CN107683317A - Surface treatment composition - Google Patents

Surface treatment composition Download PDF

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Publication number
CN107683317A
CN107683317A CN201680037178.0A CN201680037178A CN107683317A CN 107683317 A CN107683317 A CN 107683317A CN 201680037178 A CN201680037178 A CN 201680037178A CN 107683317 A CN107683317 A CN 107683317A
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carbon number
monomer
weight
surface treatment
water
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CN107683317B (en
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南晋
南晋一
福森正树
宫原正弘
井置正人
山本育男
榎本孝司
陈涛
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Daikin Industries Ltd
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    • 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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • 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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • 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
    • 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
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Combustion & Propulsion (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (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)

Abstract

The present invention provides a kind of surface treatment composition, and it contains：(I) there is the 1st fluoropolymer of the repeat unit from fluorochemical monomer (a) and the repeat unit from alkenyl halide (b)；(II) there is 2nd fluoropolymer of the repeat unit from fluorochemical monomer (a) without the repeat unit from alkenyl halide；(III) liquid medium.

Description

Surface treatment composition
Technical field
The present invention relates to a kind of inorganic agent, particularly water extraction oil extracticn agent composition containing fluoropolymer blends etc. Surface treatment composition.Specifically, the present invention relates to it is a kind of to fibre (such as carpet), paper, non-woven fabrics, stone material, Electrostatic filter, dust mask, fuel cell part for, have excellent water-repellancy, dial oiliness, soil resistance, particularly The excellent water extraction oil extracticn agent composition of high processing continuation in the continuous water-repellent oil-repellent processing of fiber.
Background technology
It is currently suggested various fluorochemicals.Fluorochemical has the characteristics such as heat resistance, oxidative resistance, against weather The advantages of excellent.Using the free energy of fluorochemical it is low, be difficult to the characteristic adhered to, fluorochemical is used as such as drying Oil extracticn agent and anti-fouling agent.
As the fluorochemical that may be used as water extraction oil extracticn agent, can enumerate with (methyl) propylene with fluoro-alkyl Acid esters is as the fluoropolymer for forming monomer.It is various by so far in surface conditioning agent in the practical processing of fiber Result of study is shown, as its surface characteristic, important is not quiet contact angle, but dynamic contact angle, particularly Receding Contact Angle.That is, the advancing contact angle of water is not rely on the side chain carbon number of fluoro-alkyl, but for water receding contact angle and Speech, compared with side chain carbon number is more than 8 situation, the situation that carbon number is less than 7 shows that the receding contact angle is notable Diminish.Correspondingly, X-ray analysis shows the crystallization that side chain is produced when side chain carbon number is more than 7.Known practical is dialled It is water-based that there is dependency relation with side chain crystallinity, and the motility of surface treatment agent molecule is to show the weight of practical performance Want reason (for example, preceding river Long Mao, FINE CHEMICAL (Off ァ イ Application ケ ミ カ Le), Vol23, No.6, P12 (1994)).Root According to above-mentioned reason, (methyl) acrylic ester of the short fluoro-alkyl for being less than 7 (particularly less than 6) with side chain carbon number Polymer is because side chain crystallinity is low, the problem of accordingly, there exist can not directly meet practical performance.In addition, add in water-repellent oil-repellent Continuous maching is generally carried out in work, from the aspect of draining, productivity ratio, seeks a kind of drying with high processing continuation and dials Finish.
Japanese Unexamined Patent Publication 2001-98257 publications disclose a kind of with comprising the polymerizable monomer with poly- fluoro-alkyl The polymer (A) of polymerized unit, the surfactant (B) with specific Draves wetting time and water-medium (C) are made For the composition of required composition.Japanese Unexamined Patent Publication 2004-262970 publications disclose it is a kind of containing fluorine system water extraction oil extracticn agent (A), The water extraction oil extracticn agent waterborne compositions of emulsion (B) and organic acid (C) containing paraffin and the polyethylene containing carboxyl.
In these patents, processing continuation is not described.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-98257 publications
Patent document 2：Japanese Unexamined Patent Publication 2004-262970 publications
The content of the invention
Invent problem to be solved
It is an object of the present invention to：There is provided a kind of processing continuation of the water-repellent oil-repellent processing of fiber etc. excellent table Face agent composition.
For solving the technical scheme of problem
The present invention relates to a kind of surface treatment composition, and it contains：
(I) the 1st with the repeat unit from fluorochemical monomer (a) and the repeat unit from alkenyl halide (b) is fluorine-containing Polymer；
(II) there is the repeat unit from fluorochemical monomer (a) without the 2nd of the repeat unit from alkenyl halide Fluoropolymer；With
(III) liquid medium.
Invention effect
The processing continuation of the water-repellent oil-repellent processing of the surface treatment composition of the present invention is excellent.
According to the present invention it is possible to obtain excellent water-repellancy, dial oiliness, soil resistance and decontamination, such as water-repellent oil-repellent Excellent durability.
The surface treatment composition of the present invention may be used as water extraction oil extracticn agent composition, antifoulant composition and/or take off Dirty agent composition.
Embodiment
(1) fluoropolymer
In the present invention, fluoropolymer is the combination of the 1st fluoropolymer and the 2nd fluoropolymer.
As form fluoropolymer repeat unit monomer, using fluorochemical monomer (a), alkenyl halide monomer (b) with And other monomers (c) beyond monomer (a) and (b).
In the present invention, the 1st fluoropolymer and the 2nd fluoropolymer are as water extraction oil extracticn agent, anti-fouling agent and soil release agent Active ingredient play a role.
(a) fluorochemical monomer
Fluorochemical monomer is usually to have perfluoroalkyl or perfluor and acrylic or methacrylic acid group or alpha-substituted The polymerizable compound of acrylic.
Fluorochemical monomer (a) for example can be formula：CH2Compound shown in=C (- X)-C (=O)-Y-Z-RF (I).
[in formula, X is hydrogen atom, the organic group or halogen atom of monovalence,
Y is-O- or-NH-,
Z is the organic group of Direct Bonding or divalence,
Rf is the fluoro-alkyl of carbon number 1~20.]
Fluorochemical monomer (a) is preferably formula：CH2Compound shown in=C (- X)-C (=O)-Y-Z-RF (I).
[in formula, X is hydrogen atom, the alkyl of the straight-chain of carbon number 1~21 or branched, fluorine atom, chlorine atom, bromine Atom, iodine atom, CFX1X2Base (wherein, X1And X2For hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom.), cyano group, The straight-chain of carbon number 1~21 or the fluoro-alkyl of branched, substituted or non-substituted benzyl, substituted or non-substituted benzene Base,
Y is-O- or-NH-,
Z is Direct Bonding；Or
Straight-chain or branched aliphatic group (particularly alkylidene), such as formula-(CH of carbon number 1~202)x- Group shown in (in formula, x is 1~10)；Or
The aromatic group or cyclic aliphatic group of carbon number 6~30；Or
Formula-R2(R1)N-SO2- or formula-R2(R1) shown in N-CO- group (in formula, R1For the alkyl of carbon number 1~10, R2Straight-chain alkyl-sub or branched alkylidene for carbon number 1~10.)；Or
Formula-CH2CH(OR3)CH2-(Ar-O)p- (in formula, R3The acyl group of expression hydrogen atom or carbon number 1~10 (such as first Acyl group or acetyl group etc.), Ar represents the arlydene as needed with substituent, and p represents 0 or 1.) shown in group；Or
Formula-CH2-Ar-(O)q- (in formula, Ar is according to the arlydene for needing to have substituent, and q is 0 or 1.) shown in base Group；Or
-(CH2)m-SO2-(CH2)n- base or-(CH2)m-S-(CH2)n(wherein, m is that 1~10, n is 0~10 to-base.),
Rf is the straight-chain of carbon number 1~20 or the fluoro-alkyl of branched.]
