such as, formoxyl or acetyl group) with 1-10 carbon atom] Or by formula-Ar-CH2-[wherein Ar is the arlydene optionally with substituent group] or by formula -(CH2)m-SO2-(CH2)n-group or-(CH2)m-S-(CH2)n[wherein m is 1-10, n to-group For 0-10] group that represents.
X it may be that such as, H, Me(methyl), Cl, Br, I, F, CN or CF3。
The acrylate that fluorochemical monomer (A) is the most represented by the formula:
CH2=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, atomic iodine, CFX1X2Group (wherein X1And X2In each be hydrogen atom, Fluorine atom, chlorine atom, bromine atoms or atomic iodine), cyano group, there is the straight chain of 1-21 carbon atom Or branched fluoroalkyl, substituted or unsubstituted benzyl or substituted or unsubstituted phenyl；
Y is-O-or-NH-group；
Z is to have the aliphatic group of 1-10 carbon atom, the aromatics with 6-18 carbon atom or ring grease Race's group ,-CH2CH2N(R1)SO2-group (wherein R1For having the alkyl of 1-4 carbon atom), -CH2CH(OZ1)CH2-group (wherein Z1For hydrogen atom or acetyl group), -(CH2)m-SO2-(CH2)n-group or-(CH2)m-S-(CH2)n-group (wherein m be 1-10 and N is 0-10),
Rf is straight chain or the linear fluoroalkyl group with 1-20 carbon atom.
Fluorochemical monomer (A) can be with halogen atom etc. at (acrylate or methacrylate) Replace on alpha-position.Therefore, in formula (1), X can be the straight chain with 2-21 carbon atom Or branched alkyl, fluorine atom, chlorine atom, bromine atoms, atomic iodine, CFX1X2Group is (wherein X1And X2Represent hydrogen atom, fluorine atom, chlorine atom, bromine atoms or atomic iodine), cyano group, tool Have the straight or branched fluoroalkyl of 1-21 carbon atom, substituted or unsubstituted benzyl or replacement or Unsubstituted phenyl.
In formula (1), Rf group is preferably perfluoroalkyl.The number of Rf group is preferably 1-12, Such as 1-6, especially 4-6.The example of Rf group includes-CF3、-CF2CF3、-CF2CF2CF3、 -CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3、-(CF2)4CF3、 -(CF2)2CF(CF3)2、-CF2C(CF3)3、-CF(CF3)CF2CF2CF3、-(CF2)5CF3、 -(CF2)3CF(CF3)2、-(CF2)4CF(CF3)2With-C8F17。
Z preferably has the aliphatic group of 1-10 carbon atom, has the virtue of 6-18 carbon atom Race or cycloaliphatic groups ,-CH2CH2N(R1)SO2-group (wherein R1Former for having 1-4 carbon The alkyl of son) or-CH2CH(OZ1)CH2-group (wherein Z1For hydrogen atom or acetyl group) or -(CH2)m-SO2-(CH2)n-group or-(CH2)m-S-(CH2)n(wherein m is 1-10, n to-group For 0-10).Aliphatic group be preferably alkylene (especially there is 1-4, such as 1 or 2 Individual carbon atom).Aromatic group or cycloaliphatic groups can be substituted or unsubstituted.S group Or SO2Group can directly and Rf group bonding.
The instantiation of fluorochemical monomer (A) includes, but are not limited to the following:
CH2=C(-H)-C(=O)-O-(CH2)2-Rf
CH2=C(-H)-C(=O)-O-C6H4-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2N(-CH3)SO2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2N(-C2H5)SO2-Rf
CH2=C(-H)-C(=O)-O-CH2CH(-OH)CH2-Rf
CH2=C(-H)-C(=O)-O-CH2CH(-OCOCH3)CH2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-H)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-H)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CH3)-C(=O)-NH-(CH2)2-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-F)-C(=O)-NH-(CH2)2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-Cl)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CN)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-NH-(CH2)2-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-F)-C(=O)-NH-(CH2)3-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
Wherein Rf is the fluoroalkyl with 1-20 carbon atom.
