TW201414899A - Moisture permeable waterproof fabric and manufacturing method thereof - Google Patents
Moisture permeable waterproof fabric and manufacturing method thereof Download PDFInfo
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Abstract
Description
本發明係關於一種可使用來作為衣料、防水片、鞋子以及手套等之透濕防水布帛。 The present invention relates to a moisture permeable waterproof fabric which can be used as a clothing, a waterproof sheet, a shoe, a glove, and the like.
以往，關於透濕防水布帛，曾提出各種技術(例如，日本特公昭60-47955號公報或特公平4-18066號公報)。 In the past, various techniques have been proposed for the moisture-permeable waterproof fabric (for example, Japanese Patent Publication No. Sho 60-47955 or Japanese Patent Publication No. Hei 4-18066).
含氟聚合物係不僅可對布帛賦予撥水撥油性及耐水壓性，於塗布形成透濕防水層之合成樹脂時，亦可利用來作為合成樹脂朝布基材相反側滲出之抑制劑。 The fluoropolymer can impart not only water repellency and water repellency to the fabric, but also can be used as an inhibitor of the synthetic resin oozing toward the opposite side of the cloth substrate when the synthetic resin forming the moisture permeable waterproof layer is applied.
然而，因應環境問題之氟烷基碳數為6以下之含氟烷基的聚合物，於塗布合成樹脂時之滲出的抑制效果低，而容易引起合成樹脂滲入布基材相反側的問題。 However, the fluorine-containing alkyl group having a fluoroalkyl group having 6 or less in response to environmental problems has a low effect of suppressing bleeding when the synthetic resin is applied, and is liable to cause a problem that the synthetic resin penetrates into the opposite side of the cloth substrate.
又，當貼附合成樹脂之薄膜時，由於黏著劑會滲入布帛，故黏著效果變弱，而有合成樹脂薄膜之剝離強度降低的問題。 Further, when a film of a synthetic resin is attached, since the adhesive penetrates into the fabric, the adhesive effect is weak, and the peeling strength of the synthetic resin film is lowered.
專利文獻1：日本特公昭60-47955號公報 Patent Document 1: Japanese Patent Publication No. 60-47955
專利文獻2：日本特公平4-18066號公報 Patent Document 2: Japanese Special Fair 4-18066
本發明之目的在於提供一種透濕性、耐水性及耐洗滌性優異之透濕防水布帛。 An object of the present invention is to provide a moisture-permeable waterproof fabric which is excellent in moisture permeability, water resistance and washing resistance.
本發明之另一目的在於提供一種透濕防水布帛，其係將形成透濕防水層之合成樹脂塗布於布基材時，合成樹脂不會朝布基材之相反側的表面滲出。 Another object of the present invention is to provide a moisture-permeable waterproof fabric which is formed by applying a synthetic resin which forms a moisture-permeable waterproof layer to a cloth substrate, so that the synthetic resin does not bleed toward the surface on the opposite side of the cloth substrate.
本發明人等發現，將含有特定之含氟聚合物之中間層設置於布基材與透濕防水層之間時，可達成上述目的，終完成本發明。 The present inventors have found that the above object can be attained when an intermediate layer containing a specific fluoropolymer is disposed between a cloth substrate and a moisture permeable waterproof layer, and the present invention has been completed.
本發明係提供一種透濕防水布帛用之含氟處理劑，係包含：具有由下述(a)至(c)所衍生之重複單位的含氟聚合物，且該含氟聚合物在160℃之動態黏彈性為100Pa．s以上，(a)式：CH2=C(-X)-C(=O)-Y-Z-Rf所示之含氟單體[式中，X為甲基以外之一價之有機基或鹵素原子，Y為-O-或-NH-，Z為直接鍵結或二價之有機基，Rf為碳數1至6之氟烷基。]、(b)鹵化烯烴單體、及(c)視需要所使用之不含氟原子且至少具有一個碳-碳雙鍵之非氟單體。 The present invention provides a fluorine-containing treatment agent for a moisture-permeable waterproof fabric, comprising: a fluorine-containing polymer having a repeating unit derived from the following (a) to (c), and the fluorine-containing polymer is at 160 ° C The dynamic viscoelasticity is 100Pa. s or more, formula (a): CH 2 =C(-X)-C(=O)-YZ-Rf fluorinated monomer [wherein, X is a monovalent organic group or halogen other than methyl group The 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 6 carbon atoms. And (b) a halogenated olefin monomer, and (c) a non-fluorine monomer having no fluorine atom and having at least one carbon-carbon double bond, as needed.
本發明中，有如下之樣態。 In the present invention, there are the following aspects.
A.一種纖維布帛之處理方法，其特徵係對纖維布帛使用含有含氟聚合物之含氟處理劑，以形成含有含氟聚合物之中間層。 A. A method of treating a fiber fabric, characterized in that a fluorine-containing treatment agent containing a fluorine-containing polymer is used for the fiber cloth to form an intermediate layer containing a fluorine-containing polymer.
B.一種透濕防水布帛之製造方法，其特徵係具有下述(i)及(ii) 之步驟：(i)對纖維布帛使用含有含氟聚合物之含氟處理劑，以形成含有含氟聚合物之中間層的步驟、及(ii)於含氟聚合物之中間層之上使用合成樹脂(例如藉由塗布合成樹脂、或藉由貼附合成樹脂之薄膜)，藉此形成透濕防水層的步驟。 B. A method for producing a moisture permeable waterproof fabric, characterized by having the following (i) and (ii) The steps of: (i) using a fluorine-containing treatment agent containing a fluorine-containing polymer to form an intermediate layer containing a fluorine-containing polymer, and (ii) using a synthetic layer on the intermediate layer of the fluorine-containing polymer A resin (for example, by coating a synthetic resin or a film of a synthetic resin), thereby forming a moisture-permeable waterproof layer.
C.一種透濕防水布帛用之基材布帛，其係具有含有由含氟處理劑所形成之含氟聚合物的中間層。 C. A substrate fabric for a moisture permeable waterproofing fabric comprising an intermediate layer comprising a fluoropolymer formed of a fluorine-containing treating agent.
D.一種透濕防水布帛，其係具有：由申請專利範圍第1項所述之含氟處理劑形成之含氟聚合物之中間層、及由合成樹脂形成之透濕防水層。 D. A moisture-permeable waterproof fabric comprising: an intermediate layer of a fluorine-containing polymer formed from the fluorine-containing treating agent according to claim 1; and a moisture-permeable waterproof layer formed of a synthetic resin.
本發明之透濕防水布帛，係透濕性、耐水性、耐洗滌性優異。 The moisture-permeable waterproof fabric of the present invention is excellent in moisture permeability, water resistance, and washing resistance.
藉由本發明，將形成透濕防水層之合成樹脂塗布於布基材時，合成樹脂不會滲出至布基材之相反側的表面。 According to the present invention, when the synthetic resin forming the moisture-permeable waterproof layer is applied to the cloth substrate, the synthetic resin does not bleed out to the surface on the opposite side of the cloth substrate.
透濕防水布帛係具有：布基材、含有位於布基材之一表面上之含氟聚合物之中間層、及位於中間層之上之透濕防水層。中間層可形成於布基材之內部。於透濕防水層之上，可設置表現圖型或裝飾之圖型層。於布基材之另一表面，可不設置層。 The moisture permeable waterproofing fabric has a cloth substrate, an intermediate layer containing a fluoropolymer on one surface of the cloth substrate, and a moisture permeable waterproof layer on the intermediate layer. The intermediate layer can be formed inside the cloth substrate. On top of the moisture permeable waterproof layer, a pattern layer representing a pattern or decoration may be provided. On the other surface of the cloth substrate, no layer may be provided.
