TW201321418A - Fluorine-containing composition and fluorine-containing polymer - Google Patents

Fluorine-containing composition and fluorine-containing polymer Download PDF

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TW201321418A
TW201321418A TW101138379A TW101138379A TW201321418A TW 201321418 A TW201321418 A TW 201321418A TW 101138379 A TW101138379 A TW 101138379A TW 101138379 A TW101138379 A TW 101138379A TW 201321418 A TW201321418 A TW 201321418A
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fluorine
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carbon atoms
containing composition
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Jun Miki
Kouji Kubota
Kensuke Mohara
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Daikin Ind Ltd
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/295—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing fluorine

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Abstract

The present invention discloses a fluorine-containing composition which contains a fluorine-containing polymer having a repeat unit derived from a fluorine-containing monomer (a) represented by the formula: CH2=C(-X)-C(=O)-Y-Z-A-(CF2-CH2)a-Rf [wherein, X represents a hydrogen atom, a monovalent organic group or a halogen atom, Y represents -O- or -NH-, Z represents a direct bond or a divalent organic group, Rf represents a fluoroalkyl group with acarbonnumberof 1 to 20, A represents a linear (with acarbonnumberof an odd number of 3 or more) or a branch (with acarbonnumberof an integer of 3 or more) alkylene, a represents an integer of 1 to 50.] The fluorine-containing composition has properties required as a surface treating agent, such as water-/oil-repellent ability, soil resistance, mold releasing ability, adhesiveness to substrate, corrosion resistance, touch feeling, water resistance, oil resistance, and the durability thereof.

Description

含氟組成物及含氟聚合物 Fluorine-containing composition and fluoropolymer

本發明是關於含氟組成物及含氟聚合物。含氟組成物可使用於做為良好的表面處理劑，例如，撥水撥油劑、抗污劑及脫模劑。 This invention relates to a fluorine-containing composition and a fluorine-containing polymer. The fluorine-containing composition can be used as a good surface treatment agent, for example, a water-repellent oil-repellent agent, an anti-fouling agent, and a mold release agent.

向來，有種種的含氟化合物的提案。含氟化合物有耐熱性、耐氧化性、耐候性等特性優異的有利之點。利用含氟化合物的自由能低，即，不容易附著的特性，含氟化合物是例如，做為撥水撥油劑及抗污劑而被使用。例如，在美國發明專利第5247008號說明書中，有陳述一種纖維製品、皮革、紙及礦物基材的塗飾劑(finishing agent)，該塗飾劑係為(甲基)丙烯酸的全氟烷酯、與(甲基)丙烯酸的烷酯、及(甲基)丙烯酸的胺基烷酯的共聚物的水性分散物。 There have always been proposals for various fluorine-containing compounds. The fluorine-containing compound is advantageous in that it has 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 anti-fouling agent, because of the low free energy of the fluorine-containing compound, that is, the property of not easily adhering. For example, in the specification of U.S. Patent No. 5,247,008, there is a finishing agent for a fibrous product, a leather, a paper, and a mineral substrate, the finishing agent being a perfluoroalkyl ester of (meth)acrylic acid, and An aqueous dispersion of a copolymer of an alkyl (meth)acrylate and an aminoalkyl (meth)acrylate.

對於撥水撥油劑及抗污劑的表面機能的安定的顯現，由全氟烷基在表面會安定定向排列的具有碳數8以上的全氟烷基的含氟單體所構成的聚合物或共聚物被認為有效。 For the stability of the surface function of the water- and oil-repellent agent and the anti-fouling agent, a polymer composed of a fluorine-containing monomer having a perfluoroalkyl group having a carbon number of 8 or more and a perfluoroalkyl group which is stably aligned on the surface Or a copolymer is considered to be effective.

但是，近年來，EPA(美國環境保護廳)指出，具有碳數8以上的全氟烷基的含氟單體的分解生成物是有對環境成為負荷高的可能性的化合物，有對由不含碳數8以上的全氟烷基的含氟單體所 構成的聚合物或共聚物的撥水撥油劑或抗污劑的需求。向來的(甲基)丙烯酸的(全)氟烷酯如為碳數6以下的全氟烷基則在表面的全氟烷基的定向排列不安定，做為撥水撥油劑、抗污劑或脫模劑則有不能充分給予所需求的性能的不利情況。 However, in recent years, the EPA (United States Environmental Protection Agency) pointed out that a decomposition product of a fluorine-containing monomer having a perfluoroalkyl group having a carbon number of 8 or more is a compound having a high potential for environmental load, and there is a right a fluorine-containing monomer containing a perfluoroalkyl group having 8 or more carbon atoms The need for a water- and oil-repellent or anti-fouling agent for the polymer or copolymer. The (per)fluoroalkyl ester of (meth)acrylic acid, such as a perfluoroalkyl group having a carbon number of 6 or less, is unstable in the orientation of the perfluoroalkyl group on the surface, and is used as a water-repellent oil-repellent agent and an anti-fouling agent. Or mold release agents have the disadvantage of not being able to adequately impart the desired properties.

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

[專利文獻1]美國發明專利第5247008號說明書 [Patent Document 1] US Invention Patent No. 5247008

本發明的一個目的是提供一種使用作為含氟單體的含氟化合物，該含氟化合物即使是有碳數6以下的全氟烷基仍給予做為撥水撥油劑、抗污劑或脫模劑所需求的充分的性能。本發明的其他目的是提供一種含氟組成物，該含氟組成物具有做為表面處理劑所需求的性能，例如，撥水撥油性、抗污性、脫模性、對基材的密著性、防蝕性、觸感、耐水性、耐油性、這些性能的耐久性。 An object of the present invention is to provide a fluorine-containing compound which is used as a fluorine-containing monomer which is imparted as a water- and oil-repellent agent, an antifouling agent or a dechlorination even if it has a perfluoroalkyl group having a carbon number of 6 or less. The sufficient performance required for the molding agent. Another object of the present invention is to provide a fluorine-containing composition having properties required as a surface treating agent, for example, water repellency, stain resistance, mold release property, adhesion to a substrate Sex, corrosion resistance, touch, water resistance, oil resistance, durability of these properties.

本發明是提供式：CH2=C(-X)-C(=O)-Y-Z-A-(CF2-CH2)a-Rf所示的含氟化合物，[式中，X是氫原子、一價有機基或鹵素原子，Y是-O-或-NH-，Z是直接鍵結或二價有機基，Rf是碳數1至20的氟烷基，A是直鏈(碳數是3以上的奇數)或分枝鏈(碳數是3以上的整 數)的伸烷基(alkylene)，a是1至50的整數]。 The present invention provides a fluorine-containing compound represented by the formula: CH 2 =C(-X)-C(=O)-YZA-(CF 2 -CH 2 ) a -Rf, wherein X is a hydrogen atom, a valence organic group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms, and A is a linear chain (carbon number is 3 or more) An odd number) or a branched chain (an alkylene having a carbon number of 3 or more), a is an integer from 1 to 50].

再者，本發明是提供一種含氟聚合物，該含氟聚合物具有由該含氟化合物(含氟單體)所衍生的重複單元。 Further, the present invention provides a fluorine-containing polymer having a repeating unit derived from the fluorine-containing compound (fluoromonomer).

再者，本發明是提供含有該含氟聚合物的含氟組成物。 Furthermore, the present invention provides a fluorine-containing composition containing the fluoropolymer.

依本發明則可得，做為撥水撥油劑、抗污劑或脫模劑所需求的充分的性能。含氟組成物具有做為表面處理劑所需求的性能，例如，良好的撥水撥油性、抗污性、脫模性、對基材的密著性、防蝕性、觸感、耐水性、耐油性、這些性能的耐久性。 According to the present invention, it is available as a sufficient performance for water-repellent, anti-fouling or mold release agents. The fluorine-containing composition has properties required as a surface treatment agent, for example, good water repellency, stain resistance, mold release property, adhesion to a substrate, corrosion resistance, touch, water resistance, and oil resistance Sex, the durability of these properties.

在本發明中，含氟組成物可做為表面處理劑(例如，撥水撥油劑、抗污劑及脫模劑)而使用。 In the present invention, the fluorine-containing composition can be used as a surface treatment agent (for example, a water-repellent oil-repellent agent, an anti-fouling agent, and a mold release agent).

含氟組成物含有含氟聚合物。含氟聚合物具有由含氟單體衍生的重複單元。 The fluorine-containing composition contains a fluorine-containing polymer. The fluoropolymer has repeating units derived from a fluoromonomer.

在本發明中，構成含氟聚合物的單體是使用含氟單體(a)。有必要則可使用非氟非交聯性單體(b)及/或非氟交聯性單體(c)。 In the present invention, the monomer constituting the fluoropolymer is a fluoromonomer (a). If necessary, a non-fluorine non-crosslinkable monomer (b) and/or a non-fluorine crosslinkable monomer (c) may be used.

含氟聚合物可以是只由含氟單體(a)所成的聚合物(即，同元聚合物，或2種以上的含氟單體(a)所成的共聚物)，或由在含氟單體(a)之外復有非氟非交聯性單體(b)及/或非氟交聯性單體(c)所成的共聚物。 The fluoropolymer may be a polymer formed only of the fluoromonomer (a) (that is, a homopolymer or a copolymer of two or more fluoromonomers (a)), or A copolymer of a non-fluorine non-crosslinkable monomer (b) and/or a non-fluorine crosslinkable monomer (c) in addition to the fluorine-containing monomer (a).

(a)含氟單體 (a) fluoromonomer

含氟單體(a)是式：CH2=C(-X)-C(=O)-Y-Z-A-(CF2-CH2)a-Rf所示的含氟單體，[式中，X是氫原子、一價有機基或鹵素原子，Y是-O-或-NH-，Z是直接鍵結或二價有機基，Rf是碳數1至20的氟烷基，A是直鏈(碳數是3以上的奇數)或分枝鏈(碳數是3以上的整數)的伸烷基，a是1至50的整數]。 The fluorine-containing monomer (a) is a fluorine-containing monomer represented by the formula: CH 2 =C(-X)-C(=O)-YZA-(CF 2 -CH 2 ) a -Rf, [wherein, X Is a hydrogen atom, a monovalent organic group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms, and A is a linear chain ( The carbon number is an odd number of 3 or more or a branched chain (the carbon number is an integer of 3 or more), and a is an integer of 1 to 50].

