TW201331239A - Fluorine-contained composition and fluorine-contained polymer - Google Patents
Fluorine-contained composition and fluorine-contained polymer Download PDFInfo
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Abstract
Description
本發明是有關含氟組成物及含氟聚合物。若藉由本發明，即可製造一種含氟聚合物，其對纖維製品(例如，地毯)、紙、不織布、石材、靜電濾器、防塵罩、燃料電池的零件賦與優異的撥水性、撥油性、防污性。 The present invention relates to a fluorine-containing composition and a fluorine-containing polymer. According to the present invention, a fluoropolymer can be produced which imparts excellent water repellency and oil repellency to parts of fibrous products (for example, carpets), paper, non-woven fabrics, stone materials, electrostatic filters, dust covers, and fuel cells. Antifouling.
以往，即有各種的含氟化合物之提案。含氟化合物，具有耐熱性、耐氧化性、耐候性等特性優異之優點。利用含氟化合物的自由能低，即利用不易附著的特性，而使用含氟化合物作為例如撥水撥油劑及防污劑。例如，美國專利第5247008號所述之作為纖維製品、皮革、紙及礦物基材用的加工劑，其為丙烯酸或甲基丙烯酸的全氟烷酯、與丙烯酸或甲基丙烯酸的烷酯、與丙烯酸或甲基丙烯酸的胺基烷酯之共聚合物的水性分散物。 In the past, there have been proposals for various fluorine-containing compounds. The fluorine-containing compound has an advantage of excellent properties such as heat resistance, oxidation resistance, and weather resistance. The fluorine-containing compound has a low free energy, that is, a property of not easily adhering, and a fluorine-containing compound is used as, for example, a water-repellent oil-repellent agent and an antifouling agent. For example, U.S. Patent No. 5,247,008, which is a processing agent for fiber products, leather, paper, and mineral substrates, which is a perfluoroalkyl ester of acrylic acid or methacrylic acid, an alkyl ester with acrylic acid or methacrylic acid, and An aqueous dispersion of a copolymer of an aminoalkyl ester of acrylic acid or methacrylic acid.
以往，就提昇對於洗滌或乾洗等的撥水潑油性之耐久性之目的，嘗試使含有氟烷基的聚合性單體與具有接著性基的單體一起共聚合，或者將含有氟烷基的聚合物與皮膜強度高的聚合物混合。在塗料(塗布劑)領域中，藉由使用具有多層結構的粒子聚合物而維持氟之特性，成功賦與加工性的新穎特性(例如，日 本特開平06-56944)。 In the past, in order to improve the durability against water repellency of washing or dry cleaning, it has been attempted to copolymerize a fluoroalkyl group-containing polymerizable monomer with a monomer having a binder group, or to contain a fluoroalkyl group. The polymer is mixed with a polymer having a high film strength. In the field of coatings (coating agents), by using a particle polymer having a multilayer structure to maintain the characteristics of fluorine, the novel properties of processability are successfully imparted (for example, Bent Kaiping 06-56944).
同時，提倡多層結構粒子聚合物之組成物以具有耐久性、低溫硬化等特性(例如，日本特開平02-001795、日本特開平07-278422、日本特開平11-172126、日本特開平2007-291373)。 At the same time, a composition of a multi-layered structure of a polymer is proposed to have properties such as durability, low-temperature hardening, and the like (for example, Japanese Patent Laid-Open No. Hei 02-001795, Japanese Patent Application Laid-Open No. Hei No. Hei 07-278422, Japanese Patent Application Laid-Open No. Hei No. Hei 11-172126 ).
又，在已往的將一般的水性分散液稀釋並調合之撥水撥油劑加工浴中，因放入處理基材時所受到之機械衝擊而使分散液崩壞，造成乳膠粒子凝聚或沉降，而常常發生聚合物附著在撥輪上而致使基材受到污染、滾輪受到污染等問題。雖然已提案有數項使夾雜物的安定性優化的方法之(例如，日本特開平9-118877、WO 2004/069924)，但隨著近年來的撥水撥油加工之多樣性，其未必達到提供充分滿足的安定性。同時，對於聚合物附著在滾輪上的問題，聚合物的黏著性越高時越容易產生問題。同時，含有氟烷基的聚合物之氟烷基的碳數為6以下時，因聚合物的熔點降低而有使黏著性變得高於碳數8以上的聚合物之傾向。 Further, in the conventional water-repellent oil-repellent processing bath in which a general aqueous dispersion is diluted and blended, the dispersion is collapsed due to mechanical shock received when the substrate is treated, and the latex particles are agglomerated or settled. However, problems such as contamination of the substrate and contamination of the roller are often caused by the adhesion of the polymer to the dial. Although several methods for optimizing the stability of inclusions have been proposed (for example, Japanese Patent Laid-Open No. Hei 9-118877, WO 2004/069924), with the diversity of water- and oil-repellent processing in recent years, it may not be provided. Fully satisfied with stability. At the same time, as the polymer adheres to the roller, the higher the adhesion of the polymer, the more likely it is to cause problems. Meanwhile, when the fluoroalkyl group of the fluoroalkyl group-containing polymer has a carbon number of 6 or less, the polymer has a tendency to increase the viscosity to a polymer having a carbon number of 8 or more due to a decrease in the melting point of the polymer.
[專利文獻1]美國專利第5247008號說明書 [Patent Document 1] US Patent No. 5247008
[專利文獻2]日本特開平06-56944號公報 [Patent Document 2] Japanese Laid-Open Patent Publication No. 06-56944
[專利文獻3]日本特開平02-001795號公報 [Patent Document 3] Japanese Patent Laid-Open No. 02-001795
[專利文獻4]日本特開平07-278422號公報 [Patent Document 4] Japanese Patent Laid-Open No. 07-278422
[專利文獻5]日本特開平11-172126號公報 [Patent Document 5] Japanese Patent Laid-Open No. Hei 11-172126
[專利文獻6]日本特開平2007-291373號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2007-291373
[專利文獻7]日本特開平9-118877號公報 [Patent Document 7] Japanese Patent Laid-Open No. Hei 9-118877
[專利文獻8]WO 2004/069924號公報 [Patent Document 8] WO 2004/069924
本發明的目的是提供一種撥水撥油劑組成物，其賦與纖維製品等基材優異的撥水撥油性，在其加工處理中，防止聚合物對滾輪的附著性優異。 An object of the present invention is to provide a water-repellent and oil-repellent composition which is excellent in water-repellent and oil-repellent properties of a substrate such as a fiber product, and which is excellent in adhesion of a polymer to a roller during processing.
本發明人等為了解決上述問題而進行深入的探討，目的是提供一種撥水撥油劑組成物，其抑制高黏著性的聚合物部份之生成、發揮高度撥水撥油性且耐久性優異。結果發現使含氟聚合物的非氟聚合物部份具有特定的組成時，即可達成上述目的，而完成本發明。 The inventors of the present invention have intensively studied in order to solve the above problems, and an object of the invention is to provide a water-repellent and oil-repellent composition which suppresses formation of a highly adhesive polymer portion, exhibits high water-repellent oil-repellent property, and is excellent in durability. As a result, it has been found that the above object can be attained when the non-fluoropolymer portion of the fluoropolymer has a specific composition, and the present invention has been completed.
本發明提供一種含氟聚合物，其具有：(a)由具有氟烷基的含氟單體所衍生之重複單元、(b)由第2單體所衍生之重複單元，該第2單體為具有碳數12至30的直鏈狀或分枝狀烴基之丙烯酸酯單體的、及(c)由第3單體所衍生之重複單元，該第3單體為均質聚合物的玻璃轉移點(Tg)或熔點(Tm)為50℃以上之(甲基)丙烯酸酯單體；含氟聚合物中，相對於第2單體(b)與第3單體(c)之量的合計100重量份，第2單體(b)之量為82至99.9重量份或2至60重量份，第3單體(c)之量為0.1至18重量份或40至98重量份。 The present invention provides a fluoropolymer having: (a) a repeating unit derived from a fluoromonomer having a fluoroalkyl group, and (b) a repeating unit derived from the second monomer, the second monomer a repeating unit derived from a linear or branched hydrocarbon group having 12 to 30 carbon atoms, and (c) a repeating unit derived from a third monomer, which is a glass transition of a homogeneous polymer a (meth) acrylate monomer having a point (Tg) or a melting point (Tm) of 50 ° C or higher; and a total amount of the fluoropolymer relative to the amount of the second monomer (b) and the third monomer (c) 100 parts by weight, the amount of the second monomer (b) is 82 to 99.9 parts by weight or 2 to 60 parts by weight, and the amount of the third monomer (c) is 0.1 to 18 parts by weight or 40 to 98 parts by weight.