(B) there is (methyl) acrylate monomer of cyclic hydrocarbon radical
There is the monomer that (methyl) acrylate monomer (B) of cyclic hydrocarbon radical is the most fluorine-containing. (methyl) acrylate monomer (B) with cyclic hydrocarbon radical is to have (preferably unit price) cyclic hydrocarbon Base and the compound of unit price (methyl) acrylate group.Monovalent cyclic hydrocarbon base and unit price (methyl) Acrylate group Direct Bonding.The example of cyclic hydrocarbon radical include saturated or undersaturated monocyclic groups, Polycyclic moiety or bridged cyclic group.Cyclic hydrocarbon radical is preferably saturated group.Cyclic hydrocarbon radical preferably has 4-20 Carbon atom.The example of cyclic hydrocarbon radical includes having 4-20 carbon atom, especially 5-12 carbon atom Cycloaliphatic groups, there is the aromatic group of 6-20 carbon atom, and there is 7-20 carbon atom Araliphatic groups.The carbon number of cyclic hydrocarbon radical is particularly preferably at most 15, the most at most 10.Cyclic hydrocarbon Carbon atom in base preferably with the ester group Direct Bonding in (methyl) acrylate group.Cyclic hydrocarbon Base is preferably saturated cycloaliphatic groups.The instantiation of cyclic hydrocarbon radical includes cyclohexyl, the tert-butyl group Cyclohexyl, isobornyl, bicyclopentyl and dicyclopentenyl.(methyl) acrylate group is Acrylate group or methacrylic acid ester group, preferred methacrylate group.
The instantiation of the monomer with cyclic hydrocarbon radical includes cyclohexyl methacrylate, metering system Acid t-butyl cyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, acrylic acid are different Norbornene ester, methacrylic acid bicyclo-pentyl ester, acrylic acid bicyclo-pentyl ester, methacrylic acid bicyclo-penta Alkene ester and acrylic acid dicyclopentenyl ester.
(C) other monomers
The fluoropolymer of the present invention can be different from monomer (A) and (B) containing deriving from The repetitive of other monomers (C).Other monomers (C) preferably do not contain fluorine atom.Other The example of monomer (C) includes (C-1) non-crosslinkable monomer and (C-2) crosslinkable monomer.
(C-1) non-crosslinkable monomer
Not as crosslinkable monomer (C-2), non-crosslinkable monomer (C-1) does not have cross-linking Property.Non-crosslinkable monomer (C-1) is preferably without the monomer of fluorine atom, and have carbon- Carbon double bond.Non-crosslinkable monomer (C-1) is preferably the vinyl monomer without fluorine atom.No Crosslinkable monomer (C-1) usually has the compound of carbon-to-carbon double bond.Non-crosslinkable monomer Preferred embodiment include, but not limited to ethylene, vinyl acetate, vinyl halide such as Vinyl chloride, vinylidene halide such as vinylidene chloride, acrylonitrile, styrene, poly-second two Alcohol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate and vinyl alkyl Ether.Non-crosslinkable monomer (C-1) is not limited to above example.Non-crosslinkable monomer (C-1) It is preferably at least one in vinyl halide and vinylidene halide.
Non-crosslinkable monomer (C-1) can be to have alkyl (methyl) acrylate.Alkane Base can have 1-30 carbon atom, such as 6-30, such as 10-30 carbon atom.Such as, Non-crosslinkable monomer (C-1) can be the acrylate of following formula:
CH2=CA1COOA2
Wherein A1For the halogen atom beyond hydrogen atom or methyl or fluorine atom, (such as, chlorine atom, bromine are former Son and atomic iodine), and A2For by CnH2n+1(n=1-30) alkyl represented.
(C-2) crosslinkable monomer
The fluoropolymer of the present invention can be containing the repetition deriving from crosslinkable monomer (C-2) Unit.Crosslinkable monomer (C-2) can be free from fluorine atom and have at least two reaction Group and/or the compound of carbon-to-carbon double bond.Crosslinkable monomer (C) can be to have at least two The compound of individual carbon-to-carbon double bond or there is at least one carbon-to-carbon double bond and at least one reactive group Compound.The example of reactive group includes hydroxyl, epoxy radicals, chloromethyl, end-blocking Carbimide. Ester group, amino and carboxyl.
The example of crosslinkable monomer (C-2) include, but not limited to N-[2-(2-methyl-4-oxopentyl), (methyl) acrylamide, N hydroxymethyl acrylamide, (methyl) acrylate, (first Base) 2-(Acryloyloxy)ethanol, (methyl) acrylic acid 3-chloro-2-hydroxypropyl acrylate, 2-acetoacetyl (first Base) ethyl acrylate, (methyl) acrylic acid N, N-dimethylaminoethyl, (methyl) acrylic acid N, N-lignocaine ethyl ester, butadiene, isoprene, chlorobutadiene and (methyl) acrylic acid Ethylene oxidic ester.
