TWI698518B - Fluoride-free water repellent - Google Patents
Fluoride-free water repellent Download PDFInfo
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Abstract
一種無氟水性撥水劑,由下列單體所聚合而成,包含有:(A)具有碳數12至24直鏈烷基(甲基)丙烯酸酯,50至89重量%;(B)具有碳數6至20單環、多環或交聯狀烷基(甲基)丙烯酸酯,10至20重量%;(C)反應基團(羥基、胺基、氯基、環氧基)的烷基(甲基)丙烯酸酯為1至10重量%;以及(D)改質後的聚氨酯單體為5至20重量%。本發明之無氟水性撥水劑,可以提高無氟超疏水撥水劑的防水性和耐洗性。 A fluorine-free water-repellent water repellent made by polymerizing the following monomers, containing: (A) a linear alkyl (meth)acrylate with a carbon number of 12 to 24, 50 to 89% by weight; (B) Monocyclic, polycyclic or crosslinked alkyl (meth)acrylate with carbon number of 6 to 20, 10 to 20% by weight; (C) Alkyl of reactive groups (hydroxyl, amino, chloro, epoxy) The base (meth)acrylate is 1 to 10% by weight; and (D) the modified polyurethane monomer is 5 to 20% by weight. The fluorine-free water-repellent water repellent of the present invention can improve the water resistance and washing resistance of the fluorine-free superhydrophobic water-repellent.
Description
本發明係有關於一種撥水劑,特別是有關於一種無氟水性撥水劑。 The present invention relates to a water-repellent agent, in particular to a fluorine-free water-repellent agent.
隨著人類環保意識的抬頭,開始對綠環境和低碳產品有了訴求,歐美及日本等先進國家,甚至開始禁止和降低氟系產品的使用,由於氟化物可能會從終端產品釋放出來,並隨著雨水進入附近的水源、土壤或食物,長期累積在動物骨骼及外殼內,中等量的氟化物對牙齒有影響,而長期攝入大量的氟化物可能會導致嚴重的骨骼問題,變得更脆更易裂。 With the rise of human environmental protection awareness, there are demands for green environment and low-carbon products. Advanced countries such as Europe, America and Japan have even begun to ban and reduce the use of fluorine-based products. As fluoride may be released from end products, As rainwater enters nearby water sources, soil or food, it accumulates in animal bones and shells for a long time. Moderate amounts of fluoride affect teeth, and long-term intake of large amounts of fluoride may cause serious bone problems and become more serious. Brittle and easier to crack.
為了適應人們對紡織品的不斷要求,越來越多的紡織品被賦予功能性,而防水功能就是一個重要的分支。目前應用較多的仍然是氟碳型撥水劑,但是隨著人們對環保要求的不斷提高,氟碳型撥水劑的應用被嚴格限制。雖然近年來越來越多的科研人員在研究大量的短鏈性氟碳撥水劑,但是隨著人們對紡織品以及化學品安全的要求進一步的提高,環保無氟型撥水劑將會越來越受歡迎。無氟水性超疏水撥水劑對於純棉織物、滌綸織物、滌棉混紡織物具有良好的初始防水性能。提高無氟超疏水撥水劑的防水性和耐洗性,將是未來環保無氟型撥水劑的發展趨勢。 In order to meet people's continuous requirements for textiles, more and more textiles are given functionality, and waterproof function is an important branch. At present, fluorocarbon water repellents are still widely used, but with the continuous improvement of people's environmental protection requirements, the application of fluorocarbon water repellents is strictly restricted. Although more and more researchers are studying a large number of short-chain fluorocarbon water repellents in recent years, as people's requirements for textile and chemical safety are further improved, environmentally friendly fluorine-free water repellents will increase The more popular. Fluorine-free water-based superhydrophobic water repellent has good initial waterproof performance for pure cotton fabrics, polyester fabrics, and polyester-cotton blended fabrics. Improving the water repellency and washing resistance of fluorine-free superhydrophobic water repellents will be the development trend of environmentally friendly fluorine-free water repellents in the future.