本發明也提供含有上述含氟聚合物的含氟組成物。 The present invention also provides a fluorine-containing composition containing the above fluorine-containing polymer.
本發明的含氟組成物賦與纖維製品等基材優異的撥水潑油性，在其加工處理中，可防止聚合物對滾輪的附著性優異。 The fluorine-containing composition of the present invention imparts excellent water repellency and oil repellency to a substrate such as a fiber product, and is excellent in adhesion of the polymer to the roller during the processing.
本發明中，黏著性及黏附(gum up)率低，進行良好的加工處理。 In the present invention, the adhesion and the stick up rate are low, and a good processing is performed.
本發明中，使用(a)含氟單體、(b)含有直鏈狀或分枝狀烴基的丙烯酸酯單體以及(c)單體(a)及(b)以外的第3單體。 In the present invention, (a) a fluorine-containing monomer, (b) an acrylate monomer containing a linear or branched hydrocarbon group, and (c) a third monomer other than the monomers (a) and (b) are used.
本發明的含氟聚合物，具有：(a)由含氟單體(例如，丙烯酸酯、甲基丙烯酸酯、α-氯取代丙烯酸酯)所衍生之重複單元、(b)由含有直鏈狀或分枝狀烴基之丙烯酸酯單體所衍生的重複單元、及(c)由第3單體所衍生之重複單元。 The fluoropolymer of the present invention has: (a) a repeating unit derived from a fluorine-containing monomer (for example, acrylate, methacrylate, or α-chloro-substituted acrylate), and (b) a linear one Or a repeating unit derived from a branched hydrocarbon-based acrylate monomer, and (c) a repeating unit derived from the third monomer.
本發明的含氟聚合物，可僅含由單體(a)、單體(b)與單體(c)所衍生的重複單元，或者除了由單體(a)、單體(b)與單體(c)所衍生的重複單元之外，也可復具有由其他的單體所衍生之重複單元。 The fluoropolymer of the present invention may contain only repeating units derived from monomer (a), monomer (b) and monomer (c), or in addition to monomer (a), monomer (b) and In addition to the repeating unit derived from the monomer (c), a repeating unit derived from another monomer may also be added.
含氟單體(a)，是下式所表示的含氟單體：CH2=C(-X)-C(=O)-Y-Z-Rf The fluorine-containing monomer (a) is a fluorine-containing monomer represented by the following formula: CH 2 =C(-X)-C(=O)-YZ-Rf
[式中，X是氫原子、一價的有機基或鹵素原子，Y是-O-或-NH-，Z是直接鍵結或二價的有機基，Rf是碳數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 bonded or divalent organic group, and Rf is a fluoroalkane having a carbon number of 1 to 20. base].
含氟單體(a)是(丙烯酸酯(X：氫原子)或甲基丙烯酸酯(X：甲基)的)α位有時經鹵素原子等取代。因此，X可為碳數2至21的直鏈狀或分枝狀之烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(惟，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的直鏈狀或分枝狀之氟烷基、經取代或未經取代的苯甲基、經取代或未經取代的苯基。X尤其宜為氯原子。 The fluorine-containing monomer (a) is an α-position of (acrylate (X: hydrogen atom) or methacrylate (X: methyl)) which may be substituted with a halogen atom or the like. Therefore, 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 (only, X 1 and X 2 are hydrogen atoms). , fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or not Substituted phenyl. X is especially preferably a chlorine atom.
含氟單體(a)宜為Y基是-O-的丙烯酸酯。 The fluorine-containing monomer (a) is preferably an acrylate having a Y group of -O-.
具體上，Z基是碳數1至20(例如，碳數1至10，尤其是1至4，特別是1或2)的直鏈狀或分枝狀脂肪族基(例如，伸烷基)，例如式-(CH2)x-(式中，x是1至10)所表示的基、或碳數6至18的芳香族基或環狀脂肪族基、式-R2(R1)N-SO2-或式-R2(R1)N-CO-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)，例如-CH2CH2N(R1)SO2-基(惟，R1是碳數1至4的烷基)、或式-CH2CH(OR3)CH2-[Ar-(O)q]p-(式中，R3是氫原子或碳數1至10的醯基(例如，甲醯基或乙醯基等)，Ar是視需要而具有取代基的伸芳基(例如，伸苯基)，p是0或1，q是0或1)所表示的基、或 式-(CH2)n-Ar-(O)q-(式中，Ar是視需要而具有取代基的伸芳基(例如，伸苯基)，n是0至10，q是0或1)所表示的基、或-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(惟，m是1至10，n是0至10)。 Specifically, the Z group is a linear or branched aliphatic group having a carbon number of 1 to 20 (for example, a carbon number of 1 to 10, particularly 1 to 4, particularly 1 or 2) (for example, an alkyl 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 18 carbon atoms, and 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 linear extension of 1 to 10 carbon atoms; An alkyl group or a branched alkyl group), for example, a -CH 2 CH 2 N(R 1 )SO 2 - group (except that R 1 is an alkyl group having 1 to 4 carbon atoms), or a formula -CH 2 CH (OR) 3 ) CH 2 -[Ar-(O) q ] p - (wherein R 3 is a hydrogen atom or a fluorenyl group having 1 to 10 carbon atoms (for example, a decyl group or an ethyl fluorenyl group), and Ar is as needed And a substituted aryl group having a substituent (for example, a phenyl group), p is 0 or 1, q is a group represented by 0 or 1), or a formula -(CH 2 ) n -Ar-(O) q -( Wherein Ar is an optionally substituted aryl group (for example, a phenyl group) having a substituent, n is 0 to 10, q is a group represented by 0 or 1), or -(CH 2 ) m -SO 2 -(CH 2 ) n -yl or -(CH 2 ) m -S-(CH 2 ) n -yl (except that m is 1 to 10 and n is 0 to 10).
芳香族基或環狀脂肪族基，可以經取代或未經取代。S基或SO2基可直接與Rf鍵結。 An aromatic group or a cyclic aliphatic group may be substituted or unsubstituted. The S group or SO 2 group can be directly bonded to the Rf.
Rf基宜為全氟烷基。Rf基的碳數是1至12，例如1至6，尤其宜為4至6。Rf基之例，可列舉：例如-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 include, for example, -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.
含氟單體(a)的具體例，雖然可列示如以下之例，但並不侷限於此等單體。 Specific examples of the fluorine-containing monomer (a) include the following examples, but are not limited to these monomers.
