TWI798251B - 含熱塑性聚胺基甲酸酯薄膜層之複合積層體及製造複合積層體結構的方法 - Google Patents

含熱塑性聚胺基甲酸酯薄膜層之複合積層體及製造複合積層體結構的方法 Download PDF

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TWI798251B
TWI798251B TW107130077A TW107130077A TWI798251B TW I798251 B TWI798251 B TW I798251B TW 107130077 A TW107130077 A TW 107130077A TW 107130077 A TW107130077 A TW 107130077A TW I798251 B TWI798251 B TW I798251B
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thermoplastic polyurethane
layer
prepreg
film
microns
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TW107130077A
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TW201919863A (zh
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沙塔納瑞亞那 尼斯塔拉
約瑟夫Ｊ 小凡托席克
葛列格Ｓ 內斯特羅德
約瑟 西特拉諾三世
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美商盧伯利索先進材料有限公司
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Abstract

一種複合積層體結構，其包括一或多層預浸體及一在該一或多層預浸體的表面上之熱塑性聚胺基甲酸酯薄膜層。亦提供一種製造包括一熱塑性聚胺基甲酸酯薄膜的複合積層體結構之方法。

Description

含熱塑性聚胺基甲酸酯薄膜層之複合積層體及製造複合積層體結構的方法
本發明係關於一種含熱塑性聚胺基甲酸酯薄膜層之複合積層體及製得此等物件的方法。該等物件包含一或多層具有一熱塑性聚胺基甲酸酯薄膜黏合至表面的含纖維預浸體。本發明之結構及方法消除對該預浸體施加塗層來授予諸如顏色、抗UV性、抗磨性及其類似性質之性質的需求。
複合積層體結構係從預浸體的堆疊薄片製得。該等積層體結構典型會在外表面上塗佈一或多層塗層來提供某些性質，諸如對水、溶劑、或UV光、天氣、磨損及/或腐蝕的抗性。該等塗層亦可對該積層體提供與應用相依的裝飾。用於該複合積層體結構之塗層的製備及施用可係耗時且昂貴的製程。此外，在某些情況中，該等塗層缺乏耐久性而必需定期再施加或必需置換該積層體。
因此，對提供一耐用的複合積層體結構及一製得具有想要及有益性質之複合積層體結構的方法存在有需求。
本發明提供一種具有改良的表面性質之複合積層體及製得該複合積層體的方法。該複合積層體包含一或多層含纖維預浸體層及一熱塑性聚胺基甲酸酯薄膜層。該預浸體層包含一已經浸漬樹脂(熱塑性或熱固性)的纖維性基材。該預浸體層可包括單向纖維、編織纖維、或不織織物、或其組合。該熱塑性薄膜層係黏附在該預浸體層的外表面。在本發明中，除了該預浸體樹脂及該熱塑性聚胺基甲酸酯層外，不需要額外的黏著材料。
1‧‧‧含單向安排的纖維之預浸體層
2‧‧‧經噴沙的補土層
3‧‧‧底塗層
5,15‧‧‧TPU薄膜
10‧‧‧積層體結構
11‧‧‧表面
12‧‧‧具有編織纖維的預浸體
14‧‧‧具有單向纖維的預浸體
16‧‧‧UV塗層
18‧‧‧透明塗層