X representational concrete example is Cl, Br, I, F, CN, CF3, preferably Cl.Particularly it is the feelings of chlorine atom in α positions Under condition, the practical water-repellancy (particularly spraying water-repellancy) of surface treatment composition is excellent.
In fluorochemical monomer, Rf bases are preferably perfluoroalkyl.The carbon number of Rf bases is preferably 1~12, and for example, 1~6, Particularly preferably 4~6, more preferably 6.The example of Rf bases is-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)2、-C8F17Deng.
Z is preferably the aromatic group or ring-shaped fat of the aliphatic group of carbon number 1~10, carbon number 6~18 Race's group ,-CH2CH 2N(R1)SO2- base (wherein, R1For the alkyl of carbon number 1~4.)、-CH2CH(OZ1)CH2-(Ph-O)p- Base (wherein, Z1For hydrogen atom or acetyl group, Ph is phenylene, and p is 0 or 1.)、-(CH2)n(wherein, Ph is sub- benzene to-Ph-O- bases Base, n are 0~10.)、-(CH2)m-SO2-(CH2)n- base or-(CH2)m-S-(CH 2)n- base (wherein, m be 1~10, n be 0~ 10).Aliphatic group is preferably alkylidene (particularly carbon number is 1~4, such as 1 or 2).Aromatic group or ring-type fat Fat race group can be substituted or non-substituted.S bases or SO2Base directly can be bonded with Rf bases.
As the concrete example of fluorochemical monomer (a), such as following material can be illustrated, but be not limited to these 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 is the fluoro-alkyl of carbon number 1~20.]
(b) alkenyl halide monomer
Alkenyl halide monomer (alkenyl halide) does not preferably have fluorine atom.
Alkenyl halide is preferably the alkene of the carbon number 2~20 substituted by 1~10 chlorine atom, bromine atoms or iodine atom Hydrocarbon.Alkenyl halide is preferably the chloroalkene of carbon number 2~20, particularly preferably the carbon number with 1~5 chlorine atom 2~5 alkene.The preferable concrete example of alkenyl halide is vinyl halides, such as vinyl chloride, bromine ethene, iodoethylene；Inclined halogen second Alkene, such as vinylidene chloride, inclined bromine ethene, inclined iodoethylene.It is preferred that vinyl chloride and vinylidene chloride, particularly preferred vinyl chloride.
(c) other monomers
Monomer (a) and other monomers (c) beyond (b) are not preferably fluorine-containing.As other monomers (c), can enumerate：Non-fluorine Non-crosslinked property monomer (c1) and non-fluorine cross-linkable monomer (c2).
(c1) the non-crosslinked property monomer of non-fluorine
The non-crosslinked property monomer (c1) of non-fluorine is the monomer without fluorine atom.The non-crosslinked property monomer (c1) of non-fluorine is without crosslinking Property functional group.The non-crosslinked property monomer (c1) of non-fluorine is different from cross-linkable monomer (c2), is non-crosslinked property.The non-crosslinked property monomer of non-fluorine (c1) it is preferably the non-fluorine monomer with carbon-to-carbon double bond.The non-crosslinked property monomer (c1) of non-fluorine is preferably not fluorine-containing vinyl list Body.The non-crosslinked property monomer (c1) of non-fluorine is usually the compound with 1 carbon-to-carbon double bond.
The preferable non-crosslinked property monomer (c1) of non-fluorine is formula：CH2Compound shown in=CA-T.
[in formula, A is the halogen atom (such as chlorine atom, bromine atoms and iodine atom) beyond hydrogen atom, methyl or fluorine atom,
T is hydrogen atom, the alkyl of the chain of carbon number 1~30 or ring-type or chain or the carbon of ring-type with ester bond The organic group of atomicity 1~31.]
The example of the chain of carbon number 1~30 or the alkyl of ring-type is the fat of the straight or branched of carbon number 1~30 Fat race alkyl, the cyclic aliphatic group of carbon number 4~30, the aromatic hydrocarbyl of carbon number 6~30, carbon number 7~ 30 aromatic-aliphatic alkyl.
The example of the organic group of the carbon number 1~31 of chain or ring-type with ester bond is-C (=O)-O-Q and-O- C (=O)-Q is (here, Q is aliphatic alkyl, the ring-type fat of carbon number 4~30 of the straight or branched of carbon number 1~30 Fat race group, the aromatic hydrocarbyl of carbon number 6~30, the aromatic-aliphatic alkyl of carbon number 7~30).
The preferable example of the non-crosslinked property monomer (c1) of non-fluorine includes such as ethene, vinyl acetate, acrylonitrile, benzene second Alkene, polyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylic acid Ester, methoxyl group polypropylene glycol (methyl) acrylate and vinyl alkyl ethers.The non-crosslinked property monomer (c1) of non-fluorine is not limited to These examples.
The non-crosslinked property monomer (c1) of non-fluorine can be (methyl) acrylate with alkyl.The carbon number of alkyl can be with For 1~30, for example, 6~30 (such as 10~30).For example, the non-crosslinked property monomer (c1) of non-fluorine can be formula：CH2= CA1COOA2Shown acrylate.
[in formula, A1For the halogen atom beyond hydrogen atom, methyl or fluorine atom, (such as chlorine atom, bromine atoms and iodine are former Son),
A2For CnH2n+1Alkyl shown in (n=1~30).]
A2Preferable concrete example for lauryl, stearyl, Shan Yu bases.
The non-crosslinked property monomer (c1) of non-fluorine can be (methyl) acrylate monomer with cyclic hydrocarbon group.
Acrylate monomer containing cyclic hydrocarbon group is preferably formula：CH2=CA21- C (=O)-O-A22Shown compound.
[in formula, A21For hydrogen atom or methyl,
A22For the group containing cyclic hydrocarbon of carbon number 4~30.]
Acrylate monomer containing cyclic hydrocarbon group for its homopolymer glass transition temperature high (such as more than 50 DEG C, spy Be not more than 80 DEG C) monomer.
Acrylate monomer containing cyclic hydrocarbon group does not have fluoro-alkyl.Acrylate monomer containing cyclic hydrocarbon group can also Containing fluorine atom, but be preferably free of fluorine atom.
A21Particularly preferably methyl.
A22For that can have the cyclic hydrocarbon group of chain-like groups (such as alkyl of straight-chain or branched).As cyclic hydrocarbon Base, it can enumerate：Saturation or undersaturated monocyclic base, more ring groups, bridged ring base etc..Cyclic hydrocarbon group is preferably saturation.Cyclic hydrocarbon group Carbon number be 4~30, preferably 6~20.As cyclic hydrocarbon group, can enumerate：Carbon number 4~20, particularly 5~12 Cyclic aliphatic group, aromatic group, the aromatic-aliphatic group of carbon number 7~20 of carbon number 6~20.Ring-type The carbon number of alkyl is particularly preferably less than 15, such as less than 12.Cyclic hydrocarbon group is preferably the cyclic aliphatic group of saturation. The concrete example of cyclic hydrocarbon group is cyclohexyl, tert-butylcyclohexyl, isobornyl, Bicvclopentyl, double cyclopentenyl, adamantyl.
As the concrete example of the acrylate monomer containing cyclic hydrocarbon group, can enumerate：(methyl) cyclohexyl acrylate, (first Base) t-butylcyclohexyl ester, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid is bicyclic Pentyl ester, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) acrylic acid Bicvclopentyl epoxide ethyl ester, the ring penta of (methyl) acrylic acid three Ester, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid -2- methyl -2- adamantane esters, (methyl) acrylic acid -2- second Base -2- adamantane esters etc..
By the acrylate monomer containing cyclic hydrocarbon group be present, water-repellancy and group oiliness that copolymer is provided uprise.