When non-crosslinkable monomer (C-1) and/or crosslinkable monomer (C-2) copolymerization, root Various character can be improved, such as water repellent and oil repellent, soil resistance, described character according to needs Dissolubility, hardness and sense of touch in resistance to spatter property and washability, solvent.
In fluoropolymer, fluorochemical monomers based on 100 weight portions (A), (methyl) propylene The amount of acid ester monomer (B) can be 0.1-300 weight portion, preferably 1-80 weight portion, and its The amount of his monomer (C) can be at most 150 weight portions, preferably 0.1-100 weight portion.
Fluorochemical monomers based on 100 weight portions (A), the amount of non-crosslinkable monomer (C-1) can With at most 100 weight portions, such as 0.1-50 weight portion, and crosslinkable monomer (C-2) Amount can be at most 50 weight portions, the most at most 20 weight portions, especially 0.1-15 weight Part.
Fluorochemical monomer (A), (methyl) acrylate monomer (B) and other lists optionally employed Body (C) can be polymerized.The reality of the olefinic unsaturated comonomer being included in monomer (A) Example includes alkyl acrylate or the methacrylate in alkyl with 1-30 carbon atom Ester, such as butyl acrylate, ethyl acrylate, acrylic acid methyl ester., methyl methacrylate or Butyl methacrylate.Alkyl acrylate or alkyl methacrylate can be used to be adjusted so as to The glass transition temperature (Tg) of the polymerizate arrived；Such as, there is 4-20 individual, especially The acrylate of the chain alkyl of 8-20 carbon atom, such as octadecyl acrylate or metering system Acid octadecyl ester, 1-Octyl acrylate, 2-EHA or dodecyl acrylate or methyl-prop Olefin(e) acid 2-Octyl Nitrite or lauryl methacrylate, can be used to be formed the softer polymerization of low Tg Thing.Can improve multiple with the copolymer of alkyl acrylate or alkyl methacrylate monomer Character, such as water repellent and oil repellent and soil release performance (soil releasability), described water and oil repellant Dissolubility in property and resistance to spatter property, washability and the wearability of soil release performance, solvent, hardness and Sense of touch (feel).
Other acrylate that can use or methacrylate co-monomers include (methyl) Isopropyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) sec-butyl acrylate, (methyl) Tert-butyl acrylate, (methyl) acrylic acid 3-methylbutyl butenoate, (methyl) acrylic acid 2-ethyl-just Own ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid ring ten diester, (methyl) propylene Acid phenenyl ester, (methyl) benzyl acrylate, (methyl) CA, (methyl) acrylic acid Bicyclo-pentyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (first Base) isobornyl acrylate, polyethylene glycol acrylate or polyethylene glycol methacrylate-styrene polymer, Methacrylatoethyl or propylene glycol methyl acrylate, methoxy polyethylene glycol acrylate or Methoxy polyethylene glycol methacrylate-styrene polymer and methoxyl group polypropylene glycol acrylate or methoxy propyl Glycol methacrylate.Other available olefinic unsaturated comonomers include vinyl chloride, partially Dichloroethylene, styrene, acrylonitrile, methacrylonitrile, ethylene, vinyl alkyl ethers, different Pentadiene or vinyl esters, such as, vinyl acetate or propionate.
Can use and there is the official not reacting with amine groups and can reacting with other organo-functional groups The olefinic unsaturated comonomer that can roll into a ball, in order to give textile and other base materials resistance to increase The character of property (ruggedness) for a long time.The example of this functional group includes hydroxyl, amino and amide groups. Example containing their olefinic unsaturated comonomer be acrylamide, Methacrylamide, N hydroxymethyl acrylamide, hydroxyethyl methylacrylate, 2-(Acryloyloxy)ethanol, acrylic acid 3-chlorine -2-hydroxypropyl acrylate or methacrylic acid 3-chloro-2-hydroxypropyl acrylate, acrylic acid N, N-dimethylamino ethyl ester or Methacrylic N, N-dimethylamino ethyl ester and acrylic acid diethylamino ethyl ester or metering system Acid diethylamino ethyl ester.