布基材一般係由天然纖維及/或合成纖維所形成。布基材之纖維可為天然纖維(例如，棉或羊毛等)、化學纖維(例如 黏液嫘縈或萊賽爾纖維(lyocell)等)、或合成纖維(例如聚酯、聚醯胺或丙烯酸纖維等)、或者纖維之混合物(例如天然纖維及合成纖維之混合物等)。布基材之形態係可舉例如織物、編物、不織布、起毛布等。布基材之厚度一般為0.05至10mm，例如0.1至1mm。 The cloth substrate is generally formed of natural fibers and/or synthetic fibers. The fibers of the cloth substrate may be natural fibers (for example, cotton or wool, etc.), chemical fibers (for example Mucus or lyocell, or synthetic fibers (such as polyester, polyamide or acrylic), or a mixture of fibers (such as a mixture of natural fibers and synthetic fibers, etc.). The form of the cloth base material may, for example, be a woven fabric, a knitted fabric, a non-woven fabric, a raised fabric or the like. The thickness of the cloth substrate is generally from 0.05 to 10 mm, for example from 0.1 to 1 mm.
透濕防水層係含有合成樹脂。透濕防水層一般係微多孔膜。合成樹脂之具體例係聚胺基甲酸酯系樹脂、聚胺基酸胺基甲酸酯系樹脂、丙烯酸系樹脂、聚酯系樹脂、聚四氟乙烯系樹脂等。透濕防水層可僅由合成樹脂所形成，或者亦可含有添加劑例如異氰酸酯。透濕防水層之厚度一般係10至100μm、例如20至50μm。 The moisture permeable waterproof layer contains a synthetic resin. The moisture permeable waterproof layer is generally a microporous film. Specific examples of the synthetic resin are a polyurethane resin, a polyurethane urethane resin, an acrylic resin, a polyester resin, and a polytetrafluoroethylene resin. The moisture permeable waterproof layer may be formed only of a synthetic resin, or may also contain an additive such as an isocyanate. The thickness of the moisture permeable waterproof layer is generally from 10 to 100 μm, for example from 20 to 50 μm.
中間層係含有含氟聚合物。中間層亦可僅由含氟聚合物所形成，或者，亦可含有添加劑例如三聚氰胺樹脂、嵌段異氰酸酯等。中間層之厚度一般係0.1至1μm，例如0.2至0.3μm。中間層係撥溶劑性優異，且可撥除二甲基甲醯胺、甲苯及甲乙酮等之有機溶劑。 The intermediate layer contains a fluoropolymer. The intermediate layer may be formed only of a fluoropolymer, or may contain an additive such as a melamine resin, a blocked isocyanate or the like. The thickness of the intermediate layer is generally from 0.1 to 1 μm, for example from 0.2 to 0.3 μm. The intermediate layer is excellent in solvent property, and an organic solvent such as dimethylformamide, toluene or methyl ethyl ketone can be removed.
含氟聚合物係具有100Pa．s以上在160℃之動態黏彈性。 The fluoropolymer system has 100 Pa. Dynamic viscoelasticity above 160 °C.
含氟聚合物在150℃之動態黏彈性為120Pa．s以上、特別以150Pa．s以上為佳。含氟聚合物在160℃之動態黏彈性為100Pa．s以上，特別是120Pa．s以上，特別以400Pa．s以上例如600Pa．s以上為佳。含氟聚合物在170℃之動態黏彈性為80Pa．s以上，特別以100Pa．s以上為佳。 The dynamic viscoelasticity of the fluoropolymer at 150 ° C is 120 Pa. Above s, especially 150Pa. Above s is better. The dynamic viscoelasticity of the fluoropolymer at 160 ° C is 100 Pa. Above s, especially 120Pa. Above s, especially at 400Pa. Above s, for example, 600Pa. Above s is better. The dynamic viscoelasticity of the fluoropolymer at 170 ° C is 80 Pa. Above s, especially at 100Pa. Above s is better.
含氟聚合物在150℃之動態黏彈性為3000Pa．s以下，例如可為2500Pa．s以下。含氟聚合物在160℃之動態黏彈性為2800Pa． s以下，特別是2500Pa．s以下，例如可為2000Pa．s以下。含氟聚合物在170℃之動態黏彈性為2500Pa．s以下，例如可為2000Pa．s以下。 The dynamic viscoelasticity of the fluoropolymer at 150 ° C is 3000 Pa. Below s, for example, it can be 2500Pa. s below. The dynamic viscoelasticity of the fluoropolymer at 160 ° C is 2800 Pa. s below, especially 2500Pa. Below s, for example, it can be 2000Pa. s below. The dynamic viscoelasticity of the fluoropolymer at 170 ° C is 2500 Pa. Below s, for example, it can be 2000Pa. s below.
當動態黏彈性過低(例如，160℃之動態黏彈性未達100Pa．s)時，會產生透印，而容易產生透濕防水層的剝離。當動態黏彈性低於一定值時，透濕防水層會充分地密著於中間層。 When the dynamic viscoelasticity is too low (for example, the dynamic viscoelasticity at 160 ° C is less than 100 Pa.s), offset is produced, and peeling of the moisture-permeable waterproof layer is liable to occur. When the dynamic viscoelasticity is lower than a certain value, the moisture-permeable waterproof layer is sufficiently adhered to the intermediate layer.
透濕防水布帛之製造，係藉由具有下述步驟的方法來進行：(i)對纖維布帛使用含氟處理劑，以形成含氟聚合物之中間層的步驟、及(ii)於含氟聚合物之中間層之上，形成合成樹脂之透濕防水層的步驟。透濕防水層之形成係例如可藉由塗布合成樹脂、或貼附合成樹脂之薄膜來進行。 The manufacture of the moisture permeable waterproof cloth is carried out by a method comprising the steps of: (i) using a fluorine-containing treatment agent for the fiber cloth to form an intermediate layer of the fluorine-containing polymer, and (ii) fluorine-containing A step of forming a moisture-permeable waterproof layer of a synthetic resin over the intermediate layer of the polymer. The formation of the moisture-permeable waterproof layer can be carried out, for example, by applying a synthetic resin or a film to which a synthetic resin is attached.
含氟聚合物係具有由含氟單體所衍生之重複單位作為必須成分。含氟聚合物可進一步具有由非氟單體所衍生之重複單位。 The fluoropolymer has a repeating unit derived from a fluorine-containing monomer as an essential component. The fluoropolymer may further have a repeating unit derived from a non-fluorine monomer.
具有由含氟單體及非氟單體所衍生之重複單位的含氟聚合物，可藉由一次饋入(一段聚合)或分次饋入(多段聚合特別是二段聚合)來製造。 The fluoropolymer having a repeating unit derived from a fluorine-containing monomer and a non-fluorine monomer can be produced by one-time feeding (one-stage polymerization) or fractional feeding (multi-stage polymerization, particularly two-stage polymerization).
在本發明中，就單體而言，係使用含氟單體(a)及鹵化烯烴單體(b)。非氟單體(c)係可視需要而使用，可為非氟非交聯性單體及/或非氟交聯性單體。非氟單體(c)係以非氟非交聯性單體為佳，及/或亦可為非氟交聯性單體。 In the present invention, as the monomer, a fluorine-containing monomer (a) and a halogenated olefin monomer (b) are used. The non-fluorine monomer (c) may be used as needed, and may be a non-fluorine non-crosslinkable monomer and/or a non-fluorine crosslinkable monomer. The non-fluorine monomer (c) is preferably a non-fluorine non-crosslinkable monomer, and/or may be a non-fluorine crosslinkable monomer.