含氟單體(a)是以通式：CH2=C(-X)-C(=O)-Y-Z-A-(CF2-CH2)a-Rf所示的丙烯酸酯或丙烯醯胺為理想，[式中，X是氫原子、碳數1至21的直鏈狀或分枝狀的烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(但，X1及X2是氫原子、氟原子、氯原子、溴原子或碘原子)、氰基、碳數1至21的直鏈狀或分枝狀氟烷基、有取代或未經取代的苄基、有取代或未經取代的苯基；Y是-O-或-NH-；Z是直接鍵結、式-R2(R1)NSO2-或式-R2(R1)NCO-所表示的基(式中，R1是碳數1至10的烷基，R2是碳數1至10的直鏈伸烷基或分枝狀伸烷基)、式-CH2CH(OR3)CH2-(式中，R3表示氫原子或碳數1至10的醯基)所表示的基、或 -(CH2)m-SO2-基或-(CH2)m-S-基(但，m是1至10)，Rf是碳數1至20的直鏈狀或分枝狀的氟烷基，A是直鏈(碳數是3以上的奇數)或分枝鏈(碳數是3以上的整數)的伸烷基，a是1至50的整數]。 The fluorine-containing monomer (a) is preferably an acrylate or acrylamide represented by the formula: CH 2 =C(-X)-C(=O)-YZA-(CF 2 -CH 2 ) a -Rf [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 (however, 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 substituted or unsubstituted phenyl group; Y is -O- or -NH-; Z is a direct bond, a formula -R 2 (R 1 )NSO 2 - or a formula -R 2 (R 1 )NCO- a group (wherein R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group), and -CH 2 CH(OR 3 )CH a group represented by 2 - (wherein R 3 represents a hydrogen atom or a fluorenyl group having 1 to 10 carbon atoms), or a -(CH 2 ) m -SO 2 - group or a -(CH 2 ) m -S- group ( However, m is 1 to 10), Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, and A is a linear chain (odd number having a carbon number of 3 or more) or a branched chain (carbon number is An alkyl group of 3 or more integers, a is an integer of 1 to 50].

含氟單體(a)有時(丙烯酸酯或甲基丙烯酸酯之)α位經鹵素原子等取代。因此，在含氟單體(a)中，X可以是碳數2至21的直鏈狀或分枝狀的烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(但，X1及X2是氫原子、氟原子、氯原子、溴原子或碘原子)、氰基、碳數1至21的直鏈狀或分枝狀的氟烷基、有取代或未經取代的苄基、有取代或未經取代的苯基。 The fluorine-containing monomer (a) is sometimes substituted with a halogen atom or the like at the α position (of the acrylate or methacrylate). Therefore, in the fluorine-containing monomer (a), X may be a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group ( However, X 1 and X 2 are 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, substituted or not. Substituted benzyl, substituted or unsubstituted phenyl.

就X的具體例而言，可舉H、Me(甲基)、Cl、Br、I、F、CN、CF3。 Specific examples of X include H, Me (methyl), Cl, Br, I, F, CN, and CF 3 .

Z的例可以是直接鍵結、-CH2CH2N(R1)SO2-基(但，R1是碳數1至4的烷基)、或式-CH2CH(OR3)CH2-(式中，R3表示氫原子或碳數1至10的醯基(例如，甲醯基或乙醯基等))所表示的基，例如，-CH2CH(OZ1)CH2-基(但，Z1是氫原子或乙醯基)、或式-Ar-CH2-(式中，Ar是必要時有取代基的伸芳基)所表示的基、或-(CH2)m-SO2-基或-(CH2)m-S-基(但，m是1至10)。 An example of Z may be a direct bond, a -CH 2 CH 2 N(R 1 )SO 2 - group (however, R 1 is an alkyl group having 1 to 4 carbon atoms), or a formula -CH 2 CH(OR 3 )CH 2- (wherein R 3 represents a hydrogen atom or a group represented by a fluorenyl group having 1 to 10 carbon atoms (for example, a decyl group or an ethyl fluorenyl group, etc.), for example, -CH 2 CH(OZ 1 )CH 2 a group (but, Z 1 is a hydrogen atom or an ethyl fluorenyl group), or a group represented by the formula -Ar-CH 2 - (wherein Ar is a aryl group having a substituent if necessary), or -(CH 2 ) m -SO 2 - group or -(CH 2 ) m -S- group (however, m is 1 to 10).

Z是以直接鍵結、-CH2CH2N(R1)SO2-基(但，R1是碳數1至4的烷基)或-CH2CH(OZ1)CH2-基(但，Z1是氫原子或乙醯基)或-(CH2)m-SO2-基或-(CH2)m-S-基(但，m是1至10)為理想。 Z is a direct bond, -CH 2 CH 2 N(R 1 )SO 2 - group (however, R 1 is an alkyl group having 1 to 4 carbon atoms) or -CH 2 CH(OZ 1 )CH 2 - group ( However, it is preferable that Z 1 is a hydrogen atom or an ethane group or a -(CH 2 ) m -SO 2 - group or a -(CH 2 ) m -S- group (however, m is from 1 to 10).

Rf基是以全氟烷基為理想。Rf基的碳數是1至12，例如1至6，特別是以4至6為理想。Rf基的例有-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。 The Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is from 1 to 12, for example from 1 to 6, particularly preferably from 4 to 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.

A基的碳數是3以上，例如3至20，特別是3至10。A基是直鏈或分枝鏈。 The carbon number of the A group is 3 or more, for example, 3 to 20, particularly 3 to 10. The A group is a straight chain or a branched chain.

直鏈的A基是有3以上的奇數的碳原子。直鏈的A基中，A基的碳數的例是3、5、7、9及11。 The linear A group has an odd number of carbon atoms of 3 or more. In the linear A group, examples of the carbon number of the A group are 3, 5, 7, 9, and 11.

分枝鏈的A基是由與Z基及(CF2-CH2)基鍵結的主鏈(直鏈的伸烷基)，及與主鏈鍵結的支鏈(烷基)所形成。在A基中的主鏈(除去支鏈的直鏈的伸烷基)的碳數可以是1至12，例如2至10。在A基中，就支鏈而言，可舉甲基、乙基等碳數1至5的烷基(直鏈或分枝鏈的烷基)。在A基中的支鏈的數可以是1至5，例如1至3。 The A group of the branched chain is formed by a main chain (linear alkyl group) bonded to a Z group and a (CF 2 -CH 2 ) group, and a branched chain (alkyl group) bonded to the main chain. The main chain in the A group (excluding the branched linear alkyl group) may have a carbon number of 1 to 12, for example 2 to 10. In the A group, as the branched chain, an alkyl group having 1 to 5 carbon atoms such as a methyl group or an ethyl group (linear or branched alkyl group) may be mentioned. The number of branches in the A group may be from 1 to 5, such as from 1 to 3.

A基可由碳數3以上的烴系烯烴類(例如，丙烯等單烯烴類)衍生。 The A group may be derived from a hydrocarbon olefin having 3 or more carbon atoms (for example, a monoolefin such as propylene).

就分枝鏈伸烷基的A基的具體例而言，可舉伸異丙基[-CH(CH3)-CH2-及-CH2-CH(CH3)-]、乙基伸乙基[-CH(C2H5)-CH2-及-CH2-CH(C2H5)-]、-CH(CH3)-CH(CH3)-、-C(CH3)2-CH2-、-CH2-C(CH3)2-、-CH(C3H7)-CH2-、-CH2-CH(C3H7)-、-CH(C2H5)-CH(CH3)-、-CH(CH3)-CH(C2H5)-、2-甲基伸丙基[-CH2-CH(CH3)-CH2-]、伸異丁基[-CH(CH3)-CH2-CH2-、-CH2-CH2-CH(CH3)-]、伸異戊基[-CH(CH3)-CH2-CH2-CH2-、-CH2-CH2-CH2-CH(CH3)-]、2-甲基伸丁基[-CH2-CH(CH3)-CH2-CH2-、-CH2-CH2-CH(CH3)-CH2-]等伸烷基 (alkylene)；可舉亞乙基、亞丙基、亞異丙基、亞丁基、亞異丁基、亞戊基及亞異戊基等亞烷基(alkylidene)。 Specific examples of the A group of the branched alkyl group include isopropyl [-CH(CH 3 )-CH 2 - and -CH 2 -CH(CH 3 )-], and ethyl ethyl [-CH(C 2 H 5 )-CH 2 - and -CH 2 -CH(C 2 H 5 )-], -CH(CH 3 )-CH(CH 3 )-, -C(CH 3 ) 2 - CH 2 -, -CH 2 -C(CH 3 ) 2 -, -CH(C 3 H 7 )-CH 2 -, -CH 2 -CH(C 3 H 7 )-, -CH(C 2 H 5 ) -CH(CH 3 )-, -CH(CH 3 )-CH(C 2 H 5 )-, 2-methylpropyl propyl [-CH 2 -CH(CH 3 )-CH 2 -], Base [-CH(CH 3 )-CH 2 -CH 2 -, -CH 2 -CH 2 -CH(CH 3 )-], isoamyl [-CH(CH 3 )-CH 2 -CH 2 -CH 2-- , -CH 2 -CH 2 -CH 2 -CH(CH 3 )-], 2-methyl-tert-butyl [-CH 2 -CH(CH 3 )-CH 2 -CH 2 -, -CH 2 - CH 2 -CH(CH 3 )-CH 2 -] is an alkylene; exemplified by ethylene, propylene, isopropylidene, butylene, isobutylene, pentylene and iso An alkylidene such as a pentyl group.

-(CF2-CH2)a-基可由氟化亞乙烯(vinylidene fluoride)衍生。 The -(CF 2 -CH 2 ) a - group can be derived from vinylidene fluoride.

a可以是1至20的整數，例如2至10的整數。 a may be an integer from 1 to 20, such as an integer from 2 to 10.

含氟單體(a)是以通式：CH2=C(-X)-C(=O)-O-A-(CF2-CH2)a-Rf所示的化合物為理想，[式中，X、Rf、A、a與上述意義相同]。 The fluorine-containing monomer (a) is preferably a compound represented by the formula: CH 2 =C(-X)-C(=O)-OA-(CF 2 -CH 2 ) a -Rf, [wherein, X, Rf, A, a have the same meaning as above].

就含氟單體(a)的具體例而言，例如可例示以下的含氟單體，但並不限定於這些。 Specific examples of the fluorine-containing monomer (a) include, for example, the following fluorine-containing monomers, but are not limited thereto.