CH2=C(-H)-C(=O)-O-(CH2)2-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -Rf
CH2=C(-H)-C(=O)-O-C6H4-Rf CH 2 =C(-H)-C(=O)-OC 6 H 4 -Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -Rf
CH2=C(-H)-C(=O)-O-(CH2)2N(-CH3)SO2-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 N(-CH 3 )SO 2 -Rf
CH2=C(-H)-C(=O)-O-(CH2)2N(-C2H5)SO2-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 N(-C 2 H 5 )SO 2 -Rf
CH2=C(-H)-C(=O)-O-CH2CH(-OH)CH2-Rf CH 2 =C(-H)-C(=O)-O-CH 2 CH(-OH)CH 2 -Rf
CH2=C(-H)-C(=O)-O-CH2CH(-OCOCH3)CH2-Rf CH 2 =C(-H)-C(=O)-O-CH 2 CH(-OCOCH 3 )CH 2 -Rf
CH2=C(-H)-C(=O)-O-(CH2)2-S-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -S-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf
CH2=C(-H)-C(=O)-O-(CH2)3-SO2-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf
CH2=C(-H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2- SO 2 -(CH 2 ) 2 -Rf
CH2=C(-H)-C(=O)-NH-(CH2)2-Rf CH 2 =C(-H)-C(=O)-NH-(CH 2)2 -Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-S-Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -S-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf
CH2=C(-CH3)-C(=O)-O-(CH2)3-SO2-Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-CH3)-C(=O)-NH-(CH2)2-Rf CH 2 =C(-CH 3 )-C(=O)-NH-(CH 2 ) 2 -Rf
CH2=C(-F)-C(=O)-O-(CH2)2-S-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -S-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf
CH2=C(-F)-C(=O)-O-(CH2)2-SO2-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf
CH2=C(-F)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-F)-C(=O)-NH-(CH2)2-Rf CH 2 =C(-F)-C(=O)-NH-(CH 2 ) 2 -Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-S-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -S-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-Cl)-C(=O)-NH-(CH2)2-Rf CH 2 =C(-Cl)-C(=O)-NH-(CH 2 ) 2 -Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-S-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -S-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-CF3)-C(=O)-NH-(CH2)2-Rf CH 2 =C(-CF 3 )-C(=O)-NH-(CH 2 ) 2 -Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -S-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-CF2H)-C(=O)-NH-(CH2)2-Rf CH 2 =C(-CF 2 H)-C(=O)-NH-(CH 2 ) 2 -Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-S-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -S-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-CN)-C(=O)-NH-(CH2)2-Rf CH 2 =C(-CN)-C(=O)-NH-(CH 2 ) 2 -Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -S-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-CF2CF3)-C(=O)-NH-(CH2)2-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-NH-(CH 2 ) 2 -Rf
CH2=C(-F)-C(=O)-O-(CH2)3-S-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -S-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf
CH2=C(-F)-C(=O)-O-(CH2)3-SO2-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf
CH2=C(-F)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-F)-C(=O)-NH-(CH2)3-Rf CH 2 =C(-F)-C(=O)-NH-(CH 2 ) 3 -Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-S-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -S-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-S-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -S-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -S-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-S-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -S-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -S-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-SO2-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf
CH2=C(-Cl)-C(=O)-O-CH2CH2N(CH3)SO2-Rf CH 2 =C(-Cl)-C(=O)-O-CH 2 CH 2 N(CH 3 )SO 2 -Rf
CH2=C(-Cl)-C(=O)-O-CH2CH(OCOCH3)CH2-Rf CH 2 =C(-Cl)-C(=O)-O-CH 2 CH(OCOCH 3 )CH 2 -Rf
CH2=C(-Cl)-C(=O)-O-CH2-Ph-O-Rf(此處，Ph是1,4-伸苯基) CH 2 =C(-Cl)-C(=O)-O-CH 2 -Ph-O-Rf (here, Ph is 1,4-phenylene)
CH2=C(-Cl)-C(=O)-O-CH2CH(OH)CH2-Ph-O-Rf CH 2 =C(-Cl)-C(=O)-O-CH 2 CH(OH)CH 2 -Ph-O-Rf
CH2=C(-Cl)-C(=O)-O-CH2-Ph-Rf CH 2 =C(-Cl)-C(=O)-O-CH 2 -Ph-Rf
CH2=C(-Cl)-C(=O)-O-CH2CH(OCOCH3)CH2-Ph-Rf CH 2 =C(-Cl)-C(=O)-O-CH 2 CH(OCOCH 3 )CH 2 -Ph-Rf
[上述式中，Rf是碳數1至20的氟烷基]。 [In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms].
第2單體(b)，是不具有氟烷基的單體。第2單體(b)， 不具有環狀烴基。第2單體(b)，通常是不含有氟原子的單體。直鏈狀或分枝狀的烴基，尤其宜為直鏈狀的烴基。直鏈狀或分枝狀的烴基，其碳數為12至30，一般宜為飽和的脂肪族烴基。 The second monomer (b) is a monomer having no fluoroalkyl group. Second monomer (b), Does not have a cyclic hydrocarbon group. The second monomer (b) is usually a monomer which does not contain a fluorine atom. A linear or branched hydrocarbon group is particularly preferably a linear hydrocarbon group. A linear or branched hydrocarbon group having a carbon number of 12 to 30, and is generally preferably a saturated aliphatic hydrocarbon group.
第2單體(b)可為丙烯酸烷酯。烷基的碳原子數是12至30，例如12至22，尤其可為14至20。例如，第2單體(b)可為下式所表示的丙烯酸酯：CH2=CHCOOA1 The second monomer (b) may be an alkyl acrylate. The alkyl group has a carbon number of 12 to 30, for example 12 to 22, particularly 14 to 20. For example, the second monomer (b) may be an acrylate represented by the following formula: CH 2 =CHCOOA 1
[式中，A1是CnH2n+1(n=12至30，尤其是12至22)所表示的烷基]。 [wherein, A 1 is an alkyl group represented by C n H 2n+1 (n = 12 to 30, especially 12 to 22).
第2單體(b)的具體例，雖然可列舉如以下之例，但並不侷限於此等單體。 Specific examples of the second monomer (b) include the following examples, but are not limited to these monomers.
CH2=C(-H)-C(=O)-O-(CH2)11-CH3 CH 2 =C(-H)-C(=O)-O-(CH 2 ) 11 -CH 3
CH2=C(-H)-C(=O)-O-(CH2)13-CH3 CH 2 =C(-H)-C(=O)-O-(CH 2 ) 13 -CH 3
CH2=C(-H)-C(=O)-O-(CH2)15-CH3 CH 2 =C(-H)-C(=O)-O-(CH 2 ) 15 -CH 3
CH2=C(-H)-C(=O)-O-(CH2)17-CH3 CH 2 =C(-H)-C(=O)-O-(CH 2 ) 17 -CH 3
CH2=C(-H)-C(=O)-O-(CH2)21-CH3 CH 2 =C(-H)-C(=O)-O-(CH 2 ) 21 -CH 3
(即，丙烯酸十二酯、丙烯酸十四酯、丙烯酸十六酯、丙烯酸十八酯、丙烯酸二十二酯) (ie, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, behenyl acrylate)
第3單體(c)是均質聚合物的玻璃轉移點(Tg)或熔點(Tm)為50℃以上(例如60℃以上)的(甲基)丙烯酸酯單體。玻璃轉移點、熔點，分別是以JIS K7121-1987「塑膠的轉移溫度測定方法」所規定的外插玻璃轉移結束溫度(Teg)、熔解波峯溫度(Tpm)。玻璃 轉移點(Tg)或熔點(Tm)的上限是300℃，例如可為200℃。 The third monomer (c) is a (meth) acrylate monomer having a glass transition point (Tg) or a melting point (Tm) of a homogeneous polymer of 50 ° C or higher (for example, 60 ° C or higher). The glass transition point and melting point are the transition temperature (T eg ) of the extrapolation glass and the melting peak temperature (T pm ) defined by JIS K7121-1987 "Method for measuring the transfer temperature of plastics". The upper limit of the glass transition point (Tg) or melting point (Tm) is 300 ° C, for example 200 ° C.
第3單體(c)是單體(a)與單體(b)以外的單體。第3單體(c)不具有氟烷基。 The third monomer (c) is a monomer other than the monomer (a) and the monomer (b). The third monomer (c) does not have a fluoroalkyl group.
第3單體(c)宜為下式所表示的丙烯酸酯化合物：CH=CR11-C(=O)O-R12 The third monomer (c) is preferably an acrylate compound represented by the following formula: CH=CR 11 -C(=O)OR 12
[式中，R11是H、C1至C4的烷基或鹵素，R12是C1至C30的直鏈狀、分枝狀或環狀的脂肪族基；C6至C20的芳香族基；C7至C25的芳香脂肪族基]。 Wherein R 11 is H, a C 1 to C 4 alkyl group or a halogen, and R 12 is a C 1 to C 30 linear, branched or cyclic aliphatic group; C 6 to C 20 Aromatic group; C 7 to C 25 aromatic aliphatic group].
R11之例，為氫原子、甲基、氯原子、溴原子、碘原子。R11宜為甲基。 Examples of R 11 are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, and an iodine atom. R 11 is preferably a methyl group.
R12之例，有(例如，碳數1至6的)烷基(例如，甲基、乙基、丙基、丁基)、(例如，碳數5至10的)環烷基(例如，環己基)、(例如，碳數7至20的)多環式脂肪族基(例如，降冰片基、冰片基、異冰片基、金剛烷基)、苯基、萘基、苯甲基。 Examples of R 12 are (for example, a carbon number of 1 to 6) alkyl group (e.g., methyl, ethyl, propyl, butyl), (e.g., a carbon number of 5 to 10) cycloalkyl group (for example, Cyclohexyl), (for example, a carbon number of 7 to 20) polycyclic aliphatic groups (for example, norbornyl, borneol, isobornyl, adamantyl), phenyl, naphthyl, benzyl.
R12宜為具有環狀的基，宜為環烷基、多環式脂肪族基、芳香族基或芳香脂肪族基。尤其在R11為氫原子時，R12宜為具有環狀的基，一般是環烷基、多環式脂肪族基、芳香族基或芳香脂肪族基。 R 12 is preferably a cyclic group, preferably a cycloalkyl group, a polycyclic aliphatic group, an aromatic group or an aromatic aliphatic group. In particular, when R 11 is a hydrogen atom, R 12 is preferably a cyclic group, and is generally a cycloalkyl group, a polycyclic aliphatic group, an aromatic group or an aromatic aliphatic group.
