TW201710465A - Surface treatment composition - Google Patents

Surface treatment composition Download PDF

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TW201710465A
TW201710465A TW105119919A TW105119919A TW201710465A TW 201710465 A TW201710465 A TW 201710465A TW 105119919 A TW105119919 A TW 105119919A TW 105119919 A TW105119919 A TW 105119919A TW 201710465 A TW201710465 A TW 201710465A
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carbon atoms
monomer
fluorine
surface treatment
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TWI656207B (en
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南晋一
福森正樹
宮原正弘
井置正人
山本育男
榎本孝司
陳濤
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大金工業股份有限公司
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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

Abstract

The present invention provides a surface treatment composition which comprises: (I) a first fluorine-containing polymer, which contains a repeating unit derived from a fluorine-containing monomer (a) and a repeating unit derived from a halogenated olefin (b); (II) a second fluorine-containing polymer, which contains a repeating unit derived from a fluorine-containing monomer (a), and doesn't contain a repeating unit derived from a halogenated olefin (b); (III) a fluid medium.

Description

表面處理劑組成物 Surface treatment composition

本發明係關於一種處理劑，特別是含有含氟聚合物混合物的撥水撥油劑組成物等表面處理劑組成物。具體而言，本發明係關於一種對纖維製品(例如地毯)、紙、不織布、石材、靜電過濾器、防塵面具、燃料電池的零件而言，具有優異的撥水性、撥油性、防污性，特別是在纖維的連續撥水撥油加工時高加工持續性優異的撥水撥油劑組成物。 The present invention relates to a treating agent, particularly a surface treating agent composition such as a water- and oil-repellent composition containing a fluoropolymer mixture. Specifically, the present invention relates to an excellent water repellency, oil repellency, and antifouling property for a fiber product (for example, a carpet), a paper, a non-woven fabric, a stone, an electrostatic filter, a dust mask, and a fuel cell. In particular, it is a water-repellent and oil-repellent composition which is excellent in high processing durability during continuous water-repellent oil processing of fibers.

以往提出了各種含氟化合物。含氟化合物具有耐熱性、耐氧化性、耐氣候性等特性優異的優點。利用含氟化合物的自由能低、即難以附著的特性，含氟化合物被用作例如撥水撥油劑及防污劑。 Various fluorine-containing compounds have been proposed in the past. The fluorine-containing compound has an advantage of excellent properties such as heat resistance, oxidation resistance, and weather resistance. The fluorine-containing compound is used as, for example, a water-repellent oil-repellent agent and an antifouling agent, because of the low free energy of the fluorine-containing compound, that is, the property of being difficult to adhere.

作為可以用作撥水撥油劑的含氟化合物者，可以舉出以具有氟烷基的(甲基)丙烯酸酯作為構成單體的含氟聚合物。在表面處理劑對纖維的實用處理中，由迄今為止的各種研究結果顯示，作為其表面特性，重要的並不是靜接觸角，而是動接觸角，特別是後退接觸角。即，水的前進接觸角並不依賴於氟烷基的側鏈碳原子數，但對 於水的後退接觸角而言，與側鏈碳原子數為8以上的情況相比，碳原子數為7以下的情況顯示該後退接觸角顯著變小。與此對應，X射線分析顯示側鏈碳原子數為7以上時產生側鏈的結晶化。已知實用的撥水性與側鏈的結晶性具有相關關係，以及表面處理劑分子的運動性是表現出實用性能的重要原因(例如，前川隆茂，FINE CHEMICAL，Vol23，No.6，P12(1994))。根據上述理由，具有側鏈碳原子數短為7以下(特別是6以下)的氟烷基的(甲基)丙烯酸酯系聚合物由於側鏈結晶性低，因此，存在不能直接滿足實用性能的問題。另外，在撥水撥油加工中通常進行連續加工，從排水、生產率的方面考慮，尋求一種具有高加工持續性的撥水撥油劑。 As a fluorine-containing compound which can be used as a water-repellent oil-repellent agent, a fluorine-containing polymer having a fluoroalkyl group-containing (meth) acrylate as a constituent monomer can be given. In the practical treatment of the fibers by the surface treatment agent, it has been revealed from various research results so far that, as the surface characteristics, it is not the static contact angle but the dynamic contact angle, particularly the receding contact angle. That is, the advancing contact angle of water does not depend on the number of side chain carbon atoms of the fluoroalkyl group, but In the case of the receding contact angle of water, the number of carbon atoms is 7 or less as compared with the case where the number of carbon atoms in the side chain is 8 or more, and the receding contact angle is remarkably small. Corresponding to this, X-ray analysis showed that the side chain crystallization occurred when the number of side chain carbon atoms was 7 or more. It is known that the practical water repellency has a correlation with the crystallinity of the side chain, and the mobility of the surface treatment agent molecule is an important reason for exhibiting practical properties (for example, Masahiro Ryukawa, FINE CHEMICAL, Vol23, No. 6, P12 (1994) )). For the reason described above, the (meth) acrylate-based polymer having a fluoroalkyl group having a side chain carbon number of 7 or less (especially 6 or less) has low crystallinity in side chains, and therefore cannot directly satisfy practical properties. problem. In addition, continuous processing is usually performed in the water-repellent oil-discharging processing, and in view of drainage and productivity, a water-repellent and oil-repellent agent having high processing durability is sought.

日本特開2001-98257號公報揭示一種以包含具有聚氟烷基的聚合性單體的聚合單元的聚合物(A)、具有特定的德拉夫斯(Draves)潤濕時間的表面活性劑(B)及水系介質(C)作為必需成分的組成物。日本特開2004-262970號公報揭示一種含有氟系撥水撥油劑(A)、含有石蠟和含羧基聚乙烯的乳化物(B)以及有機酸(C)的撥水撥油劑水性組成物。 Japanese Laid-Open Patent Publication No. 2001-98257 discloses a polymer (A) comprising a polymerized unit having a polymerizable monomer having a polyfluoroalkyl group, and a surfactant having a specific Draves wetting time (B) And the aqueous medium (C) as a constituent of the essential component. Japanese Laid-Open Patent Publication No. 2004-262970 discloses an aqueous composition containing a fluorine-based water-repellent oil-removing agent (A), an emulsion containing paraffin wax and a carboxyl group-containing polyethylene (B), and an organic acid (C). .

在這些專利中，未對加工持續性進行描述。 In these patents, processing continuity is not described.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

專利文獻1：日本特開2001-98257號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-98257

專利文獻2：日本特開2004-262970號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2004-262970

本發明的一個目的在於：提供一種纖維等的撥水撥油加工的加工持續性優異的表面處理劑組成物。 An object of the present invention is to provide a surface treatment agent composition excellent in processing durability of water-repellent oil-repellent processing such as fibers.

本發明係關於一種表面處理劑組成物，其含有：(I)具有由含氟單體(a)衍生的重複單元及由鹵化烯烴(b)衍生的重複單元的第1含氟聚合物；(II)具有由含氟單體(a)衍生的重複單元而不具有由鹵化烯烴衍生的重複單元的第2含氟聚合物；以及(III)液狀介質。 The present invention relates to a surface treatment composition comprising: (I) a first fluoropolymer having a repeating unit derived from a fluoromonomer (a) and a repeating unit derived from a halogenated olefin (b); II) a second fluoropolymer having a repeating unit derived from a fluoromonomer (a) without a repeating unit derived from a halogenated olefin; and (III) a liquid medium.

本發明的表面處理劑組成物的撥水撥油加工的加工持續性優異。 The water repellent oil processing of the surface treatment agent composition of the present invention is excellent in processing durability.

根據本發明，可以得到優異的撥水性、撥油性、防污性及脫污性，例如撥水撥油性優異的耐久性。 According to the present invention, excellent water repellency, oil repellency, antifouling property, and detergency property can be obtained, and durability such as water repellency is excellent.

本發明的表面處理劑組成物可以用作撥水撥油劑組成物、防污劑組成物及/或脫污劑組成物。 The surface treatment composition of the present invention can be used as a water and oil repellent composition, an antifouling agent composition and/or a detergent composition.

(1)含氟聚合物 (1) Fluoropolymer

在本發明中，含氟聚合物為第1含氟聚合物和第2含氟聚合物的組合。 In the present invention, the fluoropolymer is a combination of the first fluoropolymer and the second fluoropolymer.

作為構成含氟聚合物的重複單元的單體者，使用含氟單體(a)、鹵化烯烴單體(b)以及單體(a)及(b)以外的其它單體(c)。 As the monomer constituting the repeating unit of the fluoropolymer, the fluorine-containing monomer (a), the halogenated olefin monomer (b), and the monomer (c) other than the monomers (a) and (b) are used.

在本發明中，第1含氟聚合物及第2含氟聚合物作為撥水撥油劑、防污劑及脫污劑的有效成分發揮作用。 In the present invention, the first fluorine-containing polymer and the second fluorine-containing polymer function as an active ingredient of a water- and water-repellent agent, an antifouling agent, and a detergent.

(a)含氟單體 (a) fluoromonomer

含氟單體通常為具有全氟烷基或全氟烯基及丙烯酸基或甲基丙烯酸基或α-取代丙烯酸基的聚合性化合物。 The fluorine-containing monomer is usually a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic group or a methacryl group or an α-substituted acrylic group.

含氟單體(a)例如可以為通式：CH2=C(-X)-C(=O)-Y-Z-Rf (I)所示的化合物。 The fluorine-containing monomer (a) may, for example, be a compound represented by the formula: CH 2 =C(-X)-C(=O)-YZ-Rf (I).

[式中，X為氫原子、一價的有機基或鹵素原子，Y為-O-或-NH-，Z為直接鍵結或二價的有機基，Rf為碳原子數1至20的氟烷基] Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, and Rf is a fluorine having 1 to 20 carbon atoms. alkyl]

含氟單體(a)較佳為通式：CH2=C(-X)-C(=O)-Y-Z-Rf (I)所示的化合物。 The fluorine-containing monomer (a) is preferably a compound represented by the formula: CH 2 =C(-X)-C(=O)-YZ-Rf (I).

[式中，X為氫原子、碳原子數1至21的直鏈狀或支鏈狀 的烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(其中，X1及X2為氫原子、氟原子、氯原子、溴原子或碘原子)、氰基、碳原子數1至21的直鏈狀或支鏈狀的氟烷基、取代或非取代的苄基、取代或非取代的苯基，Y為-O-或-NH-；Z為直接鍵結，或者碳原子數1至20的直鏈狀或支鏈狀脂肪族基(特別是伸烷基)、例如式-(CH2)x-(式中，x為1至10)所示的基，或者碳原子數6至30的芳香族基或環狀脂肪族基，或者式-R2(R1)N-SO2-或式-R2(R1)N-CO-所示的基(式中，R1為碳原子数1至10的烷基，R2為碳原子数1至10的直鏈伸烷基或支鏈伸烷基)，或者式-CH2CH(OR3)CH2-(Ar-O)p-(式中，R3表示氫原子或碳原子數1至10的醯基(例如甲醯基或乙醯基等)，Ar表示根據需要具有取代基的伸芳基，p表示0或1)所示的基，或者式-CH2-Ar-(O)q-(式中，Ar為根據需要具有取代基的伸芳基，q為0或1)所示的基，或者-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(其中，m為1至10，n為0至10)；Rf為碳原子數1至20的直鏈狀或支鏈狀的氟烷基] [wherein, X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (wherein X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, and a substitution. Or an unsubstituted phenyl group, Y is -O- or -NH-; Z is a direct bond, or a linear or branched aliphatic group having 1 to 20 carbon atoms (particularly an alkylene group), for example a group represented by the formula -(CH 2 ) x - (wherein, x is 1 to 10), or an aromatic group or a cyclic aliphatic group having 6 to 30 carbon atoms, or a formula -R 2 (R 1 ) N-SO 2 - or a group represented by the formula -R 2 (R 1 )N-CO- (wherein R 1 is an alkyl group having 1 to 10 carbon atoms, and R 2 is a straight one having 1 to 10 carbon atoms) a chain alkyl group or a branched alkyl group), or a formula -CH 2 CH(OR 3 )CH 2 -(Ar-O) p - (wherein R 3 represents a hydrogen atom or a cesium having 1 to 10 carbon atoms) group (e.g., methyl acyl or acetyl group), Ar represents an arylene group having a substituent group according to need, P represents 0 or 1) group as shown, or the formula -CH 2 -Ar- (O) q - ( An arylene group, Ar is a substituted needed, q is 0 or 1) as shown yl, or - (CH 2) m -SO 2 - (CH 2) n - group or a - (CH 2) m -S-(CH 2 ) n - group (wherein m is 1 to 10, n is 0 to 10); and Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms]

X的代表性的具體例為Cl、Br、I、F、CN、CF3，較佳為Cl。特別是在α位為氯原子的情況下，表面處理劑組成物的實用的撥水性(特別是噴淋撥水性)優異。 Representative specific examples of X are Cl, Br, I, F, CN, CF 3 , preferably Cl. In particular, when the α-position is a chlorine atom, the surface treatment agent composition is excellent in practical water repellency (especially spray water repellency).

在含氟單體中，Rf基較佳為全氟烷基。Rf 基的碳原子數較佳為1至12，例如為1至6，特佳為4至6，再更佳為6。Rf基的例子為-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、-C8F17等。 In the fluorine-containing monomer, the Rf group is preferably a perfluoroalkyl group. The number of carbon atoms of the Rf group is preferably from 1 to 12, for example from 1 to 6, particularly preferably from 4 to 6, more preferably 6. Examples of the Rf group are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , -C(CF 3 ) 3 , -(CF 2 ) 4 CF 3 , -(CF 2 ) 2 CF(CF 3 ) 2 , -CF 2 C(CF 3 ) 3 , -CF(CF 3 )CF 2 CF 2 CF 3 , -(CF 2 ) 5 CF 3 , -(CF 2 ) 3 CF(CF 3 ) 2 , -(CF 2 ) 4 CF(CF 3 ) 2 , -C 8 F 17 and the like.