CH2=C(-H)-C(=O)-O-A-(CF2-CH2)a-Rf CH 2 =C(-H)-C(=O)-OA-(CF 2 -CH 2 ) a -Rf

CH2=C(-CH3)-C(=O)-O-A-(CF2-CH2)a-Rf CH 2 =C(-CH 3 )-C(=O)-OA-(CF 2 -CH 2 ) a -Rf

CH2=C(-Cl)-C(=O)-O-A-(CF2-CH2)a-Rf CH 2 =C(-Cl)-C(=O)-OA-(CF 2 -CH 2 ) a -Rf

CH2=C(-H)-C(=O)-NH-A-(CF2-CH2)a-Rf CH 2 =C(-H)-C(=O)-NH-A-(CF 2 -CH 2 ) a -Rf

CH2=C(-H)-C(=O)-O-(CH2)2N(-CH3)SO2-A-(CF2-CH2)a-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 N(-CH 3 )SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-H)-C(=O)-O-(CH2)2N(-C2H5)SO2-A-(CF2-CH2)a-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 N(-C 2 H 5 )SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-H)-C(=O)-O-CH2CH(-OH)CH2-A-(CF2-CH2)a-Rf CH 2 =C(-H)-C(=O)-O-CH 2 CH(-OH)CH 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-H)-C(=O)-O-CH2CH(-OCOCH3)CH2-A-(CF2-CH2)a-Rf CH 2 =C(-H)-C(=O)-O-CH 2 CH(-OCOCH 3 )CH 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-H)-C(=O)-O-(CH2)2-S-A-(CF2-CH2)a-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-H)-C(=O)-O-(CH2)3-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 3 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-CH3)-C(=O)-O-(CH2)2-S-A-(CF2-CH2)a-Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-CH3)-C(=O)-O-(CH2)3-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-F)-C(=O)-O-(CH2)2-S-A-(CF2-CH2)a-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-F)-C(=O)-O-(CH2)2-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-Cl)-C(=O)-O-(CH2)2-S-A-(CF2-CH2)a-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-CF3)-C(=O)-O-(CH2)2-S-A-(CF2-CH2)a-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-A-(CF2-CH2)a-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-CN)-C(=O)-O-(CH2)2-S-A-(CF2-CH2)a-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-A-(CF2-CH2)a-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-F)-C(=O)-O-(CH2)3-S-A-(CF2-CH2)a-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-F)-C(=O)-O-(CH2)3-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-Cl)-C(=O)-O-(CH2)3-S-A-(CF2-CH2)a-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-CF3)-C(=O)-O-(CH2)3-S-A-(CF2-CH2)a-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-A-(CF2-CH2)a-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-CN)-C(=O)-O-(CH2)3-S-A-(CF2-CH2)a-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-A-(CF2-CH2)a-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -SA-(CF 2 -CH 2 ) a -Rf

CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-SO2-A-(CF2-CH2)a-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -A-(CF 2 -CH 2 ) a -Rf

[上述式中，Rf是碳數1至20的氟烷基，A是直鏈(碳數是3以上的奇數)或分枝鏈(碳數是3以上的整 數)的伸烷基，A是1至50的整數]。 [In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms, and A is a linear chain (an odd number of carbon atoms of 3 or more) or a branched chain (the carbon number is 3 or more) a number of alkylene groups, A is an integer from 1 to 50].

含氟單體是將碳數3以上的烴系烯烴類加成在I-Rf與CF2=CH2的碘移動反應物後，與CH2=C(-X)-C(=O)-Y-Z0(X及Y是與前述意義相同。Z0是一價有機基或氫原子等)進行反應而可合成。例如，CH2=C(-H)-C(=O)-O-A-(CF2-CH2)a-Rf是將碳數3以上的烴系烯烴類加成在I-Rf與CF2=CH2的碘移動反應物後，由丙烯酸鉀的脫KI反應而可合成。 The fluorine-containing monomer is obtained by adding a hydrocarbon-based olefin having 3 or more carbon atoms to the iodine-shifting reactant of I-Rf and CF 2 =CH 2 , and CH 2 =C(-X)-C(=O)- YZ 0 (X and Y are the same meanings as described above. Z 0 is a monovalent organic group or a hydrogen atom, etc.) can be synthesized by reaction. For example, CH 2 =C(-H)-C(=O)-OA-(CF 2 -CH 2 ) a -Rf is a hydrocarbon olefin having 3 or more carbon atoms added to I-Rf and CF 2 = After the iodine of CH 2 moves the reactant, it can be synthesized by a de-KI reaction of potassium acrylate.

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

非氟非交聯性單體(b)是不含氟原子的單體。非氟非交聯性單體(b)是沒有交聯性官能基。非氟非交聯性單體(b)與交聯性單體(c)不同，是非交聯性。非氟非交聯性單體(b)理想是有碳-碳雙鍵的非氟單體。非氟非交聯性單體(b)理想是不含氟的乙烯單體。非氟非交聯性單體(b)一般是有1個碳-碳雙鍵的化合物。 The non-fluorine non-crosslinkable monomer (b) is a monomer having no fluorine atom. The non-fluorine non-crosslinkable monomer (b) is a crosslinkable functional group. The non-fluorine non-crosslinkable monomer (b) is different from the crosslinkable monomer (c) and is non-crosslinkable. The non-fluorine non-crosslinkable monomer (b) is desirably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (b) is desirably a fluorine-free ethylene monomer. The non-fluorine non-crosslinkable monomer (b) is generally a compound having one carbon-carbon double bond.

理想的非氟非交聯性單體(b)可以是式：CH2=CA0-T所示的化合物，[式中，A0是氫原子、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是氫原子、氯原子、碳數1至22的鏈狀或環狀的烴基、或具有酯鍵的鏈狀或環狀的碳數1至22的有機基]。 The desired non-fluorine non-crosslinkable monomer (b) may be a compound represented by the formula: CH 2 =CA 0 -T, wherein A 0 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), T is a hydrogen atom, a chlorine atom, a chain or cyclic hydrocarbon group having 1 to 22 carbon atoms, or a chain or cyclic carbon number of 1 to 22 having an ester bond Organic base].

碳數1至22的鏈狀或環狀的烴基的例是碳數1至22的直鏈或分枝的脂肪族烴基、碳數4至22的環狀脂肪族基、碳數6至22的芳香族烴基、碳數7至22的芳香脂肪族烴基。 Examples of the chain or cyclic hydrocarbon group having 1 to 22 carbon atoms are a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, a cyclic aliphatic group having 4 to 22 carbon atoms, and a carbon number of 6 to 22 carbon atoms. An aromatic hydrocarbon group and an aromatic aliphatic hydrocarbon group having 7 to 22 carbon atoms.

具有酯鍵的鏈狀或環狀的碳數1至22的有機基的例是-C(=O)-O-Q及-O-C(=O)-Q(在這裏，Q是碳數1至22的直鏈或分枝的脂肪族烴基、碳數4至22的環狀脂肪族基、碳數6至22的芳香族烴基、碳數7至22的芳香脂肪族烴基)。 Examples of the chain or cyclic organic group having 1 to 22 carbon atoms having an ester bond are -C(=O)-OQ and -OC(=O)-Q (here, Q is a carbon number of 1 to 22). A linear or branched aliphatic hydrocarbon group, a cyclic aliphatic group having 4 to 22 carbon atoms, an aromatic hydrocarbon group having 6 to 22 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 22 carbon atoms).

非氟非交聯性單體(b)的理想例有，例如，包含乙烯，氯化乙烯等鹵化乙烯，氯化亞乙烯等鹵化亞乙烯，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、羧酸乙烯酯、及乙烯烷醚。羧酸乙烯酯是以CH2=CH-O-C(=O)R0[式中，R0是碳數1至22的脂肪族、芳香族、脂環族或芳香脂肪族的烴基]所表示的化合物為理想，羧酸乙烯酯的具體例，可舉環己烷羧酸乙烯酯、苄酸乙烯酯、丙酸乙烯酯、酪酸乙烯酯、戊酸乙烯酯、己酸乙烯酯、2-乙基己酸乙烯酯、辛酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、肉豆蔻酸乙烯酯、棕櫚酸乙烯酯、硬脂酸乙烯酯、二十二酸乙烯酯。非氟非交聯性單體(b)並不限定於這些例子。 Preferable examples of the non-fluorine non-crosslinkable monomer (b) include, for example, ethylene halide, vinyl halide such as ethylene chloride, vinylidene halide, vinyl halide, vinyl acetate, acrylonitrile, styrene, and polyethylene. Alcohol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, vinyl carboxylate, and ethylene Alkyl ether. The vinyl carboxylate is represented by CH 2 =CH-OC(=O)R 0 [wherein R 0 is an aliphatic, aromatic, alicyclic or aromatic aliphatic hydrocarbon group having 1 to 22 carbon atoms] The compound is preferably a specific example of the vinyl carboxylate, and examples thereof include vinyl cyclohexanecarboxylate, vinyl benzylate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, and 2-ethyl. Vinyl hexanoate, vinyl octanoate, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl sesquicanate. The non-fluorine non-crosslinkable monomer (b) is not limited to these examples.

非氟非交聯性單體(b)可以是具有烷基的(甲基)丙烯酸酯。烷基的碳原子數可以是1至30，例如，6至30(例如，10至30)。例如，非氟非交聯性單體(b)可以是通式：CH2=CA1COOA2所示的丙烯酸酯，[式中，A1是氫原子、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是CnH2n+1(n=1至30)所表示的烷基]。例如，可以是(甲基)丙烯酸硬脂酯、(甲基)丙烯酸二十二酯。 The non-fluorine non-crosslinkable monomer (b) 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 (for example, from 10 to 30). For example, the non-fluorine non-crosslinkable monomer (b) may be an acrylate represented by the formula: CH 2 = CA 1 COOA 2 , wherein 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 an alkyl group represented by C n H 2n+1 (n=1 to 30). For example, it may be stearyl (meth)acrylate or behenyl (meth)acrylate.

非氟非交聯性單體(b)可以是具有環狀烴基的(甲基)丙烯酸酯單體。具有環狀烴基的(甲基)丙烯酸酯單體是具有環狀烴基(理想是一價環狀烴基)及一價(甲基)丙烯酸酯基的化合物。一價環狀烴基與一價(甲基)丙烯酸酯基是直接鍵結。就環狀烴基而言，可舉飽和或不飽和的單環基、多環基、橋環基等。環狀烴基是以飽和為理想。環狀烴基的碳數是以4至20為理想。就環狀烴基而言，可舉碳數4至20(特別是5至12)的環狀脂肪族基、碳數6至20的芳香族基、碳數7至20的芳香脂肪族基。環狀烴基的碳數是以15以下，例如10以下為特別理想。環狀烴基的環中的碳原子是以與(甲基)丙烯酸酯基的酯基直接鍵結為理想。環狀烴基是以飽和的環狀脂肪族基為理想。環狀烴基的具體例是環己基、三級丁基環己基、異莰基(isobornyl)、二環戊基、二環戊烯基。(甲基)丙烯酸酯基是丙烯酸酯基或甲基丙烯酸酯基，以甲基丙烯酸酯基為理想。就具有環狀烴基的單體的具體例而言，可舉甲基丙烯酸環己酯、甲基丙烯酸三級丁基環己酯、甲基丙烯酸苄酯、甲基丙烯酸異莰酯、丙烯酸異莰酯、甲基丙烯酸二環戊酯、丙烯酸二環戊酯、丙烯酸二環戊烯酯等。 The non-fluorine non-crosslinkable monomer (b) may be a (meth) acrylate monomer having a cyclic hydrocarbon group. The (meth) acrylate monomer having a cyclic hydrocarbon group is a compound having a cyclic hydrocarbon group (ideally a monovalent cyclic hydrocarbon group) and a monovalent (meth) acrylate group. The monovalent cyclic hydrocarbon group is directly bonded to the monovalent (meth) acrylate group. The cyclic hydrocarbon group may, for example, be a saturated or unsaturated monocyclic group, a polycyclic group, a bridged ring group or the like. The cyclic hydrocarbon group is desirably saturated. The carbon number of the cyclic hydrocarbon group is preferably from 4 to 20. The cyclic hydrocarbon group may, for example, be a cyclic aliphatic group having 4 to 20 carbon atoms (particularly 5 to 12), an aromatic group having 6 to 20 carbon atoms, or an aromatic aliphatic group having 7 to 20 carbon atoms. The carbon number of the cyclic hydrocarbon group is particularly preferably 15 or less, for example, 10 or less. The carbon atom in the ring of the cyclic hydrocarbon group is preferably bonded directly to the ester group of the (meth) acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, a tertiary butylcyclohexyl group, an isobornyl group, a dicyclopentyl group, and a dicyclopentenyl group. The (meth) acrylate group is an acrylate group or a methacrylate group, and a methacrylate group is preferred. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl methacrylate, tertiary butylcyclohexyl methacrylate, benzyl methacrylate, isodecyl methacrylate, and isophthalic acid acrylate. Ester, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, and the like.