第3單體(c)的具體例，可例示：如丙烯酸環己酯、丙烯酸異冰片酯、丙烯酸冰片酯、丙烯酸金剛烷酯、丙烯酸二環戊酯、丙烯酸二環戊烯酯、丙烯酸三環癸酯、丙烯酸苯酯、丙烯酸萘酯、丙烯酸苯甲酯、丙烯酸2-第三丁基苯酯、丙烯酸萘酯等丙烯酸酯；甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異 丙酯、甲基丙烯酸第三丁酯、甲基丙烯酸環己酯、甲基丙烯酸異冰片酯、甲基丙烯酸冰片酯、甲基丙烯酸金剛烷酯、甲基丙烯酸二環戊酯、甲基丙烯酸二環戊烯酯、甲基丙烯酸三環癸酯、甲基丙烯酸苯酯、甲基丙烯酸萘酯、甲基丙烯酸苯甲酯、甲基丙烯酸(2-二甲基胺基)乙酯、甲基丙烯酸氮雜環丙酯、甲基丙烯酸氮雜環丙基乙酯、甲基丙烯酸二環戊烯酯等甲基丙烯酸酯；氯丙烯酸甲酯等氯丙烯酸酯，但並不侷限於此等單體。 Specific examples of the third monomer (c) include, for example, cyclohexyl acrylate, isobornyl acrylate, borneol acrylate, adamantyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, and tricyclic acrylate. Acrylates, phenyl acrylate, naphthyl acrylate, benzyl acrylate, 2-tert-butyl acrylate, naphthyl acrylate, etc.; methyl methacrylate, ethyl methacrylate, methacrylic acid Propyl ester, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, borneol methacrylate, adamantyl methacrylate, dicyclopentyl methacrylate, methacrylic acid Cyclopentenyl ester, tricyclodecyl methacrylate, phenyl methacrylate, naphthyl methacrylate, benzyl methacrylate, (2-dimethylamino)ethyl methacrylate, methacrylic acid A methacrylate such as aziridine ester, azacyclopropyl methacrylate or dicyclopentenyl methacrylate; or a chloroacrylate such as methyl chloroacrylate, but is not limited thereto.
也可使用單體(a)、(b)及(c)之外的其他的單體(d)，例如其他的非氟非交聯性單體。 Other monomers (d) other than the monomers (a), (b) and (c), such as other non-fluorine non-crosslinkable monomers, may also be used.
在其他的單體之例中，包含例如：乙烯、醋酸乙烯酯、丙烯腈、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。其他的單體並不侷限於此等例。 In other examples of monomers, for example, ethylene, vinyl acetate, acrylonitrile, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (A) Acrylate, methoxypolypropylene glycol (meth) acrylate and vinyl alkyl ether. Other monomers are not limited to these examples.
其他的單體，可為鹵化烯烴。 Other monomers may be halogenated olefins.
鹵化烯烴，宜為經1至10個氯原子、溴原子或碘原子取代的碳數2至20之烯烴。鹵化烯烴宜為碳數2至20的氯化烯烴，尤其宜為具有1至5個氯原子的碳數2至5之烯烴。鹵化烯烴的理想具體例，可列舉：例如鹵化乙烯，例如氯乙烯、溴乙烯、碘乙烯；鹵化亞乙烯，例如氯亞乙烯、溴亞乙烯、碘亞乙烯。 The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms which is substituted with 1 to 10 chlorine atoms, a bromine atom or an iodine atom. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly preferably a olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferable specific examples of the halogenated olefin include, for example, a halogenated ethylene such as vinyl chloride, vinyl bromide, and iodoethylene; and a vinyl halide such as vinylidene chloride, vinyl bromide, and ethyl iodide.
其他的單體，可為非氟交聯性單體。非氟交聯性單體，是不含氟原子的單體。非氟交聯性單體，可為至少具有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， 可以是至少具有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。反應性基之例，有羥基、環氧基、氯甲基、封端異氰酸酯、胺基、羧基等。 Other monomers may be non-fluorine crosslinkable monomers. The non-fluorine crosslinkable monomer is a monomer having no fluorine atom. The non-fluorine-crosslinkable monomer may be a compound having at least two reactive groups and/or carbon-carbon double bonds and no fluorine. Non-fluorine crosslinkable monomer, It 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 include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amine group, a carboxyl group and the like.
非氟交聯性單體，可以是具有反應性基的單(甲基)丙烯酸酯、二(甲基)丙烯酸酯或單(甲基)丙烯醯胺。或，非氟交聯性單體可以是二(甲基)丙烯酸酯。 The non-fluorine crosslinkable monomer may be a mono (meth) acrylate having a reactive group, a di(meth) acrylate or a mono (meth) acrylamide. Alternatively, the non-fluorine crosslinkable monomer may be di(meth)acrylate.
非氟交聯性單體之一例，是具有羥基的乙烯單體。 An example of the non-fluorine crosslinkable monomer is an ethylene monomer having a hydroxyl group.
非氟交聯性單體，雖然可列舉：例如二丙酮(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-乙醯基乙醯氧基乙酯、丁二烯、異戊二烯、氯丁二烯、單氯醋酸乙烯酯、甲基丙烯酸乙烯酯、(甲基)丙烯酸環氧丙酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯等，但並不侷限於此等化合物。 Examples of the non-fluorine-crosslinkable monomer include, for example, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, and (meth) acrylate. Hydroxyethyl ester, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-ethenylethoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, Monochlorovinyl acetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc. However, it is not limited to these compounds.
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, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide.
含氟聚合物中，含氟單體(a)之量為含氟聚合物的5至95重量%，例如10至90重量%，尤其可為20至70重量%。 In the fluoropolymer, the amount of the fluoromonomer (a) is from 5 to 95% by weight, for example from 10 to 90% by weight, particularly from 20 to 70% by weight, based on the fluoropolymer.
相對於含氟單體(a)100重量份，第2單體(b)與第3單體(c)之量的合計為5至3,000重量份，例如10至2,000重量份，尤其是30至1,000重量份。 The total amount of the second monomer (b) and the third monomer (c) is 5 to 3,000 parts by weight, for example, 10 to 2,000 parts by weight, particularly 30 to 30 parts by weight based on 100 parts by weight of the fluorine-containing monomer (a). 1,000 parts by weight.
相對於含氟單體(a)100重量份，其他的單體(d)之量為500重量份以下，例如可為1至200重量份。 The amount of the other monomer (d) is 500 parts by weight or less based on 100 parts by weight of the fluorine-containing monomer (a), and may be, for example, 1 to 200 parts by weight.
含氟聚合物中，相對於第2單體(b)與第3單體(c)之 量的合計100重量份，第2單體(b)之量為82至99.9重量份或2至60重量份，例如84至99.5重量份或5至55重量份，尤其是85至99重量份或10至50重量份，第3單體(c)之量為0.1至18重量份或40至98重量份，例如0.5至16重量份或50至95重量份，尤其是1至15重量份或50至90重量份。 In the fluoropolymer, relative to the second monomer (b) and the third monomer (c) The total amount of the second monomer (b) is 82 to 99.9 parts by weight or 2 to 60 parts by weight, for example, 84 to 99.5 parts by weight or 5 to 55 parts by weight, particularly 85 to 99 parts by weight or 10 to 50 parts by weight, the amount of the third monomer (c) is 0.1 to 18 parts by weight or 40 to 98 parts by weight, for example, 0.5 to 16 parts by weight or 50 to 95 parts by weight, particularly 1 to 15 parts by weight or 50 Up to 90 parts by weight.
如含氟聚合物含有鹵化烯烴(例如，鹵化乙烯)時，相對於第2單體(b)、第3單體(c)與鹵化烯烴之量的合計100重量份，鹵化烯烴之量為30至90重量份，例如50至85重量份，尤其宜為60至80重量份。 When the fluoropolymer contains a halogenated olefin (for example, an alkyl halide), the amount of the halogenated olefin is 30% based on 100 parts by weight of the total of the second monomer (b), the third monomer (c), and the halogenated olefin. To 90 parts by weight, for example 50 to 85 parts by weight, particularly preferably 60 to 80 parts by weight.
含氟聚合物的數量平均分子量(Mn)，一般是1,000至1,000,000，例如5,000至500,000，尤其是3,000至200,000。含氟聚合物的數量平均分子量(Mn)，通常是以GPC(gel permeation chromatography，凝膠滲透層析)測定。 The number average molecular weight (Mn) of the fluoropolymer is generally from 1,000 to 1,000,000, for example from 5,000 to 500,000, especially from 3,000 to 200,000. The number average molecular weight (Mn) of the fluoropolymer is usually measured by GPC (gel permeation chromatography).