(a)含氟單體 (a) fluoromonomer
含氟單體係以式：CH2=C(-X)-C(=O)-Y-Z-Rf[式中，X為甲基以外之一價之有機基或鹵素原子，Y為-O-或-NH-，Z為直接鍵結或二價之有機基，Rf為碳數1至6之氟烷基。]所示之含氟單體。Z係例如碳數1至20之直鏈伸烷基或分支狀伸烷基，例如以式-(CH2)x-(式中，x為1至10)所示之基、或者以式-SO2N(R1)R2-或式-CON(R1)R2所示之基(式中，R1為碳數1至10之烷基，R2為碳數1至10之直鏈伸烷基或分支狀伸烷基)、或者以式-CH2CH(OR3)CH2-(式中，R3表示氫原子、或碳數1至10之醯基(例如，甲醯基或乙醯基等))所示之基、或者以式-Ar-CH2-(式中，Ar為視需要而具有取代基之伸芳基)所示之基、以-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(其中，m為1至10、n為0至10)。X之代表性具體例為Cl、Br、I、F、CN、CF3。 The fluorine-containing single system is of the formula: CH 2 =C(-X)-C(=O)-YZ-Rf [wherein, X is an organic group or a halogen atom other than a methyl group, and Y is -O- Or -NH-, Z is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 6 carbon atoms. The fluorine-containing monomer shown. Z is, for example, a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group, for example, a group represented by the formula -(CH 2 ) x - (wherein, x is 1 to 10), or SO 2 N(R 1 )R 2 - or a group represented by the formula -CON(R 1 )R 2 (wherein R 1 is an alkyl group having 1 to 10 carbon atoms, and R 2 is a straight carbon number of 1 to 10) a chain alkyl group or a branched alkyl group), or a formula -CH 2 CH(OR 3 )CH 2 - (wherein R 3 represents a hydrogen atom, or a carbon number of 1 to 10 (for example, formazan) a group represented by a group or an ethyl fluorenyl group or the like, or a group represented by the formula -Ar-CH 2 - (wherein, Ar is an optionally extended aryl group having a substituent), and -(CH 2 ) m -SO 2 -(CH 2 ) n -yl or -(CH 2 ) m -S-(CH 2 ) n -yl (where m is 1 to 10 and n is 0 to 10). Representative specific examples of X are Cl, Br, I, F, CN, and CF 3 .
含氟單體(a)較佳為以通式：CH2=C(-X)-C(=O)-Y-Z-Rf (I)[式中，X為碳數2至21之直鏈狀或分支狀之烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(其中，X1及X2為氫原子、氟原子、氯原子、溴原子或碘原子)、氰基、碳數1至21之直鏈狀或分支狀之氟烷基、取代或非取代之苄基、取代或非取代之苯基；Y為-O-或-NH-；Z為碳數1至10之脂肪族基、碳數6至18之芳香族基或環狀脂肪族基、-CH2CH2N(R1)SO2-基(其中，R1為碳數1至4之烷基)、 -CH2CH(OZ1)CH2-基(其中，Z1為氫原子或乙醯基)、-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(其中，m為1至10、n為0至10)、Rf為碳數1至6之直鏈狀或分支狀之氟烷基。]所示之丙烯酸酯或丙烯醯胺。 The fluorine-containing monomer (a) is preferably of the formula: CH 2 =C(-X)-C(=O)-YZ-Rf (I) [wherein, X is a linear chain having a carbon number of 2 to 21 Or a branched alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), cyanide a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group; Y is -O- or -NH-; Z is a carbon number of 1 An aliphatic group to 10, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms, a -CH 2 CH 2 N(R 1 )SO 2 - group (wherein R 1 is an alkyl group having 1 to 4 carbon atoms) , -CH 2 CH(OZ 1 )CH 2 - group (wherein Z 1 is a hydrogen atom or an ethenyl group), -(CH 2 ) m -SO 2 -(CH 2 ) n - group or -(CH 2 ) a m- S-(CH 2 ) n - group (wherein m is 1 to 10, n is 0 to 10), and Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms. The acrylate or acrylamide shown.
含氟單體(a)係(丙烯酸酯或甲基丙烯酸酯之)α位可以鹵素原子等取代。X以氯原子為佳。 The α-position of the fluorine-containing monomer (a) (acrylic acid ester or methacrylic acid ester) may be substituted with a halogen atom or the like. X is preferably a chlorine atom.
上述式(1)中，Rf基以全氟烷基為佳。Rf基之碳數為1至6、特別是4至6。Rf基之例係-CF3、-CF2CF3、-CF2CF2CF3、-CF2(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3、-(CF2)4CF3、-(CF2)2CF(CF3)2、-CF2C(CF3)3、-CF(CF3)CF2CF2CF3、-(CF2)5CF3、-(CF2)3CF(CF3)2、-(CF2)4CF(CF3)2、-C8F17等。 In the above formula (1), the Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is from 1 to 6, especially from 4 to 6. Examples of Rf groups are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF 2 (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , -C(CF 3 ) 3 , -(CF 2 ) 4 CF 3 , -(CF 2 ) 2 CF(CF 3 ) 2 , -CF 2 C(CF 3 ) 3 , -CF(CF 3 )CF 2 CF 2 CF 3 , -(CF 2 ) 5 CF 3 , -(CF 2 ) 3 CF(CF 3 ) 2 , -(CF 2 ) 4 CF(CF 3 ) 2 , -C 8 F 17 and the like.
Z較佳為碳數1至10之脂肪族基、碳數6至18之芳香族基或環狀脂肪族基、-CH2CH2N(R1)SO2-基(其中，R1為碳數1至4之烷基)、-CH2CH(OZ1)CH2-基(其中，Z1為氫原子或乙醯基)、-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(其中，m為1至10、n為0至10))。脂肪族基較佳為伸烷基(特別是碳數1至4，例如1或2)。芳香族基或環狀脂肪族基係可為取代或非取代。S基或SO2基係亦可直接鍵結於Rf基。 Z is preferably an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms, or a -CH 2 CH 2 N(R 1 )SO 2 - group (wherein R 1 is An alkyl group having 1 to 4 carbon atoms, a -CH 2 CH(OZ 1 )CH 2 - group (wherein Z 1 is a hydrogen atom or an ethylidene group), -(CH 2 ) m -SO 2 -(CH 2 ) N -group or -(CH 2 ) m -S-(CH 2 ) n - group (where m is 1 to 10 and n is 0 to 10)). The aliphatic group is preferably an alkyl group (particularly a carbon number of 1 to 4, such as 1 or 2). The aromatic or cyclic aliphatic group may be substituted or unsubstituted. The S group or the SO 2 group may also be directly bonded to the Rf group.
含氟單體(a)之具體例係可例示如以下者，但並不限定於該等。 Specific examples of the fluorine-containing monomer (a) include the following, but are not limited thereto.
CH2=C(-F)-C(=O)-O-(CH2)2-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf CH 2 =C(-Cl)-C(=O)-O-(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[上述式中，Rf為碳數1至6之氟烷基。] CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf [In the above formula, Rf is a fluorine having a carbon number of 1 to 6 alkyl. ]
(b)鹵化烯烴單體 (b) Halogenated olefin monomer
鹵化烯烴單體(b)較佳為以1至10之氯原子、溴原子或碘原子取代之碳數2至20之烯烴。鹵化烯烴單體(b)較佳為碳數2至20之氯化烯烴，特別是具有1至5之氯原子之碳數2至5之烯烴。鹵化烯烴單體(b)較佳之具體例為鹵化乙烯例如氯乙烯、溴乙烯、碘乙烯、鹵化亞乙烯例如二氯亞乙烯、二溴亞乙烯、二碘亞乙烯。因耐水性(特別是耐水性之耐久性)變高，故以氯乙烯為佳。 The halogenated olefin monomer (b) is preferably an olefin having 2 to 20 carbon atoms which is substituted with a chlorine atom, a bromine atom or an iodine atom of 1 to 10. The halogenated olefin monomer (b) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin monomer (b) are halogenated ethylene such as vinyl chloride, vinyl bromide, iodoethylene, vinyl halide such as dichloroethylene, dibromoethylene, and diiodoethylene. Since water resistance (especially durability against water resistance) becomes high, vinyl chloride is preferred.
非氟單體(c)可為非氟非交聯性單體(c1)及/或非氟交聯性單體(c2)。 The non-fluorine monomer (c) may be a non-fluorine non-crosslinkable monomer (c1) and/or a non-fluorine crosslinkable monomer (c2).