The fluoropolymer of the present invention can be produced by arbitrary typical polymerization methods, and gathers Conjunction condition can optionally select.Polymerization includes, such as, and polymerisation in solution, suspension polymerization It is polymerized with emulsion.
In polymerisation in solution, it is possible to use following method: will be single in the presence of polymerization initiator Body dissolves in organic solvent, replaces atmosphere with nitrogen, and within the temperature range of 30 DEG C-120 DEG C This mixture of heated and stirred 1 hour-10 hours.The example of polymerization initiator includes azo two isobutyl Nitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene Hydrogen peroxide, tert-Butyl peroxypivalate and di-isopropyl peroxydicarbonate.Polymerization causes The consumption of agent can be 0.01-20 weight portion, such as 0.01-10 based on the 100 all monomers of weight portion Weight portion.
Organic solvent is inert to monomer, and dissolves described monomer, and the reality of organic solvent Example include acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, Hexamethylene, benzene,toluene,xylene, petroleum ether, oxolane, 1,4-dioxane, methyl second Base ketone, methyl iso-butyl ketone (MIBK), ethyl acetate, butyl acetate, 1,1,2,2-sym-tetrachloroethane, 1,1,1- Trichloroethane, trichloro ethylene, perchloroethylene, tetrachlorodifluoroethane and trichorotrifluoroethane.Have The consumption of machine solvent can be 50-2 based on the 100 all monomers of weight portion, 000 weight portion, such as 50-1,000 weight portion.
In emulsion is polymerized, it is possible to use following method: depositing of polymerization initiator and emulsifying agent Under in water emulsified monomer, replace atmosphere with nitrogen, and such as the temperature range of 50 DEG C-80 DEG C Interior stirring polymerization 1 hour-10 hours.As polymerization initiator, it is, for example possible to use water solublity Initiator, such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxyl Cyclohexyl hydroperoxide, 3-carboxylic propionyl peroxide, acetyl peroxide, azo two 2,2-Dimethylaziridine disalt Hydrochlorate, azodiisobutyronitrile, sodium peroxide, potassium peroxydisulfate and Ammonium persulfate.；Draw with oil-soluble Send out agent, such as azodiisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, Laurel Base peroxide, cumene hydroperoxide hydrogen, tert-Butyl peroxypivalate and peroxidating two carbon Acid diisopropyl ester.The consumption of polymerization initiator can be 0.01-10 weight based on 100 weight parts monomers Amount part.
In order to obtain in terms of storage stability the polymeric dispersions in preferably water, preferably Be by use can apply Strong shear can emulsifier unit (such as, high pressure homogenizer and ultrasonic Homogenizer) by monomer dispersion in water, and then use oil-soluble polymerization initiator gather Close.As emulsifying agent, various emulsifying agents such as anion emulsifier, cationic emulsifier and non- Ionic emulsifying agent can use with the amount of 0.5-20 weight portions based on 100 weight parts monomers.When When monomer is the most fully compatible, preferably will enable compatibilizing agent that they are fully compatible (such as, Water-miscible organic solvent and low molecular weight monomers) add to these monomers.Compatible by adding Property reagent, can improve emulsibility and polymerizability.
The example of water-miscible organic solvent include acetone, methyl ethyl ketone, ethyl acetate, the third two Alcohol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol and ethanol.Water solublity is organic molten The consumption of agent can be 1-50 weight portion based on 100 weight parts waters, such as 10-40 weight portion. The example of low molecular weight monomers is methyl methacrylate, glycidyl methacrylate, first Base acrylic acid 2,2,2-trifluoro ethyl ester.The consumption of low molecular weight monomers is based on the 100 all lists of weight portion Body can be 1-50 weight portion, such as 10-40 weight portion.
Fluoropolymer can be applied to fiber base material by any of method and (such as weave Product) thus process textile in a liquid.It is applied to fluoropolymer in the solution of textile Concentration can be in the range of 0.5-20 weight % or 1-5 weight %.When textile is cloth, This cloth may be dipped in solution or solution can adhere to or be sprayed on this cloth.Treated Textile be dried, preferably at a temperature of 100 DEG C to 200 DEG C heat, in order to formed refuse Oiliness.
Or, fluoropolymer can be applied to textile with cleaned process, such as should in laundry With or dry cleaning processes in.