(c)非氟交聯性單體 (c) 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(c)衍生的重複單元。非氟交聯性單體(c)是不含氟原子的單體。非氟交聯性單體(c)可以是至少具有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(c)可以是至少具有2個碳-碳雙鍵的化合物，或至少具有1個碳-碳雙鍵及至少具有1個反應性基的化合物。反應性基的例子是羥基、環氧基、氯甲基、嵌段異氰酸酯基、 胺基、羧基等。 The fluoropolymer of the present invention may have a repeating unit derived from the non-fluorine crosslinkable monomer (c). The non-fluorine crosslinkable monomer (c) is a monomer having no fluorine atom. The non-fluorine-crosslinkable monomer (c) may be a compound having at least two reactive groups and/or carbon-carbon double bonds and having no fluorine. The non-fluorine-crosslinkable monomer (c) 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 reactive groups are hydroxy, epoxy, chloromethyl, blocked isocyanate groups, Amine group, carboxyl group, and the like.

非氟交聯性單體(c)可以是具有反應性基的單(甲基)丙烯酸酯、(甲基)二丙烯酸酯或單(甲基)丙烯醯胺。或者，非氟交聯性單體(c)可以是二(甲基)丙烯酸酯。 The non-fluorine-crosslinkable monomer (c) may be a mono(meth)acrylate having a reactive group, (meth)diacrylate or mono(meth)acrylamide. Alternatively, the non-fluorine crosslinkable monomer (c) may be a di(meth)acrylate.

非氟交聯性單體(c)的1個例子是具有羥基的乙烯單體。 One example of the non-fluorine crosslinkable monomer (c) is an ethylene monomer having a hydroxyl group.

就非氟交聯性單體(c)而言，例如可舉，二丙酮(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、(甲基)丙烯酸羥甲酯、(甲基)丙烯酸羥乙酯、(甲基)丙烯酸3-氯-2-羥丙酯、(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、單氯乙酸乙烯酯、甲基丙烯酸乙烯酯、(甲基)丙烯酸環氧丙酯、二(甲基)丙烯酸1,6-己烷二醇酯、二(甲基)丙烯酸新戊二醇酯等，但並不限定於這些。 Examples of the non-fluorine-crosslinkable monomer (c) include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, and hydroxymethyl (meth) acrylate. Hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-ethyl ethoxyethyl (meth) acrylate, butadiene, isoprene, chlorine Butadiene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl di(meth)acrylate A glycol ester or the like is not limited thereto.

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的意思，「(甲基)丙烯醯胺」是指丙烯醯胺或甲基丙烯醯胺的意思。 In the present specification, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide.

將非氟非交聯性單體(b)及/或非氟交聯性單體(c)共聚合，可隨需要而改善撥水撥油性或抗污性及這些性能的耐洗滌性、耐洗衣性、對溶劑的溶解性、硬度、觸感等種種的性質。 By copolymerizing the non-fluorine non-crosslinkable monomer (b) and/or the non-fluorine crosslinkable monomer (c), the water repellency or the stain resistance and the washing resistance and resistance of these properties can be improved as needed. Various properties such as laundry properties, solubility in solvents, hardness, and touch.

在含氟聚合物中，相對於含氟單體(a)100重量份，非氟非交聯性單體(b)的量可以在1000重量份以下，例如0.1至300重量份，特別是1至200重量份，非氟交聯性單體(c)的量可以在50重量份以下，例如30重量份以下，特別是0.1至20重量份。 In the fluoropolymer, the amount of the non-fluorine non-crosslinkable monomer (b) may be 1000 parts by weight or less, for example, 0.1 to 300 parts by weight, particularly 1 part by weight based on 100 parts by weight of the fluoromonomer (a). The amount of the non-fluorine-crosslinkable monomer (c) may be 50 parts by weight or less, for example, 30 parts by weight or less, particularly 0.1 to 20 parts by weight to 200 parts by weight.

含氟聚合物的數量平均分子量(Mn)一般可以是1000至1000000，例如5000至500000，特別是3000至200000。含氟聚合 物的數量平均分子量(Mn)一般是用GPC(凝膠滲透層析)測定。 The number average molecular weight (Mn) of the fluoropolymer may generally be from 1,000 to 1,000,000, for example from 5,000 to 500,000, especially from 3,000 to 200,000. Fluorinated polymerization The number average molecular weight (Mn) of the substance is generally determined by GPC (gel permeation chromatography).

在本發明中的含氟聚合物是可用通常的聚合方法的任何一種製造，又聚合反應的條件也可任意選擇。做為這種聚合方法而言，可舉溶液聚合、懸浮聚合、乳化聚合。 The fluoropolymer in the present invention can be produced by any of the usual polymerization methods, and the conditions of the polymerization reaction can also be arbitrarily selected. As such a polymerization method, solution polymerization, suspension polymerization, and emulsion polymerization can be mentioned.

溶液聚合是採用，在聚合起始劑的存在下，將單體溶解於有機溶劑，必要時進行氮氣置換，在30至120℃的範圍加熱攪拌1至10小時的方法。就聚合起始劑而言，例如可舉偶氮雙異丁腈、過氧化苄醯基、過氧化二-三級丁基、過氧化月桂基、氫過氧化異丙苯、過氧三甲基乙酸三級丁酯(t-butyl peroxy pivalate)、過氧二羧酸二異丙酯等。聚合起始劑相對於單體100重量份是在0.01至20重量份，例如0.01至10重量份的範圍使用。 The solution polymerization is a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and if necessary, nitrogen is substituted, and the mixture is heated and stirred in the range of 30 to 120 ° C for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzammonium peroxide, di-tertiary butyl peroxide, lauryl peroxide, cumene hydroperoxide, and peroxytrimethyl peroxide. T-butyl peroxy pivalate, diisopropyl peroxydicarboxylate, and the like. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of the monomer.

就有機溶劑而言，對單體為惰性而能將這些單體溶解者，例如，可舉丙酮、三氯甲烷、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、1,4-二烷、甲基乙基酮、甲基異丁基酮、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。有機溶劑相對於單體的合計100重量份是在50至2000重量份，例如，在50至1000重量份的範圍使用。 In the case of an organic solvent, those monomers are inert and can be dissolved, for example, acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane Alkane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-two Alkane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene , perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in an amount of 50 to 2000 parts by weight, for example, in the range of 50 to 1000 parts by weight, based on 100 parts by total of the monomers.

乳化聚合是採用，在聚合起始劑及乳化劑的存在下，將單體在水中乳化，必要時進行氮氣置換，在50至80℃的範圍攪拌1至10小時使其共聚合的方法。聚合起始劑是使用過氧化苄醯基、過氧化月桂醯基、過氧苄酸三級丁酯、氫過氧化1-羥環己基、過氧化3-羧丙醯基、過氧乙醯基、偶氮雙異丁脒-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化合物，及 偶氮雙異丁腈、過氧化苄醯基、過氧化二-三級丁基、過氧化月桂基、氫過氧化異丙苯、過氧三甲基乙酸三級丁酯、過氧二羧酸二異丙酯等油溶性的化合物。聚合起始劑相對於單體100重量份是在0.01至10重量份的範圍使用。 The emulsion polymerization is a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and if necessary, nitrogen is substituted, and the mixture is stirred at 50 to 80 ° C for 1 to 10 hours to be copolymerized. The polymerization initiator is a benzammonium peroxide group, a lauroyl peroxide, a tertiary butyl peroxybenzylate, a 1-hydroxycyclohexyl hydroperoxide, a 3-carboxypropenyl peroxide, or a peroxetane group. a water-soluble compound such as azobisisobutylphosphonium-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate or ammonium persulfate, and Azobisisobutyronitrile, benzammonium peroxide, di-tertiary butyl peroxide, lauryl peroxide, cumene hydroperoxide, tertiary butyl peroxytrimethylacetate, peroxydicarboxylic acid An oil-soluble compound such as diisopropyl ester. The polymerization initiator is used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

為了要得到有優異的放置安定性的共聚物水分散液，而使用如高壓均質機或超音波均質機等可賦予強力破碎能的乳化裝置，將單體在水中微粒子化，使用油溶性聚合起始劑進行聚合為理想。又，就乳化劑而言可使用陰離子性、陽離子性或非離子性的各種乳化劑，相對於單體100重量份是在0.5至20重量份的範圍使用。以使用陰離子性及/或非離子性及/或陽離子性的乳化劑為理想。單體不會完全相容時，添加以使這些單體充分相容的相容化劑於單體中，例如，以添加水溶性有機溶劑或低分子量的單體為理想。相容化劑的添加，可使乳化性及共聚合性提升。 In order to obtain an aqueous dispersion of the copolymer having excellent stability, an emulsion device capable of imparting strong breaking energy, such as a high-pressure homogenizer or an ultrasonic homogenizer, is used to granulate the monomer in water, using oil-soluble polymerization. It is desirable to carry out the polymerization of the starting agent. Further, as the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and it is used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. It is preferred to use an anionic and/or nonionic and/or cationic emulsifier. When the monomers are not completely compatible, a compatibilizing agent added to make these monomers sufficiently compatible is preferably used in the monomer, for example, a water-soluble organic solvent or a low molecular weight monomer is added. The addition of a compatibilizing agent can improve emulsifying properties and copolymerization properties.

就水溶性有機溶劑而言，可舉丙酮、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，可在1至50重量份，例如10至40重量份的範圍使用。又，就低分子量的單體而言，可舉甲基丙烯酸甲酯、甲基丙烯酸環氧丙酯、甲基丙烯酸2,2,2-三氟乙酯等，相對於單體的總量100重量份，可在1至50重量份，例如10至40重量份的範圍使用。 The water-soluble organic solvent may, for example, be acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol or the like, and may be 1 to 100 parts by weight with respect to 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 monomers is 100. The parts by weight may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight.