專利合作條約PCT專利公開號碼WO2015080026、WO2015076348、WO2015076347、WO2015111668係利用非氟系聚合物含有源自(甲基)丙烯酸酯單體的構成單元來進行非氟系撥水劑的合成。而本發明使用聚氨基丙烯酸酯polyur ethane acrylate,PUA的結構,再導入到無氟壓克力系統,更提高無氟超疏水撥水劑的防水性和耐洗性。 Patent Cooperation Treaty PCT Patent Publication Nos. WO2015080026, WO2015076348, WO2015076347, and WO2015111668 utilize non-fluorine-based polymers containing structural units derived from (meth)acrylate monomers to synthesize non-fluorine-based water repellents. While the present invention uses polyamino acrylate polyur The structure of ethane acrylate and PUA is introduced into the fluorine-free acrylic system to further improve the water resistance and washing resistance of the fluorine-free superhydrophobic water repellent.
本發明之目的是提供一種無氟水性撥水劑,可以提高無氟超疏水撥水劑的防水性和耐洗性。 The purpose of the present invention is to provide a fluorine-free water-repellent agent, which can improve the water resistance and washing resistance of the fluorine-free superhydrophobic water-repellent agent.
本發明為達成上述目的提供一種無氟水性撥水劑,由下列單體所聚合而成,包含有:(A)具有碳數12至24直鏈烷基(甲基)丙烯酸酯,50至89重量%;(B)具有碳數6至20單環、多環或交聯狀烷基(甲基)丙烯酸酯,10至20重量%;(C)反應基團(羥基、胺基、氯基、環氧基)的烷基(甲基)丙烯酸酯為1至10重量%;以及(D)改質後的聚氨酯單體為5至20重量%。 The present invention provides a fluorine-free water-repellent water repellent to achieve the above-mentioned object, which is polymerized by the following monomers and contains: (A) a linear alkyl (meth)acrylate with a carbon number of 12 to 24, 50 to 89 Weight%; (B) monocyclic, polycyclic or cross-linked alkyl (meth)acrylate with carbon number 6 to 20, 10 to 20% by weight; (C) reactive groups (hydroxyl, amino, chloro , Epoxy) alkyl (meth)acrylate is 1 to 10% by weight; and (D) the modified polyurethane monomer is 5 to 20% by weight.
與習知之無氟水性撥水劑比較,本發明具有以下優點: Compared with the conventional non-fluorine water repellent, the present invention has the following advantages:
1.極佳防撥水性潑油性。 1. Excellent water repellency and oil repellency.
2.乾爽、透氣及舒適易清理且防污性佳。 2. Dry, breathable and comfortable, easy to clean and good stain resistance.
3.無毒具環保性不含碳氟化合物。 3. Non-toxic, environmentally friendly and free of fluorocarbons.
本發明之無氟水性撥水劑,由下列單體所聚合而成,包含有 The fluorine-free water repellent of the present invention is polymerized by the following monomers, including
(A)具有碳數12至24直鏈烷基(甲基)丙烯酸酯(Methyl propiolate)之含量為50至89重量%。 (A) The content of linear alkyl (meth)acrylate (Methyl propiolate) having a carbon number of 12 to 24 is 50 to 89% by weight.