Processed textile is generally fabric, including braiding, knitting and adhesive-bonded fabric, clothes Fabric in form and carpet but it also may be fiber or yarn or middle textile product the most broken Material or rove.Textile material can be natural fiber such as Cotton Gossypii or Pilus Caprae seu Ovis, and staple fibre is such as Viscose rayon yarn or lyocell (lyocell) or synthetic fibers such as polyester, polyamide or acrylic acid Fibrid, can be maybe the most natural mixture with synthetic fibers of fibre blend.The present invention Polymerizate particularly effectively make cellulose fibre such as Cotton Gossypii or artificial silk become oleophobic and refusing Oil.The method of the present invention the most also makes textile hydrophobic and water repellent.With the polymerizate of the present invention Process fabric gives fabric compared with untreated fabric and gives changing of sense of touch with oil repellent simultaneously Kind, and also give compared with the fabric processed with known fluoropolymer textile treating agent The improvement of sense of touch.
Fiber base material can be additionally leather.Polymerizate can be in each stage of leather processing From aqueous solution or emulsion applications in leather, such as during the processing of leather wet end or leather finish, So that leather becomes hydrophobic and oleophobic.
Fiber base material can be additionally paper.Polymerizate can apply to preforming paper or in papermaking Each stage in apply, such as in the dry period of paper.
The surface conditioning agent of the present invention is preferably solution, emulsion or aerocolloidal form.Surface Inorganic agent generally includes fluoropolymer and medium (particularly liquid medium, such as organic solvent And/or water).In surface conditioning agent, the concentration of fluoropolymer can be, such as 0.1-50 weight %.
The surface conditioning agent of the present invention preferably includes fluoropolymer and aqueous medium.Such as this paper institute Using, term " aqueous medium " refers to the medium being only made up of water, and the most also wraps Containing organic solvent, (based on 100 weight parts waters, the amount of organic solvent is at most 80 weight portions, example Such as 0.1-50 weight portion, particularly 5-30 weight portion) medium.Fluoropolymer preferably passes through Emulsion polymerization is prepared the dispersion of fluoropolymer and is produced.The surface conditioning agent of the present invention is preferred Including fluoropolymer particles aqueous dispersion in an aqueous medium.Fluoropolymer in dispersion Composition granule preferably has 0.01-200 micron, such as 0.1-5 micron, especially 0.05-0.2 micron Particle mean size.Particle mean size can be surveyed by dynamic light scattering device, ultramicroscope etc. Amount.
Surface conditioning agent can be applied to pending base material by known steps.Surface conditioning agent Application can by dipping, spraying and applying is carried out.Generally, surface conditioning agent is with organic Solvent or water dilution, be coated with by known steps such as dip coated, spraying and foam and adhere to In the surface of base material, and it is dried.Should together with suitable cross-linking agent if it is required, process liquid With, then solidify.It is likely to mothproofing agent, softening agent, antimicrobial, fire retardant, resists Electrostatic agent, pigment fixative, anti-creasing agent etc. add to surface conditioning agent.Contact with base material Processing the concentration of fluorochemical in liquid, based on processing liquid, can be that 0.01-10 weight %(is outstanding It is for dip coated), such as 0.05-10 weight %(is particularly with spraying).
The base material that the surface conditioning agent (such as, water repellent and oil-repellent agent) of the present invention to be used processes is excellent Elect textile as.Textile includes various example.The example of textile includes animal or plant The natural fiber in source such as Cotton Gossypii, Fructus Cannabis, Pilus Caprae seu Ovis and silkworm silk；Synthetic fibers such as polyamide, Polyester, polyvinyl alcohol, polyacrylonitrile, polrvinyl chloride and polypropylene；Semisynthetic fibre such as people Make silk and acetas；Inorfil such as glass fibre, carbon fiber and asbestos fibre；And these The mixture of fiber.
Textile can be to be any form such as fiber, yarn and fabric.
Term " processes " and refers to that inorganic agent passes through to impregnate, sprays, coating etc. is applied to base material. As inorganic agent active component fluoropolymer by process can penetrate base material inside or Can be attached on the surface of base material.
Embodiment
The present invention is explained now by embodiment, comparative example and test case.But, this Invention is not limited to these.
In following embodiment, comparative example and test case, except as otherwise noted, number and hundred Proportion by subtraction is by weight.
Testing procedure is carried out as follows.