(c1)非氟非交聯性單體 (c1) non-fluorine non-crosslinkable monomer
非氟非交聯性單體(c1)係不含氟原子之單體。非氟非交聯性單體(c1)不具有交聯性官能基。非氟非交聯性單體(c1)係與交聯性單體(c2)不同，為非交聯性。非氟非交聯性單體(c1)較佳為具有碳-碳雙鍵之非氟單體。非氟非交聯性單體(c1)較佳為不含氟之乙烯基單體。非氟非交聯性單體(c1)一般係具有一個碳-碳雙鍵之化合物。 The non-fluorine non-crosslinkable monomer (c1) is a monomer having no fluorine atom. The non-fluorine non-crosslinkable monomer (c1) does not have a crosslinkable functional group. The non-fluorine non-crosslinkable monomer (c1) is different from the crosslinkable monomer (c2) and is non-crosslinkable. The non-fluorine non-crosslinkable monomer (c1) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (c1) is preferably a fluorine-free vinyl monomer. The non-fluorine non-crosslinkable monomer (c1) is generally a compound having one carbon-carbon double bond.
較佳之非氟非交聯性單體(c1)可為式：CH2=CA-T[式中，A為氫原子、甲基、或氟原子以外之鹵素原子(例如氯原子、 溴原子及碘原子)，T為氫原子、碳數1至30(例如1至20)之鏈狀或環狀之烴基、或具有酯鍵之鏈狀或環狀之碳數1至31(例如1至20)之有機基]所表示之化合物。 A preferred non-fluorine non-crosslinkable monomer (c1) may be of the formula: CH 2 =CA-T [wherein, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom, and Iodine atom), T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20), or a chain or cyclic carbon number having an ester bond of 1 to 31 (for example, 1 to 20) The compound represented by the organic group].
碳數1至30之鏈狀或環狀之烴基之例為碳數1至30之直鏈或分支之脂肪族烴基、碳數4至30之環狀脂肪族基、碳數6至30之芳香族烴基、碳數7至30之芳香-脂肪族烴基。 Examples of the chain or cyclic hydrocarbon group having 1 to 30 carbon atoms are a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, and an aromatic having 6 to 30 carbon atoms. A hydrocarbon group, an aromatic-aliphatic hydrocarbon group having 7 to 30 carbon atoms.
具有酯鍵之鏈狀或環狀之碳數1至31之有機基之例為-C(=O)-O-Q及-O-C(=O)-Q(此處，Q為碳數1至30之直鏈或分支之脂肪族烴基、碳數4至30之環狀脂肪族基、碳數6至30之芳香族烴基、碳數7至30之芳香-脂肪族烴基)。較佳為碳數12至30(特別是18至30)之直鏈或分支之脂肪族烴基、碳數4至30之環狀脂肪族基、碳數6至30之芳香族烴基、碳數7至30之芳香脂肪族烴基，特佳為碳數12至30(特別是18至30)之直鏈或分支之脂肪族烴基、碳數4至30之環狀脂肪族基。 Examples of the organic group having a chain-like or cyclic carbon number of 1 to 31 of an ester bond are -C(=O)-OQ and -OC(=O)-Q (here, Q is a carbon number of 1 to 30) A linear or branched aliphatic hydrocarbon group, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic-aliphatic hydrocarbon group having 7 to 30 carbon atoms. A linear or branched aliphatic hydrocarbon group having a carbon number of 12 to 30 (particularly 18 to 30), a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and a carbon number of 7 are preferred. The aromatic aliphatic hydrocarbon group to 30 is particularly preferably a linear or branched aliphatic hydrocarbon group having a carbon number of 12 to 30 (particularly 18 to 30) or a cyclic aliphatic group having 4 to 30 carbon atoms.
非氟非交聯性單體(c1)之較佳例，係包含例如乙烯、乙酸乙烯酯、丙烯腈、苯乙烯、聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、及乙烯烷基醚。非氟非交聯性單體(c1)並不限定於該等之例。 Preferred examples of the non-fluorine non-crosslinkable monomer (c1) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. , methoxypolyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, and vinyl alkyl ether. The non-fluorine non-crosslinkable monomer (c1) is not limited to these examples.
非氟非交聯性單體(c1)可為具有烷基之(甲基)丙烯酸酯。烷基之碳原子之數可為1至30，例如可為6至30(例如10至30)。例如非氟非交聯性單體(c1)可為以通式：CH2=CA1COOA2 [式中，A1為氫原子、甲基、或氟原子以外之鹵素原子(例如氯原子、溴原子及碘原子)，A2為CnH2n+1(n=1至30)所表示之烷基。]所表示之丙烯酸酯。 The non-fluorine non-crosslinkable monomer (c1) may be a (meth) acrylate having an alkyl group. The number of carbon atoms of the alkyl group may be from 1 to 30, for example from 6 to 30 (e.g., from 10 to 30). For example, the non-fluorine non-crosslinkable monomer (c1) may be of the formula: CH 2 = CA 1 COOA 2 [wherein, A 1 is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, A bromine atom and an iodine atom), and A 2 is an alkyl group represented by C n H 2n+1 (n=1 to 30). The acrylate represented.
由於聚合物附著於輥之抑制性變高，故含氟聚合物較佳係具有由A2為碳數12至30、特別是18至30之烷基之丙烯酸酯(CH2=CA1COOA2)所衍生之重複單位。 Since the polymer roll is attached to the suppression becomes high, so the system having a fluorine-containing polymer is preferably A 2 is from 12 to 30 carbon atoms, particularly an alkyl group of 18 to 30 of acrylate (CH 2 = CA 1 COOA 2 ) the repeating unit derived.
非氟非交聯性單體(c1)可為具有環狀烴基之(甲基)丙烯酸酯單體。具有環狀烴基之(甲基)丙烯酸酯單體(B)係具有(較佳為一價之)環狀烴基及一價之(甲基)丙烯酸酯基之化合物。一價之環狀烴基與一價之(甲基)丙烯酸酯基係直接鍵結。環狀烴基係可舉例如飽和或不飽和之單環基、多環基、交聯環基等。環狀烴基係以飽和為佳。環狀烴基之碳數係以4至20為佳。環狀烴基係可舉例如碳數4至20、特別是5至12之環狀脂肪族基、碳數6至20之芳香族基、碳數7至20之芳香-脂肪族基。環狀烴基之碳數為15以下，例如以10以下為特佳。環狀烴基之環之碳原子較佳為直接鍵結於(甲基)丙烯酸酯基之酯基。環狀烴基係以飽和之環狀脂肪族基為佳。環狀烴基之具體例為環己基、三級丁基環己基、異莰基、二環戊基、二環戊烯基。(甲基)丙烯酸酯基係丙烯酸酯基或甲基丙烯酸酯基，但以甲基丙烯酸酯基為佳。具有環狀烴基之單體之具體例係可舉例如甲基丙烯酸環己酯、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 (c1) may be a (meth) acrylate monomer having a cyclic hydrocarbon group. The (meth) acrylate monomer (B) having a cyclic hydrocarbon group is a compound having a (preferably 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 or a crosslinked cyclic group. The cyclic hydrocarbon group is preferably 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 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or an aromatic-aliphatic group having 7 to 20 carbon atoms. The number of carbon atoms of the cyclic hydrocarbon group is 15 or less, and particularly preferably 10 or less. The carbon atom of the ring of the cyclic hydrocarbon group is preferably an ester group directly bonded to 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 isodecyl group, a dicyclopentyl group, and a dicyclopentenyl group. The (meth) acrylate group is an acrylate group or a methacrylate group, but a methacrylate group is preferred. Specific examples of the monomer having a cyclic hydrocarbon group include, for example, cyclohexyl methacrylate, tertiary butylcyclohexyl methacrylate, benzyl methacrylate, isodecyl methacrylate, isodecyl acrylate, Dicyclopentyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, and the like.