(c2) non-fluorine cross-linkable monomer
The fluoropolymer of the present invention can have the repeat unit from non-fluorine cross-linkable monomer (c2).Non-fluorine bridging property Monomer (c2) is the monomer without fluorine atom.Non-fluorine cross-linkable monomer (c2) can be with least two reactive group and/or Carbon-to-carbon double bond and not fluorine-containing compound.Non-fluorine cross-linkable monomer (c2) can be the chemical combination with least two carbon-to-carbon double bond Thing or the compound with least one carbon-to-carbon double bond and at least one reactive group.The example of reactive group is hydroxyl Base, epoxy radicals, chloromethyl, blocked isocyanate base, amino, carboxyl etc..Non-fluorine cross-linkable monomer (c2) can be with reaction Property list (methyl) acrylate of group, two (methyl) acrylate or single (methyl) acrylamide.Or non-fluorine bridging property list Body (c2) can be two (methyl) acrylate.
As non-fluorine cross-linkable monomer (c2), such as can illustrate：Two acetone (methyl) acrylamide, (methyl) acryloyl Amine, N- methylols (methyl) acrylamide, (methyl) dihydroxypropyl methyl esters, (methyl) Hydroxyethyl Acrylate, the chloro- 2- hydroxyls of 3- Base propyl group (methyl) acrylate, 2- acetoacetoxyethyls (methyl) acrylate, butadiene, isoprene, neoprene two Alkene, (methyl) glycidyl acrylate, 1,6-HD two (methyl) acrylate, neopentyl glycol two (methyl) acrylate Deng.
By being copolymerized the non-crosslinked property monomer (c1) of non-fluorine and/or non-fluorine cross-linkable monomer (c2), can change as needed Kind water-repellent oil-repellent, the resistance to spatter property of soil resistance and these performances, washing fastness, dissolubility in a solvent, hardness, sense of touch Etc. various properties.
In this manual, it is not only that hydrogen is former comprising α positions in the case of referred to as " acrylate " or " acrylamide " The compound of son, is also taken comprising α positions by other groups (such as organic group or halogen atom comprising the monovalence including methyl) The compound in generation.In this manual, " (methyl) acrylate " refers to acrylate or methacrylate, " (methyl) third Acrylamide " refers to acrylamide or Methacrylamide.
Monomer (a), monomer (b), monomer (c) (such as monomer (c1) and (c2) are each) can be used alone respectively, or It can also be combination of more than two kinds.
The amount of each monomer in 1st fluoropolymer is as described below.
In the 1st fluoropolymer, the amount of fluorochemical monomer (a) can be 20 weight %~100 relative to fluoropolymer The weight % of weight %, preferably 30 weight %~90.
In the 1st fluoropolymer, relative to the parts by weight of fluorochemical monomer (a) 100, the amount of alkenyl halide monomer (b) for 5~ 300 parts by weight, for example, 10~200 parts by weight, specifically for 20~100 parts by weight, specifically for 30~80 parts by weight, other monomers (c) amount can be 0~800 parts by weight, for example, 1~300 parts by weight, specifically for 2~200 parts by weight, specifically for 3~100 Parts by weight.
In the 1st fluoropolymer, relative to the parts by weight of fluorochemical monomer (a) 100, the amount of the non-crosslinked property monomer (c1) of non-fluorine Can be 0~500 parts by weight, for example, 1~300 parts by weight, specifically for 2~200 parts by weight, specifically for 3~100 parts by weight, The amount of non-fluorine cross-linkable monomer (c2) can be 0~80 parts by weight, for example, 0~50 parts by weight, specifically for 0.1~30 weight Part, specifically for 1~20 parts by weight.
The amount of each monomer in 2nd fluoropolymer is as described below.
In the 2nd fluoropolymer, the amount of fluorochemical monomer (a) can be 20 weight %~100 relative to fluoropolymer The weight % of weight %, preferably 30 weight %~90.
2nd fluoropolymer does not have the repeat unit from alkenyl halide.
In the 2nd fluoropolymer, relative to the parts by weight of monomer (a) 100, the amount of other monomers (c) can be 0~800 Parts by weight, for example, 1~300 parts by weight, specifically for 2~200 parts by weight, specifically for 3~100 parts by weight.
In the 2nd fluoropolymer, relative to the parts by weight of fluorochemical monomer (a) 100, the amount of the non-crosslinked property monomer (c1) of non-fluorine Can be 0~500 parts by weight, for example, 1~300 parts by weight, specifically for 2~200 parts by weight, specifically for 3~100 parts by weight. The amount of non-fluorine cross-linkable monomer (c2) can be 0~80 parts by weight, for example, 0~50 parts by weight, specifically for 0.1~30 weight Part, specifically for 1~20 parts by weight.
Fluorochemical monomer (a) and other monomers (c) in 1st fluoropolymer and the 2nd fluoropolymer can be identical respectively It is or different.
In surface treatment composition, the weight ratio of the 1st fluoropolymer and the 2nd fluoropolymer can be 5 ﹕ 95~ 95 ﹕ 5, for example, 20 ﹕ 80~20 ﹕ 80.
In the mixture of the 1st fluoropolymer and the 2nd fluoropolymer, the molecule and the 2nd of usual 1st fluoropolymer The molecule of fluoropolymer is not chemically bonded.
(2) surfactant
In the inorganic agent of the present invention, surfactant includes nonionic surfactant and cationic surface's activity One of agent or both.And then surfactant can also contain amphoteric surfactant.Surfactant preferably without it is cloudy from Sub- property surfactant.
(2-1) nonionic surfactant
Nonionic surfactant is the nonionic surfactant with oxyalkylene.Alkylene in oxyalkylene The carbon number of base is preferably 2~10.Oxyalkylene quantity in the molecule of nonionic surfactant is preferably generally 2~ 100。
Nonionic surfactant can be aliphatic (saturation and/or unsaturation) base of straight-chain and/or branched Group alkylene oxide adducts, straight-chain and/or branched aliphatic acid (saturation and/or unsaturation) PAG ester, Polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (random copolymer or block copolymer), the epoxyalkane of acetylenediol Addition product etc..Wherein, preferably the structure of epoxyalkane addition part and polyalkylene glycol moiety is polyoxyethylene (POE) or gathered Oxypropylene (POP) or POE/POP copolymers (can be random copolymer, or block copolymer).
In addition, nonionic surfactant from environmentally the problem of (biological degradability, environmental hormone etc.) consider, preferably Structure without aromatic group.
Nonionic surfactant can be formula：R1O-(CH2CH2O)p-(R2O)q-R3Shown compound.
[in formula, R1The alkenyl or acyl group of alkyl or carbon number 2~22 for carbon number 1~22, R2For carbon number 3 The alkylidene of (such as 3~10) above, R3For the alkenyl of hydrogen atom, the alkyl of carbon number 1~22 or carbon number 2~22, p For more than 2 number, q is 0 or more than 1 number.]
R1Preferably carbon number 8~20, particularly preferably 10~18.As R1Preferable concrete example, can enumerate： Lauryl, tridecyl, oil base.
R2Example for propylidene, butylidene.
In nonionic surfactant, p can be more than 3 number (such as 5~200).Q can be more than 2 number (such as 5~200).That is ,-(R2O)q- polyoxy alkylidene chain can be formed.
Nonionic surfactant can be to contain hydrophilic polyoxyethylene chain and hydrophobic oxygen alkylene in center The polyoxyethylene alkylidene alkyl ether of base chain (particularly polyoxy alkylidene chain).As hydrophobic oxyalkylene chain, Ke Yiju Go out：Oxypropylene chain, oxygen butylene chain, oxygen styrene chain etc., wherein, preferred oxypropylene chain.
Preferable nonionic surfactant is formula：R1O-(CH2CH2O)pSurfactant shown in-H.
[in formula, R1With p and above-mentioned R1It is identical with p meanings.]
