TW201714549A - 錶帶 - Google Patents
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- TW201714549A TW201714549A TW105121572A TW105121572A TW201714549A TW 201714549 A TW201714549 A TW 201714549A TW 105121572 A TW105121572 A TW 105121572A TW 105121572 A TW105121572 A TW 105121572A TW 201714549 A TW201714549 A TW 201714549A
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Abstract
本發明涉及由氟化聚氨酯聚合物製成的錶帶,該聚氨酯聚合物包含衍生自至少一種羥基封端的(全)氟聚醚聚合物的重複單元。
Description
本申請要求於2015年9月3日提交的歐洲申請號15183605.3的優先權,出於所有的目的將此申請的全部內容通過引用結合在此。
本發明涉及由氟化聚氨酯聚合物製成的錶帶,該聚氨酯聚合物包含衍生自(全)氟聚醚聚合物的重複單元。
在本領域中已經披露了由聚合物材料製成的錶帶。例如,EP 2468127 B(BIWI S.A.)披露了由組合物製成的珠寶物件,這些組合物包含具有分散在其中的增強填充劑的彈性體基體,這些增強填充劑選自由以下各項組成之群組:微纖維、聚四氟乙烯納米顆粒、以及其混合物,所述複合材料是從以下組合物獲得的,該組合物包含基於該組合物的總重量在按重量計60%與95%之間的至少一種彈性體、按重量計從0%至5%的微纖維和按重量計從
0%至40%的聚四氟乙烯納米顆粒,存在所述增強填充劑中的至少一種。GB 2460890 A(最終有限公司(EVENTUAL LIMITED))披露了一種帶,該帶包括電子標籤的防護部分以及形成被人佩戴的帶的第二部分,其中該帶材料可以是彈性體材料如橡膠,特別是矽酮橡膠,並且該防護部分可以是由金屬或尼龍製成的。
除此以外,具有至少一個由聚氨酯聚合物製成的或塗覆有聚氨酯聚合物的部件的可佩帶的裝置已經例如披露於US 2013/0197680(耐克公司(NIKE INC.))、US 2014/0155724(KONINKLI JKE飛利浦公司(KONINKLI JKE PHILIPS N.V.))、US 2013/0088408(電子和電信研究院(ELECTRONICS AND TELECOMMUNICATIONS RESEARCH INSTITUTE))和JP H0925405(日本聚氨酯KOGYO株式會社(NIPPON POLYURETHANE KOGYO KK))中。
包含(全)氟聚醚嵌段的熱可加工的彈性體聚氨酯例如披露於US 5,332,798(蒙特公司(AUSIMONT S.P.A.))中。
本申請人面鄰的問題是提供可用於錶帶製造的新聚合物材料。
本申請人已經出人意料地發現包含衍生自
(全)氟聚醚聚合物的重複單元的聚氨酯聚合物具有以下特性,值得注意地耐污性、耐化學性和耐磨性、低溫柔性、絲綢般的手感和機械特性,使得它可以用於製造錶帶。
此外,本申請人已經出人意料地發現當與從完全氫化的聚氨酯獲得的錶帶相比時,根據本發明的錶帶具有值得注意地關於耐污性、耐磨性和耐化學性的改進的特性。
因此,在第一方面,本發明涉及由組合物[組合物(C)]製成的錶帶,該組合物包含至少一種氟化聚氨酯[F-TPU聚合物],所述F-TPU聚合物包含衍生自以下項的重複單元:(a)至少一種選自下組的二醇,該組包括聚醚類型二醇、聚酯類型二醇、聚丁二烯-二醇和聚碳酸酯-二醇;(b)至少一種羥基封端的(全)氟聚醚聚合物[PFPE聚合物];(c)至少一種芳香族的、脂肪族的或脂環族的二異氰酸酯;以及(d)至少一種具有1至14個碳原子的脂肪族的、脂環族的或芳香族的二醇。
