CN105908508A - Aqueous Polymer Dispersion Composition And Water-Repellent Oil-Repellent Agent - Google Patents

Aqueous Polymer Dispersion Composition And Water-Repellent Oil-Repellent Agent Download PDF

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CN105908508A
CN105908508A CN201610388062.3A CN201610388062A CN105908508A CN 105908508 A CN105908508 A CN 105908508A CN 201610388062 A CN201610388062 A CN 201610388062A CN 105908508 A CN105908508 A CN 105908508A
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polymer
monomer
alkyl
water
base
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岸川洋介
武内留美
山本育男
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
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    • 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
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    • 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
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    • 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
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
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    • D06M2101/16—Synthetic fibres, other than mineral fibres
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    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
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Abstract

Disclosed is a water-dispersed water-repellent oil-repellent composition which can exhibit high water/oil repellency and durability thereof even when the amount of an Rf-containing resin used therein is significantly reduced. The water-repellent oil-repellent composition is characterized by containing a polymer (A) and a polymer (B) which are not present in a same one particle. The polymer (A) is an addition polymer containing a polymerization unit of a polymerizable monomer (a) described below and a polymerization unit of a polymerizable monomer (b) or (c) described below. The polymer (B) is an addition polymer not containing a polymerization unit of the polymerizable monomer (a) but containing a polymerization unit of the polymerizable monomer (c) or a polymerizable monomer (y). The polymerizable monomer (a) is a (meth)acrylate having a polyfluoroalkyl group or an acrylate halogen-substituted at the a-position. The polymerizable monomers (b) and (c) are acrylates having an alkyl group but not having a polyfluoroalkyl group, which may be halogen-substituted at the a-position. The polymerizable monomer (y) is a polymerizable monomer wherein a halogen atom is bonded to a carbon atom constituting an unsaturated double bond.

Description

Aqueous polymer dispersion composition and water extraction oil extracticn agent
The application be international filing date be on February 20th, 2009, international application no be PCT/JP2009/052999, national applications number be 200980105944.2, the divisional application of application for a patent for invention invention entitled " aqueous polymer dispersion composition and water extraction oil extracticn agent "
Technical field
Also can be to fibre even if it is an object of the invention to provide a kind of usage amount reducing fluorochemical monomer The article such as dimension pay water-repellent oil-repellent (particularly water-repellancy) and the drying of durability thereof of excellence Oil extracticn agent compositions (particularly dryingagent compositions).
Background technology
It is known in the art that by the polymer or common of the polymerizable monomer containing fluoro-alkyl Polymers or containing the compound of fluoro-alkyl as organic solvent solution or aqueous dispersion, Fibre etc. is processed, thus their surface is paid the technology of water-repellent oil-repellent.
For the purpose of the durability improving the water-repellent oil-repellent to washing or dry-cleaning etc., attempt making Polymerizable monomer containing fluoro-alkyl and there is the method that the monomer of cementability group carries out copolymerization. It addition, also attempted mixing the polymer without fluoro-alkyl and the polymer containing fluoro-alkyl Close, create the water-repellent oil-repellent compositions (patent documentation 1～2) that economy is excellent.
It addition, as the polymer that antifouling property and endurance quality etc. can not be made to add with reducing, Copolymer, advocates and uses the polymerizable monomer (patent documentation 3) with ad hoc structure.
In recent years, disclose a kind of resin combination, by the mixing polymer containing fluoro-alkyl The different two kinds of polymer of content and polymer without fluoro-alkyl, thus obtain having and dial The surfaces characteristic such as water-repellent oil and maintenance thereof obtain the resin combination (patent on the surface improved Document 4).
It addition, disclose by the homopolymer of at least one in hydrocarbon mixture polymerizable compound Or copolymer and polymer that glass transition point is more than 50 DEG C, thus improve slip resistance Scheme (patent documentation 5), also discloses a kind of carpet with dialling liquor, it is characterised in that mixing Polymer containing fluoro-alkyl and the polymer without fluoro-alkyl, the glass transition of any one Point or fusing point are all more than 45 DEG C (patent documentation 6).
Patent documentation 1: Japanese Patent Publication 38-22487
Patent documentation 2: Japanese Patent Publication 41-8579
Patent documentation 3: Japanese Patent Publication 49-42878
Patent documentation 4: Japanese Unexamined Patent Publication 06-228241
Patent documentation 5: Japanese Laid-Open Patent Publication 61-264081
Patent documentation 6:US4043964
Summary of the invention
In existing water extraction oil extracticn agent, to improve water-repellent oil-repellent to washing or dry-cleaning etc. For the purpose of durability, attempt making the polymerizable monomer containing fluoro-alkyl and there is cementability group Monomer carry out copolymerization, or the mixing polymer containing fluoro-alkyl and the high polymerization of film-strength The scheme of thing.But, although it is capable of higher drying by a large amount of importing fluorinated monomers and dials Oiliness, but cause the result that durability is not enough.On the contrary, although have viscous by a large amount of importings The monomer of connecing property group can pay sufficient durability, but lacks water-repellent oil-repellent.It addition, In order to show sufficient water-repellent oil-repellent, it is necessary to import substantial amounts of fluoromonomers, due to fluoro list Body is much more expensive, thus cost improves.
Even if expecting that obtaining a kind of usage amount reducing fluoromonomers also can play high water-repellent oil-repellent Property and the also excellent processing agent of the durability of water-repellent oil-repellent.
The present inventor is in order to solve the problems referred to above, even if to provide one to reduce fluoro list The usage amount of body also can play high water-repellent oil-repellent and the water-repellent oil-repellent of durability also excellence For the purpose of agent compositions, conduct in-depth research.It was found that by mixing with having spy Determine the polymer of the polymerized unit of chemical constitution, there is the polymerization being derived from the monomer containing fluoro-alkyl The polymer of unit and aqueous liquid dispersion, it is possible to there is significant water-repellent oil-repellent and durability, Achieve above-mentioned purpose, thus complete the present invention.
That is, the present invention provides a kind of containing water-medium, following polymer (A) and following polymerization The water-dispersion type water extraction oil extracticn agent compositions of thing (B).
Polymer (A) is the polymer containing fluoro-alkyl,
Polymer (B) is the polymer on main chain containing halogen atom.