圖1闡明一種製得複合積層體結構的先前技術方法。
圖2闡明根據本發明的一個具體實例之製得複合積層體結構的方法。
圖3闡明一種製得複合積層體結構的第二先前技術方法。
圖4闡明根據本發明的另一個具體實例之製得複合積層體結構的方法。
本發明包含一種由一或多層含纖維預浸體層及一熱塑性聚胺基甲酸酯薄膜層所構成的複合積層體結構。下列更詳細描述出該複合積層體結構的每層及用以製造該複合積層體結構的方法。
含纖維預浸體
如於本文中所使用，用語「預浸體」指為浸漬樹脂的纖維薄片。該預浸體包括一可選自於單向纖維、從編織纖維製得的織物或不織織物之纖維性基材。該用於纖維(或構成該纖維之細絲)的材料可選自於由熟習該項技術者已知之任何材料，包括但不限於碳、石墨纖維、玻璃、礦物或甚至聚合物，諸如從下列製得之纖維：聚烯烴、聚乙烯、聚丙烯、聚芳醯胺、聚吲哚、聚胺基甲酸酯、聚乙烯醇、聚丙烯腈、液晶共聚酯、聚醯胺、聚酯或其組合。
為了形成預浸體薄片，可對各別由所選擇的材料的各別細絲或細絲束所形成之連續纖維進行線性定向來形成單向纖維薄片，或可編織該細絲或纖維而形成如由一般熟悉此技藝之人士已知的編織薄片。然後，以樹脂浸漬該纖維性薄片來形成該預浸體薄片。使用來形成該預浸體的樹脂可包括由熟習該項技術者知曉之任何樹脂，例如，環氧樹脂、酚樹脂、雙馬來醯亞胺、聚醯亞胺、氰酸酯、聚碳酸酯、聚酯、聚苯乙烯、聚醚、丙烯腈、丁二烯、丙烯酸酯、甲基丙烯酸酯、聚縮醛、聚碸、聚胺基甲酸酯、熱塑性聚胺基甲酸酯及其混合物。有用的樹脂可係熱固性或熱塑性或其組合。該以樹脂浸漬該纖維性薄片之方法係在技藝中熟知。在一個具體實例中，使用於該預浸體的樹脂包含環氧樹脂，例如，熱固性環氧樹脂。
在一個具體實例中，於本發明的複合積層體中所使用之預浸體包含碳纖維。在另一個具體實例中， 該複合積層體之預浸體層包括由碳纖維組成的纖維。在此具體實例中，可以環氧樹脂浸漬該碳纖維。在一個具體實例中，以熱固性環氧樹脂浸漬該碳纖維。
可從諸如Cytec and Zoltek(Toray)公司商業購得多種型式的預浸體，及如以LTM®預浸體、MTM®預浸體、HTM®預浸體、VTM®預浸體、CYCOM®預浸體、DForm® technology、BPS-Body Panel Systems預浸體及CYFORM®預浸體出售。
熱塑性聚胺基甲酸酯薄膜
本發明的複合積層體包括一熱塑性聚胺基甲酸酯薄膜層。熱塑性聚胺基甲酸酯(TPU)係藉由多異氰酸酯、多元醇中間體及選擇性，鏈伸長劑組分之反應獲得。 在此反應中，若需要時，使用觸媒。
可使用由熟習該項技術者已知的任何多異氰酸酯來製得在本發明中有用的TPU組成物。在某些具體實例中，該多異氰酸酯組分包括一或多種二異氰酸酯，其可選自於芳香族二異氰酸酯或脂肪族二異氰酸酯或其組合。有用的多異氰酸酯之實施例包括但不限於芳香族二異氰酸酯，諸如4,4’-亞甲基雙(苯基異氰酸酯)(MDI)、間-二甲苯二異氰酸酯(XDI)、伸苯基-1,4-二異氰酸酯、3,3’-二甲基-4,4’-伸聯苯二異氰酸酯(TODI)、1,5-伸萘二異氰酸酯(NDI)及甲苯二異氰酸酯(TDI)；和脂肪族二異氰酸酯，諸如異佛爾酮二異氰酸酯(IPDI)、1,6-六伸甲基二異氰酸酯(HDI)、1,4-環己基二異氰酸酯(CHDI)、癸烷-1,10-二異氰酸酯、離胺酸二異氰酸酯(LDI)、1,4-丁烷二 異氰酸酯(BDI)、五伸甲碁二異氰酸酯(PDI)及二環己基甲烷-4,4’-二異氰酸酯(H12MDI)。可使用二或更多種多異氰酸酯之混合物。
如將由熟習該項技術者察知，使用來製得在本發明中有用的TPU薄膜之異氰酸酯將依最後複合積層體結構想要的性質而定。
在本發明中有用的TPU組成物亦使用多元醇中間體組分製得。該多元醇中間體包括聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、聚矽氧烷多元醇及其組合。