CH3(CH2) n OC(O)CR=CH2 式中n=11至21的整數;R=H或CH3 CH 3 (CH 2 ) n OC(O)CR=CH 2 where n=an integer from 11 to 21; R=H or CH 3
(B)具有碳數6至20單環、多環或交聯狀烷基(甲基)丙烯酸酯,(甲基)丙烯酸異冰片酯、丙烯酸異冰片酯、甲基丙烯酸叔丁基環己酯、(甲基)丙烯酸雙環戊基酯、苯乙烯、1,3氯甲基苯乙烯、1,4氯甲基苯乙烯與甲基丙烯酸環己酯,單環、多環或交聯狀烷基(甲基)丙烯酸酯之含量為10至20重量%; (B) Monocyclic, polycyclic or cross-linked alkyl (meth)acrylate with carbon number of 6-20, isobornyl (meth)acrylate, isobornyl acrylate, tert-butyl cyclohexyl methacrylate , Dicyclopentyl (meth)acrylate, styrene, 1,3 chloromethyl styrene, 1,4 chloromethyl styrene and cyclohexyl methacrylate, monocyclic, polycyclic or cross-linked alkyl The content of (meth)acrylate is 10 to 20% by weight;
(C)反應基團(羥基、胺基、氯基、環氧基)的烷基(甲基)丙烯酸酯為1至10重量%,此反應基團的烷基(甲基)丙烯酸酯為HOC2H4-OC(O)CR=CH2 (C) The alkyl (meth)acrylate of the reactive group (hydroxyl, amino, chloro, epoxy) is 1 to 10% by weight, and the alkyl (meth)acrylate of this reactive group is HOC 2 H 4 -OC(O)CR=CH 2
R-(OC2H4)m-OC(O)CR=CH2 R-(OC 2 H 4 ) m -OC(O)CR=CH 2
R-(OC3H6)m-OC(O)CR=CH2 R-(OC 3 H 6 ) m -OC(O)CR=CH 2
NH2-C(O)CR=CH2 NH 2 -C(O)CR=CH 2
HOC2H4-NH-C(O)CR=CH2 HOC 2 H 4 -NH-C(O)CR=CH 2
C2H6NC2H4-OC(O)CR=CH2 C 2 H 6 NC 2 H 4 -OC(O)CR=CH 2
C3H9N+(Cl-)C2H4-OC(O)CR=CH2 C 3 H 9 N + (Cl -) C 2 H 4 -OC (O) CR = CH 2
ClH2CH(OH)CH2 OC(O)CR=CH2 ClH 2 CH(OH)CH 2 OC(O)CR=CH 2
(D)改質後的聚氨酯(Polyurethane)單體為5至20重量%,上述改質的聚氨酯單體(聚氨基丙烯酸酯polyurethane acrylate,PUA)為
本發明之無氟水性撥水劑可使用的聚合方式,包括溶液聚合、懸浮聚合與乳化聚合等。本發明之無氟水性撥水劑聚合物進行乳化聚合方式中,所使用到的乳化劑包含單獨或混合使用非離子乳化劑、反應型非離子乳化劑、陽離子乳化劑,進行乳化共聚合反應。所使用的非離子乳化劑為下式:R-X-(EO)n- (PO)m-H(其中,R為碳數8至30的直鏈、支鏈烷基,包含油酸基;X為氧或是氮;n與m分別為0至50的整數,n與m的總和需大於3。)。非離子乳化劑為聚氧乙烯(03)月桂醚(中日化學SP1203)、聚氧乙烯(09)月桂醚(中日化學SP1209)、聚氧乙烯(20)月桂醚(中日化學SP1220)、聚氧乙烯(07)硬酯醚(中日化學SP1807)、聚氧乙烯(30)硬酯醚(中日化學SP1830)或是聚氧乙烯(13)油酸醚(中日化學SP1213)。所使用的陽離子乳化劑為下式:(R’4N+)‧X-(其中,R’可能為氫原子、碳數1~30的烷基、碳數2~30的鏈烷基或是EO鏈段,4個R’可相同,也可以為不相同的構形;X為氯原子、乙基硫酸離子或是乙酸離子)。陽離子乳化劑為十六烷基三甲基氯化銨(CTAC)、十八烷基三甲基氯化銨(SMTAC)、雙十八烷基雙甲基氯化銨(花王-D86P)、雙牛酯基氯化銨(台界-CNA90)或雙脂肪烷基乙酯基羥乙基甲基硫酸甲酯銨(REWOQUAT WE-18)。本發明所使用的兩性離子乳化劑包含酸性兩性界面活性劑、多元醇胺硫酸酯類、烷胺磺酸鹽類介面活性劑,陽離子官能基為銨鹽與四級銨鹽,陰離子官能基為羧酸鹽、硫酸鹽與磺酸鹽類。 The fluorine-free water-repellent water repellent of the present invention can be used in polymerization methods, including solution polymerization, suspension polymerization and emulsion polymerization. In the fluorine-free water-repellent polymer of the present invention, the emulsifier used includes nonionic emulsifiers, reactive nonionic emulsifiers, and cationic emulsifiers used alone or in combination to perform emulsification copolymerization. The nonionic emulsifier used is the following formula: R-X-(EO)n- (PO)mH (where R is a linear or branched alkyl group having 8 to 30 carbons, including oleic acid group; X is oxygen or nitrogen; n and m are integers from 0 to 50, respectively, and n and m are The sum must be greater than 3.). Non-ionic emulsifiers are polyoxyethylene (03) lauryl ether (China-Japan Chemical SP1203), polyoxyethylene (09) lauryl ether (China-Japan Chemical SP1209), polyoxyethylene (20) lauryl ether (China-Japan Chemical