" containing halogen atom on main chain " refers on the carbon atom of main chain constituting polymer direct It is combined with halogen atom.
Invention effect
According to the present invention, by mixing the polymerization with the polymerized unit with specified chemical structure Thing (B) and there is the polymer (A) of the polymerized unit being derived from the monomer containing fluoro-alkyl and obtain To water-dispersion type water-repellent oil-repellent compositions there is significant water-repellent oil-repellent and durability.Therefore, The present invention can provide the usage amount by reduction fluoromonomers to reduce cost, play high dialling The water extraction oil extracticn agent that water-repellent oil and durability are also excellent.
Detailed description of the invention
Hereinafter, the present invention is described in detail.
The present invention provides a kind of water extraction oil extracticn agent compositions, it is characterised in that containing following polymerization Thing (A) and following polymer (B), and polymer (A) and polymer (B) do not exist In same granule.Generally, polymer (A) granule that formed and by polymer (B) shape The granule become is respectively present in aqueous liquid dispersion.
Polymer (A) is polymerized unit (preferably 50 weights containing following polymerizable monomer (a) Amount more than %) and following polymerizable monomer (b) or polymerizable monomer (c) at least one Polymerized unit (below preferably 50 weight % (also include being the situation of 0 weight %, but preferably 1 More than weight %)) polymer.
Polymer (B) is free from the polymerized unit of polymerizable monomer (a) and contains polymerism The polymer of at least one in monomer (y) or polymerizable monomer (c).
Polymerizable monomer (a) is to have multi-fluorinated alkyl (methyl) acrylate or α position by halogen The substituted esters of acrylic acid of element.
Polymerizable monomer (b) is to have alkyl and do not have multi-fluorinated alkyl (methyl) propylene Acid esters.
Polymerizable monomer (c) is to have alkyl and do not have multi-fluorinated alkyl, α position by halogen The substituted acrylate of element.
Polymerizable monomer (y) is the polymerism in addition to polymerizable monomer (a), (b), (c) Monomer, is combined with halogen atom on the carbon atom forming unsaturated double-bond.
It addition, the present invention provides the thing using this water extraction oil extracticn agent compositions to carry out processing and to obtain Product.
In this manual, acrylic acid and methacrylic acid are referred to as (methyl) acrylic acid.(first Base) token of acrylate etc. is the most identical.It addition, multi-fluorinated alkyl to be designated as Rf base.
Polymer (A) be preferably containing polymerizable monomer (a) polymerized unit 50 weight % with The polymerized unit 50 of at least one in upper, polymerizable monomer (b) or polymerizable monomer (c) (include the situation of 0 weight %) below weight %, as required, containing polymerizable monomer (a), B the polymerizable monomer (x) beyond () (such as, is tied on the carbon atom forming unsaturated double-bond Close have (y) of halogen atom or there is the polymerizable monomer (z) of reactive group) polymerization list Unit, and, the polymerized unit of polymerizable monomer (a), polymerizable monomer (b) and polymerism The addition polymers adding up to more than 50 weight % of the polymerized unit of monomer (c).That is, polymer (A) In can not contain polymerizable monomer (b) or the polymerized unit of (c).
Polymerizable monomer (a) is to have Rf base (methyl) acrylate or α position is optionally substituted by halogen Esters of acrylic acid [following, to be designated as monomer (a) or the monomer containing Rf base].There is (the first of Rf base Base) esters of acrylic acid that is optionally substituted by halogen of acrylate or α position refers to that Rf base is present in (methyl) third The compound of the alcohol residue moiety of olefin(e) acid or α substituted acrylate.
Rf base is the group that the two or more hydrogen atom of alkyl is replaced by fluorine atoms.The carbon of Rf base is former Subnumber is preferably 2～20, more preferably 4～16, particularly preferably 4～6.Carbon number is less than When 2, there is the tendency that water-repellancy declines；During more than 20, there is monomer (a) and become at normal temperatures Also increase for solid, sublimability, operate the tendency becoming difficult.
It addition, Rf base can also be containing other the halogen atom beyond fluorine removal atom.As other Halogen atom, preferably chlorine atom.Furthermore it is also possible to insert ether type between carbon-carbon bond in Rf base Oxygen atom or the sulphur atom of thioether-type.As the structure of the end section of Rf base, can enumerate CF3CF2-, (CF3)2CF-, CHF2-, CH2F-, CClF2-etc., preferably CF3CF2 -.
Rf base is the group that the plural hydrogen atom of saturated alkyl is replaced by fluorine atoms.Rf base In ratio (number of fluorine atoms in the Rf base)/(number of fluorine atoms+Rf in Rf base of fluorine atom Number of hydrogen atoms in base) it is preferably more than 40%, particularly preferred more than 60%.It addition, Rf base Part or all of hydrogen atom can be substituted by a chlorine atom both.
The preferred straight chain of Rf base or the structure of side chain, the structure of particularly preferred straight chain.For side chain During structure, preferably component is present near the end of Rf base.Additionally, it is preferred that component Be carbon number be the short chain of 1～about 4.It addition, the preferred carbon number of Rf base is 1～12.
As Rf base, the ratio of particularly preferred above-mentioned fluorine atom is essentially the perfluor alkane of 100% Base or the Rf base containing perfluoroalkyl moieties.Perfluoroalkyl is it is also preferred that the structure of straight chain.As The perfluoroalkyl of straight chain, preferably with CmF2m+1-(wherein, m is the integer of 2～20) represents Situation.
The concrete example of Rf is listed below.Wherein, in the following examples, including having same point The group that the structure of minor is different, i.e. includes isomerism group.C4F9-[F (CF2)4-, (CF3)2CFCF2-, (CF3)3C-], C5F11-[F (CF2)5-, (CF3)3CCF2-etc.], C6F13 -[F (CF2)6-etc.], C7F15-, C8H17-, C9F19-, C10F21-, Cl (CF2)t-, H(CF2)tThe integer of 2～20 (t be), (CF3)2CF(CF2)y-the integer of 1～17 (y be) Deng.
In monomer containing Rf base, Rf base and polymerism unsaturated group directly in conjunction with or by knot Close group indirectly to combine, situation about preferably indirectly combining.As conjugated group, more than divalent Conjugated group, preferably alkylidene, ester group, amide groups, amino, urethane groups, ether, Asia Phenoxy group, sulfonyl or the conjugated group containing these structures.These contain the monomer of Rf, Known or known compound can be used, it is possible to by the alcohol containing Rf base, carboxylic acid containing Rf base Or the sulfonic acid etc. containing Rf base is easily synthesized.