本發明中，使單體(a)至(c)(及視需要的其他單體(d))共聚合，而獲得在媒體中分散或溶解有含氟聚合物的含氟組成物。 In the present invention, the monomers (a) to (c) (and optionally other monomers (d)) are copolymerized to obtain a fluorine-containing composition in which a fluorine-containing polymer is dispersed or dissolved in a medium.
可在選自封端異氰酸酯化合物及有機聚矽氧烷化合物所形成的群組中之至少1種化合物的存在下將單體聚合。相對於單體100重量份，封端異氰酸酯化合物(或有機聚矽氧烷化合物)之量為0至100重量份，例如可為1至50重量份。 The monomer may be polymerized in the presence of at least one compound selected from the group consisting of a blocked isocyanate compound and an organopolyoxyalkylene compound. The blocked isocyanate compound (or organopolyoxane compound) is used in an amount of from 0 to 100 parts by weight, for example, from 1 to 50 parts by weight, per 100 parts by weight of the monomer.
可藉由在封端異氰酸酯化合物的存在下將單體聚合，而獲得具有封端異氰酸酯基的含氟聚合物。封端異氰酸酯化合物，是藉由至少一種封端劑(block agent)而封端的異氰酸酯。封端劑之例，可列舉：例如肟類、酚類、醇類、硫醇類、醯胺類、醯亞胺類、咪唑類、尿素類、胺類、亞胺類、吡唑類及活性亞甲 基化合物類。其他的封端劑之例，可列舉：例如吡啶酚(pyridinol)類、硫酚(thiophenol)類、二酮類及酯類。封端異氰酸酯化合物可經具有親水性基的化合物改質。 The fluoropolymer having a blocked isocyanate group can be obtained by polymerizing a monomer in the presence of a blocked isocyanate compound. The blocked isocyanate compound is an isocyanate blocked by at least one block agent. Examples of the blocking agent include, for example, anthraquinones, phenols, alcohols, mercaptans, decylamines, quinones, imidazoles, ureas, amines, imines, pyrazoles, and actives. Mia Base compound class. Examples of other blocking agents include pyridinols, thiophenols, diketones, and esters. The blocked isocyanate compound can be modified with a compound having a hydrophilic group.
可藉由在有機聚矽氧烷化合物(例如，巰基官能性有機聚矽氧烷、乙烯基官能性有機聚矽氧烷)的存在下將單體聚合，而獲得具有矽氧烷基的含氟聚合物。在1個實施形態中，巰基官能性有機聚矽氧烷具有具下述平均式的矽氧基單元：(R2SiO)a(RRNSiO)b(RRsSiO)c The fluorine-containing alkyl group can be obtained by polymerizing a monomer in the presence of an organopolyoxyalkylene compound (for example, a mercapto functional organopolyoxyalkylene or a vinyl functional organopolyoxyalkylene). polymer. In one embodiment, the fluorenyl functional organopolyoxane has a decyloxy unit having the following average formula: (R 2 SiO) a (RR N SiO) b (RR s SiO) c
[式中，a是0至4,000或0至1,000或0至400，b是1至1,000或1至100或1至50，c是1至1,000或1至100或1至50；R獨立地為一價有機基，或R是碳數1至30的烴基，或R是碳數1至12的一價烷基，或R是甲基；RN是一價的胺基官能性之有機基，RS是一價的巰基官能性之有機基]。 Wherein a is 0 to 4,000 or 0 to 1,000 or 0 to 400, b is 1 to 1,000 or 1 to 100 or 1 to 50, and c is 1 to 1,000 or 1 to 100 or 1 to 50; R is independently a monovalent organic group, or R is a hydrocarbon group having 1 to 30 carbon atoms, or R is a monovalent alkyl group having 1 to 12 carbon atoms, or R is a methyl group; R N is a monovalent amino group-functional organic group, R S is a monovalent thiol-functional organic group].
作為有機官能性基的胺基官能性之有機基RN，可以例示如具有式：-R1NHR2、式：-R1NR2 2或式：-R1NHR1NHR2(式中，各別的R1獨立地為碳數2以上之二價烴基，R2是氫或碳數1至20的烷基)之基。典型上，各別的R1是碳數2至20的伸烷基。 The organofunctional R N group as the organofunctional group may be exemplified by the formula: -R 1 NHR 2 , the formula: -R 1 NR 2 2 or the formula: -R 1 NHR 1 NHR 2 (wherein Each of R 1 is independently a divalent hydrocarbon group having 2 or more carbon atoms, and R 2 is a group of hydrogen or an alkyl group having 1 to 20 carbon atoms. Typically, each R 1 is an alkylene group having 2 to 20 carbon atoms.
在適宜的胺基官能性烴基之數個例中，有下述之例。 Among the several examples of suitable amine-functional hydrocarbon groups, the following are exemplified.
-CH2CH2NH2、-CH2CH2CH2NH2、-CH2CHCH3NH2、-CH2CH2CH2CH2NH2、 -CH2CH2CH2CH2CH2NH2、-CH2CH2CH2CH2CH2CH2NH2、-CH2CH2NHCH3、-CH2CH2CH2NHCH3、-CH2(CH3)CHCH2NHCH3、-CH2CH2CH2CH2NHCH3、-CH2CH2NHCH2CH2NH2、-CH2CH2CH2NHCH2CH2CH2NH2、-CH2CH2CH2CH2NHCH2CH2CH2CH2NH2、-CH2CH2NHCH2CH2NHCH3、-CH2CH2CH2NHCH2CH2CH2NHCH3、-CH2CH2CH2CH2NHCH2CH2CH2CH2NHCH3、及-CH2CH2NHCH2CH2NHCH2CH2CH2CH3。典型上，胺基官能性基是-CH2CH2CH2NH2。 -CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 NH 2 , -CH 2 CHCH 3 NH 2 , -CH 2 CH 2 CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 NH 2 , -CH 2 CH 2 NHCH 3 , -CH 2 CH 2 CH 2 NHCH 3 , -CH 2 (CH 3 )CHCH 2 NHCH 3 , -CH 2 CH 2 CH 2 CH 2 NHCH 3 , -CH 2 CH 2 NHCH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 CH 2 NH 2 , -CH 2 CH 2 NHCH 2 CH 2 NHCH 3 , -CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 NHCH 3 , -CH 2 CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 CH 2 NHCH 3 , and -CH 2 CH 2 NHCH 2 CH 2 NHCH 2 CH 2 CH 2 CH 3 . Typical, amine functional group is -CH 2 CH 2 CH 2 NH 2 .
RS可以例示如式：-R1SR2(式中，各別的R1獨立地為碳數2以上之二價烴基，R2是氫或碳數1至20的烷基。式中，各別的R1及R2是與上述相同)所示的基。典型上，各別的R1是碳數2至20的伸烷基。巰基官能性基之例為下式的基。 R S can be exemplified by the formula: -R 1 SR 2 (wherein, each R 1 is independently a divalent hydrocarbon group having 2 or more carbon atoms, and R 2 is hydrogen or an alkyl group having 1 to 20 carbon atoms. Each of R 1 and R 2 is the same as defined above. Typically, each R 1 is an alkylene group having 2 to 20 carbon atoms. An example of a thiol-functional group is a group of the following formula.
-CH2CH2CH2SH、-CH2CHCH3SH、-CH2CH2CH2CH2SH、-CH2CH2CH2CH2CH2SH、-CH2CH2CH2CH2CH2CH2SH、-CH2CH2SCH3。典型上，巰基官能性基是-CH2CH2CH2SH。 -CH 2 CH 2 CH 2 SH, -CH 2 CHCH 3 SH, -CH 2 CH 2 CH 2 CH 2 SH, -CH 2 CH 2 CH 2 CH 2 CH 2 SH, -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 SH, -CH 2 CH 2 SCH 3 . Typical, mercapto functional group is -CH 2 CH 2 CH 2 SH.
本發明中的含氟聚合物可以任何一種通常的聚合方法製造，同時也可任意的選擇聚合反應的條件。這種聚合方法，可舉出溶液聚合、懸浮聚合、乳化聚合。 The fluoropolymer in the present invention can be produced by any usual polymerization method, and the conditions of the polymerization reaction can be arbitrarily selected. Examples of the polymerization method include solution polymerization, suspension polymerization, and emulsion polymerization.