合適的羥基終端聚酯中間體包括具有數量平均分子量(Mn)約300至約10,000，約400至約5,000，或約500至約4,000的線性聚酯。該分子量係藉由分析終端官能基而決定及係相關於數量平均分子量。該聚酯中間體可藉由下列製造：(1)一或多種二醇與一或多種二羧酸或酐之酯化反應；或(2)轉酯基反應，即，一或多種二醇與二羧酸的酯之反應。該二醇對酸的莫耳比率通常過量多於一莫耳係較佳，以便獲得具有終端羥基優勢之線性鏈。合適的聚酯中間體亦包括多種內酯，諸如典型從ε-己內酯與雙官能基起始劑諸如二甘醇製得的聚己內酯。想要的聚酯之二羧酸可係脂肪族、環脂族、芳香族或其組合。可單獨或以混合物使用之合適的二羧酸通常具有總共4至15個碳原子，及包括：琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸、異酞酸、對酞酸、環己烷二羧酸及其類似物。亦可使用上述二羧酸的酐，諸如酞酸酐、四氫酞酸酐或其類 似物。己二酸係較佳的酸。該將進行反應以形成想要的聚酯中間體之二醇可係脂肪族、芳香族或其組合，包括上述在鏈伸長劑章節中所描述且具有總共2至20或2至12個碳原子的任何二醇。合適的實施例包括乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2,2-二甲基-1,3-丙二醇、1,4-環己烷二甲醇、十伸甲基二醇、十二伸甲基二醇及其混合物。
在某些具體實例中，可使用脂肪酸二聚物來製備聚酯多元醇，其中該聚酯多元醇可使用來製造在本發明中有用的TPU組成物。可使用來製備聚酯多元醇的脂肪酸二聚物之實施例包括可從Croda商業購得的PriplastTM聚酯二醇/多元醇，及可從Oleon商業購得的Radia®聚酯二醇。
該多元醇組分亦可包含一或多種聚己內酯聚酯多元醇。在本文描述的技術中有用之聚己內酯聚酯多元醇包括衍生自己內酯單體的聚酯雙醇。該聚己內酯聚酯多元醇係由一級羥基終端化。合適的聚己內酯聚酯多元醇可從ε-己內酯與雙官能基起始劑製得，諸如二甘醇、1,4-丁二醇或於本文中列出的任何其它二醇及/或雙醇。在某些具體實例中，該聚己內酯聚酯多元醇係衍生自己內酯單體的線性聚酯雙醇。
有用的實施例包括CAPATM 2202A，一種數量平均分子量(Mn)2,000的線性聚酯二醇；及CAPATM2302A，一種Mn 3,000的線性聚酯二醇，此二者可從Perstorp Polyols Inc.商業購得。這些材料亦可描述為2- 氧雜環庚酮(2-oxepanone)與1,4-丁二醇之聚合物。
該聚己內酯聚酯多元醇可從2-氧雜環庚酮與二醇製備，其中該二醇可係1,4-丁二醇、二甘醇、單乙二醇、1,6-己二醇、2,2-二甲基-1,3-丙二醇或其任何組合。在某些具體實例中，該使用來製備聚己內酯聚酯多元醇的二醇係線性。在某些具體實例中，該聚己內酯聚酯多元醇係從1,4-丁二醇製備。在某些具體實例中，該聚己內酯聚酯多元醇具有數量平均分子量300至10,000，或400至5,000，或400至4,000，或甚至1,000至4,000。
在製造本發明的TPU組成物時有用之羥基終端的聚醚中間體包括衍生自具有總共2至15個碳原子之二醇或多元醇的聚醚多元醇，在某些具體實例中，該二醇係烷基二醇或雙醇，其係與包含具有2至6個碳原子的環氧烷烴，典型為環氧乙烷或環氧丙烷或其混合物之醚進行反應。例如，該羥基官能性聚醚可藉由首先讓丙二醇與環氧丙烷反應，接著為隨後與環氧乙烷反應來製造。產生自環氧乙烷的一級羥基比二級羥基更具反應性，因此較佳。可商業購得的聚醚多元醇包括包含環氧乙烷與乙二醇反應之聚(乙二醇)、包含環氧丙烷與丙二醇反應之聚(丙二醇)、包含水與四氫呋喃反應的聚(四伸甲基醚二醇)，其亦可描述為聚合的四氫呋喃且其通常指為PTMEG。合適的聚醚多元醇亦包括環氧烷烴之聚醯胺加成物，及可包括例如包含乙二胺與環氧丙烷之反應產物的乙二胺加成物、包含二伸乙基三胺與環氧丙烷之反 應產物的二伸乙基三胺加成物及類似的聚醯胺型式聚醚多元醇。