Wherein, one as the monomer containing Rf base of the present invention, preferably Rf base is passed through divalent The compound of structure that is connected with polymerism unsaturated group of conjugated group.The most preferably containing Rf The acrylate of base, the methacrylate containing Rf base, styrene containing Rf base, containing Rf base Vinyl acetate and containing the fumarate etc. of Rf base.
It addition, as the monomer containing Rf base of the present invention, from the viewpoint of versatility, especially Preferably comprise (methyl) acrylate of Rf base or acrylate that α position is chlorinated.
Preferably the monomer containing Rf base is by general formula R f-Q1-X1Represent,
[in formula, Rf represents fluoro-alkyl, Q1Represent the organic group of bivalence, X1Expression contains The monovalent organic group of polymerism unsaturated group.]
Q1Represent divalent organic group, preferably-(CH2)n+p-,-(CH2)nC(O)ON H(CH2)p-,-(CH2)nCONH(CH2)p-,-(CH2)nSO2NH(C H2)p-,-(CH2)nNHC(O)NH(CH2)p-etc..Wherein, n and p represents 0 Or the integer of more than 1, n+p is the integer of 2～22.Wherein, as Q1, preferably-(C H2)n+p-,-(CH2)nC(O)ONH(CH2)p-,-(CH2)nSO2NH(C H2)p-, and p is the integer of more than 2, n+p is the situation of 2～6.Particularly preferably n+ When p is 2～6-(CH2)n+p-, i.e. preferably dimethylene～hexa-methylene.
X1The expression 1 valency organic group containing polymerism unsaturated group, preferred alkenes class residue, Ethylene ethers residue, vinyl esters residue, (methyl) esters of acrylic acid residue, phenylethylene residue Deng.As olefines residue, preferably-CR1=CH2Or As (methyl) esters of acrylic acid residue, preferably-OC (O) CR1=CH2；Make For ethylene ethers residue, preferably-OCR1=CH2；As vinyl esters residue, preferably- C(O)OCR1=CH2；As phenylethylene residue, preferablyOrWherein, R1Be hydrogen atom, carbon number be 1～21 straight Chain or the alkyl of branched, fluorine atom, chlorine atom, bromine atoms, atomic iodine, CFX1X2Base (wherein, X1And X2Hydrogen atom, fluorine atom, chlorine atom, bromine atoms or atomic iodine), cyanogen Base, carbon number are the straight-chain of 1～the 21 or fluoro-alkyl of branched, substituted or non-substituted Benzyl, substituted or non-substituted phenyl,It it is phenylene.Wherein, as X1, preferably (first Base) residue of esters of acrylic acid, particularly preferred R1Be hydrogen atom, methyl or chlorine atomic time- OC(O)CR1=CH2, i.e. preferably acryloxy, methacryloxy or α- Chloropropene acyloxy.As containing Rf monomer, from the polymerism with other monomer and at fiber The flexibility of the film of upper formation, the cementability to base material, the dissolubility to solvent, emulsion polymerization Easiness etc. from the viewpoint of, particularly preferably (methyl) esters of acrylic acid.
Monomer containing Rf base can use one or use two or more.
As the example of the monomer containing Rf base, it can be the material of below formula.
Formula: CH2=C (-X)-C (=O)-Y-Z-Rf
[in formula, X be hydrogen atom, carbon number be 1～21 straight-chain or the alkyl of branched, Fluorine atom, chlorine atom, bromine atoms, atomic iodine, CFX1X2Base (wherein, X1And X2It is hydrogen Atom, fluorine atom, chlorine atom, bromine atoms or atomic iodine), cyano group, carbon number be 1～21 Straight-chain or the fluoro-alkyl of branched, substituted or non-substituted benzyl, substituted or non-substituted Phenyl；Y is-O-or-NH-；Z be carbon number be 1～10 fatty group, Carbon number is aromatic series base or annular aliphatic base, the CH (R of 6～181)SO2-base is (wherein, R1Be carbon number be the alkyl of 1～4) ,-CH2CCH(OZ1)CH2-base (wherein, Z1 Hydrogen atom or acetyl group) ,-(CH2)m-SO2-(CH2)n-base or-(CH2)m-S- (CH2)n-base (wherein, m is 1～10, n is 0～10), Rf be carbon number be 1～21 Straight-chain or the fluoro-alkyl of branched.]
As the concrete example of the monomer containing Rf base, following material can be illustrated, but not by this The restriction of a little materials.
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
[in above-mentioned formula, Rf be carbon number be the fluoro-alkyl of 1～21, particularly preferred carbon atom Number is the fluoro-alkyl of 1～6.]
Monomer containing Rf base can be two or more mixture.Relative to polymer (A), contain The amount of the monomer of Rf base is 50～100 weight %, for example, 50～90 weight %.
Polymerizable monomer (b) be that there is alkyl and do not have Rf base (methyl) acrylate (with Under, it is designated as monomer (b)).(methyl) acrylate with alkyl refers to that alkyl is present in (methyl) The compound of the alcohol residue moiety of acrylate.As alkyl, preferably carbon number be more than 2, The alkyl (the ring-type and alkyl of chain) of such as 2～30, the alkyl of particularly preferred linear chain structure.
As the concrete example of monomer (b), (methyl) ethyl acrylate, (methyl) propylene can be enumerated Acid N-butyl, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) acrylic acid-2- Octyl Nitrite, (methyl) isodecyl acrylate, (methyl) acrylic acid cetyl, (methyl) acrylic acid Stearyl ester, (methyl) acrylic acid behenyl ester, (methyl) lauryl acrylate, (methyl) acrylic acid ring Own ester etc..Monomer (b) can be to have alkyl and do not have the two of the polymerizable monomer of Rf base More than Zhong.
Polymerizable monomer (c) be that there is alkyl and not there is Rf base, α position is optionally substituted by halogen Acrylate (following, to be designated as monomer (c)).There is alkyl and propylene that α position is optionally substituted by halogen Acid esters refers to the acrylate that the α position of acrylate is optionally substituted by halogen, and it is residual to be that alkyl is present in alcohol The compound of base section.It is more than 2, such as 2～30 as alkyl, preferably carbon number Alkyl (the ring-type and alkyl of chain), the alkyl of particularly preferred linear chain structure.