在溶液聚合中，採用在聚合起始劑的存在下使單體溶解於有機溶劑中，取代成氮氣後，以30至120℃的範圍加熱攪 拌1至10小時的方法。聚合起始劑，可列舉：例如偶氮雙異丁腈、苯甲醯基過氧化物、二-第三丁基過氧化物、十二基過氧化物、異丙苯氫過氧化物、過氧新戊酸第三丁酯、過氧二碳酸二異丙酯等。相對於單體100重量份，可使用聚合起始劑0.01至20重量份，例如0.01至10重量份的範圍。 In solution polymerization, the monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after being replaced with nitrogen, it is heated at a temperature of 30 to 120 ° C. Mix for 1 to 10 hours. The polymerization initiator may, for example, be azobisisobutyronitrile, benzhydryl peroxide, di-tert-butyl peroxide, dodecyl peroxide, cumene hydroperoxide, or Third butyl p-oxypivalate, diisopropyl peroxydicarbonate, and the like. The polymerization initiator may be used in an amount 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，是對於單體為惰性且溶解此等單體者，可列舉：例如丙酮、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、1,4-二烷、甲基乙基酮、甲基異丁基酮、醋酸乙酯、醋酸丁酯、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，可使用有機溶劑50至2,000重量份，例如50至1,000重量份的範圍。 The organic solvent is inert to the monomer and dissolves the monomers, and examples thereof include acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, and 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 may be used in an amount of 50 to 2,000 parts by weight, for example, 50 to 1,000 parts by weight, based on 100 parts by weight of the total of the monomers.
在乳化聚合中，可採用在聚合起始劑及乳化劑的存在下使單體於水中乳化，取代成氮氣後，以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，可使用：苯甲醯基過氧化物、月桂醯基過氧化物、過苯甲酸第三丁酯、1-羥基環己基氫過氧化物、3-羧基丙醯基過氧化物、乙醯基過氧化物、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、過硫酸銨等水溶性化合物，或偶氮雙異丁腈、苯甲醯基過氧化物、二-第三丁基過氧化物、十二基過氧化物、異丙苯氫過氧化物、過氧新戊酸第三丁酯、過氧二碳酸二異丙酯等油溶性化合物。相對於單體100重量份，可使用聚合起始劑0.01至10重量份的範圍。 In the emulsion polymerization, a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after being substituted with nitrogen, it is stirred at 50 to 80 ° C for 1 to 10 hours to be copolymerized. As the polymerization initiator, it can be used: benzhydryl peroxide, lauryl peroxide, tert-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropenyl peroxide , water-soluble compounds such as acetaminophen, azobisisobutylphosphonium-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, or azobisisobutyl Nitrile, benzhydryl peroxide, di-tert-butyl peroxide, dodecyl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, peroxydicarbonate An oil-soluble compound such as isopropyl ester. A polymerization initiator may be used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.
如欲獲得放置安定性優異的共聚合物水分散液時，宜為使用如高壓均質器或超音波均質器之可賦與強力破碎能之乳 化裝置，使單體在水中微粒化而聚合。同時，可使用陰離子性、陽離子性或非離子性的各種乳化劑作為乳化劑，相對於單體100重量份，其可使用0.5至20重量份的範圍。宜使用陰離子性及/或非離子性及/或陽離子性的乳化劑。如單體不完全相溶時，宜在此等單體中添加使其充分相溶的增溶劑，例如，水溶性有機溶劑或低分子量的單體。藉由增溶劑的添加，可能使乳化性及共聚合性提高。 If you want to obtain a copolymer dispersion with excellent stability, it is advisable to use a strong crushing energy such as a high pressure homogenizer or an ultrasonic homogenizer. The device is a monomer that is micronized in water to polymerize. Meanwhile, various anionic, cationic or nonionic emulsifiers can be used as the emulsifier, and it can be used in the range 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. When the monomers are not completely compatible, it is preferred to add a solubilizing agent which is sufficiently compatible with the monomers, for example, a water-soluble organic solvent or a low molecular weight monomer. Emulsifying properties and copolymerization properties may be improved by the addition of a solubilizing agent.
水溶性有機溶劑，可列舉：例如丙酮、甲基乙基酮、醋酸乙酯、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，可使用1至50重量份，例如10至40重量份的範圍。同時，低分子量的單體，可列舉：例如甲基丙烯酸甲酯、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，可使用1至50重量份，例如10至40重量份的範圍。 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 1 to 50 can be used with respect to 100 parts by weight of water. Parts by weight, for example, in the range of 10 to 40 parts by weight. Meanwhile, examples of the low molecular weight monomer include, for example, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and the like, and 100 parts by weight based on the total amount of the monomers. The fraction may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight.
本發明的含氟組成物，宜為溶液、乳膠(尤其是水性分散液)或氣膠(aerosol)的形態。含氟組成物，含有含氟聚合物(表面處理劑的活性成分)及媒體(尤其是液狀媒體，例如有機溶劑及/或水)。相對於含氟組成物，媒體的量例如為5至99.9重量%，尤其可為10至80重量%。 The fluorine-containing composition of the present invention is preferably in the form of a solution, a latex (especially an aqueous dispersion) or an aerosol. The fluorine-containing composition contains a fluorine-containing polymer (active ingredient of a surface treatment agent) and a medium (especially a liquid medium such as an organic solvent and/or water). The amount of the medium is, for example, from 5 to 99.9% by weight, particularly from 10 to 80% by weight, based on the fluorine-containing composition.
含氟組成物中，含氟聚合物的濃度是0.01至95重量%，例如可為5至50重量%。 The concentration of the fluoropolymer in the fluorine-containing composition is from 0.01 to 95% by weight, for example, from 5 to 50% by weight.
本發明的含氟組成物，可以以往已知的方法而應用於被處理物上。通常採用的方法，是將該含氟組成物分散在有機溶劑或水中並稀釋，以浸漬塗布、噴塗、泡塗等已知的方法，附 著在被處理物的表面並乾燥的方法。同時，如有需要，可同時適用適當的交聯劑，並進行硬化。並且，在本發明的含氟組成物中，可添加併用防蟲劑、柔軟劑、抗菌劑、阻燃劑、抗靜電劑、塗料定著劑、防皺劑等。與基材接觸的處理液中的含氟聚合物之濃度，是0.01至10重量%(尤其在浸漬塗布時)，例如可為0.05至10重量%。 The fluorine-containing composition of the present invention can be applied to a workpiece by a conventionally known method. A commonly used method is to disperse the fluorine-containing composition in an organic solvent or water and dilute it by a known method such as dip coating, spray coating, or bubble coating. A method of drying on the surface of the object to be treated. At the same time, if necessary, appropriate cross-linking agents can be applied and hardened. Further, in the fluorine-containing composition of the present invention, an insecticide, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a coating fixative, an anti-wrinkle agent, or the like may be added in combination. The concentration of the fluoropolymer in the treatment liquid in contact with the substrate is 0.01 to 10% by weight (especially at the time of dip coating), and may be, for example, 0.05 to 10% by weight.
可經本發明的含氟組成物(例如，撥水撥油劑)處理的被處理物，可列舉：例如纖維製品、石材、濾器(例如，靜電濾器)、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、窯業製品、塑膠、塗面及石膏等。纖維製品，可舉出各種的例。可列舉：例如棉、麻、羊毛、絲等動植物性天然纖維；聚醯胺、聚酯、聚乙烯醇、聚丙烯腈、聚氯乙烯、聚丙烯等合成纖維；嫘縈、醋酸酯等半合成纖維；玻璃纖維、碳纖維、石棉纖維等無機纖維，或此等的混合纖維。 Examples of the object to be treated which can be treated with the fluorine-containing composition (for example, a water-repellent oil-repellent agent) of the present invention include, for example, a fiber product, a stone material, a filter (for example, an electrostatic filter), a dust cover, and a fuel cell (for example, Gas diffusion electrode and gas diffusion support), glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide, kiln products, plastic, coated surface and plaster. The fiber product can be exemplified by various examples. Examples thereof include animal and plant natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; and semi-synthesis such as hydrazine and acetate. Fiber; inorganic fiber such as glass fiber, carbon fiber, asbestos fiber, or the like.
纖維製品，可以是纖維、布等任何形態。 The fibrous product may be in any form such as fiber or cloth.
本發明的含氟組成物，可使用作為內部離型劑或外部離型劑。 The fluorine-containing composition of the present invention can be used as an internal release agent or an external release agent.