Z較佳為碳原子數1至10的脂肪族基、碳原子數6至18的芳香族基或環狀脂肪族基、-CH2CH2N(R1)SO2-基(其中，R1為碳原子數1至4的烷基)、-CH2CH(OZ1)CH2-(Ph-O)p-基(其中，Z1為氫原子或乙醯基，Ph為伸苯基，p為0或1)、-(CH2)n-Ph-O-基(其中，Ph為伸苯基，n為0至10)、-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(其中，m為1至10，n為0至10)。脂肪族基較佳為伸烷基(特別是碳原子數為1至4、例如1或2)。芳香族基或環狀脂肪族基可以為取代或非取代。S基或SO2基可以直接與Rf基鍵結。 Z is preferably an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group, or a -CH 2 CH 2 N(R 1 )SO 2 - group (wherein R 1 is an alkyl group having 1 to 4 carbon atoms), -CH 2 CH(OZ 1 )CH 2 -(Ph-O) p - group (wherein Z 1 is a hydrogen atom or an ethenyl group, and Ph is a phenyl group) , p is 0 or 1), -(CH 2 ) n -Ph-O- group (where Ph is a phenyl group, n is 0 to 10), -(CH 2 ) m -SO 2 -(CH 2 ) An n- group or a -(CH 2 ) m -S-(CH 2 ) n - group (wherein m is from 1 to 10 and n is from 0 to 10). The aliphatic group is preferably an alkyl group (particularly, having 1 to 4 carbon atoms, for example, 1 or 2). The aromatic group or the cyclic aliphatic group may be substituted or unsubstituted. The S group or the SO 2 group may be directly bonded to the Rf group.

作為含氟單體(a)的具體例者，例如可以例示以下的物質，但並不限定於這些物質。 Specific examples of the fluorine-containing monomer (a) include, for example, the following, but are not limited thereto.

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[上述式中，Rf為碳原子數1至20的氟烷基] CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -Rf CH 2 =C(-H)-C(=O)-OC 6 H 4 -Rf CH 2 =C( -Cl)-C(=O)-O-(CH 2 ) 2 -Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 N(-CH 3 )SO 2 - Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 N(-C 2 H 5 )SO 2 -Rf CH 2 =C(-H)-C(=O)- O-CH 2 CH(-OH)CH 2 -Rf CH 2 =C(-H)-C(=O)-O-CH 2 CH(-OCOCH 3 )CH 2 -Rf CH 2 =C(-H) -C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 - SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-H)-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 =C(-CH 3 )-C(=O)- O-(CH 2 ) 2 -S-Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(- CH 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -( CH 2 ) 2 -Rf CH 2 =C(-CH 3 )-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-F)-C( =O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 = C(-F)-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-Cl)-C(= O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-Cl)-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 =C( -CF 3 )-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-CF 3 )-C(=O)-O -(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CF 3 )-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 2 -Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-CF 2 H)-C(=O)- O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CF 2 H)-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 =C(- CN)-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CN)-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 =C(-CF 2 CF 3 )-C( =O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-CF 2 CF 3 )-C(=O )-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 = C(-F)-C(=O)-O-(CH 2 ) 3 -S-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-F)-C(=O)-O-( CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-F)-C(=O)-NH-(CH 2 ) 3 -Rf CH 2 =C(-Cl)-C( =O)-O-(CH 2 ) 3 -S-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf CH 2 = C(-Cl)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -SO 2 - (CH 2 ) 2 -Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -S-Rf CH 2 =C(-CF 3 )-C(=O)- O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C( -CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -S-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf CH 2 =C(-CF 2 H )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -S-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-CN)-C (=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -S-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf [In the above formula, Rf a fluoroalkyl group having 1 to 20 carbon atoms]

(b)鹵化烯烴單體 (b) Halogenated olefin monomer

鹵化烯烴單體(鹵化烯烴)較佳為不具有氟原子。 The halogenated olefin monomer (halogenated olefin) preferably has no fluorine atom.

鹵化烯烴較佳為被1至10個氯原子、溴原子或碘原子取代的碳原子數2至20的烯烴。鹵化烯烴較佳為碳原子數2至20的氯化烯烴，特佳為具有1至5個氯原子的碳原子數2至5的烯烴。鹵化烯烴的較佳的具體例為鹵化乙烯，例如氯乙烯、溴乙烯、碘乙烯；偏二鹵乙烯，例如偏二氯乙烯、偏二溴乙烯、偏二碘乙烯。較佳為氯乙烯及偏二氯乙烯，特佳為氯乙烯。 The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms which is substituted by 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly preferably an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin are halogenated ethylene such as vinyl chloride, vinyl bromide, iodoethylene; vinylidene halide such as vinylidene chloride, vinylidene bromide or vinylidene iodide. Preferred is vinyl chloride and vinylidene chloride, and particularly preferably vinyl chloride.

((c)其它單體 ((c) other monomers

單體(a)及(b)以外的其它單體(c)較佳為不含氟。作為其它單體(c)者，可以舉出：非氟非交聯性單體(c1)及非氟交聯性單體(c2)。 The monomer (c) other than the monomers (a) and (b) is preferably fluorine-free. Examples of the other monomer (c) include a non-fluorine non-crosslinkable monomer (c1) and a non-fluorine crosslinkable monomer (c2).

(c1)非氟非交聯性單體 (c1) non-fluorine non-crosslinkable monomer

非氟非交聯性單體(c1)為不含氟原子的單體。非氟非交聯性單體(c1)不具有交聯性官能基。非氟非交聯性單體(c1)與交聯性單體(c2)不同，為非交聯性。非氟非交聯性單體(c1)較佳為具有碳-碳雙鍵的非氟單體。非氟非交聯性單體(c1)較佳為不含氟的乙烯基單體。非氟非交聯性單體(c1)通常為具有1個碳-碳雙鍵的化合物。 The non-fluorine non-crosslinkable monomer (c1) is a monomer having no fluorine atom. The non-fluorine non-crosslinkable monomer (c1) does not have a crosslinkable functional group. The non-fluorine non-crosslinkable monomer (c1) is different from the crosslinkable monomer (c2) and is non-crosslinkable. The non-fluorine non-crosslinkable monomer (c1) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (c1) is preferably a fluorine-free vinyl monomer. The non-fluorine non-crosslinkable monomer (c1) is usually a compound having one carbon-carbon double bond.

較佳的非氟非交聯性單體(c1)為式：CH2= CA-T所示的化合物。 A preferred non-fluorine non-crosslinkable monomer (c1) is a compound of the formula: CH 2 = CA-T.

[式中，A為氫原子、甲基或氟原子以外的鹵原子(例如氯原子、溴原子及碘原子)，T為氫原子、碳原子數1至30的鏈狀或環狀的烴基、或具有酯鍵的鏈狀或環狀的碳原子數1至31的有機基] In the formula, A is a hydrogen atom, a halogen atom other than a methyl group or a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom), and T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, Or a chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond]

碳原子數1至30的鏈狀或環狀的烴基的例子為碳原子數1至30的直鏈或支鏈的脂肪族烴基、碳原子數4至30的環狀脂肪族基、碳原子數6至30的芳香族烴基、碳原子數7至30的芳香脂肪族烴基。 Examples of the chain or cyclic hydrocarbon group having 1 to 30 carbon atoms are a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, and a carbon number. An aromatic hydrocarbon group of 6 to 30 and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms.

具有酯鍵的鏈狀或環狀的碳原子數1至31的有機基的例子為-C(=O)-O-Q及-O-C(=O)-Q(在此，Q為碳原子數1至30的直鏈或支鏈的脂肪族烴基、碳原子數4至30的環狀脂肪族基、碳原子數6至30的芳香族烴基、碳原子數7至30的芳香脂肪族烴基)。 Examples of the chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond are -C(=O)-OQ and -OC(=O)-Q (here, Q is a carbon number of 1 to A linear or branched aliphatic hydrocarbon group of 30, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms.

非氟非交聯性單體(c1)的較佳的例子包括例如乙烯、乙酸乙烯酯、丙烯腈、苯乙烯、聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯及乙烯基烷基醚。非氟非交聯性單體(c1)並不限定於這些例子。 Preferable examples of the non-fluorine non-crosslinkable monomer (c1) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, Methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate and vinyl alkyl ether. The non-fluorine non-crosslinkable monomer (c1) is not limited to these examples.

非氟非交聯性單體(c1)可以為具有烷基的(甲基)丙烯酸酯。烷基的碳原子數可以為1至30，例如為6至30(例如10至30)。例如，非氟非交聯性單體(c1)可以為通式：CH2=CA1COOA2所示的丙烯酸酯。 The non-fluorine non-crosslinkable monomer (c1) may be a (meth) acrylate having an alkyl group. The alkyl group may have a carbon number of from 1 to 30, for example from 6 to 30 (e.g., from 10 to 30). For example, the non-fluorine non-crosslinkable monomer (c1) may be an acrylate represented by the formula: CH 2 =CA 1 COOA 2 .

[式中，A1為氫原子、甲基或氟原子以外的鹵素原子(例如 氯原子、溴原子及碘原子)，A2為CnH2n+1(n=1至30)所示的烷基] In the formula, A 1 is a halogen atom other than a hydrogen atom, a methyl group or a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom), and A 2 is represented by C n H 2n+1 (n=1 to 30). alkyl]

A2的較佳的具體例為月桂基、硬脂基、二十二烷基(behenyl)。 Preferred specific examples of A 2 are lauryl, stearyl and behenyl.

非氟非交聯性單體(c1)可以為具有環狀烴基的(甲基)丙烯酸酯單體。 The non-fluorine non-crosslinkable monomer (c1) may be a (meth) acrylate monomer having a cyclic hydrocarbon group.

含環狀烴基的丙烯酸酯單體較佳為式：CH2=CA21-C(=O)-O-A22所示的化合物。 The cyclic hydrocarbon group-containing acrylate monomer is preferably a compound represented by the formula: CH 2 =CA 21 -C(=O)-OA 22 .

[式中，A21為氫原子或甲基，A22為碳原子數4至30的含環狀烴的基] [wherein, A 21 is a hydrogen atom or a methyl group, and A 22 is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms]

含環狀烴基的丙烯酸酯單體為其均聚物的玻璃轉移溫度高(例如50℃以上，特別是80℃以上)的單體。 The cyclic hydrocarbon group-containing acrylate monomer is a monomer whose homopolymer has a high glass transition temperature (for example, 50 ° C or higher, particularly 80 ° C or higher).

含環狀烴基的丙烯酸酯單體不具有氟烷基。含環狀烴基的丙烯酸酯單體也可以含有氟原子，但較佳為不含氟原子。 The cyclic hydrocarbon group-containing acrylate monomer does not have a fluoroalkyl group. The cyclic hydrocarbon group-containing acrylate monomer may also contain a fluorine atom, but is preferably a fluorine-free atom.

A21特佳為甲基。 A 21 is particularly preferred as a methyl group.

A22為可以具有鏈狀基(例如直鏈狀或支鏈狀的烴基)的環狀烴基。作為環狀烴基者，可以舉出：飽和或不飽和的單環基、多環基、橋環基等。環狀烴基較佳為飽和。環狀烴基的碳原子數為4至30，較佳為6至20。作為環狀烴基者，可以舉出：碳原子數4至20、特別是5至12的環狀脂肪族基、碳原子數6至20的芳香族基、碳原子數7至20的芳香脂肪族基。環狀烴基的碳原子數特佳為15以下、例如12以下。環狀烴基較佳為飽和的環狀脂肪族基。 環狀烴基的具體例為環己基、第三丁基環己基、異冰片基、二環戊基、二環戊烯基、金剛烷基。 A 22 is a cyclic hydrocarbon group which may have a chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include a saturated or unsaturated monocyclic group, a polycyclic group, a bridged ring group, and the like. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group has 4 to 30, preferably 6 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12, an aromatic group having 6 to 20 carbon atoms, and an aromatic aliphatic group having 7 to 20 carbon atoms. base. The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example, 12 or less. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, a tert-butylcyclohexyl group, an isobornyl group, a dicyclopentyl group, a dicyclopentenyl group, and an adamantyl group.

作為含環狀烴基的丙烯酸酯單體的具體例者，可以舉出：(甲基)丙烯酸環己酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊基氧基乙酯、(甲基)丙烯酸三環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸-2-甲基-2-金剛烷基酯、(甲基)丙烯酸-2-乙基-2-金剛烷基酯等。 Specific examples of the cyclic hydrocarbon group-containing acrylate monomer include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, and benzyl (meth)acrylate. Isobornyl methyl methacrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, tricyclo(methyl) acrylate Amyl ester, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and the like.

藉由存在含環狀烴基的丙烯酸酯單體，共聚物所提供的撥水性及撥油性變高。 By the presence of the acrylate monomer having a cyclic hydrocarbon group, the water repellency and oil repellency provided by the copolymer become high.