本申請人已經出人意料地發現由所述組合物(C)製成的錶帶提供了柔軟的絲綢般的觸感,而沒有將塑化劑添加至所述組合物(C)中。這從毒理學觀點來看提供了優點,因為這些塑化劑可以從物體的表面遷移並且
從那兒至使用者的皮膚上,因此導致使皮膚變紅、刺激和過敏的可能問題。
出於本說明的目的:- 術語“(全)氟聚醚”旨在指示“完全或部分氟化的聚醚”;- 表述“(全)氟聚氧亞烷基鏈”旨在指示部分或完全氟化的、直鏈或支鏈聚氧亞烷基鏈;- 在標識化合物、化學式或式的部分的符號或數位之前和之後的圓括號的使用具有僅僅使那些符號或數位與該文本的剩餘部分的更好區別目的,並且因此所述圓括號還可以被省略。
較佳地,該F-TPU聚合物是嵌段共聚物,即,包含嵌段(還被稱為“區段”)的聚合物,每種嵌段包含衍生自如以上定義的單體(a)、單體(b)、單體(c)或單體(d)的重複單元。
較佳地,所述F-TPU聚合物具有從30,000至約70,000Da的數量平均分子量。
較佳地,所述F-TPU聚合物具有從約120℃至約240℃的熔點(Tm)。
較佳地,所述至少一種單體(a)具有從500至4,000Da、更佳從1,000至4,000的數量平均分子量。
較佳地,所述至少一種單體(a)選自下組,
該組包括聚乙二醇、聚丙二醇、聚(四亞甲基)二醇(PTMG)、聚(1,4-丁二醇)己二酸酯、聚(乙二醇-1,4-丁二醇)己二酸酯、聚(1,6-己二醇-新戊基)二醇己二酸酯、聚-己內酯-二醇(PCL)和聚碳酸酯-二醇。聚(四亞甲基)二醇、聚碳酸酯-二醇和聚-己內酯-二醇是特佳的。
較佳地,所述至少一種單體(b)是包括具有兩個鏈末端的(全)氟聚氧亞烷基鏈[鏈(Rpf)]的羥基封端的(全)氟聚醚聚合物[PFPE聚合物],其中一個或兩個鏈末端以至少一個-OH基團封端。
較佳地,所述鏈(Rpf)的至少一個鏈末端以具有以下式的基團封端:-CH2(OCH2CH2)t-OH (I)
其中t是0或從1至5。
更佳地,所述鏈(Rpf)的兩個鏈末端以如以上定義的具有式(I)的基團封端。
較佳地,所述鏈(Rpf)是具有以下式的鏈-(CFX)hO(Rf)(CFX')i-
其中h和i,彼此相同或不同,等於或高於1、較佳地從1至10、更佳地從1至3;X和X’,彼此相同或不同,是-F或-CF3,其條件是當h和/或i高於1時,X和X’是-F;(Rf)包含重複單元Ro、較佳地由重複單元Ro組成,
所述重複單元獨立地選自由以下所組成之群組:(i)-CFXO-,其中X是F或CF3;(ii)-CFXCFXO-,其中X在每次出現時相同或不同,是F或CF3,其條件是X中的至少一個是-F;(iii)-CF2CF2CW2O-,其中每個W彼此相同或不同,是F、Cl、H;(iv)-CF2CF2CF2CF2O-;(v)-(CF2)j-CFZ-O-,其中j是0至3的整數並且Z是具有通式-O-R(f-a)-T的基團,其中R(f-a)是包含0至10個的多個重複單元的氟聚氧化烯基(fluoropolyoxyalkene)鏈,所述重複單元是選自以下:-CFXO-、-CF2CFXO-、-CF2CF2CF2O-、-CF2CF2CF2CF2O-,其中每個X獨立地是F或CF3並且T是C1-C3全氟烷基基團。
更佳地,鏈(Rf)選自以下式(Rf-a)至(Rf-c):(Rf-a) -(CF2O)n(CF2CF2O)m(CF2CF2CF2O)p(CF2CF2CF2CF2O)q-
其中m、n、p、q是0或者以使得鏈Rf滿足以上數量平均分子量要求的方式選擇的整數,其條件是如果p和q同時是0,n不是0;當m非0時,該m/n比較佳地是在0.1與20之間;當(m+n)非0時,(p+q)/(m+n)較佳地是在0與0.2之間;(Rf-b) -(CF2CF(CF3)O)a(CF2CF2O)b(CF2O)c(CF(CF3)O)d-
其中a、b、c、d是0或者以使得鏈Rf滿足以上數量平均分子量要求的方式選擇的整數;其條件是,a、c和d
中的至少一個不是0;當b非0時,a/b較佳地是在0.1與10之間;當(a+b)不同於0時,(c+d)/(a+b)較佳地是在0.01與0.5之間、更佳在0.01與0.2之間;(Rf-c) -(CF2CF(CF3)O)e(CF2O)f(CF(CF3)O)g-