含氟聚合物，可以藉任何已知用以使用液體處理纖維製品的方法而應用於纖維狀基材(例如，纖維製品等)上。纖維製品為布時，可將布浸泡在溶液中，或將溶液附著或噴霧在布上。經處理過的纖維製品，宜使其乾燥以顯現撥油性，例如可以100℃至200℃加熱。 The fluoropolymer can be applied to fibrous substrates (e.g., fibrous articles, etc.) by any method known for treating liquid fibrous articles using liquids. 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 preferably dried to exhibit oil repellency, for example, heated at 100 ° C to 200 ° C.
或以清洗法使含氟聚合物應用於纖維製品上，例如 在洗濯應用或乾洗法等中應用於纖維製品上。 Or applying a fluoropolymer to a fibrous product by a cleaning method, for example It is applied to fiber products in washing applications or dry cleaning methods.
典型上處理的纖維製品是布，其中包含織物、針織物及不織物、衣料品形態的布及地毯，但也可以是纖維或紗線或中間纖維製品(例如，棉條(sliver)或粗紗等)。纖維製品材料，可以是天然纖維(例如，棉或羊毛等)、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、聚醯胺或丙烯酸系纖維等)，或是纖維的混合物(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，在使纖維素系纖維(例如，棉或嫘縈等)具有疏油性及撥油性時特別有效果。同時，本發明的方法，通常是使纖維製品具有疏水性及撥水性。 Typically treated fibrous articles are fabrics comprising fabrics, knits and fabrics and carpets in the form of fabrics, garments, but also fibers or yarns or intermediate fabrics (eg, slivers or rovings, etc.) ). The fibrous product material may be natural fiber (for example, cotton or wool, etc.), chemical fiber (for example, viscose rayon or lyocell), or synthetic fiber (for example, polyester, polyfluorene). Amine or acrylic fiber, etc., or a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers, etc.). The polymer produced by the present invention is particularly effective in imparting oleophobicity and oil repellency to cellulose fibers (for example, cotton or enamel). At the same time, the method of the present invention generally results in a fibrous article having hydrophobicity and water repellency.
或者，纖維狀基材可以是皮革。可在各種的皮革加工階段中，例如，在皮革的濕潤加工期間或皮革的整飾期間，將製造聚合物以水溶液或水性乳化物而應用於皮革，以使皮革具有疏水性及疏油性。 Alternatively, the fibrous substrate may be leather. The production of the polymer can be applied to the leather as an aqueous solution or an aqueous emulsion during various leather processing stages, for example, during wet processing of the leather or during finishing of the leather, to impart hydrophobicity and oleophobicity to the leather.
或者，纖維狀基材可以是紙。可將製造聚合物應用於已預先形成的紙上，或在製紙的各種階段中，例如可應用於紙的乾燥期間。 Alternatively, the fibrous substrate can be paper. The manufactured polymer can be applied to pre-formed paper, or at various stages of papermaking, for example, during drying of the paper.
「處理」是指以浸漬、噴霧、塗布等將處理劑應用於被處理物之意。藉由處理，使處理劑的有效成分之含氟聚合物滲透至被處理物的內部及/或附著在被處理物的表面上。 "Processing" means the application of a treating agent to a workpiece by dipping, spraying, coating, or the like. By the treatment, the fluoropolymer of the active ingredient of the treating agent is allowed to permeate into the inside of the object to be treated and/or adhere to the surface of the object to be treated.
以下，舉出實施例以更詳細說明本發明，但本發明並不侷限於此等實施例。 Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.
以下所述中的「份」或「%」或「比」，如無特別的 限定，表示「重量份」或「重量%」或「重量比」。 "Parts" or "%" or "ratio" in the following, if there is no special Limited, means "parts by weight" or "% by weight" or "weight ratio".
試驗的步驟如下述。 The steps of the test are as follows.
依照JIS-L-1092進行沖淋式撥水性試驗。沖淋式撥水性試驗是(如下述記載的表1所表示)以撥水性No.表示。 The shower water repellency test was carried out in accordance with JIS-L-1092. The shower water repellency test (shown in Table 1 below) is indicated by water repellency No.
使用體積至少250mL的玻璃漏斗及可將250mL的水經20秒至30秒噴霧的噴嘴。試驗片框是直徑15cm的金屬框。準備三片大小約20cm×20cm的試驗片板，將板(sheet)固定在試驗片支撐框(hold frame)上，並使板不起皺。將噴霧的中心置於板的中心。將室溫的水(250mL)放入玻璃漏斗中，對試驗片板噴霧(經25秒至30秒的時間)。由台座取下支撐框，握住支撐框的一端，使前方表面為下側，以堅硬的物質輕輕敲打相反側的那端。再使支撐框旋轉180°，重複相同的步驟，將過剩的水滴滴落。與濕潤比較標準物質比較，以撥水性不良至優良的順序，將濕的試驗片評分為0、50、70、80、90及100。由測定3次的平均獲得結果。 A glass funnel having a volume of at least 250 mL and a nozzle that can spray 250 mL of water for 20 seconds to 30 seconds are used. The test piece frame was a metal frame having a diameter of 15 cm. Three test pieces having a size of about 20 cm x 20 cm were prepared, and the sheets were fixed on the test piece holding frame so that the sheets did not wrinkle. Place the center of the spray in the center of the plate. Room temperature water (250 mL) was placed in a glass funnel and the test piece was sprayed (over 25 seconds to 30 seconds). Remove the support frame from the pedestal, hold one end of the support frame, and make the front surface the lower side. Gently tap the opposite end with a hard substance. Then, the support frame was rotated by 180°, and the same procedure was repeated to drip excess water droplets. The wet test pieces were scored as 0, 50, 70, 80, 90, and 100 in the order of poor water repellency to excellent quality as compared with the wet comparative standard materials. The results were obtained from the average of 3 measurements.
以硬水B(硬度216；氯化鈣1.9425g、氯化鎂0.3975g、硫酸鈉4.63g/水10L)將聚合物分散液稀釋以使固形份濃度成為5重量%，調製1,000g的稀釋液，放到可調整溫度至40℃的墊子(pad)中。在軋布機(mangle)上將寬度20cm及長度80cm的聚酯布作成輪狀並使其可連續處理，以軋布機壓0.4MPa進行1小時的連續處理。 The polymer dispersion was diluted with hard water B (hardness 216; calcium chloride 1.9425 g, magnesium chloride 0.3975 g, sodium sulfate 4.63 g/water 10 L) to make the solid content concentration 5% by weight, and 1,000 g of the diluted solution was prepared and placed. The temperature can be adjusted to a pad of 40 ° C. A polyester cloth having a width of 20 cm and a length of 80 cm was formed into a wheel shape on a mangle and allowed to be continuously treated, and subjected to continuous treatment at a pressure of 0.4 MPa by a rolling mill for 1 hour.
黏附率是以下式求得。 The adhesion rate is obtained by the following formula.
(軋布機的黏附率)=(聚酯布的處理前之重量+處理前的稀釋液固形份重量)-(聚酯布的處理後之重量+處理後的稀釋液固形份重量) (Adhesion rate of the rolling mill) = (weight before treatment of polyester cloth + solid weight of diluted solution before treatment) - (weight after treatment of polyester cloth + solid weight of diluted solution after treatment)
(黏附率)=100×(對於軋布機的黏附率)/(處理前的稀釋液固形份重量) (Adhesion rate) = 100 × (adhesion rate for the mill) / (diluted solid weight before treatment)
黏附率未達4%時，為黏附受到抑制。 When the adhesion rate is less than 4%, the adhesion is suppressed.
在金屬平板(plate)上稱取含氟聚合物的固體1g，以60℃進行1小時的加熱之後，以手指接觸含氟聚合物，如下述評估手指離開時以手指所感覺到的黏著性。 1 g of a solid of the fluoropolymer was weighed on a metal plate, and after heating at 60 ° C for 1 hour, the fluoropolymer was contacted with a finger, and the adhesion felt by the finger when the finger was left was evaluated as follows.
○：完全未感覺到黏著性 ○: No adhesion at all
△：感覺稍微有黏著性 △: I feel a little sticky
×：感覺有黏著性 ×: I feel sticky.