As the concrete example of monomer (c), preferably enumerate α-chloro-acrylicacid ethyl ester, alpha-chloro third Olefin(e) acid N-butyl, α-chloro-acrylicacid isobutyl ester, the α-chloro-acrylicacid tert-butyl ester, alpha-chloro propylene Acid-2-Octyl Nitrite, α-chloro-acrylicacid isodecyl ester, α-chloro-acrylicacid cetyl, alpha-chloro third Olefin(e) acid stearyl ester, α-chloro-acrylicacid behenyl ester, α-chloro-acrylicacid lauryl, alpha-chloro propylene Acid cyclohexyl etc..Monomer (c) can be to have alkyl and do not have the polymerizable monomer of Rf base Two or more.
In polymer (A), when the polymerized unit containing monomer (b) or monomer (c), excellent The weight of the polymerized unit of the polymerized unit of menu body (a)/(monomer (b)+monomer (c)) Ratio is more than 1.
Polymer (A) is preferably and contains as required except polymerizable monomer (a), (b), (c) Polymerizable monomer (x) in addition (such as, is combined with on the carbon atom forming unsaturated double-bond (y) of chlorine atom or there is the polymerizable monomer (z) of reactive group) polymerized unit, And the polymerized unit of polymerizable monomer (a) and polymerizable monomer (b) and polymerizable monomer (c) Polymerized unit add up to relative to the addition polymers that polymer is more than 70 weight %.
Relative to polymer, in polymer (A), the ratio of the polymerized unit of monomer (a) is 50 More than weight %, the most preferably 50～90 weight %, particularly preferably 60～80 weight %. Relative to polymer, in polymer (A), the ratio of the polymerized unit of monomer (b) is 50 weight % Hereinafter, the most preferably 1～40 weight %, particularly preferably 3～30 weight %.Relative to poly- Compound, in polymer (A), the ratio of the polymerized unit of monomer (c) is below 50 weight %, Such as it is preferably 0～40 weight %, more preferably 0～30 weight %, particularly preferably 1～10 Weight %.
Relative to polymer (A), the polymerized unit of monomer (a), the polymerization list of monomer (b) Unit, the polymerized unit of monomer (c) and monomer (x) polymerized unit add up to 90 weight % Above, the most preferably 95～100 weight %.
Relative to polymer (A), the ratio of the polymerized unit of monomer (x) be 70 weight % with Under, the most preferably 0～40 weight %, particularly preferably 1～30 weight %.
Monomer (x), particularly monomer (y) can be free from the compound of fluorine atom.As list Body (x), can be the co-polymerized monomer with phenyl ring.Now, preferably there is (methyl) of phenyl ring Acrylate.Phenyl ring can have substituent group (such as, carbon number be 1～10 alkyl or Alkoxyl or halogen atom).As there is (methyl) esters of acrylic acid of phenyl ring, preferably (methyl) Phenyl acrylate, (methyl) benzyl acrylate, or be combined with on their phenyl ring methyl, The compound of methoxyl group, chlorine atom etc..
Furthermore it is also possible to be ethylene, phenylethylene etc..
As the list being combined with halogen atom in monomer (x) on the carbon atom forming unsaturated double-bond Body (y), exists on the carbon atom constituting main chain directly in conjunction with the repetitive having halogen atom. Such repetitive can be derived from the carbon atom forming carbon-to-carbon double bond former directly in conjunction with there being halogen The monomer (being referred to as " there is the backbone monomers of halogen atom " in this specification) of son.The example of halogen atom Son is fluorine, chlorine, bromine and iodine.
As the example of the backbone monomers (i.e. monomer (y)) with halogen atom, chlorine can be enumerated The vinylidene halides such as the ethylene halide such as ethylene and fluorothene, vinylidene chloride or vinylidene fluoride, CTFE, there is alpha-chloro (methyl) acrylate etc. of alkyl.Due to have the α of alkyl- Chloro (methyl) esters of acrylic acid is included in monomer (c), is therefore not belonging to monomer (y).Make For monomer (y), preferably vinyl chloride, vinylidene chloride.The backbone monomers with halogen atom is permissible It is one or more kinds of combinations.
Relative to polymer (A), the amount of the polymerized unit of monomer (y) is below 40 weight %, Such as it is preferably 0～30 weight %, particularly preferably 1～25 weight %.
As having the polymerizable monomer (z) of reactive group, ethyoxyl, halogen can be contained former Son, hydroxyl, amide groups, amino, imino group, alkoxysilyl, N-methylol, N- Alkoxyalkyl, blocked NCO etc. polymerism unsaturated bond beyond reactivity Group.As the polymerizable monomer (z) containing reactive group, for example, it is preferable to (methyl) propylene Acid-3-chlorine-2-hydroxyl propyl ester, (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylamide, N- Methylol (methyl) acrylamide, diacetone (methyl) acrylamide, N, N-dimethyl (methyl) third Acrylamide, N, N-diethyl (methyl) acrylamide, N, N-diisopropyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, γ-trimethoxy-silylpropyl (methyl) acrylic acid Ester, (+)-2,3-Epoxy-1-propanol (methyl) acrylate etc..
As (methyl) acrylate containing hydroxyl, for example, it is preferable to (methyl) acrylic acid-2-hydroxyl Ethyl ester, (methyl) 2-hydroxypropyl acrylate, list (methyl) acrylic acid binaryglycol ester, poly-the third two Alcohol list (methyl) acrylate, poly-(ethylene glycol/propylene glycol) single (methyl) acrylate, list (methyl) Glycerol acrylate, trimethylolpropane list (methyl) acrylate etc..
As having the co-polymerized monomer of blocked NCO, preferably make containing hydroxyl (methyl) acrylate reacts with the ratio at least remaining a NCO with polyisocyanates And the block compound of the reaction product obtained, make (methyl) acrylate containing hydroxyl and have At least one blocked NCO and the polyisocyanic acid of at least one cyanic acid ester group freely The reaction product etc. that ester derivant reacts and obtains.