(c2)非氟交聯性單體 (c2) non-fluorine crosslinkable monomer
本發明之含氟聚合物可具有由非氟交聯性單體(c2)所衍生之重複單位。非氟交聯性單體(c2)為不含氟原子之單體。非氟交聯性單體(c2)可為至少具有2個反應性基及/或碳-碳雙鍵，且不含有氟之化合物。非氟交聯性單體(c2)可為至少具有2個碳-碳雙鍵之化合物，或至少具有一個碳-碳雙鍵及至少一個反應性基之化合物。反應性基之例係羥基、環氧基、氯甲基、嵌段異氰酸酯基、胺基、羧基等。非氟交聯性單體(c2)可為具有反應性基之單(甲基)丙烯酸酯、(甲基)二丙烯酸酯或單(甲基)甲烯醯胺。或者，非氟交聯性單體(c2)可為二(甲基)丙烯酸酯。 The fluoropolymer of the present invention may have a repeating unit derived from a non-fluorine crosslinkable monomer (c2). The non-fluorine crosslinkable monomer (c2) is a monomer having no fluorine atom. The non-fluorine-crosslinkable monomer (c2) may be a compound having at least two reactive groups and/or carbon-carbon double bonds and containing no fluorine. The non-fluorine crosslinkable monomer (c2) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of the reactive group are a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amine group, a carboxyl group and the like. The non-fluorine crosslinkable monomer (c2) may be a mono (meth) acrylate having a reactive group, (meth) diacrylate or mono (methyl) methyl decylamine. Alternatively, the non-fluorine crosslinkable monomer (c2) may be a di(meth)acrylate.
非氟交聯性單體(c2)可例示如二丙酮(甲基)丙烯醯胺、(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、羥基甲基(甲基)丙烯酸酯、羥基乙基(甲基)丙烯酸酯、3-氯-2-羥基丙基(甲基)丙烯酸酯、2-乙醯乙醯氧基乙基(甲基)丙烯酸酯、丁二烯、異戊二烯、氯丁二烯、(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，但並不限定於該等。 The non-fluorine-crosslinkable monomer (c2) may, for example, be diacetone (meth) acrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (methyl) Acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetamethylene ethoxyethyl (meth) acrylate, butadiene , isoprene, chloroprene, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc., but It is not limited to these.
本說明書中，所謂「(甲基)丙烯酸酯」意指丙烯酸酯或甲基丙烯酸酯，所謂「(甲基)丙烯醯胺」意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.
藉由使非氟非交聯性單體(c1)及/或非氟交聯性單體(c2)共聚合，可視需要而改善撥水撥油性或防污性及該等性能之耐清洗性、耐洗滌性、對溶劑之溶解性、硬度、觸感等之各種性質。 By copolymerizing the non-fluorine non-crosslinkable monomer (c1) and/or the non-fluorine crosslinkable monomer (c2), the water repellency or the antifouling property and the cleaning resistance of the properties can be improved as needed. Various properties such as washing resistance, solubility in a solvent, hardness, and touch.
於含氟聚合物中，相對於含氟單體(a)100重量份， 鹵化烯烴(b)之量為2至500重量份，例如5至200重量份，特別是10至150重量份，更特別是15至50重量份，非氟單體(c)之量可為1200重量份以下，例如0.1至400重量份，特別是0.5至250重量份，更特別是1至50重量份。於含氟聚合物中，相對於含氟單體(a)100重量份，非氟非交聯性單體(c1)之量為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(c2)之量為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, relative to 100 parts by weight of the fluoromonomer (a), The amount of the halogenated olefin (b) is from 2 to 500 parts by weight, for example from 5 to 200 parts by weight, particularly from 10 to 150 parts by weight, more particularly from 15 to 50 parts by weight, and the amount of the non-fluorinated monomer (c) may be 1200. The parts by weight or less, for example, 0.1 to 400 parts by weight, particularly 0.5 to 250 parts by weight, more specifically 1 to 50 parts by weight. In the fluoropolymer, the amount of the non-fluorine non-crosslinkable monomer (c1) is 1000 parts by weight or less, for example, 0.1 to 300 parts by weight, particularly 1 to 1 part by weight based on 100 parts by weight of the fluoromonomer (a). The amount of the non-fluorine-crosslinkable monomer (c2) is 50 parts by weight or less, for example, 30 parts by weight or less, particularly preferably 0.1 to 20 parts by weight, per 100 parts by weight.
本發明之含氟聚合物能以一般之聚合方法的任一種來製造，且聚合反應之條件亦可任意地選擇。就如此之聚合方法，可舉例如溶液聚合、懸浮聚合、乳化聚合。 The fluoropolymer of 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. Examples of such a polymerization method include solution polymerization, suspension polymerization, and emulsion polymerization.
在溶液聚合中係採用下述方法：於聚合起始劑之存在下，使單體溶解於有機溶劑中，氮氣置換後，以30至120℃之範圍進行加熱攪拌1至10小時。聚合起始劑係可舉例如偶氮雙異丁腈、過氧化苯甲醯、過氧化二-第三級丁基、過氧化月桂醯、氫過氧化異丙苯、過氧異丁酸三級丁酯、過氧二碳酸二異丙酯等。聚合起始劑係相對於單體100重量份，以0.01至20重量份例如0.01至10重量份的範圍使用。 In the solution polymerization, the following method is employed: in the presence of a polymerization initiator, the monomer is dissolved in an organic solvent, and after nitrogen substitution, heating and stirring is carried out in the range of 30 to 120 ° C for 1 to 10 hours. The polymerization initiator may, for example, be azobisisobutyronitrile, benzammonium peroxide, di-tertiary butyl peroxide, laurel peroxide, cumene hydroperoxide or peroxyisobutyric acid. Butyl ester, diisopropyl peroxydicarbonate, and the like. The polymerization initiator is 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.
有機溶劑係對單體為惰性且可溶解該等者，例如可為酯(例如碳數2至30之酯，具體而言，為乙酸乙酯、乙酸丁酯)、酮(例如碳數2至30之酮，具體而言，為甲乙酮、二異丁基酮)、醇(例如碳數1至30之醇，具體而言，為異丙醇)。有機溶劑之具體例係可舉例如丙酮、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、1,4-二噁烷、甲乙酮、甲基異丁基酮、二異丁基酮、乙酸乙酯、乙酸丁酯、1,1,2,2-四氯乙烷、1,1,1-三氯乙烷、三氯乙烯、全氯乙烯、四氯二氟乙烷、三氯三氟乙烷等。有機溶劑係相對於單體之合計100重量份，以10至2000重量份例如50至1000重量份之範圍使用。 The organic solvent is inert to the monomer and can dissolve the same, and may be, for example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate) or a ketone (for example, carbon number 2 to The ketone of 30, specifically, methyl ethyl ketone, diisobutyl ketone), an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropanol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropanol, pentane, and hexane. Heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, acetic acid Butyl ester, 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 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total of the monomers.
在乳化聚合係採用下述之方法：於聚合起始劑及乳化劑的存在下，使單體於水中乳化，氮氣置換後，以50至80℃之範圍下攪拌1至10小時而使之共聚合。聚合起始劑係可使用過氧化苯甲醯、過氧化月桂醯、過氧苯甲酸三級丁酯、氫過氧化1-羥基環己基、過氧化3-羧基丙醯基、過氧化乙醯、偶氮雙異丁基脒-二鹽酸鹽、偶氮雙異丁腈、過氧化鈉、過硫酸鉀、過硫酸銨等之水溶性者、或偶氮雙異丁腈、過氧化苯甲醯、過氧化二-三級丁基、過氧化月桂醯、氫過氧化異丙苯、過氧異丁酸三級丁酯、過氧二碳酸二異丙酯等之油溶性者。聚合起始劑係相對於單體100重量份，以0.01至10重量份之範圍使用。 In the emulsion polymerization, the following method is employed: in the presence of a polymerization initiator and an emulsifier, the monomer is emulsified in water, and after nitrogen substitution, stirring is carried out at a temperature of 50 to 80 ° C for 1 to 10 hours. polymerization. As the polymerization initiator, benzammonium peroxide, laurel peroxide, tertiary butyl peroxybenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropenyl peroxide, ethidium peroxide, Aqueous azobisisobutylphosphonium-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, or azobisisobutyronitrile, benzammonium peroxide Oil-soluble ones of di-tertiary butyl peroxide, lauryl peroxide, cumene hydroperoxide, tertiary butyl peroxyisobutyrate, diisopropyl peroxydicarbonate, and the like. The polymerization initiator is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.