(c2)非氟交聯性單體 (c2) non-fluorine crosslinkable monomer

本發明的含氟聚合物可以具有由非氟交聯性單體(c2)衍生的重複單元。非氟交聯性單體(c2)為不含氟原子的單體。非氟交聯性單體(c2)可以為具有至少2個反應性基及/或碳-碳雙鍵、且不含氟的化合物。非氟交聯性單體(c2)可以為具有至少2個碳-碳雙鍵的化合物、或者具有至少1個碳-碳雙鍵及至少1個反應性基的化合物。反應性基的例子為羥基、環氧基、氯甲基、封端異氰酸酯基、胺基、羧基等。非氟交聯性單體(c2)可以為具有反應性基的單(甲基)丙烯酸酯、二(甲基)丙烯酸酯或單(甲基)丙烯醯胺。或者，非氟交聯性單體(c2)可以為二(甲基)丙烯酸酯。 The fluoropolymer of the present invention may have a repeating unit derived from a non-fluorine crosslinkable monomer (c2). The non-fluorine crosslinkable monomer (c2) is a monomer having no fluorine atom. The non-fluorine-crosslinkable monomer (c2) may be a compound having at least two reactive groups and/or carbon-carbon double bonds and containing no fluorine. The non-fluorine-crosslinkable monomer (c2) may be a compound having at least two carbon-carbon double bonds or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of the reactive group are a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amine group, a carboxyl group and the like. The non-fluorine crosslinkable monomer (c2) may be a mono(meth)acrylate, di(meth)acrylate or mono(meth)acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer (c2) may be a di(meth)acrylate.

作為非氟交聯性單體(c2)者，例如可以例 示：二丙酮(甲基)丙烯醯胺、(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸3-氯-2-羥基丙酯、(甲基)丙烯酸2-乙醯乙醯氧基乙酯、丁二烯、異戊二烯、氯丁二烯、(甲基)丙烯酸縮水甘油酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯等。 As the non-fluorine crosslinkable monomer (c2), for example, Show: diacetone (meth) acrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth)acrylate, 2-ethoxyethyloxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, (methyl) Glycidyl acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and the like.

藉由使非氟非交聯性單體(c1)及/或非氟交聯性單體(c2)共聚，可以根據需要改善撥水撥油性、防污性以及這些性能的耐清潔性、耐洗滌性、在溶劑中的溶解性、硬度、觸感等各種性質。 By copolymerizing the non-fluorine non-crosslinkable monomer (c1) and/or the non-fluorine crosslinkable monomer (c2), it is possible to improve water repellency, antifouling property, and resistance to cleaning and resistance of these properties as needed. Various properties such as washing property, solubility in a solvent, hardness, and touch.

在本說明書中，在簡稱為“丙烯酸酯”或“丙烯醯胺”的情況下，不僅包含α位為氫原子的化合物，還包含α位被其它基(例如包含甲基在內的一價的有機基或鹵素原子)取代的化合物。在本說明書中，“(甲基)丙烯酸酯”是指丙烯酸酯或甲基丙烯酸酯，“(甲基)丙烯醯胺”是指丙烯醯胺或甲基丙烯醯胺。。 In the present specification, in the case of abbreviated as "acrylate" or "acrylamide", not only a compound having an α-position as a hydrogen atom but also an alpha-position by another group (for example, a monovalent group including a methyl group) A compound substituted with an organic group or a halogen atom). In the present specification, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide. .

單體(a)、單體(b)、單體(c)(例如單體(c1)及(c2)各自)分別可以單獨使用1種，或者也可以為2種以上的組合。 The monomer (a), the monomer (b), and the monomer (c) (for example, each of the monomers (c1) and (c2)) may be used alone or in combination of two or more.

第1含氟聚合物中的各個單體的量如下所述。 The amount of each monomer in the first fluoropolymer is as follows.

在第1含氟聚合物中，含氟單體(a)的量相對於含氟聚合物可以為20重量%至100重量%，較佳為30重量%至90重量%。 In the first fluoropolymer, the amount of the fluorinated monomer (a) may be from 20% by weight to 100% by weight, preferably from 30% by weight to 90% by weight based on the fluoropolymer.

在第1含氟聚合物中，相對於含氟單體(a)100重量份， 鹵化烯烴單體(b)的量為5至300重量份，例如為10至200重量份，特別為20至100重量份，特別為30至80重量份，其它單體(c)的量可以為0至800重量份，例如為1至300重量份，特別為2至200重量份，特別為3至100重量份。 In the first fluoropolymer, with respect to 100 parts by weight of the fluoromonomer (a), The amount of the halogenated olefin monomer (b) is 5 to 300 parts by weight, for example, 10 to 200 parts by weight, particularly 20 to 100 parts by weight, particularly 30 to 80 parts by weight, and the amount of the other monomer (c) may be 0 to 800 parts by weight, for example, 1 to 300 parts by weight, particularly 2 to 200 parts by weight, particularly 3 to 100 parts by weight.

在第1含氟聚合物中，相對於含氟單體(a)100重量份，非氟非交聯性單體(c1)的量可以為0至500重量份，例如為1至300重量份，特別為2至200重量份，特別為3至100重量份，非氟交聯性單體(c2)的量可以為0至80重量份，例如為0至50重量份，特別為0.1至30重量份，特別為1至20重量份。 In the first fluoropolymer, the amount of the non-fluorine non-crosslinkable monomer (c1) may be from 0 to 500 parts by weight, for example, from 1 to 300 parts by weight, per 100 parts by weight of the fluoromonomer (a). In particular, it is from 2 to 200 parts by weight, particularly from 3 to 100 parts by weight, and the amount of the non-fluorine-crosslinkable monomer (c2) may be from 0 to 80 parts by weight, for example from 0 to 50 parts by weight, particularly from 0.1 to 30 parts by weight. Part by weight, particularly 1 to 20 parts by weight.

第2含氟聚合物中的各個單體的量如下所述。 The amount of each monomer in the second fluoropolymer is as follows.

在第2含氟聚合物中，含氟單體(a)的量相對於含氟聚合物可以為20重量%至100重量%，較佳為30重量%至90重量%。 In the second fluoropolymer, the amount of the fluorinated monomer (a) may be from 20% by weight to 100% by weight, preferably from 30% by weight to 90% by weight based on the fluoropolymer.

第2含氟聚合物不具有由鹵化烯烴衍生的重複單元。 The second fluoropolymer does not have a repeating unit derived from a halogenated olefin.

在第2含氟聚合物中，相對於單體(a)100重量份，其它單體(c)的量可以為0至800重量份，例如為1至300重量份，特別為2至200重量份，特別為3至100重量份。 In the second fluoropolymer, the amount of the other monomer (c) may be from 0 to 800 parts by weight, for example, from 1 to 300 parts by weight, particularly from 2 to 200 parts by weight per 100 parts by weight of the monomer (a). Parts, particularly from 3 to 100 parts by weight.

在第2含氟聚合物中，相對於含氟單體(a)100重量份，非氟非交聯性單體(c1)的量可以為0至500重量份，例如為1至300重量份，特別為2至200重量份，特別為3至100重量份。非氟交聯性單體(c2)的量可以為0至80重量份，例如為0至50重量份，特別為0.1至30重量份，特 別為1至20重量份。 In the second fluoropolymer, the amount of the non-fluorine non-crosslinkable monomer (c1) may be from 0 to 500 parts by weight, for example, from 1 to 300 parts by weight, per 100 parts by weight of the fluoromonomer (a). It is especially 2 to 200 parts by weight, particularly 3 to 100 parts by weight. The amount of the non-fluorine crosslinkable monomer (c2) may be from 0 to 80 parts by weight, for example from 0 to 50 parts by weight, particularly from 0.1 to 30 parts by weight, Do not be 1 to 20 parts by weight.

第1含氟聚合物及第2含氟聚合物中的含氟單體(a)及其它單體(c)可以分別相同或不同。 The fluorine-containing monomer (a) and the other monomer (c) in the first fluorine-containing polymer and the second fluorine-containing polymer may be the same or different.

在表面處理劑組成物中，第1含氟聚合物和第2含氟聚合物的重量比可以為5：95至95：5，例如為20：80至80：20。 In the surface treatment composition, the weight ratio of the first fluoropolymer to the second fluoropolymer may be from 5:95 to 95:5, for example, from 20:80 to 80:20.

在第1含氟聚合物及第2含氟聚合物的混合物中，通常第1含氟聚合物的分子和第2含氟聚合物的分子未進行化學鍵結。 In the mixture of the first fluoropolymer and the second fluoropolymer, the molecules of the first fluoropolymer and the molecules of the second fluoropolymer are not chemically bonded.

(2)表面活性劑 (2) Surfactant

在本發明的處理劑中，表面活性劑包含非離子性表面活性劑及陽離子性表面活性劑的一者或兩者。進而，表面活性劑也可以含有兩性表面活性劑。表面活性劑較佳為不含陰離子性表面活性劑。 In the treatment agent of the present invention, the surfactant contains one or both of a nonionic surfactant and a cationic surfactant. Further, the surfactant may also contain an amphoteric surfactant. The surfactant is preferably free of an anionic surfactant.

(2-1)非離子性表面活性劑 (2-1) Nonionic surfactant

非離子性表面活性劑為具有氧伸烷基的非離子性表面活性劑。氧伸烷基中的伸烷基的碳原子數較佳為2至10。非離子性表面活性劑的分子中的氧伸烷基數量通常較佳為2至100。 The nonionic surfactant is a nonionic surfactant having an oxygen alkyl group. The alkylene group in the oxygen alkyl group preferably has 2 to 10 carbon atoms. The amount of the oxygen alkyl group in the molecule of the nonionic surfactant is usually preferably from 2 to 100.

非離子性表面活性劑可以為直鏈狀及/或支鏈狀的脂肪族(飽和及/或不飽和)基的環氧烷烴加成物、直鏈狀及/或支鏈狀脂肪酸(飽和及/或不飽和)的聚伸烷基二醇酯、聚 氧乙烯(POE)/聚氧丙烯(POP)共聚物(無規共聚物或嵌段共聚物)、乙炔二醇的環氧烷烴加成物等。其中，較佳為環氧烷烴加成部分及聚伸烷基二醇部分的結構為聚氧乙烯(POE)或聚氧丙烯(POP)或POE/POP共聚物(可以為無規共聚物，也可以為嵌段共聚物)。 The nonionic surfactant may be a linear and/or branched aliphatic (saturated and/or unsaturated) group of alkylene oxide adducts, linear and/or branched fatty acids (saturated and / or unsaturated) polyalkylene glycol esters, poly An oxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, and the like. Wherein, the structure of the alkylene oxide addition moiety and the polyalkylene glycol moiety is preferably polyoxyethylene (POE) or polyoxypropylene (POP) or POE/POP copolymer (may be a random copolymer, also It can be a block copolymer).

另外，非離子性表面活性劑從環境上的問題(生物降解性、環境激素等)考慮，較佳為不含芳香族基的結構。 Further, the nonionic surfactant is preferably a structure containing no aromatic group from the viewpoint of environmental problems (biodegradability, environmental hormone, etc.).

非離子性表面活性劑可以為式：R1O-(CH2CH2O)p-(R2O)q-R3所示的化合物。 The nonionic surfactant may be a compound represented by the formula: R 1 O-(CH 2 CH 2 O) p -(R 2 O) q -R 3 .

[式中，R1為碳原子數1至22的烷基或碳原子數2至22的烯基或醯基，R2為碳原子數3以上(例如3至10)的伸烷基，R3為氫原子、碳原子數1至22的烷基或碳原子數2至22的烯基，p為2以上的數，q為0或1以上的數] Wherein R 1 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or a fluorenyl group having 2 to 22 carbon atoms, and R 2 is an alkylene group having 3 or more (for example, 3 to 10) carbon atoms, R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more]

R1較佳為碳原子數8至20，特佳為10至18。作為R1的較佳的具體例者，可以舉出：月桂基、十三烷基、油基。 R 1 is preferably from 8 to 20 carbon atoms, particularly preferably from 10 to 18 carbon atoms. Preferred examples of R 1 include a lauryl group, a tridecyl group, and an oil group.

R2的例子為伸丙基、伸丁基。 Examples of R 2 are a propyl group and a butyl group.

在非離子性表面活性劑中，p可以為3以上的數(例如5至200)。q可以為2以上的數(例如5至200)。即，-(R2O)q-可以形成聚氧伸烷基鏈。 In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q can be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - can form a polyoxyalkylene chain.

非離子性表面活性劑可以為在中央含有親水性的聚氧乙烯鏈和疏水性的氧伸烷基鏈(特別是聚氧伸烷基鏈)的聚氧乙烯伸烷基烷基醚。作為疏水性的氧伸烷基鏈者，可以舉出：氧丙烯鏈、氧丁烯鏈、氧苯乙烯鏈等，其中，較 佳為氧丙烯鏈。 The nonionic surfactant may be a polyoxyethylene alkylene ether having a hydrophilic polyoxyethylene chain and a hydrophobic oxygen alkyl chain (particularly a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxygen-extended alkyl chain include an oxypropylene chain, an oxybutylene chain, an oxystyrene chain, and the like. Good for the oxypropylene chain.

較佳的非離子性表面活性劑為式：R1O-(CH2CH2O)p-H所示的表面活性劑。 A preferred nonionic surfactant is a surfactant of the formula: R 1 O-(CH 2 CH 2 O) p -H.