Water repellency is tested
The fabric processed is saved in the Constant Temperature and Humidity Chambers that temperature is 21 DEG C and humidity is 65% at least 4 hours.Use at 21 DEG C preserve test liquid (isopropanol (IPA), water and Its mixture, as shown in table 2).In the air-conditioned room that temperature is 21 DEG C and humidity is 65% Test.A droplet 0.05ML test liquid is dropped on fabric lightly by micropipet. It is retained on fabric if left standing for drop after 30 seconds, then test liquid test passes.Water repellency table It is shown as right with the maximum level of isopropanol in the test liquid of test passes (IPA) (volume %) The point answered.Water repellency is evaluated as 12 levels, for defective, 0,1,2,3,4,5,6, 7,8,9 and 10, its order is that poor level is to excellent level.Add to the symbol of numeral "+", refers to that result is better than this numeral itself, and the symbol "-" adding to numeral refers to result It is inferior to this numeral itself.
Table 1. water repellency test liquid
Contact angle
When water droplet drops on base material, use automatic contact angle meter DROPMASTER700 (being manufactured by Kyowa Interface Science Co.Ltd.) measures advancing contact angle, Receding Contact Each of angle and drift angle.
Preparation example 1
In 1 liter of autoclave, load CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2 (n=2.0) (13FMA) (78.4g), isobornyl methacrylate (IBMA) (26.0g), Pure water (250g), tripropylene glycol (35.1g), polyoxyethylene oleyl ether (5.4g) and polyoxy second Alkene isotridecyl ether (5.4g) also stirs 15 minutes at a temperature of 60 DEG C, then uses ultrasound wave Emulsifying also disperses.With after the atmosphere in nitrogen displacement autoclave, load vinyl chloride by injection (VCM) (30g).Additionally, add 2,2-azo pair-(2-amidine propane) dihydrochloride (0.91 G) thus carry out reacting 5 hours at 60 DEG C, and obtain the aqueous dispersion of polymer.Obtain In polymer, the composition (weight ratio) of monomer is 13FMA/IBMA/VCM=60/20/20.
Preparation example 2
In 1 liter of autoclave, load CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2 (n=2.0) (13FMA) (78.4g), cyclohexyl methacrylate (CHMA) (26.0g), Pure water (250g), tripropylene glycol (35.1g), polyoxyethylene oleyl ether (5.4g) and polyoxy second Alkene isotridecyl ether (5.4g) also stirs 15 minutes at a temperature of 60 DEG C, then uses ultrasound wave Emulsifying also disperses.With after the atmosphere in nitrogen displacement autoclave, load vinyl chloride by injection (VCM) (30g).Additionally, add 2,2-azo pair-(2-amidine propane) dihydrochloride (0.91 G) thus carry out reacting 5 hours at 60 DEG C, and obtain the aqueous dispersion of polymer.Obtain In polymer, the composition (weight ratio) of monomer is 13FMA/CHMA/VCM=60/20/20.
Preparation example 3
In 1 liter of autoclave, load CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2 (n=2.0) (13FMA) (78.4g), isobornyl methacrylate (IBMA) (13.0g), Octadecyl acrylate (StA) (13.0g), pure water (250g), tripropylene glycol (34.3g), poly- Oxygen ethylene oleyl ether (5.4g) and polyoxyethylene isotridecyl ether (5.4g) 60 DEG C of temperature The lower stirring of degree 15 minutes, then with ultrasonic emulsification and disperse.With in nitrogen displacement autoclave After atmosphere, load vinyl chloride (VCM) (30g) by injection.Additionally, add 2,2-azo is double -(2-amidine propane) dihydrochloride (0.91g) thus carry out reacting 5 hours at 60 DEG C, and obtain Obtain the aqueous dispersion of polymer.In the polymer obtained, the composition (weight ratio) of monomer is 13FMA/StA/IBMA/VCM=60/10/10/20。
Relatively preparation example 1
In 1 liter of autoclave, load CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2 (n=2.0) (13FMA) (78.4g), octadecyl methacrylate (StA) (26.0g), pure Water (250g), tripropylene glycol (35.1g), polyoxyethylene oleyl ether (5.4g) and polyoxyethylene Isotridecyl ether (5.4g) also stirs 15 minutes, then with ultrasound wave breast at a temperature of 60 DEG C Change and disperse.With after the atmosphere in nitrogen displacement autoclave, load vinyl chloride (VCM) by injection (30g).Additionally, add 2,2-azo is double-(2-amidine propane) dihydrochloride (0.91g) thus Carry out reacting 5 hours at 60 DEG C, and obtain the aqueous dispersion of polymer.The polymer obtained The composition (weight ratio) of middle monomer is 13FMA/StA/VCM=60/20/20.