As polyisocyanates, hexamethylene diisocyanate, lysine two isocyanide can be enumerated The aliphatic polyisocyantes such as acid esters, or isophorone diisocyanate, 4,4 '-dicyclohexyl first The fat of alkane diisocyanate, cyclohexylene diisocyanate, two (isocyanatomethyl) hexamethylene etc. Ring race polyisocyanates, and their uric acid modifier, prepolymer modifier, biuret change Property thing etc., preferred fat (cyclo) aliphatic diisocyanates or alicyclic diisocyanate.
As for obtaining the block agent of blocked NCO, can enumerate oximes, Alkyl ketone oximes, phenols, beta-diketon class, malonic acid esters, lactams, alkanols etc.. The object lesson of block agent can enumerate hexamethylene oxime, methyl ethyl ketoxime, phenol, cresol, acetyl Acetone, diethyl malonate, isopropanol, the tert-butyl alcohol, 'epsilon '-hexanolactam, maleimide, Asia Sodium bisulfate etc., preferably hexamethylene oxime, methyl ethyl ketoxime etc..
Relative to polymer (A), in polymer (A), the amount of the polymerized unit of monomer (z) is Below 10 weight %, the most preferably 0.1～8 weight %.
Relative to the monomer (x) beyond polymer (A), demonomerization (y) and monomer (z) The amount of polymerized unit is below 30 weight %, the most preferably 0～10 weight %.
As obtaining the polymerization of polymer (A), utilizing emulsion polymerization method or dispersin polymerization When method is polymerized, can be illustrated in the presence of emulsifying agent and polymerisation medium, to above-mentioned polymerization Property monomer add polymerization initiator and the method that carries out being polymerized.It is not particularly limited as emulsifying agent, Known or the known breast of nonionic, cationic, anionic, amphoteric can be used More than one of agent.Relative to 100 weight parts of polymer monomers, the amount of emulsifying agent is preferably 0.5～20 weight portions, from the viewpoint of the stability of water-repellent oil-repellent and dispersion liquid, the most excellent Select about 1～10 weight portions.
Polymerisation medium is the medium containing water, it is also possible to according to expectation containing organic solvent.As Organic solvent, the most water miscible organic solvent, preferably esters, ketone, ethers (alcohols) Deng organic solvent.As the organic solvent of esters, ethyl acetate, butyl acetate, amber Amber diethyl phthalate etc..As the organic solvent of ketone, preferably butanone, methyl iso-butyl ketone (MIBK), Acetone etc..As the organic solvent of ethers (alcohols), preferably diglycol, a contracting two Propylene glycol, tripropylene glycol, triethylene glycol, ethylene glycol and their monomethyl ether or dimethyl ether, Diethyl ether etc..Wherein, as organic solvent, from viewpoints such as ignitability are low, preferably ethers The organic solvent of (alcohols).The ratio of water and organic solvent is not particularly limited, and can be to appoint Meaning ratio.Relative to 100 weight parts waters, the amount of organic solvent is below 100 weight portions, example As being 1～10 weight portions.Relative to 1 weight parts of polymer monomer, the amount of polymerisation medium It is 0.5～100 weight portions, for example, 1～20 weight portions.
As polymerization initiator, preferably water solublity or oil-soluble polymerization initiator, can basis Polymerization temperature use persulfuric acid salt, azo, peroxide, oxidoreduction class general Initiator.Polymerization temperature is not particularly limited, preferably 20 DEG C～150 DEG C.
It addition, in the polyreaction of the first polymer, for the purpose of controlling molecular weight, permissible Containing chain-transferring agent.As chain-transferring agent, thio-alcohol is preferably used.
As the last stage starting polymerization in polyreaction, it is possible to use homogenizer or high-pressure emulsification The mixture being made up of polymerizable monomer, water and emulsifying agent is processed by machines etc., or in advance Carry out front dispersion.
The polymer (A) (the first polymer) synthesized by said method, the most in media as well with micro- Granular state exists.The particle diameter of the microgranule of polymer (A) is preferably 0.001～1 μm, the most excellent Elect 0.01～0.5 μm as.If in such range, it is possible to obtain stable dispersion liquid, thus The amount of emulsifying agent can reduce, and water-repellent oil-repellent is high, polymer particles stable existence in media as well. During more than 0.5 μm, in the case of long-term preservation, can settle.This particle diameter can be in order to It is measured with dynamic light scattering device, ultramicroscope etc..Utilizing common emulsion polymerization Method, in the presence of emulsifying agent implement polymerization time, mean diameter be generally in above-mentioned preferably In the range of.
Polymer (B) is preferably the polymerized unit without polymerizable monomer (a) and contains poly- The polymerized unit of at least one of conjunction property monomer (c) and polymerizable monomer (y) adds up to 10 weight % Above, containing gathering in addition to single thing (y) in polymerizable monomer (b) or polymerizable monomer (x) Conjunction property monomer or there is the addition polymers of polymerized unit of polymerizable monomer (z) of reactive group.
Polymer (B) can also be free from the polymer of fluorine atom.
Monomer (a), (b), (c), (x), (y), (z) and polymer in polymer (B) (A) monomer (a) in, (b), (c), (x), (y), (z) same meaning.Polymer (B) In there is not monomer (a).
Monomer (b), (c), (x), (y), (z) and polymer (A) in polymer (B) In monomer (b), (c), (x), (y), (z) can be identical, it is also possible to different.It addition, Monomer (b), (c), (x), (y), (z) can use two or more respectively.
Polymer (B) exists at least one of monomer (c) or monomer (y).
In polymer (B), the amount of (relative to polymer) monomer (b) is below 90 weight %, Such as be preferably 5～80 weight %, more preferably 10～70 weight %, particularly preferably 30～ 65 weight %.The amount of monomer (c) is such as preferably 0～8 weight %, particularly preferably 0.5～5 Weight %.The amount of monomer (y) is more than 20 weight %, the most preferably 25～85 weight %, Particularly preferably 30～80 weight %.The total amount of monomer (c) and monomer (y) is 10 weight % Above, the most preferably 20～90 weight %, particularly preferably 30～80 weight %.Demonomerization Y the amount of () and monomer (z) monomer (x) outward is below 40 weight %, the most preferably 0～ 30 weight %, particularly preferably 0～20 weight %.The amount of monomer (z) is below 10 weight %, Such as it is preferably 0.1～8 weight %.