[式中，R1及p與上述的R1和p意義相同] [Wherein, R 1 is p, and the above-described R 1 and the same significance as p]

非離子性表面活性劑的具體例為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等。 A specific example of the nonionic surfactant is C 10 H 21 O-(CH 2 CH 2 O) p -(C 3 H 6 O) q -HC 12 H 25 O-(CH 2 CH 2 O) p -( C 3 H 6 O) q -HC 16 H 31 O-(CH 2 CH 2 O) p -(C 3 H 6 O) q -HC 16 H 33 O-(CH 2 CH 2 O) p -(C 3 H 6 O) q -HC 18 H 35 O-(CH 2 CH 2 O) p -(C 3 H 6 O) q -HC 18 H 37 O-(CH 2 CH 2 O) p -(C 3 H 6 O) q -HC 12 H 25 O-(CH 2 CH 2 O) p -(C 3 H 6 O) q -C 12 H 25 C 16 H 31 O-(CH 2 CH 2 O) p -(C 3 H 6 O) q -C 16 H 31 C 16 H 33 O-(CH 2 CH 2 O) p -(C 3 H 6 O) q -C 12 H 25 iso-C 13 H 27 O-(CH 2 CH 2 O) p -(C 3 H 6 O) q -HC 10 H 21 COO-(CH 2 CH 2 O) p -(C 3 H 6 O) q -HC 16 H 33 COO-(CH 2 CH 2 O ) p -(C 3 H 6 O) q -C 12 H 25 or the like.

[式中，p及q與上述的p及q意義相同] [wherein, p and q have the same meaning as p and q above]

非離子性表面活性劑的具體例可以包含環氧乙烷和己基苯酚、異辛基苯酚、十六醇、油酸、烷烴(C12-C16)硫醇、山梨糖醇酐單脂肪酸(C7-C19)或烷基(C12-C18)胺等的縮合生成物。 Specific examples of the nonionic surfactant may comprise ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16) thiol, sorbitan mono-fatty acid anhydrides (C A condensation product of 7- C 19 ) or an alkyl (C 12 -C 18 )amine or the like.

聚氧乙烯嵌段的比例相對於非離子性表面活性劑(共聚物)的分子量，可以為5至80重量%，例如為 30至75重量%，特別為40至70重量%。 The proportion of the polyoxyethylene block may be from 5 to 80% by weight, based on the molecular weight of the nonionic surfactant (copolymer), for example 30 to 75% by weight, in particular 40 to 70% by weight.

非離子性表面活性劑的平均分子量通常為300至5,000，例如為500至3,000。 The average molecular weight of the nonionic surfactant is usually from 300 to 5,000, for example from 500 to 3,000.

非離子性表面活性劑可以單獨使用1種，也可以並用2種以上。 The nonionic surfactant may be used singly or in combination of two or more.

非離子性表面活性劑較佳為2種以上的組合。在2種以上的組合中，至少1種非離子性表面活性劑可以為R1基(及/或R3基)為支鏈的烷基(例如異十三烷基)的R1O-(CH2CH2O)p-(R2O)q-R3[特別是R1O-(CH2CH2O)p-H]所示的化合物。R1基為支鏈的烷基的非離子性表面活性劑的量相對於非離子性表面活性劑(B2)合計100重量份，可以為5至100重量份，例如為8至50重量份，特別為10至40重量份。在2種以上的組合中，剩餘的非離子性表面活性劑可以為R1基(及/或R3基)為(飽和及/或不飽和的)直鏈的烷基(例如月桂基(正月桂基))的R1O-(CH2CH2O)p-(R2O)q-R3[特別是R1O-(CH2CH2O)p-H]所示的化合物。 The nonionic surfactant is preferably a combination of two or more kinds. In a combination of two or more kinds, at least one nonionic surfactant may be R 1 O- (wherein the R 1 group (and/or the R 3 group) is a branched alkyl group (for example, an isotridecyl group) ( CH 2 CH 2 O) p -(R 2 O) q -R 3 [particularly R 1 O-(CH 2 CH 2 O) p -H]. The amount of the nonionic surfactant having a R 1 group of a branched alkyl group may be 5 to 100 parts by weight, for example, 8 to 50 parts by weight, based on 100 parts by weight of the total of the nonionic surfactant (B2). It is especially 10 to 40 parts by weight. In a combination of two or more kinds, the remaining nonionic surfactant may be a linear alkyl group (saturated and/or unsaturated) of the R 1 group (and/or R 3 group) (for example, lauryl (first month) A compound represented by R 1 O-(CH 2 CH 2 O) p -(R 2 O) q -R 3 [particularly R 1 O-(CH 2 CH 2 O) p -H].

作為非離子性表面活性劑者，例如可以舉出：聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚、聚氧乙烯脂肪酸酯、山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇脂肪酸酯、甘油脂肪酸酯、聚氧乙烯甘油脂肪酸酯、聚甘油脂肪酸酯、蔗糖脂肪酸酯、聚氧乙烯烷基胺、聚氧乙烯脂肪酸醯胺、脂肪酸烷基醇醯胺、烷基烷醇醯胺、乙炔二醇、乙炔二醇的氧乙烯加成物、聚乙二醇聚丙二醇嵌段共聚物等。 Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene sorbitol. Alkyd fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene Fatty acid decylamine, fatty acid alkyl decylamine, alkyl alkanohydrin, acetylene glycol, oxyethylene adduct of acetylene glycol, polyethylene glycol polypropylene glycol block copolymer, and the like.

由於水系乳液的動態表面張力變低(即，水性乳液容易滲入基材)，因此，作為非離子性表面活性劑者，較佳為乙炔醇(特別是乙炔二醇)、或乙炔醇(特別是乙炔二醇)的氧乙烯加成物。 Since the dynamic surface tension of the aqueous emulsion becomes low (that is, the aqueous emulsion easily penetrates into the substrate), as the nonionic surfactant, acetylene alcohol (especially acetylene glycol) or acetylene alcohol (especially An oxyethylene adduct of acetylene glycol).

較佳的非離子性表面活性劑為具有不飽和三鍵的醇或該醇的環氧烷烴加成物(將該醇和該環氧烷烴加成物兩者稱為“乙炔醇化合物”)。特佳的非離子性表面活性劑為具有不飽和三鍵的一元醇或多元醇的環氧烷烴加成物。 A preferred nonionic surfactant is an alcohol having an unsaturated triple bond or an alkylene oxide adduct of the alcohol (both the alcohol and the alkylene oxide adduct are referred to as "ethynyl alcohol compounds"). A particularly preferred nonionic surfactant is an alkylene oxide adduct of a monohydric or polyhydric alcohol having an unsaturated triple bond.

乙炔醇化合物為含有1個以上三鍵和1個以上羥基的化合物。乙炔醇化合物可以為含有聚氧伸烷基部分的化合物。作為聚氧伸烷基部分的例子者，可以舉出：聚氧乙烯、聚氧丙烯、聚氧乙烯和聚氧丙烯的無規加成結構、聚氧乙烯和聚氧丙烯的嵌段加成結構。 The acetylene alcohol compound is a compound containing one or more triple bonds and one or more hydroxyl groups. The acetylene alcohol compound may be a compound containing a polyoxyalkylene moiety. Examples of the polyoxyalkylene moiety include a random addition structure of polyoxyethylene, polyoxypropylene, polyoxyethylene, and polyoxypropylene, and a block addition structure of polyoxyethylene and polyoxypropylene. .

乙炔醇化合物可以為式：HO-CR11R12-C≡C-CR13R14-OH、或HO-CR15R16-C≡C-H所示的化合物。 The acetylene alcohol compound may be a compound represented by the formula: HO-CR 11 R 12 -C≡C-CR 13 R 14 -OH or HO-CR 15 R 16 -C≡CH.

[式中，R11、R12、R13、R14、R15、R16分別可以相同，也可以不同，為氫原子或碳原子數1至30的烷基] [wherein R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be the same or different and may be a hydrogen atom or an alkyl group having 1 to 30 carbon atoms]

乙炔醇化合物可以為該化學式所示的化合物的環氧烷烴加成物。烷基較佳為碳原子數1至12的直鏈狀或支鏈狀的烷基，特佳為碳原子數6至12的直鏈狀或支鏈狀的烷基。例如可以舉出：甲基、乙基、丙基、丁基、異丁基等。另外，作為環氧烷烴者，較佳為環氧乙烷、環氧丙烷等碳原子數 1至20(特別是2至5)的環氧烷烴，環氧烷烴的加成數較佳為1至50。 The acetylene alcohol compound may be an alkylene oxide adduct of the compound represented by the chemical formula. The alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and particularly preferably a linear or branched alkyl group having 6 to 12 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, etc. are mentioned. Further, as the alkylene oxide, carbon atoms such as ethylene oxide and propylene oxide are preferred. The alkylene oxide of 1 to 20 (particularly 2 to 5) preferably has an addition number of alkylene oxide of 1 to 50.

(2-2)陽離子性表面活性劑 (2-2) Cationic surfactant

陽離子性表面活性劑較佳為不具有醯胺基的化合物。 The cationic surfactant is preferably a compound having no guanamine group.

陽離子性表面活性劑可以為胺鹽、季銨鹽、氧乙烯加成型銨鹽。作為陽離子性表面活性劑的具體例者沒有特別限定，可以舉出：烷基胺鹽、胺基醇脂肪酸衍生物、聚胺脂肪酸衍生物、咪唑啉等胺鹽型表面活性劑；烷基三甲基銨鹽、二烷基二甲基銨鹽、烷基二甲基苄基銨鹽、吡啶鎓鹽、烷基異喹啉鎓鹽、苄索氯銨(benzethonium chloride)等季銨鹽型表面活性劑等。 The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene addition molding ammonium salt. Specific examples of the cationic surfactant are not particularly limited, and examples thereof include an alkylamine salt, an amino alcohol fatty acid derivative, a polyamine fatty acid derivative, and an amine salt type surfactant such as an imidazoline; Quaternary ammonium salt type surface activity such as quaternary ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, pyridinium salt, alkyl isoquinolinium salt, benzethonium chloride Agents, etc.

陽離子性表面活性劑的較佳的例子為R21-N+(-R22)(-R23)(-R24)X-的化合物。 A preferred example of the cationic surfactant is a compound of R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - .

[式中，R21、R22、R23及R24為碳原子數1至30的烴基，X為陰離子性基] Wherein R 21 , R 22 , R 23 and R 24 are a hydrocarbon group having 1 to 30 carbon atoms, and X is an anionic group]

R21、R22、R23及R24的具體例為烷基(例如甲基、丁基、硬脂基、棕櫚基)。X的具體例為鹵素(例如氯)、酸(例如鹽酸、乙酸)。 Specific examples of R 21 , R 22 , R 23 and R 24 are an alkyl group (e.g., methyl, butyl, stearyl, palmityl). Specific examples of X are halogen (e.g., chlorine) and acid (e.g., hydrochloric acid, acetic acid).

陽離子性表面活性劑特佳為單烷基三甲基銨鹽(烷基的碳原子數4至30)。 The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (the alkyl group has 4 to 30 carbon atoms).

陽離子性表面活性劑較佳為銨鹽。陽離子性表面活性劑可以為式：R1 p-N+R2 qX-所示的銨鹽。 The cationic surfactant is preferably an ammonium salt. The cationic surfactant may be an ammonium salt represented by the formula: R 1 p -N + R 2 q X - .

[式中，R1為C12以上(例如C12至C50)的直鏈狀及/或支鏈 狀的脂肪族(飽和及/或不飽和)基，R2為H或C1至4的烷基、苄基、聚氧乙烯基(氧乙烯基的數量例如為1(特別為2，特別為3)至50) [wherein, R 1 is a linear and/or branched aliphatic (saturated and/or unsaturated) group having a C12 or higher (for example, C 12 to C 50 ), and R 2 is an H or a C1 to 4 alkane. a group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50)

(特佳為CH3、C2H5)，X為鹵素原子(例如、氟原子、氯原子、溴原子、碘原子等)、C1至C4的脂肪酸鹽基，p為1或2，q為2或3，p+q=4]R1的碳原子數可以為12至50，例如為12至30。 (preferably CH 3 , C 2 H 5 ), and X is a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like), a C 1 to C 4 fatty acid salt group, and p is 1 or 2, q is 2 or 3, and p+q=4] R 1 may have a carbon number of 12 to 50, for example, 12 to 30.

陽離子性表面活性劑的具體例包含十二烷基三甲基乙酸銨、三甲基十四烷基氯化銨、十六烷基三甲基溴化銨、三甲基十八烷基氯化銨、(十二烷基甲基苄基)三甲基氯化銨、苄基十二烷基二甲基氯化銨、甲基十二烷基二(氫聚氧乙烯)氯化銨、苄基十二烷基二(氫聚氧乙烯)氯化銨、N-[2-(二乙基胺基)乙基]油酸醯胺鹽酸鹽。 Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecyl ammonium chloride, cetyltrimethylammonium bromide, and trimethyloctadecyl chloride. Ammonium, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecylbis(hydropolyethyleneethylene)ammonium chloride, benzyl Dodecyl bis(hydropolyethylene oxide) ammonium chloride, N-[2-(diethylamino)ethyl] oleic acid decylamine hydrochloride.

作為兩性表面活性劑者，可以列舉：丙胺酸類、咪唑啉鎓甜菜鹼類、醯胺甜菜鹼類、乙酸甜菜鹼等，具體而言，可以舉出：月桂基甜菜鹼、硬脂基甜菜鹼、月桂基羧甲基羥基乙基咪唑啉鎓甜菜鹼、月桂基二甲基胺基乙酸甜菜鹼、脂肪酸醯胺丙基二甲基胺基乙酸甜菜鹼等。 Examples of the amphoteric surfactant include alanine, imidazolinium betaine, guanamine betain, acetic betaine, and the like, and specific examples thereof include lauryl betaine and stearyl betaine. Lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, fatty acid guanamine propyl dimethyl acetoxy betaine, and the like.

非離子性表面活性劑、陽離子性表面活性劑及兩性表面活性劑分別可以為1種或2以上的組合。 The nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may each be used alone or in combination of two or more.