SP1220), Polyoxyethylene (07) stearyl ether (Chinichi Chemical SP1807), polyoxyethylene (30) stearyl ether (Chinichi Chemical SP1830) or polyoxyethylene (13) oleic ether (Chinichi Chemical SP1213). The cationic emulsifier used is the following formula: (R'4N+)‧X- (where R'may be a hydrogen atom, an alkyl group with 1 to 30 carbons, a chain alkyl group with 2 to 30 carbons or an EO chain In section, the 4 R's can be the same or different configurations; X is a chlorine atom, ethyl sulfate ion or acetate ion). Cationic emulsifiers are cetyl trimethyl ammonium chloride (CTAC), octadecyl trimethyl ammonium chloride (SMTAC), dioctadecyl dimethyl ammonium chloride (Kao-D86P), double Tallow ester ammonium chloride (Taijie-CNA90) or double fatty alkyl carboethoxyethyl methyl ammonium methyl sulfate (REWOQUAT WE-18). The zwitterionic emulsifiers used in the present invention include acidic amphoteric surfactants, polyolamine sulfates, and alkylamine sulfonates. The cationic functional groups are ammonium and quaternary ammonium salts, and the anionic functional groups are carboxyl. Acid salts, sulfates and sulfonates.
聚合反應中,將反應物分為油相與水相,油相包含了單體(A)、單體(B)、單體(C)、單體(D)與乳化劑;水相包含了水、酸、溶劑。在準備與聚合過程中採用一種或多種的非離子乳化劑、陽離子乳化劑與兩性離子乳化劑;反應前先將油相、水相預熱並高速分散後,再經由高壓均質機均勻分散,可獲得穩定的均勻預乳液後,再將預乳液以連續式或批次式的方式進行乳化聚合反應。 In the polymerization reaction, the reactants are divided into an oil phase and a water phase. The oil phase contains monomers (A), monomers (B), monomers (C), monomers (D) and emulsifiers; the water phase contains Water, acid, solvent. In the preparation and polymerization process, one or more nonionic emulsifiers, cationic emulsifiers and zwitterionic emulsifiers are used; the oil phase and water phase are preheated and dispersed at a high speed before the reaction, and then uniformly dispersed by a high-pressure homogenizer. After obtaining a stable uniform pre-emulsion, the pre-emulsion is then subjected to emulsion polymerization in a continuous or batch manner.
為了控制分散於乳液內微胞的電位分布,除了乳化劑外,也需利用酸與鹽類來控制適當的電位範圍,常用酸為有機酸與無機酸及其鹽類,優選為鹽酸,磷酸,硫酸,醋酸,檸檬酸、蘋果酸及其鹽類。 In order to control the potential distribution of the micelles dispersed in the emulsion, in addition to emulsifiers, it is also necessary to use acids and salts to control the appropriate potential range. Commonly used acids are organic and inorganic acids and their salts, preferably hydrochloric acid, phosphoric acid, Sulfuric acid, acetic acid, citric acid, malic acid and their salts.
本發明的無氟聚合物所構成的水性撥水劑,可以在一種織物或是織物共混物的纖維表面進行塗佈,加工方式可以與其他種類助劑一同進行噴塗、浸漬或是浸壓的方式塗佈是纖維表面,再以熱處理100~200℃,30~180秒進行固化,即可達到撥水的效果。 The water repellent composed of the fluorine-free polymer of the present invention can be coated on the fiber surface of a fabric or fabric blend, and the processing method can be sprayed, impregnated or impregnated together with other types of additives. The method is to coat the surface of the fiber, and then heat it at 100~200℃ for 30~180 seconds for curing to achieve the effect of water repellency.