含氟聚合物可用於纖維等種種的基材的表面處理而使用。 The fluoropolymer can be used for surface treatment of various substrates such as fibers.

含氟聚合物可藉由用以將纖維製品以液體進行處理的已知的任一方法而適用於纖維狀基材(例如，纖維製品等)。適用於纖維製品的溶液中的氟聚矽氧反應生成物的濃度可以是例如，0.5重量 %至20重量%，或1重量%至5重量%。纖維製品是布時，可將布浸漬於溶液中，或可使溶液附著或噴霧在布上。經處理過的纖維製品，為了使其顯現撥油性而將其乾燥，理想是例如，在100℃至200℃加熱。 The fluoropolymer can be applied to a fibrous substrate (e.g., a fibrous product, etc.) by any of the known methods for treating the fibrous article with a liquid. The concentration of the fluoropolyoxyl reaction product in the solution suitable for the fibrous product may be, for example, 0.5 weight. % to 20% by weight, or 1% to 5% by weight. When the fibrous product is a cloth, the cloth may be immersed in the solution, or the solution may be attached or sprayed onto the cloth. The treated fibrous product is dried in order to make it exhibit oil repellency, and is preferably heated, for example, at 100 ° C to 200 ° C.

或者，含氟聚合物可藉由洗滌法而適用於纖維製品，例如，可在洗衣適用或在乾洗法中等適用於纖維製品。 Alternatively, the fluoropolymer may be applied to the fibrous product by a washing method, for example, it may be applied to a fibrous product in a laundry or in a dry cleaning method.

經處理的纖維製品，典型為布，這包含梭織品、針織品及不織布、衣料品形態的布及毛毯，纖維或紗線或中間纖維製品(例如，纖維束(sliver)或粗紗(roving)等)也可以。纖維製品材料可以是天然纖維(例如，綿或羊毛等)、化學纖維(例如，黏液嫘縈(viscose rayon)或萊賽爾纖維(lyocell)等)或合成纖維(例如，聚酯、聚醯胺或丙烯酸纖維等)，或者纖維的混合物(例如，天然纖維及合成纖維的混合物等)也可以。本發明的製造聚合物是纖維素系纖維(例如，綿或嫘縈等)成為疏油性及撥油性上特別有效。又，本發明的方法一般是使纖維製品成為疏水性及撥水性。 Treated fibrous articles, typically cloth, which include woven fabrics, knits and non-woven fabrics, cloths and felts in the form of clothing, fibers or yarns or intermediate fiber products (for example, sliver or roving) ) OK. The fibrous material may be natural fibers (for example, cotton or wool, etc.), chemical fibers (for example, viscose rayon or lyocell, or synthetic fibers) (for example, polyester, polyamide). Or acrylic fibers, etc., or a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers, etc.). The production of the polymer of the present invention is particularly effective for oleophobicity and oil repellency of cellulose-based fibers (for example, cotton or crepe). Further, the method of the present invention generally makes the fibrous product hydrophobic and water repellency.

或者，纖維狀基材可以是皮革。為了使皮革成為疏水性及疏油性，在皮革加工的各種階段，例如，皮革的濕潤加工的期間中，或皮革的塗飾的期間中，可將製造聚合物由水溶液或水性乳化物適用於皮革。 Alternatively, the fibrous substrate may be leather. In order to make the leather hydrophobic and oleophobic, the manufactured polymer can be applied to the leather from an aqueous solution or an aqueous emulsion at various stages of leather processing, for example, during the wet processing of the leather, or during the period of the leather coating.

或者，纖維狀基材可以是紙。可將製造聚合物適用於預先形成的紙，或製紙的各種階段，例如，可在紙的乾燥期間中適用。 Alternatively, the fibrous substrate can be paper. The manufacture of the polymer can be applied to pre-formed paper, or to various stages of papermaking, for example, during the drying of the paper.

本發明的含氟組成物是以溶液、乳劑(特別是水性乳劑)或氣膠的形態為理想。含氟組成物含有含氟聚合物(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，相對於含氟組成物可以是5至99.9重量%，特別是10至80重量%。 The fluorine-containing composition of the present invention is preferably in the form of a solution, an emulsion (particularly an aqueous emulsion) or a gas gel. The fluorine-containing composition contains a fluorine-containing polymer (active component of a surface treatment agent) and a medium (particularly a liquid medium such as an organic solvent and/or water). Media The amount, for example, may be 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the fluorine-containing composition.

在含氟組成物中，含氟聚合物的濃度可以是0.01至95重量%，例如5至50重量%。 In the fluorine-containing composition, the concentration of the fluoropolymer may be from 0.01 to 95% by weight, for example from 5 to 50% by weight.

本發明的含氟組成物可藉由向來已知的方法適用於被處理物。通常採用，將該含氟組成物分散於有機溶劑或水中並稀釋，藉由浸漬塗布、噴霧塗布、泡沫塗布等已知的方法，在被處理物的表面附著，乾燥的方法。又，如有必要時，可以與適當的交聯劑一起適用，進行熟化。再者，可在本發明的含氟組成物中，添加併用防蟲劑、柔軟劑、抗菌劑、難燃劑、抗靜電劑、塗料固定劑、防皺劑等。與基材接觸的處理液中的含氟聚合物的濃度是0.01至10重量%(特別是浸漬塗布時)，例如可以是0.05至10重量%。 The fluorine-containing composition of the present invention can be applied to a processed object by a method known per se. A method in which the fluorine-containing composition is dispersed in an organic solvent or water and diluted, and adhered to the surface of the workpiece by a known method such as dip coating, spray coating or foam coating, and dried. Further, if necessary, it can be applied together with a suitable crosslinking agent to be aged. 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 fluorine-containing composition of the present invention. The concentration of the fluoropolymer in the treatment liquid which is in contact with the substrate is from 0.01 to 10% by weight (particularly during dip coating), and may be, for example, from 0.05 to 10% by weight.

就由本發明的含氟組成物(例如，撥水撥油劑)所處理的被處理物而言，可舉纖維製品、石材、過濾器(例如，靜電過濾器)、防塵罩、燃料電池的零組件(例如，氣體擴散電極及氣體擴散支撐物)、玻璃、紙、木材、皮革、毛皮、石綿、磚瓦、水泥、金屬及氧化物、窯業製品、塑膠、塗面、及灰泥等。就纖維製品而言可舉種種的例子。例如，可舉綿、麻、羊毛、蠶絲等動植物性天然纖維，聚醯胺、聚酯、聚乙烯醇、聚丙烯腈、聚氯化乙烯、聚丙烯等合成纖維，嫘縈、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，或這些的混合纖維。 The object to be treated which is treated by the fluorine-containing composition of the present invention (for example, a water-repellent oil-repellent agent) may be a fiber product, a stone material, a filter (for example, an electrostatic filter), a dust cover, or a fuel cell. Components (eg, gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, kiln products, plastics, coated surfaces, and plasters. There are various examples of the fiber product. For example, it may be natural animal or plant natural fibers such as cotton, hemp, wool, silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., hydrazine, acetate, etc. Semi-synthetic fibers, inorganic fibers such as glass fibers, carbon fibers, asbestos fibers, or a blend of these.

纖維製品可以是纖維、布等形態的任一種。以本發明的含氟組成物處理毛毯時，可以將纖維或紗線以含氟組成物處理後形成毛毯，或可以將所形成的毛毯以含氟組成物處理。 The fibrous product may be in the form of fibers, cloth or the like. When the felt is treated with the fluorine-containing composition of the present invention, the fiber or yarn may be treated with a fluorine-containing composition to form a felt, or the formed felt may be treated with a fluorine-containing composition.

本發明的含氟組成物可以做為內部脫模劑或外部脫模劑而使用。 The fluorine-containing composition of the present invention can be used as an internal mold release agent or an external mold release agent.

「處理」是指將處理劑藉浸漬、噴霧、塗布等而適用於被處理物的意思。藉由處理，處理劑的有效成分的含氟聚合物滲透到被處理物的內部及/或附著在被處理物的表面。 The term "treatment" means that the treatment agent is applied to the object to be treated by dipping, spraying, coating, or the like. By treatment, the fluoropolymer of the active ingredient of the treating 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) (Example)

以下，例舉實施例更詳細說明本發明，但本發明並不受這些實施例所限定。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

以下，%如無特別的說明，則表示重量%。 Hereinafter, % means % by weight unless otherwise specified.

試驗(含氟聚合物的分析及撥水撥油性的測定)是如下述方式進行。 The test (analysis of the fluoropolymer and measurement of the water repellency) was carried out as follows.

「撥水撥油性」： "Water and oil":

做為含氟聚合物的撥水撥油性評估，而將水滴(表面張力72mN/m)及正-十六烷滴(表面張力27mN/m，以下，簡稱為HD)的動態接觸角測定如下。做為動態接觸角之指標，測定滑落角(deg)，及前進接觸角與後退接觸角的差所表示之遲滯(hysteresis,deg)而評估。即，將含氟聚合物成為有機溶劑中的1%溶液，以旋轉塗佈法(2000rpm)塗布在玻璃基板後，乾燥而製膜。其次，使用協和界面科學(股)製的接觸角計(商品名「CA-VP」)，測定水滴20μl或HD滴5μl的動態接觸角。測定是遵照JISR3257，溫度是15至20℃，相對濕度是50至70%。滑落角較小者，以及遲滯較小者，表示撥水撥油性較優異。 As the water repellency evaluation of the fluoropolymer, the dynamic contact angle of water droplets (surface tension: 72 mN/m) and n-hexadecane droplets (surface tension: 27 mN/m, hereinafter, abbreviated as HD) was measured as follows. As an index of the dynamic contact angle, the slip angle (deg) was measured, and the hysteresis (deg) represented by the difference between the advancing contact angle and the receding contact angle was evaluated. That is, the fluoropolymer was used as a 1% solution in an organic solvent, and applied to a glass substrate by a spin coating method (2000 rpm), followed by drying to form a film. Next, a contact angle meter (trade name "CA-VP") manufactured by Kyowa Interface Science Co., Ltd. was used to measure a dynamic contact angle of 20 μl of water droplets or 5 μl of HD droplets. The measurement was carried out in accordance with JISR 3257, the temperature was 15 to 20 ° C, and the relative humidity was 50 to 70%. Those with a smaller slip angle and a smaller hysteresis indicate that the water repellency is superior.

「淋浴撥水性」： "Shower water repellency":

淋浴撥水性是以藉由JIS-L-1092的噴霧法的撥水性No.(參照 下述第1表)表示。 The water repellency of the shower is the water repellency No. by the spray method of JIS-L-1092 (refer to It is shown in the following Table 1).