亦可在所描述的組成物中使用共聚醚。典型的共聚醚包括THF與環氧乙烷或THF與環氧丙烷之反應產物。這些可從BASF獲得如為PolyTHF® B，一種嵌段共聚物；及PolyTHF® R，一種無規共聚物。該多種聚醚中間體通常具有數量平均分子量(Mn)大於約500，諸如約500至約10,000，約500至約5,000，或約700至約3000，如藉由分析終端官能基而決定，其係一種平均分子量。在某些具體實例中，該聚醚中間體包括二或更多種不同分子量的聚醚之摻合物，諸如2,000Mn與1,000MnPTMEG之摻合物。
在製備本發明的TPU組成物時有用之羥基終端的聚碳酸酯包括藉由二醇與碳酸酯反應所製備的那些。美國專利案號4,131,731藉此以參考方式併入本文，其揭示出羥基終端的聚碳酸酯及其製備。此等聚碳酸酯係線性及具有終端羥基且基本上排除其它終端基團。基本反應物係二醇及碳酸酯。合適的二醇係選自於包括4至40及/或甚至4至12個碳原子之環脂族及脂肪族雙醇，及每分子包括2至20個烷氧基且每個烷氧基包括2至4個碳原子之聚氧基伸烷基二醇。合適的雙醇包括含4至12個碳原子的脂肪族雙醇，諸如1,4-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、2,2,4-三甲基-1,6-己二醇、1,10-癸二醇、氫化的二亞麻油基二醇、氫化的二油基二醇、3-甲基-1,5-戊二醇；及環脂族雙醇，諸如1,3-環已烷二醇、1,4-二羥甲基環己烷二醇、1,4-環已烷二 醇、1,3-二羥甲基環己烷二醇、1,4-內亞甲基-2-羥基-5-羥甲基環己烷二醇，及聚伸烷基二醇。在該反應中所使用之雙醇可依在成品中想要的性質而係單一雙醇或雙醇的混合物。該羥基終端的聚碳酸酯中間體通常係技藝已知及在文獻中的那些。合適的碳酸酯係選自於由5至7員環構成之碳酸伸烷酯(alkylene carbonates)。合適於本文使用的碳酸酯包括碳酸伸乙酯、碳酸三伸甲酯、碳酸四伸甲酯、碳酸1,2-伸丙酯、碳酸1,2-伸丁酯、碳酸2,3-伸丁酯、碳酸1,2-伸乙酯、碳酸1,3-伸戊酯、碳酸1,4-伸戊酯、碳酸2,3-伸戊酯及碳酸2,4-伸戊酯。同樣地，於本文中合適的有碳酸二烷酯、環脂族碳酸酯及碳酸二芳酯。該碳酸二烷酯可在每個烷基中包括2至5個碳原子，及其特定實施例有碳酸二乙酯及碳酸二丙酯。該環脂族碳酸酯，特別是二環脂族碳酸酯可在每個環狀結構中包括4至7個碳原子，及可有一或二個此等結構。當一個基團係環脂族時，其它可係烷基或芳基。另一方面，若一個基團係芳基時，其它可係烷基或環脂族。合適的碳酸二芳酯之實施例可在每個芳基中包括6至20個碳原子，其有碳酸二苯酯、碳酸二甲苯酯及碳酸二萘酯。
可使用在本發明的TPU組成物中之聚矽氧烷多元醇包括α-ω-羥基或胺或羧酸或硫醇或環氧基終端的聚矽氧烷。實施例包括以羥基或胺或羧酸或硫醇或環氧基終端化的聚(二甲基矽氧烷)。在某些具體實例中，該聚矽氧烷多元醇係羥基終端的聚矽氧烷。在某些具體實例中，該聚矽氧烷多元醇具有數量平均分子量在300至 5,000，或400至3,000之範圍內。
該聚矽氧烷多元醇可藉由在聚矽氧烷氫化物與脂肪族多羥基醇或聚氧基伸烷基醇間之脫氫反應獲得，以便將酒精性羥基引進到該聚矽氧烷骨架上。
在某些具體實例中，該聚矽氧烷可由一或多種具有下列式的化合物表示：
Figure 107130077-A0202-12-0010-1
其中R1及R2各者各自獨立地係1至4個碳原子烷基、苄基或苯基；每個E係OH或NHR3，其中R3係氫、1至6個碳原子烷基或5至8個碳原子環烷基；a及b各者各自獨立地係2至8的整數；c係3至50的整數。在含胺基聚矽氧烷中，至少一個E基團係NHR3。在含羥基聚矽氧烷中，至少一個E基團係OH。在某些具體實例中，R1及R2二者係甲基。