為了得到儲存安定性優異之共聚合物水分散液，較佳為使用如高壓均質機或超音波均質機之可賦予強力之破碎能量的乳化裝置，而使單體於水中微粒子化，使用油溶性聚合起始劑而進行聚合。又，就乳化劑而言，係可使用陽離子性、陰離子性或非離子性之各種乳化劑，相對於單體100重量份，以0.5至20重量份的範圍使用。較佳為使用陰離子性及/或非離子性及/或陽離子性之乳化劑。當單體無法完全相溶時，較佳為添加能使該等單體充分相溶的增容劑，例如水溶性有機溶劑或低分子量之單 體。藉由添加增容劑，可提升乳化性及共聚合性。 In order to obtain an aqueous dispersion of the copolymer having excellent storage stability, it is preferred to use an emulsification device such as a high-pressure homogenizer or an ultrasonic homogenizer to impart a strong breaking energy, and to granulate the monomer in water, using oil-soluble The polymerization is carried out by polymerizing an initiator. Further, as the emulsifier, various cationic, anionic or nonionic emulsifiers can be used, and it is used in an amount 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 miscible, it is preferred to add a compatibilizer that will sufficiently dissolve the monomers, such as a water soluble organic solvent or a low molecular weight single. body. Emulsifying properties and copolymerization properties can be improved by adding a compatibilizer.
水溶性有機溶劑係可舉例如丙酮、甲乙酮、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，係以1至50重量份例如10至40重量份的範圍使用。又，就低分子量之單體係可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，相對於單體之總量100重量份，亦可以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 is used in an amount of 1 to 50 parts by weight, for example, 10 to 100 parts by weight of water. A range of 40 parts by weight is used. Further, examples of the low molecular weight single system include 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 also be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight.
在聚合中，亦可使用鏈轉移劑。依照鏈轉移劑之使用量，可使共聚物之分子量改變。鏈轉移劑之例係月桂硫醇、硫甘醇、硫甘油等含有硫醇基之化合物(特別是(例如碳數1至30)之烷基硫醇)、次磷酸鈉、亞硫酸氫鈉等無機鹽等。鏈轉移劑之使用量相對於單體之總量100重量份，亦可以0.01至10重量份例如0.1至5重量份的範圍使用。 In the polymerization, a chain transfer agent can also be used. The molecular weight of the copolymer can be varied depending on the amount of the chain transfer agent used. Examples of the chain transfer agent are a thiol group-containing compound such as lauryl mercaptan, thioglycol, or thioglycerol (particularly (for example, an alkylthiol having 1 to 30 carbon atoms), sodium hypophosphite, sodium hydrogen sulfite, etc. Inorganic salts, etc. The chain transfer agent may be used in an amount of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers.
含氟聚合物之共聚物係可藉由一次饋入(一段聚合)或分次饋入(多段聚合，特別是二段聚合)來製造。當一次饋入時，藉由使用交聯性單體，可提高抑制滲出的效果。 Copolymers of fluoropolymers can be produced by one feed (segment polymerization) or fractional feed (multistage polymerization, especially two stage polymerization). When a feed is applied at one time, the effect of suppressing bleeding can be enhanced by using a crosslinkable monomer.
含氟聚合物係為了於基材布上形成聚合物的膜，可藉由已知之任一方法而使用於基材布。一般，係將含有含氟聚合物及液狀介質之液使用於布基材上之後，藉由以乾燥等除去液狀介質，可於聚合物上形成含氟聚合物的膜。於含有含氟聚合物及液狀介質之液中，含氟聚合物之濃度例如可為0.01至20重量%，特別是0.05至10重量%。亦可將基材布浸漬於溶液、或者亦可將液附著於或噴霧至基材布。使用液之後的基材布係例如為了顯現撥液性，可進行乾燥，較佳為例如以100℃至200℃加熱。 The fluoropolymer is a film for forming a polymer on a substrate cloth, and can be used for a substrate cloth by any known method. Generally, after a liquid containing a fluoropolymer and a liquid medium is used on a cloth substrate, a film of a fluoropolymer can be formed on the polymer by removing the liquid medium by drying or the like. The concentration of the fluoropolymer in the liquid containing the fluoropolymer and the liquid medium may be, for example, 0.01 to 20% by weight, particularly 0.05 to 10% by weight. The substrate cloth may be immersed in a solution, or the liquid may be attached or sprayed to the substrate cloth. The substrate cloth after the use of the liquid can be dried, for example, in order to exhibit liquid repellency, and is preferably heated, for example, at 100 ° C to 200 ° C.
被處理之纖維製品典型上為布，其中係包含織物、編物及不織布、衣料品形態之布及地毯，但亦可為纖維或紗或中間纖維製品(例如棉條或粗紗等)。纖維製品材料可為天然纖維(例如棉或羊毛等)、化學纖維(例如黏液嫘縈或萊賽爾纖維(lyocell)等)、或合成纖維(例如聚酯、聚醯胺或丙烯酸纖維等)、或纖維之混合物(例如天然纖維及合成纖維之混合物等)。本發明之製造聚合物係於使纖維素系纖維(例如棉或嫘縈等)形成疏油性及撥油性上特別具有效果。又，本發明之方法一般係可使纖維製品形成疏水性及撥水性。 The treated fibrous product is typically a cloth comprising a fabric, a knitted fabric and a non-woven fabric, a cloth in the form of a garment, and a carpet, but may also be a fiber or a yarn or an intermediate fiber product (such as a sliver or roving). The fibrous material may be natural fibers (such as cotton or wool), chemical fibers (such as mucilage or lyocell, or synthetic fibers (such as polyester, polyamide or acrylic). 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 forming oleophobicity and oil repellency of cellulose-based fibers (for example, cotton or crepe). Moreover, the method of the present invention generally results in the formation of hydrophobicity and water repellency of the fibrous article.
或者，纖維狀基材可為皮革。為了使皮革形成疏水性及疏油性，於皮革加工之各個階段，例如皮革之濕潤加工期間中、或皮革之修整期間中，可使製造聚合物從水溶液或水性乳化物使用於皮革。 Alternatively, the fibrous substrate can be leather. In order to form the leather into hydrophobicity and oleophobicity, the production of the polymer from the aqueous solution or the aqueous emulsion can be applied to the leather at various stages of the leather processing, such as during the wet processing of the leather or during the finishing of the leather.
或者，纖維狀基材可為紙。可將製造聚合物使用於預先所形成之紙，或者亦可使用於製紙之各個階段例如紙的乾燥期間中。 Alternatively, the fibrous substrate can be paper. The polymer to be produced can be used for paper formed in advance, or can be used in various stages of papermaking such as drying of paper.
本發明之表面處理劑(含氟處理劑)，較佳為溶液、乳化液或氣溶膠之形態。表面處理劑係含有含氟聚合物(表面處理劑之活性成分)及介質(特別是液狀介質例如有機溶劑及/或水)所成。表面處理劑中，含氟聚合物之濃度係例如可為0.01至50重量%。 The surface treatment agent (fluorine-containing treatment agent) of the present invention is preferably in the form of a solution, an emulsion or an aerosol. The surface treatment agent is composed of a fluoropolymer (active component of a surface treatment agent) and a medium (particularly a liquid medium such as an organic solvent and/or water). The concentration of the fluoropolymer in the surface treatment agent may be, for example, 0.01 to 50% by weight.