The concrete example of nonionic surfactant is
C10H21O-(CH2CH2O)p-(C3H6O)q-H
C12H25O-(CH2CH2O)p-(C3H6O)q-H
C16H31O-(CH2CH2O)p-(C3H6O)q-H
C16H33O-(CH2CH2O)p-(C3H6O)q-H
C18H35O-(CH2CH2O)p-(C3H6O)q-H
C18H37O-(CH2CH2O)p-(C3H6O)q-H
C12H25O-(CH2CH2O)p-(C3H6O)q-C12H25
C16H31O-(CH2CH2O)p-(C3H6O)q-C16H31
C16H33O-(CH2CH2O)p-(C3H6O)q-C12H25
iso-C13H27O-(CH2CH2O)p-(C3H6O)q-H
C10H21COO-(CH2CH2O)p-(C3H6O)q-H
C16H33COO-(CH2CH2O)p-(C3H6O)q-C12H25。
[in formula, p and q are identical with above-mentioned p and q meanings.]
The concrete example of nonionic surfactant can include oxirane and hexylphenol, isooctyl phenol, 16 Alcohol, oleic acid, alkane (C12-C16) mercaptan, sorbitan mono fatty acid (C7-C19) or alkyl (C12-C18) amine etc. condensation generation Thing.
The ratio of polyoxyethylene segment relative to nonionic surfactant (copolymer) molecular weight, can be 5~ 80 weight %, for example, 30~75 weight %, specifically for 40~70 weight %.
The mean molecule quantity of nonionic surfactant is usually 300~5,000, for example, 500~3, and 000.
Nonionic surfactant can be used alone or two or more kinds may be used.
Nonionic surfactant is preferably combination of more than two kinds.In combination of more than two kinds, at least one kind of nonionic Property surfactant can be R1Base (and/or R3Base) for side chain alkyl (such as isotridecyl) R1O-(CH2CH2O)p- (R2O)q-R3[particularly R1O-(CH2CH2O)p- H] shown in compound.R1Base is the nonionic surfactant of the alkyl of side chain The amount of agent adds up to 100 parts by weight relative to nonionic surfactant (B2), can be 5~100 parts by weight, for example, 8~ 50 parts by weight, specifically for 10~40 parts by weight.In combination of more than two kinds, remaining nonionic surfactant can be R1Base (and/or R3Base) for (saturation and/or undersaturated) straight chain alkyl (such as lauryl (positive lauryl)) R1O- (CH2CH2O)p-(R2O)q-R3[particularly R1O-(CH2CH2O)p- H] shown in compound.
As nonionic surfactant, such as can enumerate：Polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl Ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene mountain Pears sugar alcohol fatty acid ester, fatty acid glyceride, polyglyceryl fatty acid ester, polyglyceryl fatty acid ester, sucrose fatty ester, Polyoxyethylene alkyl amine, polyoxyethylene fatty acid acid amides, fatty acid alkyl alcohol amide, alkylalkanol acid amides, acetylenediol, acetylene The oxygen Addition on ethylene thing of glycol, polyethylene glycol polyethylene glycol block copolymer etc..
Due to the dynamic surface tension step-down (that is, water-based emulsion easily infiltrates into base material) of water serial emulsion, therefore, as it is non-from The oxygen ethene of sub- property surfactant, preferably acetylene alcohol (particularly acetylenediol) or acetylene alcohol (particularly acetylenediol) adds Into thing.
Preferable nonionic surfactant is that the alkylene oxide adducts of alcohol or the alcohol with unsaturated three keys (will Both the alcohol and the alkylene oxide adducts are referred to as " acetylene alcoholic compound ".).Particularly preferred nonionic surfactant is With the unsaturated monohydric alcohol of three keys or the alkylene oxide adducts of polyalcohol.
Acetylene alcoholic compound is the compound containing more than 1 three keys and more than 1 hydroxyl.Acetylene alcoholic compound can be Compound containing polyoxyalkylene moieties.As the example of polyoxyalkylene moieties, can enumerate：Polyoxyethylene, polyoxy third Alkene, the random addition structure of polyoxyethylene and polyoxypropylene, the block addition structure of polyoxyethylene and polyoxypropylene.
Acetylene alcoholic compound is formula：
HO-CR11R12-C≡C-CR13R14- OH or
HO-CR15R16Compound shown in-C ≡ C-H.
[in formula, R11、R12、R13、R14、R15、R16Respectively can be with identical, can also be different, it is hydrogen atom or carbon number 1 ~30 alkyl.]
Acetylene alcoholic compound can be the alkylene oxide adducts of the compound shown in the chemical formula.The preferred carbon atom of alkyl The straight-chain of number 1~12 or the alkyl of branched, the straight-chain of particularly preferred carbon number 6~12 or the alkyl of branched.Example It can such as enumerate：Methyl, ethyl, propyl group, butyl, isobutyl group etc..In addition, as epoxyalkane, optimization ethylene oxide, epoxy third The epoxyalkane of the carbon numbers such as alkane 1~20 (particularly 2~5), the preferably adduct number of epoxyalkane is 1~50.
(2-2) cationic surfactant
Cationic surfactant is preferably the compound without amide groups.
Cationic surfactant can be amine salt, quaternary ammonium salt, oxygen Addition on ethylene type ammonium salt.As cationic surface The concrete example of activating agent is not particularly limited, and can enumerate：Alkylamine salt, amino alcohol fatty acid derivatives, polyamine aliphatic acid spread out Amine salt cationic surfactant, alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, the alkyl dimethyl benzyl of biology, imidazoline etc. Quaternary ammonium salt cationic surfactants such as base ammonium salt, pyridiniujm, alkyl isoquinolinium salt, benzethonium chloride etc..
The preferable example of cationic surfactant is R21-N+(-R22)(-R23)(-R24)X-Compound.
[in formula, R21、R22、R23And R24For the alkyl of carbon number 1~30,
X is anionic property group.]
R21、R22、R23And R24Concrete example be alkyl (such as methyl, butyl, stearyl, palmityl).X concrete example is Halogen (such as chlorine), sour (such as hydrochloric acid, acetic acid).
Cationic surfactant is particularly preferably monoalkyltrimethyl ammonium salts (carbon number 4~30 of alkyl).
Cationic surfactant is preferably ammonium salt.Cationic surfactant can be formula：R1 p-N+R2 qX-It is shown Ammonium salt.
[in formula, R1For more than C12 (such as C12~C50) straight-chain and/or branched aliphatic (saturation and/or not Saturation) group,
R2For H or the alkyl of C1~4, benzyl, polyoxyethylene groups, (quantity of oxyethylene group is, for example, 1 (specifically for 2, especially For 3)~50)
(particularly preferred CH3、C2H5),
X is halogen atom (such as, fluorine atom, chlorine atom, bromine atoms, iodine atom etc.), C1~C4Aliphatic acid alkali,
P is 1 or 2, q are 2 or 3, p+q=4.]
R1Carbon number can be 12~50, for example, 12~30.
The concrete example of cationic surfactant includes trimethyl ammonium acetate, trimethyl tetradecyl base chlorination Ammonium, cetyl trimethylammonium bromide, trimethyloctadecyl ammonium chloride, (dodecyl methyl benzyl) trimethyl ammonium chloride, Benzododecinium ammonium chloride, methyl dodecyl two (hydrogen polyoxyethylene) ammonium chloride, (hydrogen gathers benzyl dodecyl two Oxygen ethene) ammonium chloride, N- [2- (diethylamino) ethyl] oleoyl amine hydrochlorate.
As amphoteric surfactant, can enumerate：Alanine class, imidazolinium betaine class, amide betaine class, second Sour glycine betaine etc., specifically, it can enumerate：Lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl miaow Oxazoline glycine betaine, lauryl dimethyl oxyneurine, fatty acid amide propyl dimethylaminoethyl acid glycine betaine etc..
Nonionic surfactant, cationic surfactant and amphoteric surfactant can be respectively a kind or 2 Combination above.
As surfactant, nonionic surfactant can be used only or using only cationic surface's activity Agent, but preferably using the combination of nonionic surfactant and cationic surfactant.In nonionic surfactant In agent and the combination of cationic surfactant, the weight ratio of nonionic surfactant and cationic surfactant More preferably can be the ﹕ 60 of 80 ﹕ 20~40 it is preferred that can be the ﹕ 80 of 85 ﹕ 15~20.