As obtaining the polymerization of polymer (B), with the side of polymerization obtaining polymer (A) Method is again it is preferred to emulsion polymerization, suspended polymerization etc., particularly preferred emulsion polymerization.Pass through emulsifying Polymerization etc., it is possible to be dispersed in the state of water solvent (also referred to as granule using polymer (B) Dispersion) obtain.
Emulsion polymerization is preferably used polymerization initiator to be carried out.As polymerization initiator, preferably peroxide Compound or azo compound, particularly preferred azo compound.As azo compound Example, be preferably set forth in polymer (A) explanation oil-soluble polymerization initiator, 2,2'-azo is double (2-methyl-prop amidine) hydrochlorate, 2,2'-azo double [2-(2-imidazoline-2-base) propane] hydrochlorate, 2,2'- The water-soluble polymerization initiator of double [2-(2-imidazoline-2-base) propane] sulfate hydrates of azo etc..
It addition, for the purpose of controlling the molecular weight of polymer (B) obtained, can be anti-in polymerization At once chain-transferring agent is added.As chain-transferring agent, row are preferably used in the explanation of polymer (A) The chain-transferring agent lifted.
Emulsifying agent can be there is in the dispersion of polymer (B), as emulsifying agent, preferred polymeric The nonionic emulsifier of explanation, cationic emulsifier, anionic emulsifier in thing (A) Or amphoteric emulsifier.
Emulsifying agent can use more than one or two kinds of.And during with ionic different emulsifying agent, Preferably nonionic emulsifier and the combination of cationic emulsifier or nonionic emulsifier and The combination of amphoteric emulsifier.It addition, relative to 100 parts by weight polymer (B), emulsifying agent Amount is preferably 1～20 weight portions.
The mean diameter of polymer (B) is 0.001～1 μm, particularly preferably 0.03～0.5 μm. When mean diameter is less than 0.03 μm, in order to obtain stable dispersion, need substantial amounts of emulsifying agent Or there is self emulsifiable polymerizable monomer, water-repellancy may be caused to reduce.It addition, more than 0.5 μm Time, granule may be caused to settle.
In the water extraction oil extracticn agent compositions of the present invention, polymer (A) and polymer (B) are not deposited In being same granule, form respective granule respectively.The water extraction oil extracticn agent compositions of the present invention, In order to obtain polymer (A) and polymer (B), the most each carry out polyreaction, Form respective granule, obtain dispersion, mix each dispersion afterwards and modulate.
In water extraction oil extracticn agent compositions, polymer (A) is preferred with the weight ratio of polymer (B) (A)/(B)=40/60～90/10, particularly preferred 50/50～80/20.Polymer (A) or When the ratio of polymer (B) is in above-mentioned scope, water-repellent oil-repellent is excellent, water-repellent oil-repellent Durability the most excellent.It addition, polymer concentration (the solid-state one-tenth in water extraction oil extracticn agent compositions Divide concentration) it is preferably 0.1～50 weight %.
Polymer (A) and polymer (B) can use two or more polymer respectively.
In order to make the article such as fibre show various physical property, can be as required in the present invention Water extraction oil extracticn agent compositions in coordinate polymer (A) or polymer (B) beyond other Polymer, dryingagent, oil extracticn agent, the catalyst of promotion crosslinking, regulation hand feeling agent, antistatic Agent, penetrant, insect-proof agent, fire retardant, wrinkle resistant anti-piping compound, dye stability, pH adjusting agent Deng.
The water extraction oil extracticn agent compositions of the present invention can be diluted to the denseest according to purpose and purposes Spend and be applicable to article.Drying processing method to article, can be according to the kind of article and group The modulation forms of compound etc. use arbitrary method.It is for instance possible to use by being impregnated or coated with Etc. coating processing method so that it is the surface being attached to article the method being dried.It addition, If need can use suitable cross-linking agent simultaneously, carry out heat treatment.
As the drying processing method to article, preferably article are immersed in containing polymer (A) With the method in the water extraction oil extracticn agent compositions of polymer (B).Contain it addition, article are immersed in After having polymer (B) not contain in the compositions of polymer (A), it is immersed in containing poly-again Compound (A) and without polymer (B) compositions in drying processing method also be able to obtain Equal effect, thus preferably.
The article processed are carried out as the water extraction oil extracticn agent compositions (inorganic agent) using the present invention (base material or processed article), are not particularly limited, in addition to fibre, it is also possible to Enumerate stone material, filter (such as electrostatic filter), dust cover, glass, paper, timber, skin Leather, fur, asbestos, brick, cement, metal and oxide, ceramic, plastics, coating Surface and plaster etc..Thing etc. compiled by preferably fiber, fabric, fiber.As fiber, permissible Enumerate the of animal or plant nature natural fibers such as cotton, fiber crops, Pilus Caprae seu Ovis, silk, polyamide, polyester, poly-second The synthetic fibers such as enol, polyacrylonitrile, polrvinyl chloride, polypropylene, staple fibre, acetas Deng semisynthetic fibre, the inorfil such as glass fibre, carbon fiber, or their composite fibre. The article using the water extraction oil extracticn agent compositions-treated of the present invention to cross have the water-repellancy of excellence, its Durability is the most excellent.
In the present invention, utilize inorganic agent that processed article are processed." process " and refer to lead to Cross impregnate, spray, inorganic agent is used for treated object by coating etc..By processing, as process The fluoropolymer of agent effective ingredient is impregnated with the inside of treated object and/or is attached to treated object Surface.
Embodiment
Below, represent embodiment and comparative example, the present invention is described in further detail.
Hereinafter, unless otherwise specified, % and part represent weight % and weight portion.
Characteristic operates as follows and is measured.