「撥水性試驗」： "Water repellency test":

將處理過的試驗布在溫度21℃，濕度65%的恆溫恆濕機中保管4小時以上。試驗液(異丙醇(以下，簡成為IPA)、水、及其混合液，示於第2表)也在溫度21℃保存過後使用。試驗是在溫度21℃，濕度65%的恆溫恆濕室中進行。將試驗液在試驗布上緩緩滴下0.05ml，放置30秒鐘後，液滴在試驗布上有殘留時，將該試驗液認定為合格。撥水性是以合格的試驗液的IPA含量(體積%)的最大值做為點數，由撥水性不良到良好的等級分成不合格、0、1、2、3、4、5、6、7、8、9及10的12個階段而評估。 The treated test cloth was stored in a constant temperature and humidity machine at a temperature of 21 ° C and a humidity of 65% for 4 hours or more. The test solution (isopropyl alcohol (hereinafter, simply IPA), water, and a mixed solution thereof, shown in Table 2) was also used after storage at a temperature of 21 °C. The test was carried out in a constant temperature and humidity chamber at a temperature of 21 ° C and a humidity of 65%. The test solution was slowly dropped on the test cloth by 0.05 ml, and after standing for 30 seconds, when the liquid droplets remained on the test cloth, the test liquid was confirmed to be acceptable. The water repellency is based on the maximum value of the IPA content (% by volume) of the qualified test liquid, and is classified as unqualified from poor water repellency to good grade, 0, 1, 2, 3, 4, 5, 6, and 7. Evaluation of 12 stages of 8, 9, and 10.

「撥油性試驗」： "oil oil test":

將處理過的試驗布在溫度21℃，濕度65%的恆溫恆濕機中保管4小時以上。試驗液(示於第3表)也在溫度21℃保存過後使用。試驗是在溫度21℃，濕度65%的恆溫恆濕室進行。在試驗布上緩緩滴下0.05ml，放置30秒鐘後，液滴在試驗布上殘留時，將該試驗液認定為合格。撥油性是作為合格的試驗液的最高點數，由撥油性不良到良好的等級分成不合格、1、2、3、4、5、6、7及8的9個階段評估。 The treated test cloth was stored in a constant temperature and humidity machine at a temperature of 21 ° C and a humidity of 65% for 4 hours or more. The test solution (shown in Table 3) was also used after storage at a temperature of 21 °C. The test was carried out in a constant temperature and humidity chamber at a temperature of 21 ° C and a humidity of 65%. 0.05 ml of the test cloth was slowly dropped, and after leaving for 30 seconds, the test liquid was judged to be acceptable when the liquid droplet remained on the test cloth. The oil repellency is the highest point of the qualified test liquid, and is evaluated from nine stages of unqualified, 1, 2, 3, 4, 5, 6, 7, and 8 from poor oil repellency to good grade.

合成例1 Synthesis Example 1

在300ml高壓釜中，裝入I-(CF2)6F 40.0g(0.090mol)，藉由氮氣置換而將系統內的氧氣除去。其次，裝入CF2=CH2(氟化亞乙烯)14.4g(0.225mol)，過氧三甲基乙酸三級丁酯(t-butyl peroxy pivalate)0.9g，緩緩升高溫度，在60℃保持10小時進行碘移動反應。所得的碘移動反應物是藉由氣體層析、1H-NMR、19F-NMR、13C-NMR的分析而檢定。 In a 300 ml autoclave, 40.0 g (0.090 mol) of I-(CF 2 ) 6 F was charged, and oxygen in the system was removed by nitrogen substitution. Next, 14.4 g (0.225 mol) of CF 2 =CH 2 (vinylidene fluoride) and 0.9 g of t-butyl peroxy pivalate were added, and the temperature was gradually raised. The iodine shift reaction was carried out for 10 hours at °C. The obtained iodine mobile reactant was assayed by gas chromatography, 1 H-NMR, 19 F-NMR, and 13 C-NMR analysis.

其次，在300ml高壓釜中，將上述所得的碘移動反應物I-(CF2-CH2)2-(CF2)6F 25.8g(0.045mol)裝入，藉由氮氣置換而將系統內的氧氣除去。其次，裝入丙烯2.9g(0.068mol)，過氧三甲基乙酸三級丁酯0.7g，緩緩升高溫度，在60℃保持10小時進行碘移動反應。所得的碘移動反應物是藉由氣體層析、1H-NMR、19F-NMR、13C-NMR的分析而檢定。 Next, in the 300 ml autoclave, the above-obtained iodine mobile reactant I-(CF 2 -CH 2 ) 2 -(CF 2 ) 6 F 25.8 g (0.045 mol) was charged, and the system was replaced by nitrogen gas. The oxygen is removed. Next, 2.9 g (0.068 mol) of propylene and 0.7 g of tributyl butyl peroxytrimethylacetate were charged, and the temperature was gradually raised, and the iodine shift reaction was carried out at 60 ° C for 10 hours. The obtained iodine mobile reactant was assayed by gas chromatography, 1 H-NMR, 19 F-NMR, and 13 C-NMR analysis.

其次，在300ml高壓釜中裝入三級丁醇50.0g、丙烯酸鉀6.8g(0.062mol)、氫醌0.05g、及上述所得的碘移動反應物 I-CH(CH3)-CH2-(CF2-CH2)2-(CF2)6F 25.3g(0.041mol)，藉由氮氣置換而將系統內的氧氣除去，緩緩升高溫度，在180℃保持24小時進行由脫KI的酯化反應。 Next, a 300 ml autoclave was charged with 50.0 g of tertiary butanol, 6.8 g of potassium acrylate (0.062 mol), 0.05 g of hydroquinone, and the above-obtained iodine mobile reactant I-CH(CH 3 )-CH 2 - ( CF 2 -CH 2 ) 2 -(CF 2 ) 6 F 25.3 g (0.041 mol), the oxygen in the system was removed by nitrogen substitution, the temperature was gradually raised, and the temperature was maintained at 180 ° C for 24 hours. Esterification reaction.

所得的生成物是藉由氣體層析、1H-NMR、19F-NMR、13C-NMR的分析而檢定，得到含氟單體CH2=CH-COO-CH(CH3)-CH2-(CF2-CH2)2-(CF2)6F。 The obtained product was analyzed by gas chromatography, 1 H-NMR, 19 F-NMR, 13 C-NMR to give a fluorine-containing monomer CH 2 =CH-COO-CH(CH 3 )-CH 2 . -(CF 2 -CH 2 ) 2 -(CF 2 ) 6 F.

實施例1 Example 1

在300ml高壓釜中，裝入含氟單體CH2=CH-COO-CH(CH3)-CH2-(CF2-CH2)2-(CF2)6F 10.0g，HCFC225 50g，過氧三甲基乙酸三級丁酯0.1g，藉由氮氣置換而將系統內的氧氣除去。其次，緩緩升高溫度，在60℃保持12小時進行聚合反應。將冷卻至室溫的反應液投入於多量的丙酮中使聚合物沈澱，濾取，清洗後，真空乾燥而得到含氟聚合物。 In a 300 ml autoclave, a fluorine-containing monomer CH 2 =CH-COO-CH(CH 3 )-CH 2 -(CF 2 -CH 2 ) 2 -(CF 2 ) 6 F 10.0 g, HCFC225 50 g, 0.1 g of octamethyl butyl trimethylacetate was removed by nitrogen replacement to remove oxygen in the system. Next, the temperature was gradually raised, and the polymerization was carried out by maintaining at 60 ° C for 12 hours. The reaction liquid cooled to room temperature was poured into a large amount of acetone to precipitate a polymer, which was collected by filtration, washed, and dried under vacuum to obtain a fluoropolymer.

實施例2 Example 2

除了將含氟單體變更為CH2=C(CH3)-COO-CH(CH3)-CH2-(CF2-CH2)2-(CF2)6F以外，反覆與實施例1同樣的步驟，而得到含氟聚合物。 In addition to changing the fluorine-containing monomer to CH 2 =C(CH 3 )-COO-CH(CH 3 )-CH 2 -(CF 2 -CH 2 ) 2 -(CF 2 ) 6 F, the same as in Example 1 The same procedure is followed to obtain a fluoropolymer.

實施例3 Example 3

除了將含氟單體變更為CH2=CCl-COO-CH(CH3)-CH2-(CF2-CH2)6-(CF2)4F以外，反覆與實施例1同樣的步驟，得到含氟聚合物。 The same procedure as in Example 1 was repeated except that the fluorine-containing monomer was changed to CH 2 =CCl-COO-CH(CH 3 )-CH 2 -(CF 2 -CH 2 ) 6 -(CF 2 ) 4 F. A fluoropolymer is obtained.

實施例4 Example 4

除了將含氟單體變更為CH2=CH-COO-CH(CH3)-CH2-(CF2-CH2)2-(CF2)2F以外，反覆與實施例 1同樣的步驟，得到含氟聚合物。 The same procedure as in Example 1 was repeated except that the fluorine-containing monomer was changed to CH 2 =CH-COO-CH(CH 3 )-CH 2 -(CF 2 -CH 2 ) 2 -(CF 2 ) 2 F. A fluoropolymer is obtained.

比較例1 Comparative example 1

除了將含氟單體變更為CH2=CH-COO-CH2CH2-(CF2-CH2)2-(CF2)6F以外，反覆與實施例1同樣的步驟，得到含氟聚合物。 The same procedure as in Example 1 was repeated except that the fluorine-containing monomer was changed to CH 2 =CH-COO-CH 2 CH 2 -(CF 2 -CH 2 ) 2 -(CF 2 ) 6 F to obtain a fluorine-containing polymerization. Things.

比較例2 Comparative example 2

除了將含氟單體變更為CH2=CH-COO-CH(CH3)-CH2-(CF2)6F以外，反覆與實施例1同樣的步驟，得到含氟聚合物。 The same procedure as in Example 1 was repeated except that the fluorine-containing monomer was changed to CH 2 =CH-COO-CH(CH 3 )-CH 2 -(CF 2 ) 6 F to obtain a fluorine-containing polymer.

比較例3 Comparative example 3

除了將含氟單體變更為CH2=CH-COO-CH2CH2-(CF2)6F以外，反覆與實施例1同樣的步驟，得到含氟聚合物。 The same procedure as in Example 1 was repeated except that the fluorine-containing monomer was changed to CH 2 =CH-COO-CH 2 CH 2 -(CF 2 ) 6 F to obtain a fluorine-containing polymer.

比較例4 Comparative example 4

除了將含氟單體變更為CH2=C(CH3)-COO-CH2CH2-(CF2)6F以外，反覆與實施例1同樣的步驟，得到含氟聚合物。 A fluoropolymer was obtained by the same procedure as in Example 1 except that the fluorine-containing monomer was changed to CH 2 =C(CH 3 )-COO-CH 2 CH 2 -(CF 2 ) 6 F.