其中e、f、g是0或者以使得鏈Rf滿足以上數量平均分子量要求的方式選擇的整數;當e非0時,(f+g)/e較佳地是在0.01與0.5之間、更佳在0.01與0.2之間。
本發明中特佳的是PFPE聚合物,其中鏈(Rf)符合如以上定義的式(Rf-a),其中p和q是0。
在較佳的實施例中,所述PFPE聚合物符合以下式(PFPE-I):HO-(CH2CH2O)t-CH2-(Rpf)-CH2(OCH2CH2)u-OH(PFPE-I)
其中t和u,各自獨立地是0或者從1至5;並且Rpf是如以上定義的。
較佳地,所述PFPE聚合物具有從400至10,000Da、更佳從1,000至5,000的數量平均分子量。
在較佳的實施例中,在單體(a)與單體(b)之間的摩爾比是從2至20、更佳從2至10。
在較佳的實施例中,該單體(b)的量是使得該F-TPU聚合物包含從4至30wt.%的氟。
較佳地,所述至少一種單體(c)具有500Da或更低的、較佳地從10至500Da的數量分子量。
較佳地,所述至少一種單體(c)是選自下
組,該組包括以下各項、較佳地由以下各項組成:4,4’-亞甲基-二亞苯基-二-異氰酸酯(MDI)、1,6-己烷-二異氰酸酯(HDI)、2,4-甲苯-二異氰酸酯、2,6-甲苯-二異氰酸酯、二甲苯-二異氰酸酯、萘-二異氰酸酯、對亞苯基-二異氰酸酯、六亞甲基(hexamaethylen)-二異氰酸酯、異佛爾酮-二異氰酸酯、4,4’-二環己基-甲烷-二異氰酸酯和環己基-1,4-二異氰酸酯。
4,4’-亞甲基-二亞苯基-二-異氰酸酯(MDI)、1,6-己烷-二異氰酸酯(HDI)和六亞甲基-二異氰酸酯是特佳的。
較佳地,所述至少一種單體(d)是選自下組,該組包含以下各項、較佳地由以下各項組成:乙二醇、1,4-丁二醇(BDO)、1,6-己烷二醇(HDO)、N,N-二乙醇胺和N,N-二異丙醇苯胺。
BDO和HDO是特佳的。
在較佳的實施例中,衍生自單體(c)和(d)的嵌段的和是基於該F-TPU聚合物的總重量從10至60wt.%。
本領域技術人員將容易地理解包含衍生自單體(a)和(b)的重複單元的嵌段是類橡膠嵌段,而包含衍生自單體(c)和(d)的重複單元的嵌段是硬嵌段。
在較佳的實施例中,至少80%之包含衍生自所述單體(b)的重複單元的嵌段[嵌段B]的至少一個末端透過包含衍生自單體(c)的重複單元的嵌段[嵌段C]而連
接到包含衍生自單體(a)的重複單元的嵌段[嵌段A]。換言之,嵌段B的至少80%包含於以下類型:-[A-C-B-C]-的序列中。
有利地,該F-TPU聚合物可以按照在US 5,332,798(蒙特公司(AUSIMONT S.P.A.))中、特別是在實例15中披露的程序製備。
根據較佳的實施例,該錶帶是由不含塑化劑的組合物(C)製成的。
較佳地,所述組合物(C)包含如以上定義的F-TPU聚合物作為該主要組分。
更佳地,所述F-TPU聚合物是以基於所述組合物(C)的總重量的至少60wt.%、更佳至少80wt.%、甚至更佳至少85wt.%的量。
除了該F-TPU聚合物之外,所述組合物(C)可以任選地包含另外的添加劑,例如像抗氧化劑、熱穩定劑、染料和填充劑。
其中所述組合物(C)基本上是由所述F-TPU聚合物與最高達1wt.%量的以上列出的添加劑的任何一種結合製成的實施例也被本發明包括。
根據本發明的錶帶是充分可伸縮的並且有彈性的使得甚至當被拉伸時(例如在使用者的身體的手腕或其他部分上),它朝向其原始形狀返回並且通過張力保持在手腕上適當的位置,而不要求扣子、帶扣或其他專用的附接裝置。
最通常地,根據本發明的錶帶製造為使得它可以在使用者的手腕的周圍佩戴,但是它還可以適合於佩戴在使用者的身體的其他部分周圍,如頸部、手指或頭部。
根據本發明的錶帶可以按照本領域已知的方法製成。
作為實例,該錶帶可以是通過包括以下步驟的方法製造的:(i)提供模具;(ii)向所述模具填充包含至少一種彈性體氟化聚氨酯[F-TPU聚合物]的如以上定義的組合物;(iii)密封該模具;(iv)熱處理該密封的模具;並且(v)從該模具中取出該錶帶。