Water-repellent oil-repellent
When processing T/C cloth, dilute with water polymer dispersion liquid makes the solid component concentration be 30 weight %, dilute with water makes the concentration of 30 weight % dispersion liquids be 3.2%, modulation treatment liquid. By T/C cloth (twill, 200g/m2, be unstained cloth) it is immersed in treatment fluid, use mangle With 4kg/cm2, within 4m/ minute, squeeze, after carrying out 1 minute heat treatment with 170 DEG C, evaluation process The water-repellent oil-repellent of cloth.Equally, dilute with water makes the concentration of 30 weight % dispersion liquids be 4.8%, Modulation treatment liquid.When cotton is processed, by cotton (twill, 160g/m2, do not contaminate Painting cloth) it is immersed in treatment fluid, with mangle with 4kg/cm2, within 4m/ minute, squeeze, with 170 DEG C After carrying out 2 minutes heat treatments, evaluate the water-repellent oil-repellent for the treatment of cloth.Equally, dilute with water makes The concentration of 30 weight % dispersion liquids is 4.8%, modulation treatment liquid.When mylar is processed, Mylar (microfiber navy) is immersed in treatment fluid, with mangle with 4kg/cm2、 Within 4m/ minute, squeeze, after carrying out 2 minutes heat treatments with 170 DEG C, evaluate the water-repellent oil-repellent for the treatment of cloth Property.Water-repellancy is to utilize water-repellancy No. (with reference to the table 1 below) table of AATCC-21 nebulization Show.About dialling oiliness, according to AATCC-118, test cloth drips 3 table 2 below institutes The testing liquid shown, is impregnated with state after observing 30 seconds, will not show the institute of testing liquid of dipping The peak dialling oiliness paid is as dialling oiliness.During same levels, when water-repellent oil-repellent is higher With+represent, lower time with-represent.
[table 1]
[table 2] dials oiliness test liquid
The washing resistance of water-repellent oil-repellent
According to JIS L-0217-103 method, with the cleaning mixture of 40 DEG C wash 25 minutes (5 minutes × HL, continuous 5 times), it is dehydrated 3 minutes, rinses 2 minutes, be dehydrated 3 minutes, rinse 2 minutes, It is dehydrated 3 minutes, carries out cylinder dry, the water-repellent oil-repellent (HL-5) after evaluation.
Mean diameter
(big electronics corporation produces Fiber-Optics Particle to use laser type light scattering method Analyzer FPAR-1000), measure the mean diameter of discrete particles.
Hereinafter, n-butyl acrylate is designated as n-BA, N hydroxymethyl acrylamide is designated as N-MAM, is designated as T-M by methacrylic acid-3-chlorine-2-hydroxyl propyl ester, is remembered by dodecyl mercaptans For L-SH, n-BMA is designated as n-BMA, Tert-butyl Methacrylate is designated as T-BMA, is designated as StA by stearyl acrylate ester, lauryl acrylate is designated as LA, by chloroethene Alkene is designated as VCl, and by methacrylic acid-3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro monooctyl esters are designated as 13FMA, by acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-ten seven fluorine nonyl esters are designated as 17FA。
As emulsifying agent, two solidification tallow alkyl alkyl dimethyl ammonium chlorides are designated as C2ABT, by mountain Pears monoplamitate is designated as PP-40R, and polyethylene glycol lauryl ether is designated as K220, will be poly- Oxygen ethylene oleyl ether is designated as BO50.
It addition, tripropylene glycol is designated as TPG, by 2,2'-azo two (2-amidine propane) dihydrochloride It is designated as NC-32W.
Synthesis example 1
In the container of 500mL, as polymerizable monomer, add n-BA (63.11g), N-MAM (1.26g), T-M (0.63g), L-SH (0.9g), emulsifying agent C2ABT (0.91g) and PP-40R (1.22g), K220 (5.25g), BO50 (1.3g), water (103.4g), TPG (18.62g), Before carrying out with homogenizer after dispersion, using ultrasonic emulsification machine, cooling limit, limit processes 5 minutes, Obtain the emulsion of monomer mixture.
By this emulsion add possess cooling tube, nitrogen ingress pipe and thermometer 500mL can In separate type flask, after carrying out nitrogen displacement, water (4g) dissolves initiator NC-32W (0.38g) and add after, after being warming up to 60 DEG C, carry out 3 hours polymerization, obtain solid-state become Point 35.3%, the dispersion liquid (207.1g) of the non-fluorinated polymer granule of mean diameter 0.109 μm.
Synthesis example 2～16
According to the method identical with synthesis example 1, make the monomer mixture emulsifying shown in table 3, make During with VCl as monomer, using the autoclave of the stainless steel of 500mL, other situations then add Possesses the detachable flask of the 500mL of cooling tube, nitrogen ingress pipe and thermometer so that it is poly- Close, obtain various non-fluorinated polymer granule.
[table 3]
[table 4]
Synthesis example 5 Synthesis example 6 Synthesis example 7 Synthesis example 8
n-BA 13.27 13.27
n-BMA
t-BMA
LA 38.77
StA 39.02
VCl 24.4 24.6 49.6 49.8
N-MAM 1.27 1.26 1.26 1.26
T-M 0.63 0.63 0.64 0.63
L-SH 0.61 0.52 0.50 0.56
TPG 18.18 18.66 18.88 18.62
Pure water 104.45 103.15 103.92 105.9
C2ABT 0.99 1 0.96 0.21
PP40R 1.36 1.38 1.42 0.23
K220 6.07 5.89 5.91 0.89
BO50 1.46 1.5 1.45 0.26
NC-32W 0.76 0.76 0.76 0.76
Concentration after polymerization 36.9 36.9 34.2 35.2
Particle diameter (μm) after polymerization 0.113 0.115 0.199 0.284
Yield 189.6 192.1 184.5 187.94
[table 5]
Synthesis example 9 Synthesis example 10 Synthesis example 11 Synthesis example 12
13FMA 49.98 42.22 42.36
17FA 42.14
BA
StA 12.97 5.38 5.39 5.40
VCI 16.6 15.3 15.10
N-MAM 1.39 1.28 1.31 1.26
T-M 0.66 0.63 0.63 0.61
L-SH
TPG 18.62 18.68 18.54 18.30
Pure water 103.4 104.46 103.27 97.63
C2ABT 0.47 0.48 1.26 1.24
PP40R 0.63 0.69 1.07 1
K220 2.74 2.75 7.36 7.34
BO50 0.68 0.62 1.88 1.82
NC-32W 0.38 0.38 0.38 0.38
Concentration after polymerization 34.4 33.7 36.96 36.26
Particle diameter (μm) after polymerization 0.134 0.156 0.056 0.086
Yield 195.0 200.6 190.1 191.3
[table 6]
Embodiment 1～6, comparative example 1～6
The polymer particles dispersion obtained in dilute with water synthesis example 1～16, makes solid state component Concentration is 30 weight %, and dispersion liquid dilution obtained mixes with the mixing ratio shown in table 7～10, Obtain dispersion mixture.