作為表面活性劑者，可以僅使用非離子性表面活性劑或僅使用陽離子性表面活性劑，但較佳為使用非離子性表面活性劑和陽離子性表面活性劑的組合。在非離子性表面 活性劑和陽離子性表面活性劑的組合中，非離子性表面活性劑和陽離子性表面活性劑的重量比較佳可以為85：15至20：80，更佳可以為80：20至40：60。 As the surfactant, it is possible to use only a nonionic surfactant or only a cationic surfactant, but it is preferred to use a combination of a nonionic surfactant and a cationic surfactant. On non-ionic surfaces In the combination of the active agent and the cationic surfactant, the weight of the nonionic surfactant and the cationic surfactant may preferably be from 85:15 to 20:80, more preferably from 80:20 to 40:60.

表面活性劑的合計量相對於聚合物100重量份，可以為0.1至20重量份，例如為0.2至10重量份。 The total amount of the surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, based on 100 parts by weight of the polymer.

(3)液狀介質 (3) Liquid medium

表面處理劑組成物較佳為聚合物已分散於液狀介質中之分散物。 The surface treatment composition is preferably a dispersion in which the polymer has been dispersed in a liquid medium.

液狀介質可以為有機溶劑，但較佳為水性介質。本說明書中，“水性介質”意指僅由水構成之介質、及除了水之外還含有有機溶劑(通常為水溶性有機溶劑)(相對於水100重量份，有機溶劑的量為80重量份以下，例如為0.1至50重量份，特別為5至30重量份)之介質。 The liquid medium may be an organic solvent, but is preferably an aqueous medium. In the present specification, the "aqueous medium" means a medium composed only of water, and an organic solvent (usually a water-soluble organic solvent) in addition to water (the amount of the organic solvent is 80 parts by weight based on 100 parts by weight of water) Hereinafter, for example, a medium of 0.1 to 50 parts by weight, particularly 5 to 30 parts by weight, is used.

相對於表面處理劑組成物，水性介質的量可以為20至99重量%，例如為40至95重量%。 The amount of the aqueous medium may be from 20 to 99% by weight, for example from 40 to 95% by weight, relative to the surface treatment composition.

(4)其它成分 (4) Other ingredients

表面處理劑組成物也可以含有非氟撥水性化合物作為含氟聚合物及表面活性劑以外的其它成分。 The surface treatment composition may also contain a non-fluorinated water-repellent compound as a fluoropolymer and other components other than the surfactant.

非氟撥水性化合物 Non-fluorine water-repellent compound

表面處理劑組成物有時含有不含氟原子的撥水性化合物(非氟撥水性化合物)。 The surface treatment composition sometimes contains a water-repellent compound (non-fluorinated compound) which does not contain a fluorine atom.

非氟撥水性化合物可以為非氟丙烯酸酯聚合物、飽和 或不飽和的烴化合物、或矽酮系化合物。 Non-fluorinated water-repellent compounds may be non-fluorinated acrylate polymers, saturated Or an unsaturated hydrocarbon compound or an fluorenone compound.

非氟丙烯酸酯聚合物為由1種非氟丙烯酸酯單體構成的均聚物、或者由至少2種非氟丙烯酸酯單體構成的共聚物、或者由至少1種非氟丙烯酸酯單體及至少1種其它的非氟單體(乙烯性不飽和化合物、例如乙烯、乙烯基系單體)構成的共聚物。 The non-fluoroacrylate polymer is a homopolymer composed of one non-fluorinated acrylate monomer, or a copolymer composed of at least two non-fluorinated acrylate monomers, or at least one non-fluorinated acrylate monomer and A copolymer composed of at least one other non-fluorine monomer (an ethylenically unsaturated compound such as ethylene or a vinyl monomer).

構成非氟丙烯酸酯聚合物的非氟丙烯酸酯單體為式：CH2=CA-T所示的化合物。 The non-fluoroacrylate monomer constituting the non-fluoroacrylate polymer is a compound represented by the formula: CH 2 =CA-T.

[式中，A為氫原子、甲基、或氟原子以外的鹵素原子(例如氯原子、溴原子及碘原子)，T為氫原子、碳原子數1至30的鏈狀或環狀的烴基、或具有酯鍵的鏈狀或環狀的碳原子數1至31的有機基] In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom), and T is a hydrogen atom or a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms. Or a chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond]

碳原子數1至30的鏈狀或環狀的烴基的例子為碳原子數1至30的直鏈或支鏈的脂肪族烴基、碳原子數4至30的環狀脂肪族基、碳原子數6至30的芳香族烴基、碳原子數7至30的芳香脂肪族烴基。 Examples of the chain or cyclic hydrocarbon group having 1 to 30 carbon atoms are a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, and a carbon number. An aromatic hydrocarbon group of 6 to 30 and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms.

具有酯鍵的鏈狀或環狀的碳原子數1至31的有機基的例子為-C(=O)-O-Q和-O-C(=O)-Q(在此，Q為碳原子數1至30的直鏈或支鏈的脂肪族烴基、碳原子數4至30的環狀脂肪族基、碳原子數6至30的芳香族烴基、碳原子數7至30的芳香脂肪族烴基)。 Examples of the chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond are -C(=O)-OQ and -OC(=O)-Q (here, Q is a carbon number of 1 to A linear or branched aliphatic hydrocarbon group of 30, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms.

非氟丙烯酸酯單體的例子包含例如(甲基)丙烯酸烷基酯、聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙 二醇(甲基)丙烯酸酯。 Examples of the non-fluoroacrylate monomer include, for example, alkyl (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (methyl). Acrylate, methoxypolypropylene Glycol (meth) acrylate.

非氟丙烯酸酯單體較佳為(甲基)丙烯酸烷基酯。烷基的碳原子數可以為1至30，例如可以為6至30(例如10至30)。非氟丙烯酸酯單體的具體例為(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯及(甲基)丙烯酸二十二烷酯。 The non-fluoroacrylate monomer is preferably an alkyl (meth)acrylate. The alkyl group may have 1 to 30 carbon atoms, and may be, for example, 6 to 30 (for example, 10 to 30). Specific examples of the non-fluoroacrylate monomer are lauryl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate.

非氟丙烯酸酯聚合物可以藉由與含氟聚合物同樣的聚合方法製造。 The non-fluoroacrylate polymer can be produced by the same polymerization method as the fluoropolymer.

飽和或不飽和的烴系化合物較佳為飽和的烴。在飽和或不飽和的烴系化合物中，碳原子數可以為15以上，較佳為20至300，例如為25至100。飽和或不飽和的烴系化合物的具體例為石蠟等。 The saturated or unsaturated hydrocarbon compound is preferably a saturated hydrocarbon. In the saturated or unsaturated hydrocarbon compound, the number of carbon atoms may be 15 or more, preferably 20 to 300, for example, 25 to 100. Specific examples of the saturated or unsaturated hydrocarbon compound are paraffin or the like.

矽酮系化合物通常可以用作撥水劑。矽酮系化合物只要為顯示撥水性的化合物就沒有限定。 Anthrone-based compounds are generally used as water repellents. The anthrone-based compound is not limited as long as it is a compound exhibiting water repellency.

非氟撥水性化合物的量相對於第1含氟聚合物及第2含氟聚合物的合計100重量份，可以為0至500重量份，例如為5至200重量份，特別為5至100重量份。 The amount of the non-fluorine-containing water-repellent compound may be 0 to 500 parts by weight, for example, 5 to 200 parts by weight, particularly 5 to 100 parts by weight, based on 100 parts by total of the total of the first fluorine-containing polymer and the second fluorine-containing polymer. Share.

本發明中的含氟聚合物(第1含氟單體及第2含氟單體)可以藉由通常的聚合方法的任一者來製造，另外，聚合反應的條件也可以任意地選擇。作為這樣的聚合方法者，可以舉出：溶液聚合、懸浮聚合、乳液聚合。 The fluoropolymer (the first fluorinated monomer and the second fluorinated monomer) in the present invention can be produced by any of the usual polymerization methods, and the conditions of the polymerization reaction can be arbitrarily selected. As such a polymerization method, solution polymerization, suspension polymerization, and emulsion polymerization are mentioned.

在溶液聚合中可以採用如下方法：在聚合引發劑的存在下，使單體溶解於有機溶劑，進行氮置換，然後，在30至120℃的範圍內加熱攪拌1至10小時。作為聚合引發劑者，可以舉出例如：偶氮雙異丁腈、過氧化 苯甲醯、二第三丁基過氧化物、過氧化月桂醯、氫過氧化異丙苯、第三丁基過氧化新戊酸酯、二異丙基過氧化二碳酸酯等。相對於單體100重量份，聚合引發劑可以以0.01至20重量份、例如0.01至10重量份的範圍使用。 In the solution polymerization, a method of dissolving a monomer in an organic solvent in the presence of a polymerization initiator, performing nitrogen substitution, and then heating and stirring in the range of 30 to 120 ° C for 1 to 10 hours may be employed. As the polymerization initiator, for example, azobisisobutyronitrile and peroxidation can be mentioned. Benzoquinone, di-tert-butyl peroxide, laurel, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. The polymerization initiator may be used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, based on 100 parts by weight of the monomer.

有機溶劑為對單體呈非活性、並將其溶解的溶劑，例如可以為酯(例如碳原子數2至30的酯，具體而言為乙酸乙酯、乙酸丁酯)、酮(例如碳原子數2至30的酮，具體而言為甲基乙基酮、二異丁基酮)、醇(例如碳原子數1至30的醇，具體而言為異丙醇)。作為有機溶劑的具體例者，可以舉出：丙酮、氯仿、HCHC225、異丙醇、戊烷、己烷、庚烷、辛烷、環己烷、苯、甲苯、二甲苯、石油醚、四氫呋喃、1,4-二噁烷、甲基乙基酮、甲基異丁基酮、二異丁基酮、乙酸乙酯、乙酸丁酯、1,1,2,2-四氯乙烷、1,1,1-三氯乙烷、三氯乙烯、全氯乙烯、四氯二氟乙烷、三氯三氟乙烷等。相對於單體的合計100重量份，有機溶劑可以以10至2000重量份、例如50至1000重量份的範圍使用。 The organic solvent is a solvent which is inactive to the monomer and dissolves it, and may be, for example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate) or a ketone (for example, a carbon atom). A ketone of 2 to 30, specifically, methyl ethyl ketone, diisobutyl ketone, an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropanol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1, 1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like. The organic solvent may be used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by total of the total of the monomers.

在乳液聚合中可以採用如下方法：在聚合引發劑及乳化劑的存在下，使單體在水中乳化，進行氮置換，然後，在50至80℃的範圍內攪拌1至10小時使其共聚。聚合引發劑可以使用過氧化苯甲醯、過氧化月桂醯、過氧化苯甲酸第三丁酯、1-羥基環己基氫過氧化物、3-羧基丙醯基過氧化物、過氧化乙醯、偶氮雙異丁基脒-二鹽酸鹽、偶氮雙異丁腈、過氧化鈉、過硫酸鉀、過硫酸銨等水 溶性的物質或偶氮雙異丁腈、過氧化苯甲醯、二第三丁基過氧化物、過氧化月桂醯、氫過氧化異丙苯、第三丁基過氧化新戊酸酯、二異丙基過氧化二碳酸酯等油溶性的物質。相對於單體100重量份，聚合引發劑可以以0.01至10重量份的範圍使用。 In the emulsion polymerization, a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, nitrogen substitution, and then stirred in a range of 50 to 80 ° C for 1 to 10 hours may be employed. As the polymerization initiator, benzammonium peroxide, laurel peroxide, tert-butyl peroxybenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropyl hydrazine peroxide, acetoxime peroxide, Water such as azobisisobutylphosphonium-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate or ammonium persulfate Soluble substance or azobisisobutyronitrile, benzammonium peroxide, ditributyl peroxide, laurel, cumene hydroperoxide, tert-butyl peroxypivalate, An oil-soluble substance such as isopropyl peroxydicarbonate. The polymerization initiator may be used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

為了得到放置穩定性優異的聚合物水分散液，較佳使用高壓均質機或超音波均質機那樣的能夠賦予強力的破碎能量的乳化裝置，使單體在水中進行微粒化來進行聚合。另外，作為乳化劑者，可以使用陰離子性、陽離子性或者非離子性的各種乳化劑，相對於單體100重量份，可以以0.5至20重量份的範圍使用。較佳使用陰離子性及/或非離子性及/或陽離子性的乳化劑。在單體不完全相溶的情況下，較佳添加能夠使這些單體充分相溶的相溶化劑，例如水溶性有機溶劑或低分子量的單體。藉由添加相溶化劑，能夠使乳化性及共聚性提高。 In order to obtain an aqueous polymer dispersion having excellent standing stability, it is preferable to use an emulsifying device capable of imparting strong breaking energy such as a high-pressure homogenizer or an ultrasonic homogenizer, and to carry out polymerization by atomizing the monomer in water. Further, as the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and it can be used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. Anionic and/or nonionic and/or cationic emulsifiers are preferably used. In the case where the monomers are not completely compatible, it is preferred to add a compatibilizing agent capable of sufficiently intermingling these monomers, such as a water-soluble organic solvent or a low molecular weight monomer. Emulsifying properties and copolymerizability can be improved by adding a compatibilizing agent.