The total amount of surfactant can be 0.1~20 parts by weight relative to the parts by weight of polymer 100, for example, 0.2 ~10 parts by weight.
(3) liquid medium
Surface treatment composition is preferably polymer is dispersed in dispersion obtained from liquid medium.
Liquid medium can be organic solvent, but preferably aqueous medium.In this manual, " aqueous medium " refers to only The medium that is made up of water and in addition to water also containing organic solvent (being usually water-miscible organic solvent) (amount of organic solvent It is for example, 0.1~50 parts by weight, specifically for 5~30 parts by weight below 80 parts by weight relative to the parts by weight of water 100.) Jie Matter.
The amount of aqueous medium can be 20~99 weight %, such as 40~95 weights relative to surface treatment composition Measure %.
(4) other compositions
Surface treatment composition can also contain non-fluorine water-repellancy compound as fluoropolymer and surfactant Other compositions in addition.
Non-fluorine water-repellancy compound
Surface treatment composition is sometimes with the water-repellancy compound (non-fluorine water-repellancy compound) without fluorine atom.
Non-fluorine water-repellancy compound can be non-fluorine acrylate polymer, saturation or undersaturated hydrocarbon compound or silicon Ketone based compound.
Non- fluoroacrylate polymer is the homopolymer that is made up of a kind of non-fluoroacrylate monomers or by least two kinds of non- Fluoroacrylate monomers form copolymer or by least one kind of non-fluoroacrylate monomers and at least one kind of other non-fluorine lists The copolymer that body (alefinically unsaturated compounds, such as ethene, vinyl monomer) is formed.
The non-fluoroacrylate monomers for forming non-fluoroacrylate polymer are formula：CH2Compound shown in=CA-T.
[in formula, A is that (such as chlorine atom, bromine atoms and iodine are former for halogen atom beyond hydrogen atom, methyl or fluorine atom Son),
T is hydrogen atom, the alkyl of the chain of carbon number 1~30 or ring-type or chain or the carbon of ring-type with ester bond The organic group of atomicity 1~31.]
The example of the chain of carbon number 1~30 or the alkyl of ring-type is the fat of the straight or branched of carbon number 1~30 Fat race alkyl, the cyclic aliphatic group of carbon number 4~30, the aromatic hydrocarbyl of carbon number 6~30, carbon number 7~ 30 aromatic-aliphatic alkyl.
The example of the organic group of the carbon number 1~31 of chain or ring-type with ester bond is-C (=O)-O-Q and-O- C (=O)-Q is (here, Q is aliphatic alkyl, the ring-type fat of carbon number 4~30 of the straight or branched of carbon number 1~30 Fat race group, the aromatic hydrocarbyl of carbon number 6~30, the aromatic-aliphatic alkyl of carbon number 7~30).
The example of non-fluoroacrylate monomers includes such as (methyl) alkyl acrylate, polyethylene glycol (methyl) acrylic acid Ester, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) third Olefin(e) acid ester.
Non- fluoroacrylate monomers are preferably (methyl) alkyl acrylate.The carbon number of alkyl can be 1~30, example Such as can be 6~30 (such as 10~30).The concrete example of non-fluoroacrylate monomers is (methyl) lauryl acrylate, (methyl) Stearyl acrylate ester and (methyl) acrylic acid Shan Yu esters.
Non- fluoroacrylate polymer can be manufactured by the polymerization same with fluoropolymer.
Saturation or undersaturated hydrocarbon system compound are preferably the hydrocarbon of saturation.In saturation or undersaturated hydrocarbon system compound, Carbon number can be more than 15, preferably 20~300, for example, 25~100.The tool of saturation or undersaturated hydrocarbon system compound Style is paraffin etc..
Silicone compound generally may be used as dryingagent.As long as silicone compound for show water-repellancy compound just Do not limit.
The amount of non-fluorine water-repellancy compound relative to the 1st fluoropolymer and the 2nd fluoropolymer total 100 weight Part, can be 0~500 parts by weight, for example, 5~200 parts by weight, specifically for 5~100 parts by weight.
Fluoropolymer (the 1st fluorochemical monomer and the 2nd fluorochemical monomer) in the present invention can pass through common polymerization Any one manufacture, in addition, the condition of polymerisation can also be selected arbitrarily.As such polymerization, Ke Yiju Go out：Polymerisation in solution, suspension polymerisation, emulsion polymerization.
Can be with the following method in polymerisation in solution：In the presence of polymerization initiator, it is dissolved in monomer organic molten Agent, carry out nitrogen displacement, then, heating stirring 1~10 hour in the range of 30~120 DEG C.As polymerization initiator, Ke Yiju Go out for example：Azobis isobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, T-butylperoxy pivarate, diisopropyl peroxydicarbonate etc..Relative to the parts by weight of monomer 100, polymerization initiator It can be used with 0.01~20 parts by weight, the scope of such as 0.01~10 parts by weight.
Organic solvent is in the nonactive and solvent that dissolve to monomer, such as can be ester (such as carbon number 2 ~30 ester, specifically ethyl acetate, butyl acetate), ketone (such as the ketone of carbon number 2~30, specifically methyl Ethyl ketone, DIBK), alcohol (such as the alcohol of carbon number 1~30, specifically isopropanol).As organic solvent Concrete example, it can enumerate：Acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, hexamethylene, benzene, toluene, Dimethylbenzene, petroleum ether, tetrahydrofuran, 1,4- dioxanes, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, ethyl acetate, Butyl acetate, 1,1,2,2- tetrachloroethanes, 1,1,1- trichloroethanes, trichloro ethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorine HFC-143a etc..Relative to total 100 parts by weight of monomer, organic solvent can with 10~2000 parts by weight, such as 50~ The scope of 1000 parts by weight uses.
Can be with the following method in emulsion polymerization：In the presence of polymerization initiator and emulsifying agent, make monomer in water Middle emulsification, nitrogen displacement is carried out, then, being stirred 1~10 hour in the range of 50~80 DEG C makes its copolymerization.Polymerization initiator can be with Use benzoyl peroxide, lauroyl peroxide, peroxidized t-butyl perbenzoate, 1- hydroxycyclohexyl hydroperoxides, 3- carboxyls Propiony peroxide, acetyl peroxide, azobisisobutylonitrile base amidine-dihydrochloride, azobis isobutyronitrile, sodium peroxide, over cure The water miscible material such as sour potassium, ammonium persulfate or azobis isobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, peroxide Change the oil-soluble things such as lauroyl, cumene hydroperoxide, t-butylperoxy pivarate, diisopropyl peroxydicarbonate Matter.Relative to the parts by weight of monomer 100, polymerization initiator can be used with the scope of 0.01~10 parts by weight.
In order to obtain the excellent aqueous polymer dispersion of shelf-stability, preferably using high pressure homogenizer or ultrasonic wave homogeneous The emulsifier unit of the crushing energy of strength can be assigned as machine, monomer is carried out micronized in water to be polymerize.Separately Outside, can be using the various emulsifying agents of anionic property, cationic or nonionic, relative to monomer 100 as emulsifying agent Parts by weight, it can be used with the scope of 0.5~20 parts by weight.It is preferred that use anionic property and/or nonionic and/or cation The emulsifying agent of property.In the case where monomer is not exclusively compatible, preferably addition can make compatibility agent that these monomers are fully compatible, Such as water-miscible organic solvent or the monomer of low molecule amount.It by adding compatibility agent, can improve emulsibility and copolymerizable.
As water-miscible organic solvent, can enumerate：Acetone, methyl ethyl ketone, ethyl acetate, propane diols, DPG Monomethyl ether, DPG, tripropylene glycol, ethanol etc., relative to the parts by weight of water 100, can with 1~50 parts by weight, such as 10~ The scope of 40 parts by weight uses.In addition, the monomer as low molecule amount, can be enumerated：Methyl methacrylate, methacrylic acid Ethylene oxidic ester, 2,2,2- trifluoroethyl methacrylates etc., can be with 1~50 relative to the parts by weight of total amount 100 of monomer The scope of parts by weight, such as 10~40 parts by weight uses.