[table 7]
[table 8]
[table 9]
[table 10]
Example Comparative example 6
Non-fluorine emulsion Synthesis example 1
Fluorine-containing latex Synthesis example 10
Non-fluorinated polymer/fluoropolymer 20.0/80.0
Fluorochemical monomer total content (weight %) 56.0
Test example 1～6
The polymer particles dispersion obtained in above-described embodiment 1～6 is evaluated water-repellent oil-repellent.
Evaluation result is as shown in table 11.
[table 11]
Comparative test example 1～6
The polymer particles dispersion obtained in above-mentioned comparative example 1～6 is evaluated water-repellent oil-repellent.
Evaluation result is as shown in table 12.
[table 12]
Comparative test example 7～10
The polymer particles dispersion obtained in above-mentioned synthesis example 13～16 is evaluated water-repellent oil-repellent Property.
Evaluation result is as shown in table 13.
[table 13]
Test example 7～8 and comparative test example 11～12
For the resin aqueous shown in table 14, table 15 being divided according to the method shown in test example 1 The various blanks that scattered liquid carries out processing and obtains, evaluate the washing resistance of water-repellent oil-repellent.
Evaluation result is as shown in table 14～15.

Claims (16)

1. a water-dispersion type water extraction oil extracticn agent compositions, it is characterised in that:
Containing water-medium, following polymer (A) and following polymer (B), wherein,
Polymer (A) is the polymer containing fluoro-alkyl,
Polymer (B) is the polymer on main chain containing halogen atom.
2. water-dispersion type water extraction oil extracticn agent compositions as claimed in claim 1, it is characterised in that:
Polymer (B) has the acrylate of alkyl, vinyl chloride containing what α position was optionally substituted by halogen Or at least one in vinylidene chloride is as polymerized unit.
3. water-dispersion type water extraction oil extracticn agent compositions as claimed in claim 2, it is characterised in that:
Polymer (B) has the acrylate of alkyl, vinyl chloride containing what α position was optionally substituted by halogen Polymerized unit 10～100 weight % with at least one in vinylidene chloride.
4. the water-dispersion type water extraction oil extracticn agent compositions as according to any one of claims 1 to 3, It is characterized in that:
Polymer (A) is the polymer of the polymerized unit containing the monomer being derived from containing fluoro-alkyl.
5. water-dispersion type water extraction oil extracticn agent compositions as claimed in claim 4, it is characterised in that:
Polymer (A) is polymerized unit 50～100 weight containing the monomer being derived from containing fluoro-alkyl The polymer of amount %.
6. the water-dispersion type water extraction oil extracticn agent compositions as according to any one of Claims 1 to 5, It is characterized in that:
Fluoro-alkyl is with formula CmF2m+1-(wherein, m is the integer of 2～20) or (CF3)2CF(CF2CF2)n-(wherein, n is the integer of 0～10) represents.
7. the water-dispersion type water extraction oil extracticn agent compositions as described in claim 5 or 6, its feature It is:
Monomer containing fluoro-alkyl is with general formula R f-Q1-X1Represent,
In formula, Rf represents fluoro-alkyl, Q1Represent the organic group of bivalence, X1Represent containing poly- The monovalent organic group of conjunction property unsaturated group.
8. the water-dispersion type water extraction oil extracticn agent compositions as described in claim 5 or 6, its feature It is:
Monomer containing fluoro-alkyl is formula CH2=C (-X)-C (=O)-Y-Z-Rf institute The compound shown,
In formula, X be hydrogen atom, carbon number be 1～21 straight-chain or the alkyl of branched, Fluorine atom, chlorine atom, bromine atoms, atomic iodine, CFX1X2Base (wherein, X1And X2It is hydrogen Atom, fluorine atom, chlorine atom, bromine atoms or atomic iodine), cyano group, carbon number be 1～21 Straight-chain or the fluoro-alkyl of branched, substituted or non-substituted benzyl, substituted or non-substituted Phenyl,
Y is-O-or-NH-,
Z be carbon number be 1～10 fatty group, carbon number be 6～18 aromatic series base Or annular aliphatic base ,-CH2CH2N(R1)SO2-base (wherein, R1Be carbon number be 1～ The alkyl of 4) ,-CH2CH(OZ1)CH2-base (wherein, Z1It is hydrogen atom or acetyl group), -(CH2)m-SO2-(CH2)n-base or-(CH2)m-S-(CH2)n(wherein, m is-base 1～10, n are 0～10),
Rf be carbon number be straight-chain or the fluoro-alkyl of branched of 1～21.
9. the water-dispersion type water extraction oil extracticn agent compositions as described in claim 5 or 6, its feature It is:
Polymer (A) is containing other monomer 10～50 weight in addition to the monomer containing fluoro-alkyl Amount %.
10. water-dispersion type water extraction oil extracticn agent compositions as claimed in claim 9, its feature exists In:
Other monomer is to mix containing the monomer of at least one in vinyl chloride or vinylidene chloride Thing.
The 11. water-dispersion type water extraction oil extracticn agent combinations as according to any one of claim 1～10 Thing, it is characterised in that:
The particle diameter of polymer (A) is 0.001～1 μm.
The 12. water-dispersion type water extraction oil extracticn agent combinations as according to any one of claim 1～10 Thing, it is characterised in that:
The particle diameter of polymer (B) is 0.001～1 μm.
The 13. water extraction oil extracticn agent compositionss as according to any one of claim 1～12, its feature It is:
Polymer (A) is the polymerized unit containing following polymerizable monomer (a) and following poly- The polymer of the polymerized unit of at least one in conjunction property monomer (b) or polymerizable monomer (c).
The 14. water extraction oil extracticn agent compositionss as according to any one of claim 1～12, its feature It is:
Polymer (B) is free from the polymerized unit of polymerizable monomer (a) and contains polymerism The polymer of at least one in monomer (y) and polymerizable monomer (c).
15. 1 kinds of water extraction oil extracticn agent compositionss utilized according to any one of claim 1～14 The method that base material is processed.
16. 1 kinds of process base materials obtained by the processing method described in claim 15.
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