較佳地,所述模具是呈帶的形狀。取決於有待生產的帶的所希望的尺寸、形狀和形式,可以使用任何適合的尺寸、形狀和形式的模具。
較佳地,步驟(iv)包括兩個步驟,其中該第一步驟包括在第一溫度下加熱持續從10秒至10分鐘的時間並且該第二步驟包括在第二步驟下加熱持續從30秒至24小時的時間,所述第二溫度低於所述第一溫度。
更佳地,所述第一溫度是從120℃至300℃。
更佳地,所述第二溫度是從50℃至200℃。
可替代地,步驟(iv)包括在從50℃至300
℃的溫度下加熱持續從10秒至24小時的時間的僅僅一個步驟。
較佳地,在步驟(iv)之後並且在步驟(v)之前,允許冷卻該模具。
如果通過引用結合在此的任何專利、專利申請、和公開物的披露內容與本申請的說明相衝突的程度到了可能使術語不清楚,則本說明應該優先。
本發明將在下文中借助於包含於以下實驗部分中的實例更詳細地進行說明;這些實例僅是說明性的並且絕非解釋為限制本發明的範圍。
材料
- 單體(a):
(a1)具有約2,000的分子量(Mw)的聚己內脂二醇(PLC)
(a2)具有約2,000的Mw的聚四亞甲基二醇(PTMEG)
(a3)具有約2,000的Mw的聚碳酸酯-二醇(PCD)
(a4)具有約2,000的Mw的聚酯-二醇
- 具有以下式的單體(b):
H(OCH2CH2)pOCH2CF2O(CF2CF2O)m(CF2O)nCF2CH2O(CH2CH2O)pH
(b1)p=4.7並且約2,000的Mw
(b2)p=1.6並且約1,700的Mw
- 單體(c):
(c1)二亞苯基-4,4’-二異氰酸酯(MDI)
(c2)1,6-己烷-二異氰酸酯
- 單體(d):
(d1)1,4-丁二醇(BDO)
(d2)1,6-己二醇(HDO)
- 催化劑
新癸酸鉍
製備F-TPU聚合物樣品-方法A
從上述單體開始按照在以上列出的US 5,332,798(授予蒙特公司)的實例15中詳述的相同的程序製備處於片形式的F-TPU聚合物樣品。
因此獲得的F-TPU聚合物包含20wt.%的衍生自單體(b)的重複單元。
製備F-TPU聚合物樣品-方法B
如下製備處於片形式的F-TPU聚合物樣品5至7和8(後者作為比較):- 在90℃溫度下通過反應以當量比2比1的單體(c)和單體(a)合成該氫化的預聚物;- 在90℃溫度下通過反應以當量比2比1的單體(c)和單體(b)合成該氟化的預聚物;- 然後將該氫化的預聚物和該氟化的預聚物混合在一起並且在90℃下攪拌持續30分鐘;- 根據所選擇的化學計量進一步添加單體(c);
- 在90℃下繼續該反應持續3分鐘直到完成鏈延長;- 在100℃下流延該因此獲得的聚合物持續24小時。
在以下表1中報導了按照以上描述的方法A和B獲得的F-TPU聚合物的組成以及對比氫化的聚氨酯聚合物(H-TPU)的組成。
作為進一步比較,使用可商購的氫化的TPU(H-TPU 9*)。用於H-TPU 9*的單體比率不是公開可獲得的。
(*)比較
n/a=不可獲得的值
評估了由F-TPU和H-TPU聚合物製成的片的機械特性並且結果報導於表2中。
(*)比較
以上結果示出了根據本發明的F-TPU聚合物具有與在鞋類物品的上部的生產中典型地使用的H-TPU聚合物的機械特性可比較的機械特性,並且因此F-TPU聚合物為該完成的上部提供良好的機械特性。
在下文中描述的實例中使用這些片。
實例1-接觸角
這個試驗被認為是預測用於耐污性和耐化學性兩者。
用DSA30儀器(Krüss GmbH,德國)測量水和正十六烷(作為溶劑)的座滴(約5μL)的靜態接觸角(SCA)。在十個接觸角之中計算SCA值以及標準差。
按照Owens,Wendt,Rabel和Kaelble方法
(WORK方法)計算表面自由能,該方法是用於從具有若干液體的接觸角計算固體的表面自由能的標準方法。
結果匯總在下表3中。
(*)比較
SCA=靜態接觸角
H2O=水
C16=十六烷
SFE=表面自由能
以上結果示出了用水(H2O)和十六烷(C16)兩者測量的接觸角增加,然而與用作參比化合物使用的氫化的熱塑性聚氨酯的31mN/m相比表面能下降直到從15至16mN/m的範圍。這些資料與就與H-TPU相比由這些F-TPU授予的耐污性和耐化學性而言的增加一致。