In polymerization, chain-transferring agent can also be used.The molecule of polymer can be changed according to the usage amount of chain-transferring agent Amount.The example of chain-transferring agent be lauryl mercaptan, thio glycol, thioglycerol etc. containing mercapto compound (particularly (such as Carbon number 1~30) alkyl hydrosulfide), sodium hypophosphite, inorganic salts such as sodium hydrogensulfite etc..Relative to the weight of total amount 100 of monomer Part is measured, the usage amount of chain-transferring agent can be used with 0.01~10 parts by weight, the scope of such as 0.1~5 parts by weight.
The agent composition of the present invention can be the form of solution, emulsion (particularly, aqueous liquid dispersion) or aerosol, Preferably aqueous liquid dispersion.Agent composition contains polymer (active component of surface conditioning agent) and medium (particularly liquid Shape medium, such as organic solvent and/or water).The amount of medium can be 5~99.9 weights for example relative to agent composition % is measured, specifically for 10~80 weight %.
In agent composition, the concentration of polymer can be 0.01~95 weight %, for example, 5~50 weight %.
The agent composition of the present invention can utilize existing known method to be applied to treated object.Generally use should Agent composition, which is scattered in organic solvent or water, to be diluted, and utilizes the known side of dip-coating, spraying, bubble painting or the like Method, it is set to be attached to the surface of treated object and the method being dried.In addition, if need, can also be with appropriate crosslinking Agent is applied and solidified simultaneously.And then can also the addition and with insect-proof agent, softness in the agent composition of the present invention Agent, antiseptic, fire retardant, antistatic additive, coating fixative, anti-creasing agent etc..Polymer in the treatment fluid contacted with base material Concentration can be 0.01~10 weight % (the particularly situation of dip-coating), be, for example, 0.05~10 weight %.
As the treated object handled by the agent composition (such as water extraction oil extracticn agent) with the present invention, can enumerate： Fibre, stone material, filter (such as electrostatic filter), dust cover, fuel cell part (such as gas-diffusion electrode and Gas diffusion supporting mass), glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide, ceramic industry product, Plastics, painted surface and calcimine etc..As fibre, various examples can be enumerated.Such as it can enumerate：Cotton, fiber crops, wool, silk The synthetic fibers such as the of animal or plant nature such as silk fabric natural fiber, polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, The inorfils such as the semisynthetic fibres such as artificial silk, acetate fiber, glass fibre, carbon fiber, asbestos fibre or their mixing are fine Dimension.
Fibre can be any of the forms such as fiber, cloth.
The agent composition of the present invention can be used as internal mold release or external release agent uses.
Polymer can be using in order to fibre be handled and any application of known method in a liquid In fibrous substrate (such as fibre etc.).When fibre is cloth, cloth can be soaked in solution, or can be Attachment or spray solution on cloth.In order that oiliness is dialled in treated fibre performance, it is dried, preferably for example 100 DEG C~200 DEG C are heated.
Or polymer can be applied to fibre using cleaning method, such as it can apply and wash or in dry cleaning process etc. In be applied to fibre.
For typical case, processed fibre is cloth, including woven product, knitwear, non-woven fabrics, dress material product form Cloth and carpet, but can also be fiber or yarn or median fiber product (such as sliver or rove etc.).Fabric material can Think natural fiber (such as cotton or wool etc.), chemical fibre (such as viscose or Lay haussaire (Lyocell) etc.) or synthesis Fiber (such as polyester, polyamide or acrylic fiber etc.), or can be fiber mixture (such as natural fiber and synthesis it is fine Mixture of dimension etc.).Oleophobic property is being made in cellulosic fibre (such as cotton or artificial silk etc.) by the manufacture polymer of the present invention It is especially effective with the aspect of group oiliness.In addition, generally hydrophobicity and water-repellancy is made in fibre by the method for the present invention.
Or fibrous substrate can be leather.In order that leather is hydrophobicity and oleophobic property, can be in leather processing In each stage, for example, leather wetting processing during in or the finishing of leather during in, will manufacture polymer by water Solution or aqueous emulsifying thing are applied to leather.
Or fibrous substrate can be paper.Manufacture polymer can be applied to preformed paper, or can made Middle application during the various stages of paper, the drying of such as paper.
" processing " refers to inorganic agent being applied to treated object using dipping, spraying, coating etc..By processing, as place The polymer for managing the active ingredient of agent is impregnated with the inside of treated object and/or is attached to the surface of treated object.
[embodiment]
Hereinafter, enumerate embodiment and explain the present invention.But the present invention is not limited to these embodiments.
Hereinafter, unless otherwise specified, part or % or ratio represent parts by weight or weight % or weight ratio.
The step of experiment, is as described below.
Spray water-repellancy experiment
Carry out spraying water-repellancy experiment according to JIS-L-1092.Water-repellancy experiment is sprayed (as shown in the table 1 of following records) Represented using water-repellancy No..
The use of volume is that 250ml glass funnel and 250ml water can at least be sprayed with 20 seconds~30 seconds Nozzle.Test film frame is diameter 15cm metal frame.Prepare 3 experiment sheets that size is about 20cm × 20cm, by sheet material Test film holding frame is fixed on, sheet material is not had fold.The center of spraying is placed in the center of sheet material.Added in glass funnel The water (250mL) of room temperature, experiment sheet (time for passing through 25 seconds~30 seconds) is sprayed.Holding frame is removed from platform, Catching one end of holding frame makes forward surface be in downside, and opposite side one end is gently knocked using hard material.Make holding frame again 180 ° of rotation, identical step is repeated, falls excessive water droplet.For the order with water-repellancy from bad to excellent, carry out 0th, 50,70,80,90 and 100 scoring, by the test film of moistening compared with soaking standard of comparison thing.What is determined from 3 times is flat Obtain result.
The Continuous maching of drying
Prepare 10 experiment sheets that size is about 20cm × 50cm, utilize the water-repellent oil-repellent for being diluted to defined concentration Agent treatment fluid is continuously handled.Above-mentioned spray water-repellancy is carried out to each sheet material to test, and is evaluated.
Production Example 1
CF is put into 1000mL autoclaves3CF2-(CF2CF2)n-CH2CH2OCOC (Cl)=CH2(n=2.0) (13FC1A) 108g, lauryl acrylate (LA) 24.0g, isobornyl methacrylate (IBMA) 57.7g, pure water 565g, water soluble clycol Series solvent 47g, polyoxyethylene oleyl ether 2.5g, polyoxyethylene alkyl ether 27.8g, make it under agitation, with 60 DEG C with ultrasonic wave Emulsion dispersion 15 minutes.After nitrogen displacement is carried out in autoclave, press-in filling vinyl chloride (VCM) 62g, add containing azo group Water soluble starter 0.4g, reacted 20 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.The composition of polymer is with entering material list The composition of body is basically identical.
Production Example 2
CF is put into 500mL reaction flasks3CF2-(CF2CF2)n-CH2CH2OCOC (Cl)=CH2(n=2.0) (13FC1A) 51.2g, stearyl acrylate ester (StA) 85.4g, pure water 194g, water soluble clycol series solvent 34.1g, chlorination alkyl Trimethyl ammonium 6.3g, polyoxyethylene alkyl ether 7.0g, make its emulsion dispersion 15 minutes under agitation, with 60 DEG C with ultrasonic wave.Will After carrying out nitrogen displacement in reaction flask, the solution of water soluble starter 0.4g and water 9g containing azo group are added, it is anti-with 60 DEG C Answer 20 hours, obtain the aqueous liquid dispersion of polymer.The composition of polymer and the composition of charged monomer are basically identical.