本發明之表面處理劑(含氟處理劑)，較佳為含有含氟聚合物及水性介質。本說明書中，所謂「水性介質」係指僅含水之介質、及除水之外亦含有有機溶劑(有機溶劑之量相對於水100重量份為80重量份以下，例如0.1至50重量份，特別是5至 30重量份)之介質。含氟聚合物較佳為藉由乳化聚合而製造含氟聚合物之水性分散液。表面處理劑較佳為含氟聚合物之粒子分散於水性介質之水性分散液。分散液中，含氟聚合物之平均粒徑較佳為0.01至200μm，例如0.1至5μm，特別是0.05至0.2μm。平均粒徑可藉動態光散射裝置、電子顯微鏡等進行測定。 The surface treatment agent (fluorine-containing treatment agent) of the present invention preferably contains a fluorine-containing polymer and an aqueous medium. In the present specification, the term "aqueous medium" means a medium containing only water and an organic solvent in addition to water (the amount of the organic solvent is 80 parts by weight or less, for example, 0.1 to 50 parts by weight, based on 100 parts by weight of water, particularly Is 5 to 30 parts by weight of the medium. The fluoropolymer is preferably an aqueous dispersion of a fluoropolymer produced by emulsion polymerization. The surface treatment agent is preferably an aqueous dispersion in which particles of the fluoropolymer are dispersed in an aqueous medium. The average particle diameter of the fluoropolymer in the dispersion is preferably from 0.01 to 200 μm, for example from 0.1 to 5 μm, particularly from 0.05 to 0.2 μm. The average particle diameter can be measured by a dynamic light scattering device, an electron microscope, or the like.
本發明之表面處理劑可藉以往習知之方法使用於被處理物。通常，採用下述方法：將該表面處理劑分散於有機溶劑或水而進行稀釋，藉由如浸漬塗布、噴霧塗布、泡塗布等之既知的方法，使附著於被處理物表面，進行乾燥。又，若需要，亦可與適當之交聯劑一起使用，進行固化。再者，於本發明之表面處理劑中，亦可添加併用防蟲劑、柔軟劑、抗菌劑、阻燃劑、抗靜電劑、塗料固定劑、防皺劑等。與基材接觸之處理液中之含氟聚合物的濃度可為(特別是浸漬塗布時)0.01至20重量%，特別是0.05至10重量%。 The surface treating agent of the present invention can be used for the object to be treated by a conventional method. Usually, the surface treatment agent is diluted in an organic solvent or water, and is adhered to the surface of the object to be dried by a known method such as dip coating, spray coating or bubble coating. Further, if necessary, it may be used together with a suitable crosslinking agent to carry out curing. Further, in the surface treatment agent of the present invention, 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 in combination. The concentration of the fluoropolymer in the treatment liquid in contact with the substrate may be (particularly, during dip coating) of 0.01 to 20% by weight, particularly 0.05 to 10% by weight.
接著，舉出實施例、比較例及試驗例而具體地說明本發明。唯，此等之說明並非限定本發明。 Next, the present invention will be specifically described by way of examples, comparative examples and test examples. However, the description of these does not limit the invention.
以下，份或%只要無特別聲明，係表示重量份或重量%。 Hereinafter, the parts or % are expressed by weight or % by weight unless otherwise stated.
特性係以如下之方法進行測定。 The characteristics were measured in the following manner.
聚合物中之單體組成 Monomer composition in the polymer
對於聚合物，進行元素分析(F原子、Cl原子及C原子)、IR分光法、1H NMR分光法及19F NMR分光法，求出聚合物中之單體組成(重量%)。 For the polymer, elemental analysis (F atom, Cl atom, and C atom), IR spectrometry, 1 H NMR spectroscopy, and 19 F NMR spectroscopy were carried out to determine the monomer composition (% by weight) in the polymer.
動態黏彈性測定 Dynamic viscoelasticity measurement
將聚合物之水性分散液10g分散於甲醇20g而形成者以10000rpm、60分鐘施加於離心器而分離丙烯酸聚合物與乳化劑，得到測定用試樣聚合物。以動態黏彈性測定裝置RHEOSOL-G3000((股)UBM製)測定該聚合物之複數黏度(η*)。以試樣聚合物1g、頻率0.5Hz、測定溫度由40℃以5℃/分鐘升溫至180℃測定動態黏彈性。 10 g of the aqueous dispersion of the polymer was dispersed in 20 g of methanol, and the resultant was applied to a centrifuge at 10,000 rpm for 60 minutes to separate the acrylic polymer and the emulsifier to obtain a sample polymer for measurement. The complex viscosity (η*) of the polymer was measured by a dynamic viscoelasticity measuring apparatus RHEOSOL-G3000 (manufactured by UBM). The dynamic viscoelasticity was measured by raising the temperature of the sample polymer by 1 g, the frequency of 0.5 Hz, and the measurement temperature from 40 ° C to 5 ° C / min to 180 ° C.
撥溶劑性 Solvent
將聚合物之水性分散液以水稀釋成固形分濃度為1重量%而調整處理液。將耐綸布浸漬於處理液，以軋輥以4kg/cm2、4m/分鐘擰乾，以170℃熱處理1分鐘後，評估處理布之撥溶劑性。 The aqueous dispersion of the polymer was diluted with water to a solid concentration of 1% by weight to adjust the treatment liquid. The nylon cloth was immersed in the treatment liquid, wrung at 4 kg/cm 2 and 4 m/min with a roll, and heat-treated at 170 ° C for 1 minute, and the solvent property of the treated cloth was evaluated.
撥溶劑性係分別將DMF、MEK、甲苯、乙酸乙酯垂流一滴於試驗布上，測定溶劑被布吸收之時間最多至120秒鐘，以時間顯示撥溶劑性。數值愈高者顯示愈良好之撥溶劑性。 Dilute the solvent, DMF, MEK, toluene, and ethyl acetate were separately dropped on the test cloth, and the time when the solvent was absorbed by the cloth was measured up to 120 seconds, and the solvent property was shown by time. The higher the value, the better the solvent is displayed.
塗布樹脂之滲出 Coating resin bleed
將聚合物之水性分散液以水稀釋成固形分濃度為1重量%而調整處理液。將耐綸布浸漬於處理液，以軋輥以4kg/cm2、4m/分鐘擰乾，以170℃熱處理1分鐘後，將以MEK/甲苯/DMF為溶劑之濃度30%之聚胺基甲酸酯樹脂(大日精化工業製RESAMINE ME-3612LP)均勻地塗布於耐綸布的單面，以100℃乾燥1分鐘後，以150℃熱處理1分鐘。以目視觀察非塗布面，以下述評估樹脂之滲出。 The aqueous dispersion of the polymer was diluted with water to a solid concentration of 1% by weight to adjust the treatment liquid. The nylon cloth was immersed in the treatment liquid, wrung at 4 kg/cm 2 , 4 m/min with a roll, and heat treated at 170 ° C for 1 minute, and then a polyaminocarboxylic acid having a concentration of 30% in MEK/toluene/DMF as a solvent. The ester resin (RESAMINE ME-3612LP manufactured by Daisei Seiki Co., Ltd.) was uniformly applied to one side of the nylon fabric, dried at 100 ° C for 1 minute, and then heat-treated at 150 ° C for 1 minute. The non-coated side was visually observed, and the bleed out of the resin was evaluated as follows.