Embodiment 1
Each (each 2g and 4g) of the two kinds of waterborne liquids obtained in preparation example 1 uses pure water Dilution is to prepare test solution (1000g).By one piece of nylon taffeta cloth (510mm X205 Mm) it is immersed in test solution, locates at 160 DEG C by ironing machine and with pin stenter Manage 2 minutes.Test cloth carries out water repellency test.For nylon calico (510mm X205mm), PET taffeta cloth (510mm X205mm) and PET tropical cloth (510mm X205 Mm) repeat the above steps.Result shows in Table A.
Embodiment 2-3 and comparative example 1
Preparation example 2 and 3 and compare preparation example 1 each in preparation polymer with reality Execute the identical mode of example 1 for processing, and carry out water repellency test.Result shows at Table A In.
Table A
Table A (Continued)
Preparation example 4
In the removable glass flask of 500mL, load CF3CF2-(CF2CF2)n-CH2CH2O COC(CH3)=CH2(n=2.0) (13FMA) (36.2g), isobornyl methacrylate (IBMA) (24.0g), pure water (115g), tripropylene glycol (16.2g), polyoxyethylene oil base Ether (2.5g) and polyoxyethylene isotridecyl ether (2.5g) also stir 15 at a temperature of 60 DEG C Minute, then with ultrasonic emulsification and disperse.With after the atmosphere in nitrogen displacement flask, add 2,2-azo is double-(2-amidine propane) dihydrochloride (0.42g) thus to carry out reacting 5 at 60 DEG C little Time, and obtain the aqueous dispersion of polymer.Composition (the weight of monomer in the polymer obtained Than) it is 13FMA/IBMA=60/40.
Preparation example 5
In the removable glass flask of 500mL, load CF3CF2-(CF2CF2)n-CH2CH2O COC(CH3)=CH2(n=2.0) (13FMA) (36.2g), cyclohexyl methacrylate (24.0 G), pure water (115g), tripropylene glycol (16.2g), polyoxyethylene oleyl ether (2.5g) and poly- Oxygen ethylene isotridecyl ether (2.5g) also stirs 15 minutes, then with super at a temperature of 60 DEG C Sound wave emulsifying also disperses.With after the atmosphere in nitrogen displacement flask, add 2,2-azo pair-(2-amidine Base propane) dihydrochloride (0.42g) thus carry out reacting 5 hours at 60 DEG C, and obtain poly- The aqueous dispersion of compound.In the polymer obtained, the composition (weight ratio) of monomer is 13FMA/CHMA=60/40。
Relatively preparation example 2
In the removable glass flask of 500mL, load CF3CF2-(CF2CF2)n-CH2CH2O COC(CH3)=CH2(n=2.0) (13FMA) (40.20g), pure water (75g), 3 the third two Alcohol (10.8g), polyoxyethylene oleyl ether (1.65g) and polyoxyethylene isotridecyl ether (1.65 G) 15 minutes are stirred and at a temperature of 60 DEG C, then with ultrasonic emulsification and disperse.With nitrogen After atmosphere in displacement flask, add 2,2-azo pair-(2-amidine propane) dihydrochloride (0.28g) Thus carry out reacting 5 hours at 60 DEG C, and obtain the aqueous dispersion of polymer.Obtain is poly- In compound, the composition (weight ratio) of monomer is 13FMA=100.
Relatively preparation example 3
In the removable glass flask of 500mL, load CF3CF2-(CF2CF2)n-CH2CH2O COC(CH3)=CH2(n=2.0) (13FMA) (36.2g), octadecyl acrylate (StA) (24.0 G), pure water (115g), tripropylene glycol (16.2g), polyoxyethylene oleyl ether (2.5g) and poly- Oxygen ethylene isotridecyl ether (2.5g) also stirs 15 minutes, then with super at a temperature of 60 DEG C Sound wave emulsifying also disperses.With after the atmosphere in nitrogen displacement flask, add 2,2-azo pair-(2-amidine Base propane) dihydrochloride (0.42g) thus carry out reacting 5 hours at 60 DEG C, and obtain poly- The aqueous dispersion of compound.In the polymer obtained, the composition (weight ratio) of monomer is 13FMA/StA=60/40。
Test case 1
Use available from the fluoropolymer of each in preparation example 4 and 5 and comparative example 2 and 3 Thing, forms polymeric film the contact angle measuring on film by casting on polyester film.Result shows Show in table B.