實例2-藍色牛仔布試驗
這個試驗被認為是預測用於耐污性和耐磨性兩者。
該試驗用儀器Taber Industries 5750 Linear Abraser進行,該儀器被設置為在以下條件下運行:
- 迴圈速度:30週期/min
- 行程長度:2.54cm(1英寸)
- 週期數目:200
- 總負荷:1kg。
在F-TPU 1、F-TPU 2、F-TPU 3、F-TPU 5和F-TPU 7上一次用乾牛仔布並且一次用濕牛仔布進行試驗。
在用濕牛仔布進行該試驗之前,將牛仔布浸沒在水中持續10秒,然後將其移出並且用手擠壓水使得牛仔布不滴下水但是觸摸是濕的。
如下進行這些試驗:將約30mm×30mm測量的牛仔布樣品固定到固定裝置上以便阻止在試驗過程中該樣品的移位。然後將每個F-TPU和H-TPU的樣品放置於該牛仔布樣品上並且同樣固定到該固定裝置上。
如下設置檢驗點:- 在摩擦之後,以及- 在用異丙醇(IPA)清洗之後。
用於該乾試驗的結果:對於F-TPU 1、F-TPU 2、F-TPU 3、F-TPU 5和F-TPU 7沒有觀察到污點。
用於該濕試驗的結果:對於F-TPU 1、F-TPU 2、F-TPU 3、F-TPU 5和F-TPU 7觀察到非常輕微的暈圈。
實例3:污點試驗
將以上列出的每種染色劑的滴放置於與由F-TPU 1製成的樣品的表面接觸並且使在周圍條件下持續24小時。然後用水清洗該樣品。
由H-TPU製成的樣品用作比較並且如以上披露的處理。
結果匯總在下表4中,其中++ =沒有污點
+ =標記/暈圈
- =污點
(*)比較
以上結果清楚地示出了與該H-TPU樣品相比就該F-TPU樣品的耐污性和耐化學性兩者的增加。
實例4-觸覺特性的評價
通過主觀地由5個個體的手感測試這些材料的片測量F-TPU和H-TPU的觸覺特性(值得注意地柔軟的手感)。
柔軟的手感是主觀地由手觸摸測量的並且被以從1至5的標度評級,其中1是差的柔軟手感(硬的手感)並且5是優異的柔軟手感。參與者單獨地參加了這項研究,這樣他們不在其反應中相互影響。以隨機順序向參與者呈遞四種樣品並且要求他們感覺並且對它們評級。
結果匯總在下表5中。
(*)比較
以上結果清楚地示出了,當與由H-TPU聚合物獲得的片相比時,用根據本發明的F-TPU獲得的這些片示出了更好的觸覺特性、值得注意地改進的柔軟手感。
Claims (15)
- 一種由組合物[組合物(C)]製成的錶帶,該組合物包含至少一種氟化聚氨酯[F-TPU聚合物],所述F-TPU聚合物包含衍生自以下的重複單元:(a)至少一種選自下組的二醇,該組包括聚醚類型二醇、聚酯類型二醇、聚丁二烯-二醇和聚碳酸酯-二醇;(b)至少一種羥基封端的(全)氟聚醚聚合物[PFPE聚合物];(c)至少一種芳香族的、脂肪族的或脂環族的二異氰酸酯;以及(d)至少一種具有1至14個碳原子的脂肪族的、脂環族的或芳香族的二醇。
- 根據請求項1所述的錶帶,其中所述至少一種單體(a)選自下組,該組包括聚乙二醇、聚丙二醇、聚(四亞甲基)二醇(PTMG)、聚(1,4-丁二醇)己二酸酯、聚(乙二醇-1,4-丁二醇)己二酸酯、聚(1,6-己二醇-新戊基)二醇己二酸酯、聚-己內酯-二醇(PCL)和聚碳酸酯-二醇。
- 根據請求項1或2所述的錶帶,其中所述至少一種單體(b)是包括具有兩個鏈末端的(全)氟聚氧亞烷基鏈[鏈(Rpf)]的羥基封端的(全)氟聚醚聚合物[PFPE聚合物],其中一個或兩個鏈末端以至少一個-OH基團封端。
- 根據請求項3所述的錶帶,其中所述鏈(Rpf)的至少一個鏈末端以具有以下式的基團封端: -CH2(OCH2CH2)t-OH (I)其中t是0或1至5。
- 根據請求項4所述的錶帶,其中所述鏈(Rpf)的兩個鏈末端以具有以下式的基團封端:-CH2(OCH2CH2)t-OH (I)其中t是0或1至5。