Production Example 3
CF is put into 1000mL autoclaves3CF2-(CF2CF2)n-CH2CH2OCOC (Cl)=CH2(n=2.0) (13FC1A) 108g, lauryl acrylate (LA) 24.0g, isobornyl methacrylate (IBMA) 57.7g, pure water 565g, water soluble clycol Series solvent 47g, polyoxyethylene oleyl ether 2.5g, alkyl trimethylammonium chloride 3.9g, polyoxyethylene alkyl ether 27.8g, are being stirred Under, with 60 DEG C make its emulsion dispersion 15 minutes with ultrasonic wave.After nitrogen displacement is carried out in autoclave, press-in filling vinyl chloride (VCM) 62g, the water soluble starter 0.4g containing azo group is added, is reacted 20 hours with 60 DEG C, obtain the aqueous dispersion of polymer Liquid.The composition of polymer and the composition of charged monomer are basically identical.
Production Example 4
CF is put into 500ml reaction flasks3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2(n=2.0) (13FMA) 51.2g, stearyl acrylate ester (StA) 85.4g, pure water 194g, water soluble clycol series solvent 34.1g, chlorination alkyl three Ammonium methyl 6.3g, polyoxyethylene alkyl ether 7.0g, make its emulsion dispersion 15 minutes under agitation, with 60 DEG C with ultrasonic wave.Will be anti- Answer after carrying out nitrogen displacement in flask, add the solution of water soluble starter 0.4g and water 9g containing azo group, with 60 DEG C of reactions 20 hours, obtain the aqueous liquid dispersion of polymer.The composition of polymer and the composition of charged monomer are basically identical.
Production Example 5
CF is put into 1000mL autoclaves3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2(n=2.0) (13FMA) 108g, lauryl acrylate (LA) 24.0g, isobornyl methacrylate (IBMA) 57.7g, pure water 565g, water soluble clycol Series solvent 47g, polyoxyethylene oleyl ether 2.5g, polyoxyethylene alkyl ether 27.8g, make it under agitation, with 60 DEG C with ultrasonic wave Emulsion dispersion 15 minutes.After nitrogen displacement is carried out in autoclave, press-in filling vinyl chloride (VCM) 62g, add containing azo group Water soluble starter 0.4g, reacted 20 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.The composition of polymer is with entering material list The composition of body is basically identical.
Production Example 6
Stearyl acrylate ester (StA) 47.5g, pure water 145g, water soluble clycol series solvent are put into 500mL reaction flasks 15g, sorbitan monoalkyl ester 1.5g, polyoxyethylene alkyl ether 2g, chlorination alkyl Dimethyl Ammonium 1.5g, under agitation, with 60 DEG C make its emulsion dispersion 15 minutes with ultrasonic wave.After nitrogen displacement is carried out in reaction flask, add containing the water-soluble of azo group Property initiator 0.5g, with 60 DEG C react 3 hours, obtain the aqueous liquid dispersion of polymer.And then with pure water by solid component concentration It is adjusted to 30%.
Production Example 7
Be put into 500mL autoclaves stearyl acrylate ester (StA) 35g, pure water 145g, water soluble clycol series solvent 15g, Sorbitan monoalkyl ester 1g, polyoxyethylene alkyl ether 2g, chlorination alkyl Dimethyl Ammonium 2g, under agitation, with 60 DEG C with super Sound wave makes its emulsion dispersion 15 minutes.After nitrogen displacement is carried out in autoclave, press-in charging 12.5g vinyl chloride, addition 2,2- Double (2- amidine propanes) the dihydrochloride 0.5g of azo, are reacted 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.And then use Solid component concentration is adjusted to 30% by pure water.
Compare Production Example 1
CF is put into 500ml reaction flasks3CF2-(CF2CF2)n-CH2CH2OCOCH=CH2(n=3.2) (NSFA) 51.2g, stearyl acrylate ester (StA) 85.4g, pure water 194g, water soluble clycol series solvent 34.1g, alkyl trimethylammonium chloride 6.3g, polyoxyethylene alkyl ether 7.0g, make its emulsion dispersion 15 minutes under agitation, with 60 DEG C with ultrasonic wave.By reaction flask After interior progress nitrogen displacements, the solution of water soluble starter 0.4g and water 9g containing azo group are added, is reacted 20 hours with 60 DEG C, Obtain the aqueous liquid dispersion of polymer.The composition of polymer and the composition of charged monomer are basically identical.
Compare Production Example 2
CF is put into 1000mL autoclaves3CF2-(CF2CF2)n-CH2CH2OCOCH=CH2(n=3.2) (NSFA) 108g, Stearyl acrylate ester (StA) 81.7g, pure water 565g, water soluble clycol series solvent 47g, polyoxyethylene oleyl ether 2.5g, polyoxy second Allylic alkylation ether 27.8g, make its emulsion dispersion 15 minutes under agitation, with 60 DEG C with ultrasonic wave.Nitrogen displacement will be carried out in autoclave Afterwards, press-in filling vinyl chloride (VCM) 62g, adds the water soluble starter 0.4g containing azo group, is reacted 20 hours with 60 DEG C, Obtain the aqueous liquid dispersion of polymer.The composition of polymer and the composition of charged monomer are basically identical.
Compare Production Example 3
Paraffin (50 DEG C of fusing point) 136.6g, pure water 194g, water soluble clycol series solvent are put into 500ml reaction flasks 34.1g, alkyl trimethylammonium chloride 6.3g, polyoxyethylene alkyl ether 7.0g, make its emulsification under agitation, with 60 DEG C with ultrasonic wave It is scattered 15 minutes, obtain aqueous liquid dispersion.The composition of polymer and the composition of charged monomer are basically identical.
Embodiment 1
Using pure water the water manufactured in Production Example 1,2 is diluted in a manner of fluoropolymer concentration is 30% solid constituent Property liquid after, it is further dilute with water in a manner of the ratio of 30% dilution is 2% after mixing and be sufficiently stirred with 50 ﹕ 50 Release, prepare 2.00% experimental liquid (l00g).10 PET cloth (500mm × 200mm) are continuously soaked in the experimental liquid, By mangle, handled 1 minute with pin stenter with 170 DEG C.Then water-repellancy experiment is carried out.Show the result in Table A.On The experimental liquid of concentration 1.00%, 1.20% and 1.40%, the water-repellancy at initial stage is also determined, result is also depicted in Table A.
Embodiment 2
Using pure water the water manufactured in Production Example 1,2 is diluted in a manner of fluoropolymer concentration is 30% solid constituent After property liquid, after mixing and be sufficiently stirred with 30 ﹕ 70, handled and evaluated similarly to Example 1 later.Show the result in Table A.
Embodiment 3
Using pure water the water manufactured in Production Example 2,3 is diluted in a manner of fluoropolymer concentration is 30% solid constituent After property liquid, after mixing and be sufficiently stirred with 50 ﹕ 50, handled and evaluated similarly to Example 1 later.Show the result in Table A.
Embodiment 4
Using pure water the water manufactured in Production Example 2,3 is diluted in a manner of fluoropolymer concentration is 30% solid constituent After property liquid, after mixing and be sufficiently stirred with 70 ﹕ 30, handled and evaluated similarly to Example 1 later.Show the result in Table A.
Embodiment 5
Using pure water the water manufactured in Production Example 4,5 is diluted in a manner of fluoropolymer concentration is 30% solid constituent After property liquid, after mixing and be sufficiently stirred with 50 ﹕ 50, handled and evaluated similarly to Example 1 later.Show the result in Table A.
Embodiment 6
Using pure water the water manufactured in Production Example 1,2 and 6 is diluted in a manner of polymer concentration is 30% solid constituent After property liquid, after mixing and be sufficiently stirred with the ﹕ 32.5 of 50 ﹕ 17.5, handled and evaluated similarly to Example 1 later.Will As a result it is shown in Table A.
Embodiment 7
Using pure water the water manufactured in Production Example 1,2 and 7 is diluted in a manner of polymer concentration is 30% solid constituent After property liquid, after mixing and be sufficiently stirred with the ﹕ 25 of 50 ﹕ 25, handled and evaluated similarly to Example 1 later.By result It is shown in Table A.