作為水溶性有機溶劑者，可以舉出：丙酮、甲基乙基酮、乙酸乙酯、丙二醇、二丙二醇單甲醚、二丙二醇、三丙二醇、乙醇等，相對於水100重量份，可以以1至50重量份、例如10至40重量份的範圍使用。另外，作為低分子量的單體者，可以舉出：甲基丙烯酸甲酯、甲基丙烯酸縮水甘油酯、甲基丙烯酸2,2,2-三氟乙基酯等，相對於單體的總量100重量份，可以以1至50重量份、例如10至40重量份的範圍使用。 Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, and the like, and may be 1 based on 100 parts by weight of water. It is used in the range of 50 parts by weight, for example, 10 to 40 parts by weight. Further, examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and the like, and the total amount of the monomer. 100 parts by weight may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight.

在聚合中，也可以使用鏈轉移劑。可以根 據鏈轉移劑的使用量改變聚合物的分子量。鏈轉移劑的例子為月桂基硫醇、硫代甘醇、硫代甘油等含硫醇基的化合物(特別是(例如碳原子數1至30的)烷基硫醇)、次磷酸鈉、亞硫酸氫鈉等無機鹽等。相對於單體的總量100重量份，鏈轉移劑的使用量可以以0.01至10重量份、例如0.1至5重量份的範圍使用。 In the polymerization, a chain transfer agent can also be used. Can root The molecular weight of the polymer is varied depending on the amount of chain transfer agent used. Examples of the chain transfer agent are thiol group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly (for example, an alkylthiol having 1 to 30 carbon atoms), sodium hypophosphite, and sub An inorganic salt such as sodium hydrogen sulfate. The chain transfer agent may be used in an amount of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers.

本發明的處理劑組成物可以為溶液、乳液(特別是水性分散液)或氣溶膠的形態，較佳為水性分散液。處理劑組成物含有聚合物(表面處理劑的活性成分)及介質(特別是液狀介質，例如有機溶劑及/或水)。介質的量例如相對於處理劑組成物可以為5至99.9重量%，特別為10至80重量%。 The treatment agent composition of the present invention may be in the form of a solution, an emulsion (particularly an aqueous dispersion) or an aerosol, and is preferably an aqueous dispersion. The treatment composition contains a polymer (active ingredient of a surface treatment agent) and a medium (particularly a liquid medium such as an organic solvent and/or water). The amount of the medium can be, for example, from 5 to 99.9% by weight, particularly from 10 to 80% by weight, relative to the treatment composition.

在處理劑組成物中，聚合物的濃度可以為0.01至95重量%，例如為5至50重量%。 The concentration of the polymer in the treatment composition may be from 0.01 to 95% by weight, for example from 5 to 50% by weight.

本發明的處理劑組成物可以利用現有已知的方法適用於被處理物。通常採用將該處理劑組成物分散於有機溶劑或水中進行稀釋，利用浸塗、噴塗、泡塗等之類的已知的方法，使其附著於被處理物的表面並進行乾燥的方法。另外，如果需要，也可以與適當的交聯劑同時應用並進行固化。進而，也可以在本發明的處理劑組成物中添加併用防蟲劑、柔軟劑、抗菌劑、阻燃劑、抗靜電劑、塗料固定劑、防皺劑等。與基材接觸的處理液中的聚合物的濃度可以為0.01至10重量%(特別是在浸塗的情況)，例如為0.05至10重量%。 The treating agent composition of the present invention can be applied to the object to be treated by a conventionally known method. Usually, the treatment agent composition is dispersed in an organic solvent or water, diluted, and adhered to the surface of the workpiece by a known method such as dip coating, spray coating, or foam coating, and dried. In addition, if necessary, it can also be applied and cured simultaneously with a suitable crosslinking agent. Further, an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, or the like may be added to the treatment agent composition of the present invention. The concentration of the polymer in the treatment liquid in contact with the substrate may be from 0.01 to 10% by weight (particularly in the case of dip coating), for example, from 0.05 to 10% by weight.

作為用本發明的處理劑組成物(例如撥水撥油劑)所處理的被處理物者，可以舉出：纖維製品、石材、過濾器(例如靜電過濾器)、防塵罩、燃料電池的零件(例如氣體擴散電極及氣體擴散支撐體)、玻璃、紙、木、皮革、毛皮、石棉、磚、水泥、金屬及氧化物、陶瓷工業製品、塑膠、塗漆面及牆粉等。作為纖維製品者，可以舉出各種例子。例如可以舉出：棉、麻、羊毛、絲綢等動植物性天然纖維；聚醯胺、聚酯、聚乙烯醇、聚丙烯腈、聚氯乙烯、聚丙烯等合成纖維；人造絲、乙酸酯等半合成纖維；玻璃纖維、碳纖維、石棉纖維等無機纖維；或它們的混合纖維。 Examples of the object to be treated by the treatment agent composition (for example, a water-repellent oil-repellent agent) of the present invention include fiber products, stone materials, filters (for example, electrostatic filters), dust covers, and fuel cell parts. (such as gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide, ceramic industrial products, plastics, painted surfaces and wall powder. As a fiber product, various examples are mentioned. For example, cotton, hemp, wool, silk and other animal and plant natural fibers; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene; rayon, acetate, etc. Semi-synthetic fiber; inorganic fiber such as glass fiber, carbon fiber, asbestos fiber; or a mixed fiber thereof.

纖維製品可以為纖維、布等形態的任一種。 The fibrous product may be in any form such as a fiber or a cloth.

本發明的處理劑組成物也能夠作為內部脫模劑或外部脫模劑使用。 The treatment composition of the present invention can also be used as an internal mold release agent or an external mold release agent.

聚合物能夠利用為了將纖維製品在液體中進行處理而已知的方法的任一種應用於纖維狀基材(例如纖維製品等)。在纖維製品為布時，可以將布浸泡於溶液中，或可以在布上附著或噴霧溶液。為了使處理過的纖維製品表現撥油性，對其進行乾燥，較佳在例如100℃至200℃進行加熱。 The polymer can be applied to a fibrous substrate (e.g., a fibrous product or the like) using any of the methods known for treating a fibrous product in a liquid. When the fibrous product is a cloth, the cloth may be immersed in the solution, or the solution may be attached or sprayed on the cloth. In order to impart oil repellency to the treated fibrous product, it is dried, preferably at, for example, 100 ° C to 200 ° C.

或者，聚合物可以利用清潔法應用於纖維製品，例如可以應用洗滌或在乾洗法等中應用於纖維製品。 Alternatively, the polymer may be applied to the fiber product by a cleaning method, for example, may be applied to a fiber product by washing or in a dry cleaning method or the like.

典型而言，被處理的纖維製品為布，其中包括機織品、針織品、不織布、衣料品形態的布及地毯，但也可以為纖維或紗或中間纖維製品(例如棉條或粗紗 等)。纖維製品材料可以為天然纖維(例如棉或羊毛等)、化學纖維(例如黏膠絲(viscose rayon)或萊奧賽爾(Lyocell)等)、或合成纖維(例如聚酯、聚醯胺或丙烯酸纖維等)，或可以為纖維的混合物(例如天然纖維及合成纖維的混合物等)。本發明的製造聚合物在將纖維素類纖維(例如棉或人造絲等)製成疏油性及撥油性的方面特別有效。另外，本發明的方法通常將纖維製品製成疏水性及撥水性。 Typically, the treated fibrous product is a cloth comprising woven, knit, non-woven, cloth and carpet in the form of a garment, but may also be a fiber or yarn or an intermediate fiber product (such as a sliver or roving). Wait). The fibrous material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or Lyocell, etc.), or synthetic fibers (such as polyester, polyamide or acrylic). Etc.), or may be a mixture of fibers (eg, a mixture of natural fibers and synthetic fibers, etc.). The production of the polymer of the present invention is particularly effective in making cellulose fibers (e.g., cotton or rayon) into oleophobicity and oil repellency. Additionally, the methods of the present invention typically make the fibrous article hydrophobic and water repellency.

或者，纖維狀基材可以為皮革。為了使皮革為疏水性及疏油性，可以在皮革加工的各個階段中，例如皮革的潤濕加工的期間中、或皮革的精加工的期間中，將製造聚合物由水溶液或水性乳化物應用於皮革。 Alternatively, the fibrous substrate may be leather. In order to make the leather hydrophobic and oleophobic, the polymer can be applied from an aqueous solution or an aqueous emulsion during various stages of leather processing, such as during the wetting process of the leather, or during the finishing of the leather. leather.

或者，纖維狀基材可以為紙。可以將製造聚合物應用於預先形成的紙，或可以在造紙的各種階段、例如紙的乾燥期間中應用。 Alternatively, the fibrous substrate can be paper. The manufactured polymer can be applied to pre-formed paper, or can be applied during various stages of papermaking, such as during drying of paper.

“處理”是指將處理劑利用浸漬、噴霧、塗布等應用於被處理物。藉由處理，作為處理劑的有效成分的聚合物浸透於被處理物的內部及/或附著於被處理物的表面。 "Processing" means applying a treating agent to a workpiece by dipping, spraying, coating, or the like. By the treatment, the polymer as an active ingredient of the treatment agent penetrates into the inside of the object to be treated and/or adheres to the surface of the object to be treated.

[實施例] [Examples]

以下，舉出實施例、比較例及試驗例具體地說明本發明。但本發明並不限定於這些說明。 Hereinafter, the present invention will be specifically described by way of examples, comparative examples and test examples. However, the invention is not limited to these descriptions.

以下，只要沒有特別說明，份或%或比表示重量份或重量%或重量比。 Hereinafter, the parts or % or ratio means parts by weight or % by weight or by weight, unless otherwise specified.

試驗的步驟如下所述。 The steps of the test are as follows.

噴淋撥水性試驗 Spray water repellency test

依據JIS-L-1092進行噴淋撥水性試驗。噴淋撥水性試驗(如下述記載的表1所示)利用撥水性No.表示。 The spray water repellency test was carried out in accordance with JIS-L-1092. The spray water repellency test (shown in Table 1 below) is indicated by the water repellency No..

使用體積為至少250ml的玻璃漏斗及能夠用20秒至30秒將250ml的水進行噴霧的噴嘴。試驗片框為直徑15cm的金屬框。準備尺寸約為20cm×20cm的3張試驗片片材，將片材固定於試驗片保持框，使片材沒有褶皺。將噴霧的中心置於片材的中心。在玻璃漏斗中加入室溫的水(250mL)，對試驗片片材(經過25秒至30秒的時間)進行噴霧。從臺上取下保持框，抓住保持框的一端使前方表面處於下側，將相反側一端在堅硬的物質上輕磕，使保持框再旋轉180°，重複相同的步驟，使過量的水滴落。為了以撥水性從不良到優異的順序，進行0、50、70、80、90及100的評分，將濕潤的試驗片與潤濕比較標準物進行比較。從3次測定的平均得到結果。 A glass funnel having a volume of at least 250 ml and a nozzle capable of spraying 250 ml of water with 20 seconds to 30 seconds were used. The test piece frame was a metal frame having a diameter of 15 cm. Three test piece sheets having a size of about 20 cm × 20 cm were prepared, and the sheet was fixed to the test piece holding frame so that the sheet did not wrinkle. Place the center of the spray in the center of the sheet. Room temperature water (250 mL) was added to a glass funnel, and the test piece sheet (after 25 seconds to 30 seconds) was sprayed. Remove the retaining frame from the table, grasp one end of the retaining frame so that the front surface is on the lower side, and the opposite end is tapped on the hard material, so that the retaining frame is rotated by another 180°, repeating the same steps to make excess water droplets drop. In order to score 0, 50, 70, 80, 90, and 100 in terms of water repellency from poor to excellent, the wet test piece was compared with the wet comparison standard. The results were obtained from the average of 3 measurements.

撥水的連續加工性 Continuous processing of water

準備尺寸約為20cm×50cm的10張試驗片片材，利用稀釋成規定的濃度的撥水撥油劑處理液連續地進行處理。對各片材進行上述的噴淋撥水性試驗，進行評價。 Ten test piece sheets having a size of about 20 cm × 50 cm were prepared, and were continuously treated by a water-repellent oil-repellent treatment liquid diluted to a predetermined concentration. Each of the sheets was subjected to the above-described spray water repellency test and evaluated.

製造例1 Manufacturing example 1

在1000mL高壓釜中放入 CF3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)=CH2(n=2.0)(13FC1A)108g、丙烯酸月桂酯(LA)24.0g、甲基丙烯酸異冰片酯(IBMA)57.7g、純水565g、水溶性二醇系溶劑47g、聚氧乙烯油基醚2.5g、聚氧乙烯烷基醚27.8g，在攪拌下、以60℃用超音波使其乳化分散15分鐘。將高壓釜內進行氮置換之後，壓入填充氯乙烯(VCM)62g，添加含偶氮基的水溶性引發劑0.4g，以60℃反應20小時，得到聚合物的水性分散液。聚合物的組成與進料單體的組成基本一致。 In a 1000 mL autoclave, CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(Cl)=CH 2 (n=2.0) (13FC1A) 108 g, and lauryl acrylate (LA) 24.0 g were placed. 57.7 g of isobornyl methacrylate (IBMA), 565 g of pure water, 47 g of water-soluble diol solvent, 2.5 g of polyoxyethylene oleyl ether, and 27.8 g of polyoxyethylene alkyl ether, and stirred at 60 ° C under stirring The ultrasonic wave was emulsified and dispersed for 15 minutes. After replacing the inside of the autoclave with nitrogen, 62 g of vinyl chloride (VCM) was charged, and 0.4 g of a water-soluble initiator containing an azo group was added, and the mixture was reacted at 60 ° C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.