- 根據請求項3所述的錶帶,其中所述鏈(Rpf)是具有以下式的鏈-(CFX)hO(Rf)(CFX')i-其中h和i,彼此相同或不同,等於或高於1;X和X’,彼此相同或不同,是-F或-CF3,其條件是當h和/或i高於1時,X和X’是-F;(Rf)包含重複單元Ro、較佳地由重複單元Ro組成,所述重複單元係獨立地選自由以下所組成之群組:(i)-CFXO-,其中X是F或CF3;(ii)-CFXCFXO-,其中X在每次出現時相同或不同,是F或CF3,其條件是X中的至少一個是-F;(iii)-CF2CF2CW2O-,其中每個W彼此相同或不同,是F、Cl、H;(iv)-CF2CF2CF2CF2O-;(v)-(CF2)j-CFZ-O-,其中j是0至3的整數並且Z是 具有通式-O-R(f-a)-T的基團,其中R(f-a)是包含0至10個的多個重複單元的氟聚氧化烯基鏈,所述重複單元是選自以下:-CFXO-、-CF2CFXO-、-CF2CF2CF2O-、-CF2CF2CF2CF2O-,其中每個X獨立地是F或CF3並且T是C1-C3全氟烷基基團。
- 根據請求項6所述的錶帶,其中所述鏈(Rf)選自以下式(Rf-a)至(Rf-c):(Rf-a) -(CF2O)n(CF2CF2O)m(CF2CF2CF2O)p(CF2CF2CF2CF2O)q-其中m、n、p、q是0或者以使得鏈Rf滿足以上數量平均分子量要求的方式選擇的整數,其條件是如果p和q同時是0,則n不是0;當m非0時,該m/n比較佳地是在0.1與20之間;當(m+n)非0時,(p+q)/(m+n)較佳地是在0與0.2之間;(Rf-b) -(CF2CF(CF3)O)a(CF2CF2O)b(CF2O)c(CF(CF3)O)d-其中a、b、c、d是0或者以使得鏈Rf滿足以上數量平均分子量要求的方式選擇的整數;其條件是,a、c和d中的至少一個不是0;當b非0時,a/b較佳地是在0.1與10之間;當(a+b)不同於0時,(c+d)/(a+b)較佳地是在0.01與0.5之間、更佳在0.01與0.2之間;(Rf-c) -(CF2CF(CF3)O)e(CF2O)f(CF(CF3)O)g-其中e、f、g是0或者以使得鏈Rf滿足以上數量平均分子量要求的方式選擇的整數;當e非0時,(f+g)/e較佳地是在0.01與0.5之間、更佳在0.01與0.2之間。
- 根據請求項1所述的錶帶,其中所述PFPE聚合物 符合以下式(PFPE-I):HO-(CH2CH2O)t-CH2-(Rpf)-CH2(OCH2CH2)u-OH (PFPE-I)其中t和u,各自獨立地是0或1至5,並且Rpf是如請求項6中所定義的。
- 根據請求項1所述的錶帶,其中所述至少一種單體(c)是選自下組,該組包括4,4’-亞甲基-二亞苯基-二-異氰酸酯(MDI)、2,4-甲苯-二異氰酸酯、2,6-甲苯-二異氰酸酯、二甲苯-二異氰酸酯、萘-二異氰酸酯、對亞苯基-二異氰酸酯、六亞甲基-二異氰酸酯、異佛爾酮-二異氰酸酯、4,4’-二環己基-甲烷-二異氰酸酯和環己基-1,4-二異氰酸酯。
- 根據請求項1所述的錶帶,其中所述至少一種單體(d)是選自下組,該組包括乙二醇、1,4-丁二醇(BDO)、1,6-己烷二醇、N,N-二乙醇胺和N,N-二異丙醇苯胺。
- 根據請求項1所述的錶帶,其中至少80%之包含衍生自所述單體(b)的重複單元的嵌段[嵌段B]的至少一個末端透過包含衍生自單體(c)的重複單元的嵌段[嵌段C]而連接到包含衍生自單體(a)的重複單元的嵌段[嵌段A]。
- 根據請求項1所述的錶帶,其中所述組合物(C)不含塑化劑。
- 根據請求項1所述的錶帶,其中所述組合物 (C)包含所述F-TPU聚合物作為主要組分。
- 根據請求項13所述的錶帶,其中所述F-TPU聚合物的量是基於所述組合物(C)的總重量的至少60wt.%。
- 一種用於製造錶帶的方法,所述方法包括以下步驟:(i)提供模具;(ii)向所述模具填充根據請求項1至14中任一項所述的包含至少一種彈性體氟化聚氨酯[F-TPU聚合物]的組合物;(iii)密封該模具;(iv)熱處理該密封的模具;並且(v)從該模具中取出該錶帶。
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EP (1) | EP3344673A1 (zh) |