實施例5 Example 5

將實施例1所得的含氟聚合物成為HCFC225溶劑中的1%溶液，以旋轉塗佈法(2000rpm)塗布在玻璃基板上後，在室溫真空乾燥48小時而製膜。測定所得的塗膜的水滴的滑落角與遲滯的結果示於第4表，及將測定HD滴的滑落角與遲滯的結果示於第5表。 The fluoropolymer obtained in Example 1 was placed in a 1% solution in a solvent of HCFC225, and applied onto a glass substrate by a spin coating method (2000 rpm), followed by vacuum drying at room temperature for 48 hours to form a film. The results of measuring the slip angle and hysteresis of the water droplets of the obtained coating film are shown in Table 4, and the results of measuring the slip angle and hysteresis of the HD droplets are shown in Table 5.

實施例6 Example 6

除了使用實施例2所得的含氟聚合物以外，反覆與實施例5同樣的步驟而製膜。將測定所得的塗膜之水滴的滑落角與遲滯的結果示於第4表，及將測定HD滴的滑落角與遲滯的結果示於第5表。 A film was formed by repeating the same procedure as in Example 5 except that the fluoropolymer obtained in Example 2 was used. The results of the slip angle and hysteresis of the water droplets of the obtained coating film are shown in Table 4, and the results of measuring the slip angle and hysteresis of the HD droplets are shown in Table 5.

實施例7 Example 7

除了使用實施例3所得的含氟聚合物以外，反覆與實施例5同樣的步驟而製膜。將測定所得的塗膜之水滴的滑落角與遲滯的結果示於第4表，及將測定HD滴的滑落角與遲滯的結果示於第5表。 A film was formed by repeating the same procedure as in Example 5 except that the fluoropolymer obtained in Example 3 was used. The results of the slip angle and hysteresis of the water droplets of the obtained coating film are shown in Table 4, and the results of measuring the slip angle and hysteresis of the HD droplets are shown in Table 5.

實施例8 Example 8 除了使用實施例4所得的含氟聚合物以外，反覆與實施例5同樣的步驟而製膜。將測定所得的塗膜之水滴的滑落角與遲滯的結果示於第4表，及將測定HD滴的滑落角與遲滯的結果示於第5表。 A film was formed by repeating the same procedure as in Example 5 except that the fluoropolymer obtained in Example 4 was used. The results of the slip angle and hysteresis of the water droplets of the obtained coating film are shown in Table 4, and the results of measuring the slip angle and hysteresis of the HD droplets are shown in Table 5. 比較例5 Comparative Example 5

除了使用比較例1所得的含氟聚合物以外，反覆與實施例5同樣的步驟而製膜。將測定所得的塗膜之水滴的滑落角與遲滯的結果示於第4表，及將測定HD滴的滑落角與遲滯的結果示於第5表。 A film was formed by repeating the same procedure as in Example 5 except that the fluoropolymer obtained in Comparative Example 1 was used. The results of the slip angle and hysteresis of the water droplets of the obtained coating film are shown in Table 4, and the results of measuring the slip angle and hysteresis of the HD droplets are shown in Table 5.

比較例6 Comparative Example 6

除了使用比較例2所得的含氟聚合物以外，反覆與實施例5同樣的步驟而製膜。將測定所得的塗膜之水滴的滑落角與遲滯的結果示於第4表，及將測定HD滴的滑落角與遲滯的結果示於第5表。 A film was formed by repeating the same procedure as in Example 5 except that the fluoropolymer obtained in Comparative Example 2 was used. The results of the slip angle and hysteresis of the water droplets of the obtained coating film are shown in Table 4, and the results of measuring the slip angle and hysteresis of the HD droplets are shown in Table 5.

比較例7 Comparative Example 7

除了使用比較例3所得的含氟聚合物以外，反覆與實施例5同樣的步驟而製膜。將測定所得的塗膜之水滴的滑落角與遲滯的結果示於第4表，及將測定HD滴的滑落角與遲滯的結果示於第5表。 A film was formed by repeating the same procedure as in Example 5 except that the fluoropolymer obtained in Comparative Example 3 was used. The results of the slip angle and hysteresis of the water droplets of the obtained coating film are shown in Table 4, and the results of measuring the slip angle and hysteresis of the HD droplets are shown in Table 5.

比較例8 Comparative Example 8

除了使用比較例4所得的含氟聚合物以外，反覆與實施例5同樣的步驟而製膜。將測定所得的塗膜之水滴的滑落角與遲滯的結果示於第4表，及將測定HD滴的滑落角與遲滯的結果示於第5表。 A film was formed by repeating the same procedure as in Example 5 except that the fluoropolymer obtained in Comparative Example 4 was used. The results of the slip angle and hysteresis of the water droplets of the obtained coating film are shown in Table 4, and the results of measuring the slip angle and hysteresis of the HD droplets are shown in Table 5.

實施例9 Example 9

在1L高壓釜中，裝入含氟單體 CH2=CH-COO-CH(CH3)-CH2-(CF2-CH2)2-(CF2)6F 150g(0.268mol)、丙烯酸硬脂酯75.0g(0.231mol)、甲基丙烯酸3-氯-2-羥丙酯3.0g(0.017mol)、純水300g、三丙二醇80g、乙酸0.45g、十八烷基三甲基銨氯化物6g、聚乙二醇月桂醚9g，攪拌下在60℃以超音波乳化分散15分鐘。乳化後添加正-十二烷基硫醇1.5g，再將氯化乙烯45g(0.720mol)壓入裝填。再將2,2’-偶氮雙(2-脒基丙烷)2鹽酸鹽1.12g添加，反應5小時，得到本發明的含氟共聚物的水性分散液。最後，以水稀釋成含氟共聚物的20%水性分散液。 In a 1 L autoclave, a fluorine-containing monomer CH 2 =CH-COO-CH(CH 3 )-CH 2 -(CF 2 -CH 2 ) 2 -(CF 2 ) 6 F 150 g (0.268 mol), acrylic acid was charged. 75.0 g (0.231 mol) of stearyl ester, 3.0 g (0.017 mol) of 3-chloro-2-hydroxypropyl methacrylate, 300 g of pure water, 80 g of tripropylene glycol, 0.45 g of acetic acid, octadecyltrimethylammonium chloride 6 g of the compound and 9 g of polyethylene glycol lauryl ether were emulsified and dispersed by ultrasonic wave at 60 ° C for 15 minutes while stirring. After emulsification, 1.5 g of n-dodecyl mercaptan was added, and then 45 g (0.720 mol) of vinyl chloride was pressed into the charge. Further, 1.12 g of 2,2'-azobis(2-amidinopropane) 2 hydrochloride was added and reacted for 5 hours to obtain an aqueous dispersion of the fluorinated copolymer of the present invention. Finally, it was diluted with water to form a 20% aqueous dispersion of the fluorocopolymer.

實施例10 Example 10

除了將含氟單體變更為CH2=C(CH3)-COO-CH(CH3)-CH2-(CF2-CH2)2-(CF2)6F 150g(0.261mol)，及將丙烯酸硬脂酯變更為丙烯酸二十二酯87.9g(0.231mol)以外，反覆與實施例9同樣的步驟，得到本發明的含氟共聚物的20%水性分散液。 In addition to changing the fluorine-containing monomer to CH 2 =C(CH 3 )-COO-CH(CH 3 )-CH 2 -(CF 2 -CH 2 ) 2 -(CF 2 ) 6 F 150g (0.261 mol), and A 20% aqueous dispersion of the fluorinated copolymer of the present invention was obtained by repeating the same procedure as in Example 9 except that stearyl acrylate was changed to 87.9 g (0.231 mol) of behenyl acrylate.

比較例9 Comparative Example 9

除了將含氟單體變更為CH2=C(CH3)-COO-CH2-CH2-(CF2)8F150g(0.279mol)以外，反覆與實施例9同樣的步驟，得到含氟共聚物的20%水性分散液。 The same procedure as in Example 9 was repeated to obtain a fluorine-containing copolymer, except that the fluorine-containing monomer was changed to CH 2 =C(CH 3 )-COO-CH 2 -CH 2 -(CF 2 ) 8 F150 g (0.279 mol). A 20% aqueous dispersion of the material.

比較例10 Comparative Example 10

除了將含氟單體變更為CH2=C(CH3)-COO-CH2-CH2-(CF2)6F150g(0.347mol)以外，反覆與實施例9同樣的步驟，得到含氟共聚物的20%水性分散液。 The same procedure as in Example 9 was repeated to obtain a fluorine-containing copolymer, except that the fluorine-containing monomer was changed to CH 2 =C(CH 3 )-COO-CH 2 -CH 2 -(CF 2 ) 6 F, 150 g (0.347 mol). A 20% aqueous dispersion of the material.

比較例11 Comparative Example 11

除了將含氟單體變更為 CH2=CH-COO-CH2CH2-(CF2-CH2)2-(CF2)6F 150g(0.279mol)以外，反覆與實施例9同樣的步驟，得到含氟共聚物的20%水性分散液。 The same procedure as in Example 9 was repeated except that the fluorine-containing monomer was changed to CH 2 =CH-COO-CH 2 CH 2 -(CF 2 -CH 2 ) 2 -(CF 2 ) 6 F 150 g (0.279 mol). A 20% aqueous dispersion of the fluorocopolymer was obtained.

實施例11 Example 11

將實施例9所得的含氟共聚物的水性分散液1.0g與NICCA Assist V2(MDI系嵌段異氰酸酯，日華化學(股))0.3g以水98.7g稀釋，得到處理液。在所得的處理液中浸漬聚酯布(塔夫塔綢(taffeta)，25cm×25cm)及T/C混紡布(聚酯65/棉35，闊幅布(broad)，25cm×25cm)，以滾筒絞乾使浸吸量(wet pick up)分別成為40%、60%。其次，在120℃乾燥3分鐘，再在160℃熱處理2分鐘，完成布的處理。將所得的布，做淋浴撥水試驗、撥水性試驗、撥油性試驗的結果示於第6表。這時，以評估洗衣耐久性之目的，將處理布遵照AATCC法，在浴溫40℃每次的洗衣時間為12分鐘(不含淋洗等的時間)的正常條件洗衣，進行滾筒乾燥，以此為1循環，將此循環反覆進行的處理布也做淋浴撥水試驗、撥水性試驗、撥油性試驗。結果示於第6表。 1.0 g of the aqueous dispersion of the fluorinated copolymer obtained in Example 9 and 0.3 g of NICCA Assist V2 (MDI-based blocked isocyanate, Nisshin Chemical Co., Ltd.) were diluted with water (98.7 g) to obtain a treatment liquid. A polyester cloth (taffeta, 25 cm × 25 cm) and a T/C blended cloth (polyester 65 / cotton 35, broad cloth, 25 cm × 25 cm) were impregnated into the obtained treatment liquid to The drum was dried to make the wet pick up 40% and 60%, respectively. Next, it was dried at 120 ° C for 3 minutes, and further heat treated at 160 ° C for 2 minutes to complete the treatment of the cloth. The result of the shower water test, the water repellency test, and the oil repellency test of the obtained cloth is shown in the sixth table. At this time, in order to evaluate the durability of the laundry, the treated cloth is subjected to drum drying in accordance with the AATCC method, and the laundry is heated at a bath temperature of 40 ° C for a period of 12 minutes (excluding the time of rinsing, etc.). For one cycle, the treatment cloth that was repeatedly carried out in this cycle was also subjected to a shower water test, a water repellency test, and an oil repellency test. The results are shown in Table 6.