製造例2 Manufacturing Example 2

在500mL反應燒瓶中放入CF3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)=CH2(n=2.0)(13FC1A)51.2g、丙烯酸硬脂酯(StA)85.4g、純水194g、水溶性二醇系溶劑34.1g、氯化烷基三甲基銨6.3g、聚氧乙烯烷基醚7.0g，在攪拌下、以60℃用超音波使其乳化分散15分鐘。將反應燒瓶內進行氮置換之後，添加含偶氮基的水溶性引發劑0.4g和水9g的溶液，以60℃反應20小時，得到聚合物的水性分散液。聚合物的組成與進料單體的組成基本一致。 In a 500 mL reaction flask was placed CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(Cl)=CH 2 (n=2.0) (13FC1A) 51.2 g, stearyl acrylate (StA) 85.4 g, 194 g of pure water, 34.1 g of a water-soluble diol solvent, 6.3 g of alkyltrimethylammonium chloride, and 7.0 g of polyoxyethylene alkyl ether, and emulsified and dispersed by ultrasonic waves at 60 ° C under stirring 15 minute. After the inside of the reaction flask was replaced with nitrogen, a solution of 0.4 g of a water-soluble initiator containing an azo group and 9 g of water was added, and the mixture was reacted at 60 ° C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.

製造例3 Manufacturing Example 3

在1000mL高壓釜中放入CF3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)=CH2(n=2.0)(13FC1A)108g、丙烯酸月桂酯(LA)24.0g、甲基丙烯酸異冰片酯(IBMA)57.7g、純水565g、水溶性二醇系溶劑47g、聚氧乙烯油基 醚2.5g、氯化烷基三甲基銨3.9g、聚氧乙烯烷基醚27.8g，在攪拌下、以60℃用超音波使其乳化分散15分鐘。將高壓釜內進行氮置換之後，壓入填充氯乙烯(VCM)62g，添加含偶氮基的水溶性引發劑0.4g，以60℃反應20小時，得到聚合物的水性分散液。聚合物的組成與進料單體的組成基本一致。 In a 1000 mL autoclave, CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(Cl)=CH 2 (n=2.0) (13FC1A) 108 g, and lauryl acrylate (LA) 24.0 g were placed. 57.7 g of isobornyl methacrylate (IBMA), 565 g of pure water, 47 g of water-soluble diol solvent, 2.5 g of polyoxyethylene oleyl ether, 3.9 g of alkyltrimethylammonium chloride, polyoxyethylene alkyl ether 27.8 g was emulsified and dispersed by ultrasonic waves at 60 ° C for 15 minutes while stirring. After replacing the inside of the autoclave with nitrogen, 62 g of vinyl chloride (VCM) was charged, and 0.4 g of a water-soluble initiator containing an azo group was added, and the mixture was reacted at 60 ° C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.

製造例4 Manufacturing Example 4

在500ml反應燒瓶中放入CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2(n=2.0)(13FMA)51.2g、丙烯酸硬脂酯(StA)85.4g、純水194g、水溶性二醇系溶劑34.1g、氯化烷基三甲基銨6.3g、聚氧乙烯烷基醚7.0g，在攪拌下、以60℃用超音波使其乳化分散15分鐘。將反應燒瓶內進行氮置換之後，添加含偶氮基的水溶性引發劑0.4g及水9g的溶液，以60℃反應20小時，得到聚合物的水性分散液。聚合物的組成與進料單體的組成基本一致。 In a 500 ml reaction flask, put CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(CH 3 )=CH 2 (n=2.0) (13FMA) 51.2 g, stearyl acrylate (StA) 85.4 g, 194 g of pure water, 34.1 g of a water-soluble diol solvent, 6.3 g of alkyltrimethylammonium chloride, and 7.0 g of polyoxyethylene alkyl ether were emulsified and dispersed by ultrasonic waves at 60 ° C under stirring. 15 minutes. After nitrogen substitution in the reaction flask, a solution of 0.4 g of a water-soluble initiator containing azo groups and 9 g of water was added, and the mixture was reacted at 60 ° C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.

製造例5 Manufacturing Example 5

在1000mL高壓釜中放入CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2(n=2.0)(13FMA)108g、丙烯酸月桂酯(LA)24.0g、甲基丙烯酸異冰片酯(IBMA)57.7g、純水565g、水溶性二醇系溶劑47g、聚氧乙烯油基醚2.5g、聚氧乙烯烷基醚27.8g，在攪拌下、以60℃用超音波使其乳化分散15分鐘。將高壓釜內進行氮置換之後， 壓入填充氯乙烯(VCM)62g，添加含偶氮基的水溶性引發劑0.4g，以60℃反應20小時，得到聚合物的水性分散液。聚合物的組成與進料單體的組成基本一致。 In a 1000 mL autoclave, CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(CH 3 )=CH 2 (n=2.0) (13FMA) 108 g, and lauryl acrylate (LA) 24.0 g were placed. 57.7 g of isobornyl methacrylate (IBMA), 565 g of pure water, 47 g of water-soluble diol solvent, 2.5 g of polyoxyethylene oleyl ether, 27.8 g of polyoxyethylene alkyl ether, and 60 ° C under stirring It was emulsified and dispersed by ultrasonic waves for 15 minutes. After the inside of the autoclave was replaced with nitrogen, 62 g of vinyl chloride (VCM) was charged, and 0.4 g of a water-soluble initiator containing an azo group was added thereto, and the mixture was reacted at 60 ° C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.

製造例6 Manufacturing Example 6

在500mL反應燒瓶中放入丙烯酸硬脂酯(StA)47.5g、純水145g、水溶性二醇系溶劑15g、山梨糖醇酐單烷基酯1.5g、聚氧乙烯烷基醚2g、氯化烷基二甲基銨1.5g，在攪拌下、以60℃用超音波使其乳化分散15分鐘。將反應燒瓶內進行氮置換之後，添加含偶氮基的水溶性引發劑0.5g，以60℃反應3小時，得到聚合物的水性分散液。進而，用純水將固體成分濃度調整為30%。 In a 500 mL reaction flask, 47.5 g of stearyl acrylate (StA), 145 g of pure water, 15 g of a water-soluble glycol solvent, 1.5 g of sorbitan monoalkyl ester, 2 g of polyoxyethylene alkyl ether, and chlorination were placed. 1.5 g of alkyldimethylammonium was emulsified and dispersed by ultrasonic waves at 60 ° C for 15 minutes while stirring. After the inside of the reaction flask was replaced with nitrogen, 0.5 g of a water-soluble initiator containing an azo group was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. Further, the solid content concentration was adjusted to 30% with pure water.

製造例7 Manufacturing Example 7

在500mL高壓釜中放入丙烯酸硬脂酯(StA)35g、純水145g、水溶性二醇系溶劑15g、山梨糖醇酐單烷基酯1g、聚氧乙烯烷基醚2g、氯化烷基二甲基銨2g，在攪拌下、以60℃用超音波使其乳化分散15分鐘。將高壓釜內進行氮置換之後，壓入進料12.5g氯乙烯，添加2,2-偶氮雙(2-脒基丙烷)二鹽酸鹽0.5g，以60℃反應3小時，得到聚合物的水性分散液。進而，用純水將固體成分濃度調整為30%。 In a 500 mL autoclave, 35 g of stearyl acrylate (StA), 145 g of pure water, 15 g of a water-soluble diol solvent, 1 g of sorbitan monoalkyl ester, 2 g of polyoxyethylene alkyl ether, and an alkyl chloride were placed. 2 g of dimethylammonium was emulsified and dispersed by ultrasonic waves at 60 ° C for 15 minutes while stirring. After replacing the inside of the autoclave with nitrogen, 12.5 g of vinyl chloride was fed in, and 0.5 g of 2,2-azobis(2-amidinopropane) dihydrochloride was added thereto, and the mixture was reacted at 60 ° C for 3 hours to obtain a polymer. Aqueous dispersion. Further, the solid content concentration was adjusted to 30% with pure water.

比較製造例1 Comparative manufacturing example 1

在500ml反應燒瓶中放入 CF3CF2-(CF2CF2)n-CH2CH2OCOCH=CH2(n=3.2)(NSFA)51.2g、丙烯酸硬脂酯(StA)85.4g、純水194g、水溶性二醇系溶劑34.1g、氯化烷基三甲基銨6.3g、聚氧乙烯烷基醚7.0g，在攪拌下、以60℃用超音波使其乳化分散15分鐘。將反應燒瓶內進行氮置換之後，添加含偶氮基的水溶性引發劑0.4g及水9g的溶液，以60℃反應20小時，得到聚合物的水性分散液。聚合物的組成與進料單體的組成基本一致。 In a 500 ml reaction flask, 51.2 g of CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOCH=CH 2 (n=3.2) (NSFA), 85.4 g of stearyl acrylate (StA), pure 194 g of water, 34.1 g of a water-soluble diol solvent, 6.3 g of alkyltrimethylammonium chloride, and 7.0 g of polyoxyethylene alkyl ether were emulsified and dispersed by ultrasonic waves at 60 ° C for 15 minutes while stirring. After nitrogen substitution in the reaction flask, a solution of 0.4 g of a water-soluble initiator containing azo groups and 9 g of water was added, and the mixture was reacted at 60 ° C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.

比較製造例2 Comparative manufacturing example 2

在1000mL高壓釜中放入CF3CF2-(CF2CF2)n-CH2CH2OCOCH=CH2(n=3.2)(NSFA)108g、丙烯酸硬脂酯(StA)81.7g、純水565g、水溶性二醇系溶劑47g、聚氧乙烯油基醚2.5g、聚氧乙烯烷基醚27.8g，在攪拌下、以60℃用超音波使其乳化分散15分鐘。將高壓釜內進行氮置換之後，壓入填充氯乙烯(VCM)62g，添加含偶氮基的水溶性引發劑0.4g，以60℃反應20小時，得到聚合物的水性分散液。聚合物的組成與進料單體的組成基本一致。 In a 1000 mL autoclave, CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOCH=CH 2 (n=3.2) (NSFA) 108 g, stearyl acrylate (StA) 81.7 g, pure water were placed. 565 g, 47 g of a water-soluble diol solvent, 2.5 g of polyoxyethylene oleyl ether, and 27.8 g of polyoxyethylene alkyl ether were emulsified and dispersed by ultrasonic waves at 60 ° C for 15 minutes while stirring. After replacing the inside of the autoclave with nitrogen, 62 g of vinyl chloride (VCM) was charged, and 0.4 g of a water-soluble initiator containing an azo group was added, and the mixture was reacted at 60 ° C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.

比較製造例3 Comparative Manufacturing Example 3

在500ml反應燒瓶中放入石蠟(熔點50℃)136.6g、純水194g、水溶性二醇系溶劑34.1g、氯化烷基三甲基銨6.3g、聚氧乙烯烷基醚7.0g，在攪拌下、以60℃用超音波使其乳化分散15分鐘。得到水性分散液。聚合物的組成與進料單體的組成基本一致。 In a 500 ml reaction flask, 136.6 g of paraffin wax (melting point 50 ° C), 194 g of pure water, 34.1 g of a water-soluble glycol solvent, 6.3 g of alkyltrimethylammonium chloride, and 7.0 g of polyoxyethylene alkyl ether were placed. The mixture was emulsified and dispersed by ultrasonic waves at 60 ° C for 15 minutes while stirring. An aqueous dispersion is obtained. The composition of the polymer is substantially identical to the composition of the feed monomer.

實施例1 Example 1

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在製造例1、2中製造的水性液體後，以50：50混合並充分攪拌後，以該30%稀釋液的比例成為2%的方式用水進一步稀釋，製備2.00%的試驗液(100g)。將10張PET布(500mm×200mm)連續地浸泡於該試驗液中，通過軋布機(mangle)，以170℃用針板拉幅機處理1分鐘。然後進行撥水性試驗。將結果示於表A。針對濃度1.00%、1.20%及1.40%的試驗液，亦測定初期撥水性，將結果亦示於表A。 The aqueous liquid produced in Production Examples 1 and 2 was diluted with pure water so that the fluoropolymer concentration became a solid component of 30%, and then mixed at 50:50 and thoroughly stirred, and then the ratio of the 30% diluted solution was 2 The % method was further diluted with water to prepare 2.00% of a test solution (100 g). Ten sheets of PET cloth (500 mm × 200 mm) were continuously immersed in the test liquid, and treated by a pin tenter at 170 ° C for 1 minute by a mangle. Then the water repellency test was carried out. The results are shown in Table A. The initial water repellency was also measured for test solutions having concentrations of 1.00%, 1.20%, and 1.40%, and the results are also shown in Table A.

實施例2 Example 2

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在製造例1、2中製造的水性液體後，以30：70混合並充分攪拌後，以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Production Examples 1 and 2 was diluted with pure water so as to have a fluoropolymer concentration of 30% solid content, and then mixed at 30:70 and thoroughly stirred, and then treated in the same manner as in Example 1. Evaluation. The results are shown in Table A.

實施例3 Example 3

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在製造例2、3中製造的水性液體後，以50：50混合並充分攪拌後，以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Production Examples 2 and 3 was diluted with pure water so as to have a fluoropolymer concentration of 30% solid content, and then mixed at 50:50 and thoroughly stirred, and then treated in the same manner as in Example 1. Evaluation. The results are shown in Table A.

實施例4 Example 4

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在製造例2、3中製造的水性液體後，以70：30混合並充分攪拌後，以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Production Examples 2 and 3 was diluted with pure water so as to have a fluoropolymer concentration of 30% solid content, and then mixed at 70:30 and thoroughly stirred, and then treated in the same manner as in Example 1. Evaluation. The results are shown in Table A.

實施例5 Example 5

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在製造例4、5中製造的水性液體後，以50：50混合並充分攪拌後，以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Production Examples 4 and 5 was diluted with pure water so as to have a fluoropolymer concentration of 30% solid content, and then mixed at 50:50 and thoroughly stirred, and then treated in the same manner as in Example 1. Evaluation. The results are shown in Table A.