××：感覺有強力的黏著性 ××: I feel strong adhesion
在300mL的高壓釜中，置入CF3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)=CH2(n=2.0)(C6SFClA)18.63g、丙 烯酸十八酯(StA)42.84g、甲基丙烯酸異冰片酯(IBMA)0.62g、純水110g、二丙二醇單甲醚18.62g、氯化十八基三甲基銨2.57g、聚氧乙烯十二醚(EO：20。EO表示環氧乙烷單元數)2.65g、聚氧乙烯異十三醚(EO：3)1.21g，攪拌下以60℃、以超音波使其乳化分散15分鐘。將反應燒瓶內取代成氮氣後，添加十二基硫醇0.62g、2,2-偶氮雙(2-脒基丙烷)2鹽酸鹽0.31g(以下，簡稱為V-50)及水9g的溶液，以60℃使其反應5小時，獲得聚合物之水性分散液。聚合物的組成幾乎與裝入單體的組成一致。 In a 300 mL autoclave, CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(Cl)=CH 2 (n=2.0) (C6SFClA) 18.63 g, octadecyl acrylate (StA) was placed. 42.84g, isobornyl methacrylate (IBMA) 0.62g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, octadecyltrimethylammonium chloride 2.57g, polyoxyethylene lauryl ether (EO: 20 EO represents 2.65 g of ethylene oxide unit and 1.21 g of polyoxyethylene isotridecyl ether (EO: 3), and was emulsified and dispersed by ultrasonic waves at 60 ° C for 15 minutes while stirring. After replacing the inside of the reaction flask with nitrogen, 0.62 g of dodecylmercaptan and 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter abbreviated as V-50) and water 9 g were added. The solution was allowed to react at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the charged monomer.
進行黏附率試驗及黏著性試驗。試驗結果如表A中所示。 Adhesion test and adhesion test were performed. The test results are shown in Table A.
以與製造例1相同的步驟，使表A中表示的組成(裝入單體的種類及重量比)之單體聚合，調製聚合物的水性分散液。聚合物的組成幾乎與裝入單體的組成一致。 In the same procedure as in Production Example 1, the monomer of the composition (the type and weight ratio of the monomer charged) shown in Table A was polymerized to prepare an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the charged monomer.
試驗結果如表A中所示。 The test results are shown in Table A.
將製造例1所製造的水性液體(5g及7.5g分別)以純水稀釋，調製成試驗溶液(1,000g)。將聚酯塔夫塔(taffeta)布(510mm×205mm)浸泡在此試驗溶液中，使其通過軋布機，以160℃使用針板拉幅機(pin stenter)處理2分鐘。以此試驗布進行沖淋式撥水試驗。試驗結果如表A中所示。 The aqueous liquid (5 g and 7.5 g, respectively) produced in Production Example 1 was diluted with pure water to prepare a test solution (1,000 g). A polyester taffeta cloth (510 mm × 205 mm) was immersed in this test solution, passed through a mangle, and treated with a pin stenter at 160 ° C for 2 minutes. The test cloth was used for the shower water test. The test results are shown in Table A.
以與實施例1相同的方式，處理製造例2至51及比較製造例1至5所製造的聚合物，進行沖淋式撥水性試驗。試驗 結果如表A中所示。 The polymers produced in Production Examples 2 to 51 and Comparative Production Examples 1 to 5 were treated in the same manner as in Example 1 to carry out a shower water repellency test. test The results are shown in Table A.
表中，簡記的意義如下述。 In the table, the meaning of the abbreviations is as follows.
C6SFClA C6F13CH2CH2OCOC(Cl)=CH2 C6SFClA C 6 F 13 CH 2 CH 2 OCOC(Cl)=CH 2
C6SFMA C6F13CH2CH2OCOC(CH3)=CH2 C6SFMA C 6 F 13 CH 2 CH 2 OCOC(CH 3 )=CH 2
C8SFA C8F17CH2CH2OCOCH=CH2 C8SFA C 8 F 17 CH 2 CH 2 OCOCH=CH 2
StA 丙烯酸十八酯 StA octadecyl acrylate
BeA 丙烯酸二十二酯 BeA icosyl acrylate
IBMA 甲基丙烯酸異冰片酯(Tg>50℃) IBMA isobornyl methacrylate (Tg > 50 ° C)
StMA 甲基丙烯酸十八酯(Tg<50℃) StMA octadecyl methacrylate (Tg<50°C)
CHMA 甲基丙烯酸環己酯(Tg>50℃) CHMA cyclohexyl methacrylate (Tg>50°C)
VCM 氯乙烯 VCM vinyl chloride
DAAM 二丙酮丙烯醯胺 DAAM diacetone acrylamide
ADMA 甲基丙烯酸金剛烷酯 ADMA adamantyl methacrylate
ADA 丙烯酸金剛烷酯 ADA adamantyl acrylate
CPM 甲基丙烯酸二環戊酯 CPM dicyclopentanyl methacrylate
本發明的含氟組成物可使用於纖維製品(例如，地毯)、紙、不織布、石材、靜電濾器、防塵罩、燃料電池的零件上，以賦與優異的撥水性、撥油性、防污性。 The fluorine-containing composition of the present invention can be used for parts of fiber products (for example, carpets), paper, non-woven fabrics, stone materials, electrostatic filters, dust covers, and fuel cells to impart excellent water repellency, oil repellency, and antifouling properties. .
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| JP2011288078A JP2013136668A (en) | 2011-12-28 | 2011-12-28 | Fluorine-containing composition and fluorine-containing polymer |
| JP2011-288078 | 2011-12-28 |
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| JP (1) | JP2013136668A (en) |
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| JP6015003B2 (en) * | 2011-12-28 | 2016-10-26 | ダイキン工業株式会社 | Method for producing fluorine-containing polymer and fluorine-containing composition |
| JP6266287B2 (en) * | 2013-09-27 | 2018-01-24 | 第一工業製薬株式会社 | Polymer composition and water / oil repellent |
| US20160237614A1 (en) * | 2013-10-23 | 2016-08-18 | Daikin Industries, Ltd. | Fluorine-containing polymer and treatment agent |
| WO2015194049A1 (en) * | 2014-06-20 | 2015-12-23 | 日華化学株式会社 | Water-oil repellent composition and production method for water- and oil-repellent textile product |
| CN106319965A (en) * | 2015-06-26 | 2017-01-11 | 大金工业株式会社 | Surface conditioning agent composition |
| JP2017039318A (en) * | 2015-08-18 | 2017-02-23 | 旭硝子株式会社 | Mold release agent composition for mold |
| JP6673462B2 (en) * | 2016-02-23 | 2020-03-25 | ダイキン工業株式会社 | Surface treatment agent |
| CN107177982B (en) * | 2016-03-11 | 2021-09-07 | 大金工业株式会社 | Surface treatment agent composition |
| EP3444307A4 (en) * | 2016-04-12 | 2019-12-18 | Daikin Industries, Ltd. | Coating film, composition for coating film, film-forming agent, article having coating film, and method for forming coating film |
| CN118087269A (en) * | 2016-08-02 | 2024-05-28 | 大金工业株式会社 | Nonwoven fabric |
| CH713490A1 (en) * | 2017-02-27 | 2018-08-31 | Schoeller Tech Ag | Composition for the impregnation of wood and stone surfaces. |
| CN107724080B (en) * | 2017-10-17 | 2020-07-21 | 厦门大学 | Super-hydrophobic flame-retardant fabric with oil-water separation function and preparation method thereof |
| WO2019124585A1 (en) * | 2017-12-21 | 2019-06-27 | 니카코리아(주) | Antisoil finishing agent composition and textile product using same |
| CN108250350B (en) * | 2018-02-08 | 2020-02-07 | 江南大学 | Preparation and application of short-chain fluorine-containing copolymer water-repellent and oil-repellent finishing agent |
| JP6773922B1 (en) * | 2018-11-22 | 2020-10-21 | 東レ・ファインケミカル株式会社 | Fluorine-containing polymer particles |
| CN109665721B (en) * | 2019-01-11 | 2022-01-11 | 宁波大学 | Hydrophobic self-cleaning glass and preparation method thereof |
| KR102543248B1 (en) * | 2019-08-08 | 2023-06-14 | 주식회사 엘지에너지솔루션 | Polymer for gel polymer electrolyte, gel polymer electrolyte and lithium secondary battery comprising the same |
| KR20210101894A (en) | 2020-02-11 | 2021-08-19 | 니카코리아 (주) | Fluorine-free Water-repellent Coating Composition with Improved Processing Stability and Manufacturing Method of the Water-repellent Synthetic Leather Using the Same |
| US11945890B2 (en) | 2022-03-23 | 2024-04-02 | Mexichem Specialty Resins Inc. | Fluorinated PVC copolymer compositions for increased ultraviolet protection |
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| KR102041857B1 (en) | 2019-11-08 |
| KR20190069363A (en) | 2019-06-19 |
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