JP (1) | JP2018532446A (zh) |
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EP3620478A1 (en) | 2018-09-10 | 2020-03-11 | Covestro Deutschland AG | Use of thermoplastic polyurethanes for applications subject to significant everyday stress |
JP2021535269A (ja) * | 2018-09-06 | 2021-12-16 | コベストロ・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・アンド・コー・カーゲー | 著しい日常的応力に供する適用のための熱可塑性ポリウレタンの使用 |
EP3741247A1 (fr) * | 2019-05-23 | 2020-11-25 | The Swatch Group Research and Development Ltd | Pièce de bijouterie en matière élastomère naturelle |
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IT1252660B (it) * | 1991-12-23 | 1995-06-20 | Ausimont Spa | Poliuretani e poliuretani-uree fluorurati e processi per la loro preparazione |
JPH0925405A (ja) * | 1995-07-07 | 1997-01-28 | Nippon Polyurethane Ind Co Ltd | 熱可塑性ポリウレタン系複合樹脂の製造方法、及び該樹脂を用いた時計バンド |
CN1176966C (zh) * | 2001-02-28 | 2004-11-24 | 四川大学 | 含氟聚氨酯材料的制备方法 |
CN1535993A (zh) * | 2003-04-11 | 2004-10-13 | 中国科学院化学研究所 | 嵌段疏水/疏油聚醚型聚氨酯共聚物及其制备方法和用途 |
CH704268A2 (fr) * | 2010-12-23 | 2012-06-29 | Biwi Sa | Pièce de bijouterie et procédé de fabrication d'une telle pièce. |
CN103242505B (zh) * | 2013-05-09 | 2015-01-07 | 上海应用技术学院 | 一种热塑性含氟聚氨酯弹性体及其制备方法 |
CN103467692A (zh) * | 2013-09-23 | 2013-12-25 | 广州机械科学研究院有限公司 | 一种防水防油及耐热的热塑性聚氨酯弹性体及其制备方法 |
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- 2016-07-07 WO PCT/EP2016/066070 patent/WO2017036642A1/en active Application Filing
- 2016-07-07 CN CN201680051004.XA patent/CN108026229A/zh active Pending
- 2016-07-07 JP JP2018510367A patent/JP2018532446A/ja active Pending
- 2016-07-07 TW TW105121572A patent/TW201714549A/zh unknown
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