實施例6 Example 6

利用純水以聚合物濃度成為30%固體成分的方式稀釋在製造例1、2及6中製造的水性液體後，以50：17.5：32.5混合並充分攪拌後，以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Production Examples 1, 2, and 6 was diluted with pure water so that the polymer concentration became 30% solid content, and then mixed with 50:17.5:32.5 and thoroughly stirred, and then, the same procedure as in Example 1 was carried out. Process and evaluate. The results are shown in Table A.

實施例7 Example 7

利用純水以聚合物濃度成為30%固體成分的方式稀釋在製造例1、2及7中製造的水性液體後，以50：25：25混合並充分攪拌後，以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Production Examples 1, 2, and 7 was diluted with pure water so that the polymer concentration became 30% solid content, and then mixed at 50:25:25 and thoroughly stirred, and then, the same procedure as in Example 1 was carried out. Process and evaluate. The results are shown in Table A.

比較實施例1 Comparative Example 1

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在製造例1中製造的水性液體後，以該30%稀釋液的比例成為2%的方式用水進一步進行稀釋，製備2.00%的試驗液(100g)。以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Production Example 1 was diluted with pure water so that the fluoropolymer concentration became 30% solid content, and further diluted with water so that the ratio of the 30% diluted solution became 2%, and 2.00% was prepared. Test solution (100 g). Thereafter, the treatment was carried out in the same manner as in Example 1 and evaluated. The results are shown in Table A.

比較實施例2 Comparative Example 2

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在製造例2中製造的水性液體後，以該30%稀釋液的比例成為2%的方式用水進一步進行稀釋，製備2.00%的試驗液(100g)。以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Production Example 2 was diluted with pure water so as to have a fluoropolymer concentration of 30% solid content, and further diluted with water so that the ratio of the 30% diluted solution became 2%, and 2.00% was prepared. Test solution (100 g). Thereafter, the treatment was carried out in the same manner as in Example 1 and evaluated. The results are shown in Table A.

比較實施例3 Comparative Example 3

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在製造例3中製造的水性液體後，以該30%稀釋液的比例成為2%的方式用水進一步進行稀釋，製備2.00%的試驗液(100g)。以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Production Example 3 was diluted with pure water so as to have a fluoropolymer concentration of 30% solid content, and further diluted with water so that the ratio of the 30% diluted solution became 2%, and 2.00% was prepared. Test solution (100 g). Thereafter, the treatment was carried out in the same manner as in Example 1 and evaluated. The results are shown in Table A.

比較實施例4 Comparative Example 4

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在製造例4中製造的水性液體後，以該30%稀釋液的比例成為2%的方式用水進一步進行稀釋，製備2.00%的試 驗液(100g)。以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Production Example 4 was diluted with pure water so that the fluoropolymer concentration became 30% solid content, and further diluted with water so that the ratio of the 30% diluted solution became 2%, and 2.00% was prepared. test Test solution (100g). Thereafter, the treatment was carried out in the same manner as in Example 1 and evaluated. The results are shown in Table A.

比較實施例5 Comparative Example 5

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在製造例5中製造的水性液體後，以該30%稀釋液的比例成為2%的方式用水進一步進行稀釋，製備2.00%的試驗液(100g)。以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Production Example 5 was diluted with pure water so as to have a fluoropolymer concentration of 30% solid content, and further diluted with water so that the ratio of the 30% diluted solution became 2%, and 2.00% was prepared. Test solution (100 g). Thereafter, the treatment was carried out in the same manner as in Example 1 and evaluated. The results are shown in Table A.

比較實施例6 Comparative Example 6

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在比較製造例1中製造的水性液體後，以該30%稀釋液的比例成為2%的方式用水進一步進行稀釋，製備2.00%的試驗液(100g)。以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Comparative Production Example 1 was diluted with pure water so that the fluoropolymer concentration became 30% solid content, and further diluted with water so that the ratio of the 30% diluted solution became 2%, and 2.00% was prepared. Test solution (100g). Thereafter, the treatment was carried out in the same manner as in Example 1 and evaluated. The results are shown in Table A.

比較實施例7 Comparative Example 7

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在比較製造例2中製造的水性液體後，以該30%稀釋液的比例成為2%的方式用水進一步進行稀釋，製備2.00%的試驗液(100g)。以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Comparative Production Example 2 was diluted with pure water so that the fluoropolymer concentration became a solid component of 30%, and further diluted with water so that the ratio of the 30% diluted solution became 2%, and 2.00% was prepared. Test solution (100g). Thereafter, the treatment was carried out in the same manner as in Example 1 and evaluated. The results are shown in Table A.

比較實施例8 Comparative Example 8

利用純水以含氟聚合物濃度成為30%固體成分的方式稀釋在製造例1及比較製造例3中製造的水性液體後，以75：25混合並充分攪拌後，以該30%稀釋液的比例成為2%的方式用水進一步進行稀釋，製備2.00%的試驗液(100g)。以後與實施例1同樣地進行處理並評價。將結果示於表A。 The aqueous liquid produced in Production Example 1 and Comparative Production Example 3 was diluted with pure water so as to have a fluoropolymer concentration of 30% solid content, and then mixed at 75:25 and thoroughly stirred, and then the 30% diluted solution was used. The ratio was 2%, and the mixture was further diluted with water to prepare 2.00% of a test liquid (100 g). Thereafter, the treatment was carried out in the same manner as in Example 1 and evaluated. The results are shown in Table A.

縮寫的含義如下所述。 The meaning of the abbreviations is as follows.

[產業上的可利用性] [Industrial availability]

本發明的表面處理劑組成物例如可以用作撥水撥油劑、防污劑及脫污劑。 The surface treatment composition of the present invention can be used, for example, as a water and oil repellent, an antifouling agent, and a detergent.

Claims (13)

一種表面處理劑組成物，其含有：(I)具有由含氟單體(a)衍生的重複單元及由鹵化烯烴(b)衍生的重複單元的第1含氟聚合物；(II)具有由含氟單體(a)衍生的重複單元而不具有由鹵化烯烴衍生的重複單元的第2含氟聚合物；以及(III)液狀介質。 A surface treatment composition comprising: (I) a first fluoropolymer having a repeating unit derived from a fluoromonomer (a) and a repeating unit derived from a halogenated olefin (b); a second fluoropolymer having a fluoromonomer (a)-derived repeating unit without a repeating unit derived from a halogenated olefin; and (III) a liquid medium. 如申請專利範圍第1項所述的表面處理劑組成物，其中，含氟單體(a)為式：CH2=C(-X)-C(=O)-Y-Z-Rf (I)所示的化合物，式中，X為氫原子、碳原子數1至21的直鏈狀或支鏈狀的烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基、氰基、碳原子數1至21的直鏈狀或支鏈狀的氟烷基、取代或非取代的苄基、取代或非取代的苯基，其中，X1及X2為氫原子、氟原子、氯原子、溴原子或碘原子；Y為-O-或-NH-；Z為直接鍵結，碳原子數1至20的直鏈狀或支鏈狀脂肪族基，碳原子數6至30的芳香族基或環狀脂肪族基，式-R2(R1)N-SO2-或式-R2(R1)N-CO-所示的基，式中，R1為碳原子數1至10的烷基，R2為碳原子数1至10的直鏈伸烷基或支鏈伸烷基， 式-CH2CH(OR3)CH2-(Ar-O)p-所示的基，式中，R3為氫原子或碳原子数1至10的醯基，Ar為根據需要具有取代基的伸芳基，p表示0或1，式-CH2-Ar-(O)q-所示的基，式中，Ar為根據需要具有取代基的伸芳基，q為0或1，或者-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基，其中，m為1至10，n為0至10；Rf為碳原子數1至20的直鏈狀或支鏈狀的氟烷基。 The surface treatment composition according to claim 1, wherein the fluorine-containing monomer (a) is of the formula: CH 2 =C(-X)-C(=O)-YZ-Rf (I) A compound wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group, or a cyano group. a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, wherein X 1 and X 2 are a hydrogen atom or a fluorine atom. a chlorine atom, a bromine atom or an iodine atom; Y is -O- or -NH-; Z is a direct-bonding, linear or branched aliphatic group having 1 to 20 carbon atoms, and having 6 to 30 carbon atoms An aromatic group or a cyclic aliphatic group, a group represented by the formula -R 2 (R 1 )N-SO 2 - or a formula -R 2 (R 1 )N-CO-, wherein R 1 is a number of carbon atoms An alkyl group of 1 to 10, R 2 is a linear alkyl or a branched alkyl group having 1 to 10 carbon atoms, represented by the formula -CH 2 CH(OR 3 )CH 2 -(Ar-O) p - In the formula, R 3 is a hydrogen atom or a fluorenyl group having 1 to 10 carbon atoms, Ar is an extended aryl group having a substituent as needed, and p is 0 or 1, and the formula -CH 2 -Ar-(O) q - In the formula, wherein Ar is an extended aryl group having a substituent as required, q is 0 or 1, or -(CH 2 ) m -SO 2 -(CH 2 ) n - group or -(CH 2 ) m -S-(CH 2 ) n - group, wherein m is 1 to 10, n is 0 to 10; and Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. 如申請專利範圍第1或2項所述的表面處理劑組成物，其中，含氟單體(a)為α位被氯原子取代的丙烯酸酯。 The surface treatment composition according to claim 1 or 2, wherein the fluorine-containing monomer (a) is an acrylate having an α-position substituted with a chlorine atom. 如申請專利範圍第2項所述的表面處理劑組成物，其中，含氟單體(a)中，Rf的碳原子數為1至6。 The surface treatment composition according to claim 2, wherein, in the fluorine-containing monomer (a), Rf has 1 to 6 carbon atoms. 如申請專利範圍第1項所述的表面處理劑組成物，其中，鹵化烯烴單體(b)為氯乙烯。 The surface treatment composition according to claim 1, wherein the halogenated olefin monomer (b) is vinyl chloride. 如申請專利範圍第1至5項中任一項所述的表面處理劑組成物，其中，第1含氟聚合物及第2含氟聚合物的至少一者具有由其它單體(c)衍生的重複單元，其它單體(c)為非氟非交聯性單體(c1)，非氟非交聯性單體(c1)為式：CH2=CA-T所示的化合物，式中，A為氫原子、甲基或氟原子以外的鹵原子，T為氫原子、碳原子數1至30的鏈狀或環狀的烴基、或具有酯鍵的鏈狀或環狀的碳原子數1至31的有機基。 The surface treatment composition according to any one of claims 1 to 5, wherein at least one of the first fluoropolymer and the second fluoropolymer has a derivative derived from the other monomer (c) a repeating unit, the other monomer (c) is a non-fluorine non-crosslinkable monomer (c1), and the non-fluorine non-crosslinkable monomer (c1) is a compound represented by the formula: CH 2 =CA-T, wherein A is a hydrogen atom, a halogen atom other than a methyl group or a fluorine atom, T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic carbon atom having an ester bond 1 to 31 organic groups. 如申請專利範圍第1至6項中任一項所述的表面處理劑 組成物，其中，第1含氟聚合物中，相對於含氟單體(a)100重量份，鹵化烯烴單體(b)的量為5至300重量份，根據需要存在的其它單體(c)的量為0至800重量份，第2含氟聚合物中，相對於含氟單體(a)100重量份，根據需要存在的其它單體(c)的量為0至800重量份。 Surface treatment agent according to any one of claims 1 to 6 In the composition, in the first fluoropolymer, the amount of the halogenated olefin monomer (b) is from 5 to 300 parts by weight, based on 100 parts by weight of the fluoromonomer (a), and other monomers are present as needed ( The amount of c) is from 0 to 800 parts by weight, and the amount of the other monomer (c) present in the second fluoropolymer is from 0 to 800 parts by weight, based on 100 parts by weight of the fluoromonomer (a). . 如申請專利範圍第1至7項中任一項所述的表面處理劑組成物，其中，第1含氟聚合物和第2含氟聚合物的重量比為5：95至95：5。 The surface treatment composition according to any one of claims 1 to 7, wherein the weight ratio of the first fluoropolymer to the second fluoropolymer is from 5:95 to 95:5. 如申請專利範圍第1至8項中任一項所述的表面處理劑組成物，其中，液狀介質(III)為水、或水與水溶性有機溶劑之混合物。 The surface treatment composition according to any one of claims 1 to 8, wherein the liquid medium (III) is water or a mixture of water and a water-soluble organic solvent. 如申請專利範圍第1至9項中任一項所述的表面處理劑組成物，其為含有非離子性表面活性劑和陽離子性表面活性劑的水性分散液。 The surface treatment composition according to any one of claims 1 to 9, which is an aqueous dispersion containing a nonionic surfactant and a cationic surfactant. 如申請專利範圍第1至10項中任一項所述的表面處理劑組成物，其含有不含氟原子的撥水性化合物。 The surface treatment composition according to any one of claims 1 to 10, which contains a water-repellent compound having no fluorine atom. 如申請專利範圍第1至11項中任一項所述的表面處理劑組成物，其中，表面處理劑組成物為撥水撥油劑組成物、防污劑組成物或脫污劑組成物。 The surface treatment composition according to any one of claims 1 to 11, wherein the surface treatment composition is a water- and oil-repellent composition, an anti-fouling composition or a detergent composition. 一種基材，其係藉由申請專利範圍第1至12中任一項所述的表面處理劑組成物處理而得到者。 A substrate obtained by treating the surface treatment composition according to any one of claims 1 to 12.
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