Table B
Table B(continues)

Claims (11)

1. water repellent and an oil-repellent agent, it is the aqueous dispersion including following components:
(1) a kind of fluoropolymer, including deriving from following repetitive:
(A) by the fluorochemical monomer of following general formula:
CH2=C (-X)-C (=O)-Y-Z-Rf
Wherein
X is hydrogen atom, monovalent organic groups 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；
(B) there is (methyl) acrylate monomer of the bridged cyclic hydrocarbon group of 4-20 carbon atom；
(C) as the vinyl halide without fluorine atom of other monomer, and
(2) aqueous medium.
Water repellent the most according to claim 1 and oil-repellent agent, wherein said fluorochemical monomer (A) by Following formula represents:
CH2=C (-X)-C (=O)-Y-Z-Rf
Wherein
X is hydrogen atom；There is the straight or branched alkyl of 1-21 carbon atom；Fluorine atom；Chlorine atom； Bromine atoms；Atomic iodine；CFX1X2Group, wherein X1And X2In each be hydrogen atom, Fluorine atom, chlorine atom, bromine atoms or atomic iodine；Cyano group；There is the straight chain of 1-21 carbon atom Or branched fluoroalkyl；Substituted or unsubstituted benzyl；Or substituted or unsubstituted phenyl；
Y is-O-or-NH-group；
Z is the aliphatic group with 1-10 carbon atom；There is aromatics or the ring grease of 6-18 carbon atom Race's group；-CH2CH2N(R1)SO2-group, wherein R1For having the alkyl of 1-4 carbon atom； -CH2CH(OZ1)CH2-group, wherein Z1For hydrogen atom or acetyl group； -(CH2)m-SO2-(CH2)n-group or-(CH2)m-S-(CH2)n-group, wherein m be 1-10 and N is 0-10；
Rf is the straight or branched fluoroalkyl with 1-20 carbon atom.
Water repellent the most according to claim 1 and oil-repellent agent, wherein said (methyl) acrylate Monomer (B) is the monomer with saturated bridged cyclic hydrocarbon group.
Water repellent the most according to claim 1 and oil-repellent agent, wherein at described (methyl) acrylic acid In ester monomer (B), the carbon atom in described bridged cyclic hydrocarbon group directly with described (methyl) acrylic acid Ester group bonding in ester group.
Water repellent the most according to claim 1 and oil-repellent agent, wherein said (methyl) acrylate Bridged cyclic hydrocarbon group in monomer (B) is in isobornyl, bicyclopentyl and dicyclopentenyl At least one.
Water repellent the most according to claim 1 and oil-repellent agent, wherein said (methyl) acrylate Monomer (B) is selected from isobornyl methacrylate, isobornyl acrylate, methacrylic acid Bicyclo-pentyl ester, acrylic acid bicyclo-pentyl ester, methacrylic acid dicyclopentenyl ester and acrylic acid bicyclo-penta At least one in alkene ester.
Water repellent the most according to claim 1 and oil-repellent agent, wherein in described fluoropolymer, Fluorochemical monomers based on 100 weight portions (A), the amount of (methyl) acrylate monomer (B) is 0.1-300 weight portion, and the amount of other monomers (C) is 0.1-100 weight portion.
8., according to the water repellent described in claim 1 or 7 and oil-repellent agent, wherein said fluoropolymer exists Concentration in described water repellent and oil-repellent agent is 0.1-50 weight %.
Water repellent the most according to claim 1 and oil-repellent agent, wherein said fluoropolymer is by following Monomer forms:
Monomer (A),
Monomer (B), and
Other monomers (C), described monomer (C) is that (C-1) vinyl halide can be handed over (C-2) The combination of the monomer of connection.
10. the method processing base material, including with according to refusing according to any one of claim 1-9 Water and oil-repellent agent process described base material.
11. 1 kinds with according to the water repellent according to any one of claim 1-9 and the weaving of oil-repellent agent process Product.
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