實施例12 Example 12

除了使用實施例10所得的含氟共聚物的水性分散液以外，反覆與實施例11同樣的步驟，將布進行處理。將所得的布，試驗包含洗衣耐久性的淋浴撥水試驗、撥水性試驗、撥油性試驗的結果示於第6表。 The cloth was treated in the same manner as in Example 11 except that the aqueous dispersion of the fluorinated copolymer obtained in Example 10 was used. The obtained cloth, the results of the shower water test, the water repellency test, and the oil repellency test including the laundry durability are shown in the sixth table.

比較例12 Comparative Example 12

除了使用比較例9所得的含氟共聚物的水性分散液以外，反覆與實施例11同樣的步驟，將布進行處理。將所得的布，試驗包含洗衣耐久性的淋浴撥水試驗、撥水性試驗、撥油性試驗的結果 示於第6表。 The cloth was treated in the same manner as in Example 11 except that the aqueous dispersion of the fluorinated copolymer obtained in Comparative Example 9 was used. The obtained cloth was tested for the results of the shower water test, the water repellency test, and the oil repellency test including the laundry durability. Shown in the sixth table.

比較例13 Comparative Example 13

除了使用比較例10所得的含氟共聚物的水性分散液以外，反覆與實施例11同樣的步驟，將布進行處理。將所得的布，試驗包含洗衣耐久性的淋浴撥水試驗、撥水性試驗、撥油性試驗的結果示於第6表。 The cloth was treated in the same manner as in Example 11 except that the aqueous dispersion of the fluorinated copolymer obtained in Comparative Example 10 was used. The obtained cloth, the results of the shower water test, the water repellency test, and the oil repellency test including the laundry durability are shown in the sixth table.

比較例14 Comparative Example 14

除了使用比較例11所得的含氟共聚物的水性分散液以外，反覆與實施例11同樣的步驟，將布進行處理。將所得的布，試驗包含洗衣耐久性的淋浴撥水試驗、撥水性試驗、撥油性試驗的結果示於第6表。 The cloth was treated in the same manner as in Example 11 except that the aqueous dispersion of the fluorinated copolymer obtained in Comparative Example 11 was used. The obtained cloth, the results of the shower water test, the water repellency test, and the oil repellency test including the laundry durability are shown in the sixth table.

由第4表及第5表，可知本發明的含氟聚合物有低的滑落角以及遲滯的測定值。滑落角以及遲滯小表示對水滴及HD滴的環境應答性小，可知本發明的含氟聚合物有優異的撥水撥油性。又，由第6表，可知在纖維的撥水撥油劑用途上，本發明的含氟共聚物也有優異的撥水撥油性。 From Tables 4 and 5, it is understood that the fluoropolymer of the present invention has a low slip angle and a measured value of hysteresis. The slip angle and small hysteresis indicate that the environmental responsiveness to water droplets and HD droplets is small, and it is understood that the fluoropolymer of the present invention has excellent water repellency and oil repellency. Further, from the sixth table, it is understood that the fluorinated copolymer of the present invention also has excellent water repellency and oil repellency in the use of the water-repellent and oil-repellent agent for fibers.

Claims (12)

一種含氟組成物，係含有具有由式：CH2=C(-X)-C(=O)-Y-Z-A-(CF2-CH2)a-Rf所示之含氟單體(a)衍生之重複單元的含氟聚合物，[式中，X為氫原子、一價有機基或鹵素原子，Y為-O-或-NH-，Z為直接鍵結或二價有機基，Rf為碳數1至20的氟烷基，A為直鏈(碳數為3以上的奇數)或分枝鏈(碳數為3以上的整數)的伸烷基，a為1至50的整數]。 A fluorine-containing composition containing a fluorine-containing monomer (a) represented by the formula: CH 2 =C(-X)-C(=O)-YZA-(CF 2 -CH 2 ) a -Rf a fluoropolymer of a repeating unit, 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 carbon A fluoroalkyl group of 1 to 20, wherein A is a linear chain (odd number of carbon number 3 or more) or a branched chain (an integer number of carbon atoms of 3 or more), and a is an integer of 1 to 50]. 如申請專利範圍第1項所述之含氟組成物，其中，含氟單體(a)為通式：CH2=C(-X)-C(=O)-Y-Z-A-(CF2-CH2)a-Rf所示之丙烯酸酯或丙烯醯胺，[式中，X為氫原子、碳數1至21之直鏈狀或分枝狀烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(惟，X1及X2為氫原子、氟原子、氯原子、溴原子或碘原子)、氰基、碳數1至21之直鏈狀或分枝狀氟烷基、取代或未經取代的苄基、取代或未經取代的苯基；Y為-O-或-NH-；Z為直接鍵結、式-R2(R1)NSO2-或式-R2(R1)NCO-所示的基(式中，R1為碳數1至10的烷基，R2為碳數1至10的直鏈狀伸烷基或分枝狀伸烷基)、 式-CH2CH(OR3)CH2-(式中，R3表示氫原子或碳數1至10的醯基)所示之基，或-(CH2)m-SO2-基或-(CH2)m-S-基(惟，m為1至10)，Rf為碳數1至20的直鏈狀或分枝狀的氟烷基，A為直鏈(碳數為3以上的奇數)或分枝鏈(碳數為3以上的整數)的伸烷基，a為1至50的整數]。 The fluorine-containing composition according to claim 1, wherein the fluorine-containing monomer (a) is of the formula: CH 2 =C(-X)-C(=O)-YZA-(CF 2 -CH 2) a -Rf shown of an acrylate or acrylamide, [wherein, X is a hydrogen atom, a carbon number of 1 to 21 linear or branched alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine Atom, CFX 1 X 2 group (except that X 1 and X 2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched halane having a carbon number of 1 to 21. a substituted, unsubstituted or unsubstituted phenyl group; Y is -O- or -NH-; Z is a direct bond, a formula -R 2 (R 1 )NSO 2 - or a formula - a group represented by R 2 (R 1 )NCO- (wherein R 1 is an alkyl group having 1 to 10 carbon atoms, and R 2 is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group ), a group of the formula -CH 2 CH(OR 3 )CH 2 - (wherein R 3 represents a hydrogen atom or a fluorenyl group having 1 to 10 carbon atoms), or a -(CH 2 ) m -SO 2 - group Or -(CH 2 ) m -S- group (except that m is 1 to 10), Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, and A is a linear chain (carbon number is 3) Above an odd number or a branched chain (an integer having a carbon number of 3 or more) , A is an integer of from 1 to 50]. 如申請專利範圍第1項或第2項所述之含氟組成物，其中，含氟單體(a)為通式：CH2=C(-X)-C(=O)-O-A-(CF2-CH2)a-Rf所示者，[式中，X、Rf、A、a與前述相同意義]。 The fluorine-containing composition according to claim 1 or 2, wherein the fluorine-containing monomer (a) is of the formula: CH 2 =C(-X)-C(=O)-OA-( Where CF 2 -CH 2 ) a -Rf is represented, [wherein, X, Rf, A, a have the same meanings as described above]. 如申請專利範圍第1項至第3項中任一項所述之含氟組成物，其中，Rf為碳數1至6的全氟烷基。 The fluorine-containing composition according to any one of claims 1 to 3, wherein Rf is a perfluoroalkyl group having 1 to 6 carbon atoms. 如申請專利範圍第1項至第4項中任一項所述之含氟組成物，其中，含氟聚合物復具有自非氟非交聯性單體(b)所衍生之重複單元。 The fluorine-containing composition according to any one of claims 1 to 4, wherein the fluoropolymer has a repeating unit derived from the non-fluorine non-crosslinkable monomer (b). 如申請專利範圍第1項至第5項中任一項所述之含氟組成物，其中，含氟聚合物復具有自非氟交聯性單體(c)所衍生之重複單元。 The fluorine-containing composition according to any one of claims 1 to 5, wherein the fluoropolymer complex has a repeating unit derived from the non-fluorine crosslinkable monomer (c). 如申請專利範圍第1項至第6項中任一項所述之含氟組成物，其中，復含有液狀介質。 The fluorine-containing composition according to any one of claims 1 to 6, which further comprises a liquid medium. 如申請專利範圍第1項至第7項中任一項所述之含氟組成物，其係撥水撥油劑、抗污劑或脫模劑。 The fluorine-containing composition according to any one of claims 1 to 7, which is a water-repellent oil-repellent agent, an anti-fouling agent or a mold release agent. 一種含氟聚合物，係含有具有由式：CH2=C(-X)-C(=O)-Y-Z-A-(CF2-CH2)a-Rf所示含氟單體衍生之重複單元，[式中，X為氫原子、一價有機基或鹵素原子，Y為-O-或-NH-，Z為直接鍵結或二價有機基，Rf為碳數1至20的氟烷基，A為直鏈(碳數為3以上的奇數)或分枝鏈(碳數為3以上的整數)的伸烷基，a為1至50的整數]。 A fluoropolymer comprising a repeating unit derived from a fluorine-containing monomer represented by the formula: CH 2 =C(-X)-C(=O)-YZA-(CF 2 -CH 2 ) a -Rf, Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 20 carbon atoms. A is a linear chain (odd number having a carbon number of 3 or more) or a branched chain (an integer having 3 or more carbon atoms), and a is an integer of 1 to 50]. 一種含氟化合物，其係式：CH2=C(-X)-C(=O)-Y-Z-A-(CF2-CH2)a-Rf所示者，[式中，X為氫原子、一價有機基或鹵素原子，Y為-O-或-NH-，Z為直接鍵結或二價有機基，Rf為碳數1至20的氟烷基，A為直鏈(碳數為3以上的奇數)或分枝鏈(碳數為3以上的整數)的伸烷基，a為1至50的整數]。 A fluorine-containing compound having the formula: CH 2 =C(-X)-C(=O)-YZA-(CF 2 -CH 2 ) a -Rf, wherein X is a hydrogen atom, a valence organic group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms, and A is a linear chain (carbon number is 3 or more) An odd number) or a branched chain (an integer having a carbon number of 3 or more), and a is an integer of 1 to 50]. 一種處理基材的方法，包含以申請專利範圍第1至8項中任一項所述之含氟組成物進行處理。 A method of treating a substrate comprising treating the fluorine-containing composition according to any one of claims 1 to 8. 一種纖維製品，其係經申請專利範圍第1至8項中任一項所述之含氟組成物進行處理者。 A fiber product which is treated by the fluorine-containing composition according to any one of claims 1 to 8.
TW101138379A 2011-10-19 2012-10-18 Fluorine-containing composition and fluorine-containing polymer TW201321418A (en)

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