Comparing embodiment 1
Using pure water by fluoropolymer concentration be 30% solid constituent in a manner of be diluted in manufactured in Production Example 1 it is water-based After liquid, further it is diluted with water in a manner of the ratio of 30% dilution is 2%, prepares 2.00% experimental liquid (100g).Handled and evaluated similarly to Example 1 later.Show the result in Table A.
Comparing embodiment 2
Using pure water by fluoropolymer concentration be 30% solid constituent in a manner of be diluted in manufactured in Production Example 2 it is water-based After liquid, further it is diluted with water in a manner of the ratio of 30% dilution is 2%, prepares 2.00% experimental liquid (100g).Handled and evaluated similarly to Example 1 later.Show the result in Table A.
Comparing embodiment 3
Using pure water by fluoropolymer concentration be 30% solid constituent in a manner of be diluted in manufactured in Production Example 3 it is water-based After liquid, further it is diluted with water in a manner of the ratio of 30% dilution is 2%, prepares 2.00% experimental liquid (100g).Handled and evaluated similarly to Example 1 later.Show the result in Table A.
Comparing embodiment 4
Using pure water by fluoropolymer concentration be 30% solid constituent in a manner of be diluted in manufactured in Production Example 4 it is water-based After liquid, further it is diluted with water in a manner of the ratio of 30% dilution is 2%, prepares 2.00% experimental liquid (100g).Handled and evaluated similarly to Example 1 later.Show the result in Table A.
Comparing embodiment 5
Using pure water by fluoropolymer concentration be 30% solid constituent in a manner of be diluted in manufactured in Production Example 5 it is water-based After liquid, further it is diluted with water in a manner of the ratio of 30% dilution is 2%, prepares 2.00% experimental liquid (100g).Handled and evaluated similarly to Example 1 later.Show the result in Table A.
Comparing embodiment 6
It is diluted in using pure water in a manner of fluoropolymer concentration is 30% solid constituent and compares what is manufactured in Production Example 1 After waterborne liquid, further it is diluted with water in a manner of the ratio of 30% dilution is 2%, prepares 2.00% experiment Liquid (100g).Handled and evaluated similarly to Example 1 later.Show the result in Table A.
Comparing embodiment 7
It is diluted in using pure water in a manner of fluoropolymer concentration is 30% solid constituent and compares what is manufactured in Production Example 2 After waterborne liquid, further it is diluted with water in a manner of the ratio of 30% dilution is 2%, prepares 2.00% experiment Liquid (100g).Handled and evaluated similarly to Example 1 later.Show the result in Table A.
Comparing embodiment 8
Production Example 1 is diluted in a manner of fluoropolymer concentration is 30% solid constituent and compare Production Example using pure water After the waterborne liquid manufactured in 3, after mixing and be sufficiently stirred with 75 ﹕ 25, used in a manner of the ratio of 30% dilution is 2% Water is further diluted, and prepares 2.00% experimental liquid (100g).Handled and evaluated similarly to Example 1 later. Show the result in Table A.
The implication of abbreviation is as described below.
[table 1]
Table A
[table 2]
Table A (Continued)
Industrial applicability
The surface treatment composition of the present invention for example may be used as water extraction oil extracticn agent, anti-fouling agent and soil release agent.

Claims (13)

1. a kind of surface treatment composition, it is characterised in that contain：
(I) there is the 1st fluoropolymer of the repeat unit from fluorochemical monomer (a) and the repeat unit from alkenyl halide (b) Thing；
(II) there is the repeat unit from fluorochemical monomer (a) without the 2nd fluorine-containing of the repeat unit from alkenyl halide Polymer；With
(III) liquid medium.
2. surface treatment composition as claimed in claim 1, it is characterised in that：
Fluorochemical monomer (a) is formula：CH2Compound shown in=C (- X)-C (=O)-Y-Z-Rf (I),
In formula, X be hydrogen atom, the alkyl of the straight-chain of carbon number 1~21 or branched, fluorine atom, chlorine atom, bromine atoms, Iodine atom, CFX1X2Base, cyano group, fluoro-alkyl, the substituted or non-substituted benzyl of the straight-chain of carbon number 1~21 or branched Base, substituted or non-substituted phenyl, wherein, X1And X2For hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom, Y is-O- Or-NH-,
Z is Direct Bonding；
The straight-chain or branched aliphatic group of carbon number 1~20；
The aromatic group or cyclic aliphatic group of carbon number 6~30；
Formula-R2(R1)N-SO2- or formula-R2(R1) group shown in N-CO-, in formula, R1For the alkyl of carbon number 1~10, R2For The straight-chain alkyl-sub or branched alkylidene of carbon number 1~10；
Formula-CH2CH(OR3)CH2-(Ar-O)p- shown group, in formula, R3For hydrogen atom or the acyl group of carbon number 1~10, Ar To represent 0 or 1 according to the arlydene for needing that there is substituent, p；
Formula-CH2-Ar-(O)q- shown group, in formula, Ar is according to the arlydene for needing to have substituent, and q is 0 or 1；Or
-(CH2)m-SO2-(CH2)n- base or-(CH2)m-S-(CH2)n- base, wherein, m is that 1~10, n is 0~10,
Rf is the straight-chain of carbon number 1~20 or the fluoro-alkyl of branched.
3. surface treatment composition as claimed in claim 1 or 2, it is characterised in that：
Fluorochemical monomer (a) is the acrylate that α positions are substituted by a chlorine atom both.
4. surface treatment composition as claimed in claim 2, it is characterised in that：
In fluorochemical monomer (a), Rf carbon number is 1~6.
5. surface treatment composition as claimed in claim 1, it is characterised in that：
Alkenyl halide monomer (b) is vinyl chloride.
6. such as surface treatment composition according to any one of claims 1 to 5, it is characterised in that：1st fluoropolymer and At least one of 2nd fluoropolymer has the repeat unit from other monomers (c),
Other monomers (c) are the non-crosslinked property monomer (c1) of non-fluorine,
The non-crosslinked property monomer (c1) of non-fluorine is formula：CH2Compound shown in=CA-T,
In formula, A is the halogen atom beyond hydrogen atom, methyl or fluorine atom, and T is hydrogen atom, the chain or ring of carbon number 1~30 The alkyl of shape or chain or the organic group of the carbon number 1~31 of ring-type with ester bond.
7. such as surface treatment composition according to any one of claims 1 to 6, it is characterised in that：1st fluoropolymer In, relative to the parts by weight of fluorochemical monomer (a) 100, the amount of alkenyl halide monomer (b) is 5~300 parts by weight, is existed as needed The amounts of other monomers (c) be 0~800 parts by weight,
In 2nd fluoropolymer, relative to the amount of the parts by weight of fluorochemical monomer (a) 100, as needed existing other monomers (c) For 0~800 parts by weight.
8. such as surface treatment composition according to any one of claims 1 to 7, it is characterised in that：1st fluoropolymer and The weight ratio of 2nd fluoropolymer is the ﹕ 5 of 5 ﹕ 95~95.
9. such as surface treatment composition according to any one of claims 1 to 8, it is characterised in that：Liquid medium (III) is The mixture of water or water and water-miscible organic solvent.
10. such as surface treatment composition according to any one of claims 1 to 9, it is characterised in that：It is to contain nonionic The aqueous liquid dispersion of property surfactant and cationic surfactant.
11. such as surface treatment composition according to any one of claims 1 to 10, it is characterised in that：Contain not fluorine-containing original The water-repellancy compound of son.
12. the surface treatment composition as any one of claim 1~11, it is characterised in that：Surface conditioning agent group Compound is water extraction oil extracticn agent composition, antifoulant composition or soil release agent composition.
A kind of 13. base material, it is characterised in that：
It is handled by the surface treatment composition any one of claim 1~12 to obtain.
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