◎：完全無滲出 ◎: no leakage at all
○：僅有極少的滲出 ○: very little exudation
×：大量的滲出 ×: a large amount of exudation
合成薄膜之剝離強度 Peel strength of synthetic film
將聚合物之水性分散液以水稀釋成固形分濃度為1重量%而調整成處理液。將耐綸布浸漬於處理液，以軋輥以4kg/cm2、4m/分鐘擰乾，以170℃熱處理1分鐘後，將以MEK/乙酸乙酯作為溶劑之濃度50%之胺基甲酸酯樹脂系接著劑(DIC股份有限公司CRISVON 4010FT)點狀塗佈於耐綸布之單面，將聚胺基甲酸酯之合成薄膜壓接後，以120℃熱處理2分鐘。將所得到之耐綸布以AATCC 88B(1)(III)反覆進行洗滌20次之後，以目視觀察合成薄膜之剝離狀態，以下述評估其狀態。 The aqueous dispersion of the polymer was diluted with water to a solid content concentration of 1% by weight to adjust to a treatment liquid. The nylon cloth was immersed in the treatment liquid, wrung at 4 kg/cm 2 , 4 m/min with a roll, and heat treated at 170 ° C for 1 minute, and then a urethane having a concentration of 50% using MEK/ethyl acetate as a solvent. A resin-based adhesive (DICC CSRVON 4010FT) was applied to one side of the nylon fabric in a dot shape, and the synthetic film of the polyurethane was pressure-bonded, followed by heat treatment at 120 ° C for 2 minutes. After the obtained nylon fabric was washed repeatedly for 20 times with AATCC 88B (1) (III), the peeling state of the synthetic film was visually observed, and the state was evaluated as follows.
◎：完全無剝離 ◎: no peeling at all
○：僅有極少的剝離 ○: There is very little peeling
×：可明顯地看到剝離 ×: peeling can be clearly seen
實施例1 Example 1
於1L高壓釜中置入C6F13CH2CH2OCOCCl=CH2(C6 α-Cl)179g、丙烯酸硬脂酯25g、三丙二醇75.8g、純水446g、聚氧乙烯月桂基醚12.7g、聚氧乙烯油基醚2.47g、聚氧乙烯異十三烷基醚5.05g、氯化二烷基(牛脂)二甲基銨2.66g，以60℃加溫後，再以高壓均質機乳化分散。乳化後，加入月桂基硫醇0.63g，壓入填充氯乙烯60g。再者，添加2,2-偶氮雙(2-甲脒基丙烷)2鹽酸鹽1.92g，以60℃反應3小時，得到聚合物之水性分散液。測定以純水調整濃度成其固形分濃度為30重量%之水性分散液之特性。將結果表示於表A。 Into a 1 L autoclave, 179 g of C 6 F 13 CH 2 CH 2 OCOCCl=CH 2 (C6 α-Cl), 25 g of stearyl acrylate, 75.8 g of tripropylene glycol, 446 g of pure water, and 12.7 g of polyoxyethylene lauryl ether were placed. , 2.47g of polyoxyethylene oleyl ether, 5.05g of polyoxyethylene isotridecyl ether, 2.66g of dialkyl (tallow) dimethylammonium chloride, heated at 60 ° C, and then emulsified by high pressure homogenizer dispersion. After the emulsification, 0.63 g of lauryl mercaptan was added, and 60 g of vinyl chloride was injected. Further, 1.92 g of 2,2-azobis(2-methylamidinopropane) 2 hydrochloride was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The characteristics of the aqueous dispersion having a solid concentration adjusted to a solid concentration of 30% by weight in pure water were measured. The results are shown in Table A.
實施例2 Example 2
除於乳化後添加月桂基硫醇1.25g之外，以與實施例1同樣 之方法得到聚合物之分散液。 The same as in Example 1 except that 1.25 g of lauryl mercaptan was added after emulsification. The method provides a dispersion of the polymer.
實施例3 Example 3
除於乳化後添加月桂基硫醇1.88g之外，以與實施例1同樣之方法得到聚合物之分散液。 A dispersion of the polymer was obtained in the same manner as in Example 1 except that 1.88 g of lauryl mercaptan was added after the emulsification.
實施例4 Example 4
除使用甲基丙烯酸環己酯25g取代丙烯酸硬脂酯25g之外，以與實施例2同樣之方法得到聚合物之分散液。 A dispersion of the polymer was obtained in the same manner as in Example 2 except that 25 g of cyclohexyl methacrylate was used instead of 25 g of stearyl acrylate.
實施例5 Example 5
除使用丙烯酸異莰酯25g取代丙烯酸硬脂酯25g之外，以與實施例2同樣之方法得到聚合物之分散液。 A dispersion of the polymer was obtained in the same manner as in Example 2 except that 25 g of isopropyl acrylate was used instead of 25 g of stearyl acrylate.
實施例6 Example 6
除於實施例2中加入異丙基丙烯醯胺2.25g之外，以與實施例2同樣之方法得到聚合物之分散液。 A dispersion of the polymer was obtained in the same manner as in Example 2 except that 2.25 g of isopropylacrylamide was added to Example 2.
實施例7 Example 7
除於實施例2中加入二丙酮丙烯醯胺2.25g之外，以與實施例2同樣之方法得到聚合物之分散液。 A dispersion of the polymer was obtained in the same manner as in Example 2 except that 2.25 g of diacetone acrylamide was added in Example 2.
實施例8 Example 8
除於實施例2中加入甲基丙烯酸環氧丙酯2.25g之外，以與實施例2同樣之方法得到聚合物之分散液。 A dispersion of the polymer was obtained in the same manner as in Example 2 except that 2.25 g of glycidyl methacrylate was added in Example 2.
比較例1 Comparative example 1
除使用C6F13CH2CH2OCOC(CH3)=CH2 179g取代C6F13CH2CH2OCOCCl=CH2 179g之外，以與實施例2同樣之方法得到聚合物之分散液。 A polymer dispersion was obtained in the same manner as in Example 2 except that C 6 F 13 CH 2 CH 2 OCOC(CH 3 )=CH 2 179 g was substituted for C 6 F 13 CH 2 CH 2 OCOCCl=CH 2 179 g. .
比較例2 Comparative example 2
除於乳化後不添加月桂基硫醇以外，以與實施例1同樣之方法得到聚合物之分散液。 A dispersion of the polymer was obtained in the same manner as in Example 1 except that no lauryl mercaptan was added after the emulsification.
比較例3 Comparative example 3
除於乳化後添加月桂基硫醇2.5g以外，以與實施例1同樣之方法得到聚合物之分散液。 A dispersion of the polymer was obtained in the same manner as in Example 1 except that 2.5 g of lauryl mercaptan was added after the emulsification.
將各例之特性表示於表A中。 The characteristics of each example are shown in Table A.
本發明之透濕防水布帛係透濕性、耐水性及耐洗滌性優異。 The moisture-permeable waterproof fabric of the present invention is excellent in moisture permeability, water resistance and washing resistance.
本發明之透濕防水布帛係可使用於衣料，例如運動衣料或防寒衣料、防水片，例如帳棚、睡袋及防污防水片、鞋子及手套等。 The moisture permeable waterproofing fabric of the present invention can be used for clothing materials such as sportswear or cold-resistant fabrics, waterproof sheets such as tents, sleeping bags and anti-fouling waterproof sheets, shoes and gloves, and the like.
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| CN106319965A (en) * | 2015-06-26 | 2017-01-11 | 大金工业株式会社 | Surface conditioning agent composition |
| RU2603141C1 (en) * | 2015-12-30 | 2016-11-20 | Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) | (perfluoro-2-trichloromethylisopropyl)acrylate and polymer based thereon |
| CN107675504A (en) * | 2016-08-02 | 2018-02-09 | 大金工业株式会社 | Non-woven fabrics |
| JP6989800B2 (en) * | 2020-03-06 | 2022-01-12 | ダイキン工業株式会社 | Dispersion |
| CN115819665B (en) * | 2022-12-28 | 2023-07-04 | 浙江辉凯鼎瑞新材料有限公司 | Fluorine-containing treating agent, preparation method thereof and application of fluorine-containing treating agent to non-woven fabric |
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| TWI301152B (en) * | 2001-04-13 | 2008-09-21 | Asahi Glass Co Ltd | |
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| JP2007332482A (en) * | 2006-06-14 | 2007-12-27 | Toray Ind Inc | Moisture-permeable water-proof processed fabric |
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| JP2009242675A (en) * | 2008-03-31 | 2009-10-22 | Komatsu Seiren Co Ltd | Adhesive for moisture permeable water proofing cloth |
| WO2010030044A2 (en) * | 2008-09-15 | 2010-03-18 | Daikin Industries, Ltd. | Water- and oil-repellent composition |
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