本發明的無氟聚合物所構成的水性撥水劑的撥水評估,聚合物的溶液或乳液可利用一般處理紡織品的方式,將此應用於紡織類的人造合成纖維基材中。舉例來說,可為0.5至25重量%,或1至10重量%,更佳是1至5重量%。該紡織品之基材,則可以先將此織物浸置於溶液中,或經壓染將溶液壓出。該紡織品之基材乾燥過程,可經加熱烘乾的程序處理,在100至200℃下加熱60至90秒,更佳條件是在150至200℃下加熱60至90秒,以可產生撥水性。 In the water repellency evaluation of the water-based water repellent composed of the fluorine-free polymer of the present invention, the polymer solution or emulsion can be applied to textile man-made synthetic fiber substrates by using general textile processing methods. For example, it can be 0.5 to 25% by weight, or 1 to 10% by weight, more preferably 1 to 5% by weight. For the substrate of the textile, the fabric can be immersed in the solution first, or the solution can be pressed out by pressing dye. The substrate drying process of the textile can be processed by heating and drying procedures, heating at 100 to 200°C for 60 to 90 seconds, and better conditions are heating at 150 to 200°C for 60 to 90 seconds to produce water repellency .
本發明的無氟聚合物所構成的水性撥水劑,可加工應用的紡織纖維製品是人造合成纖維織布,包括針織布、不織布、各種成衣、外用衣形式的織布與毛毯,且也可為纖維或紗綿、綿條、粗紗的中間紡織產物。紡織製品可為人造合成纖維,包裝聚酯、聚醯胺或丙烯酸系列的合成纖維。也可為天然與合成纖維的纖維混合物。本發明在使用於尼龍或聚酯的合成纖維織布特別具有疏水性。與未經處理的織布相較,本發明之共聚產物處理織布,會提高織布撥水性並且同時優化觸感。 The water-based water-repellent agent composed of the fluorine-free polymer of the present invention can be processed and applied as synthetic synthetic fiber woven fabrics, including knitted fabrics, non-woven fabrics, various garments, woven fabrics and blankets in the form of outer clothing, and can also be used It is an intermediate textile product of fiber or yarn, cotton sliver and roving. Textile products can be man-made synthetic fibers, packaging polyester, polyamide or acrylic series synthetic fibers. It can also be a fiber mixture of natural and synthetic fibers. The present invention is particularly hydrophobic in synthetic fiber fabrics used in nylon or polyester. Compared with untreated woven fabrics, the copolymerized product of the present invention treated woven fabrics can improve the water repellency of the fabrics and optimize the touch at the same time.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103450418A (en) * | 2013-09-10 | 2013-12-18 | 合肥乐凯科技产业有限公司 | Acrylic ester-polyurethane emulsion and preparation method thereof |
TW201527326A (en) * | 2013-11-22 | 2015-07-16 | Daikin Ind Ltd | Aqueous emulsion surface treatment agent |
CN105064036A (en) * | 2015-09-08 | 2015-11-18 | 广东德美精细化工股份有限公司 | Preparation method and application of hyperbranched polyurethane acrylate interpenetrating polymer network waterproof agent |
TW201706318A (en) * | 2015-07-23 | 2017-02-16 | Nicca Chemical Co | Non-fluorinated polymer, water repellent agent composition, water-repellent fiber product, and method for producing water-repellent fiber product |
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CN103450418A (en) * | 2013-09-10 | 2013-12-18 | 合肥乐凯科技产业有限公司 | Acrylic ester-polyurethane emulsion and preparation method thereof |
TW201527326A (en) * | 2013-11-22 | 2015-07-16 | Daikin Ind Ltd | Aqueous emulsion surface treatment agent |
TW201706318A (en) * | 2015-07-23 | 2017-02-16 | Nicca Chemical Co | Non-fluorinated polymer, water repellent agent composition, water-repellent fiber product, and method for producing water-repellent fiber product |
CN105064036A (en) * | 2015-09-08 | 2015-11-18 | 广东德美精细化工股份有限公司 | Preparation method and application of hyperbranched polyurethane acrylate interpenetrating polymer network waterproof agent |
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