合適的實施例包括α,ω-羥丙基終端的聚(二甲基矽氧烷)及α,ω-胺基丙基終端的聚(二甲基矽氧烷)，此二者係可商業購得的材料。進一步實施例包括聚(二甲基矽氧烷)材料與聚(環氧烷)的共聚物。
在某些具體實例中，該多元醇中間體亦可包含遙爪聚醯胺多元醇。合適的聚醯胺寡聚物包括遙爪聚醯胺多元醇，其未過度限制及包括低分子量聚醯胺寡聚物及在骨架結構中包括N-烷基化的醯胺基團之遙爪聚醯胺(包括共聚物)。該遙爪聚合物係一包括二個反應性末 端基團的巨分子。該胺終端的聚醯胺寡聚物可有用作為在所揭示的技術中之多元醇。用語「聚醯胺寡聚物」指為具有二或更多個醯胺鏈結的寡聚物，或有時將具體指定該醯胺鏈結的量。該聚醯胺寡聚物的子集係遙爪聚醯胺。該遙爪聚醯胺係具有高百分比或具體指定百分比之二個單一化學型式的官能基之聚醯胺寡聚物，例如，二個終端胺基團(意謂著一級、二級或混合物)、二個終端羧基、二個終端羥基(再次意謂著一級、二級或混合物)或二個終端異氰酸酯基團(意謂著脂肪族、芳香族或混合物)。可符合遙爪定義的二官能基百分比範圍包括該寡聚物之至少70、80、90或95莫耳%係二官能基，如與較高或較低官能性相反。該反應性胺終端的遙爪聚醯胺有該終端基團二者皆胺型式之遙爪聚醯胺寡聚物，其中該終端基團係一級或二級及其混合物，即，排除三級胺基團。
在一個具體實例中，該遙爪寡聚物或遙爪聚醯胺將具有黏度少於100,000cps，其係於溫度70℃下藉由Brookfield圓盤黏度計與在5rpm下旋轉的圓盤測量；在70℃下少於15,000或10,000cps；在60或50℃下少於100,000cps；在60℃下少於15,000或10,000cps；或在50℃下少於15,000或10,000cps。這些黏度係沒有溶劑或塑化劑的純淨遙爪預聚物或聚醯胺寡聚物之黏度。在某些具體實例中，該遙爪聚醯胺可以溶劑稀釋來達成在這些範圍內的黏度。
在某些具體實例中，該聚醯胺寡聚物係分子 量低於20,000克/莫耳的物種，例如，經常低於10,000、5,000、2,500或2,000克/莫耳，其中每寡聚物具有二或更多個醯胺鏈結。該遙爪聚醯胺所具有的分子量較佳為與該聚醯胺寡聚物相同。多重聚醯胺寡聚物或遙爪聚醯胺可與縮合反應連結而形成通常大於100,000克/莫耳的聚合物。
通常來說，該醯胺鏈結係從羧酸基團與胺基團之反應或內醯胺的開環聚合所形成，例如，於環結構中的醯胺鏈結係轉換成在聚合物中之醯胺鏈結。在一個具體實例中，該單體的胺基團大部分係二級胺基團或該內醯胺的氮係三級醯胺基團。當胺基團與羧酸反應而形成醯胺時，二級胺基團會形成三級醯胺基團。為了本揭示的目的，例如，如在內醯胺中之醯胺的羰基將視為衍生自羧酸基團。該內醯胺的醯胺鏈結係從胺基羧酸的羧酸基團與相同胺基羧酸的胺基團之反應形成。在一個具體實例中，我們想要於製得該聚醯胺時使用少於20、10或5莫耳百分比的單體，以便在醯胺鏈結之聚合時具有官能性3或更多。
若使用來形成這些鏈結之額外單體係對該聚合物的意欲用途有用時，本揭示之聚醯胺寡聚物及遙爪聚醯胺可包括小量酯鏈結、醚鏈結、胺基甲酸酯鏈結、尿素鏈結等等。
如較早指示出，許多醯胺形成單體會產生每重覆單元平均一個醯胺鏈結。這些包括當彼此反應時的二酸與二胺、胺基羧酸及內醯胺。這些單體當以相同基 團與其它單體反應時，亦在所形成的重覆單元之二端處產生醯胺鏈結。因此，我們將使用醯胺鏈結的百分比及來自醯胺形成單體的重覆單元之莫耳百分比與重量百分比二者。將會使用醯胺形成單體來指出在正常醯胺形成縮合連結反應中將形成每重覆單元平均一個醯胺鏈結之單體。
在一個具體實例中，該連接烴型式鏈結之含雜原子鏈結總數的至少10莫耳百分比，或至少25、45或50，及或甚至至少60、70、80、90或95莫耳%具有醯胺鏈結的特徵。該雜原子鏈結有諸如醯胺、酯、胺基甲酸酯、尿素、醚鏈結之鏈結，其中該雜原子連接寡聚物或聚合物之二個通常具有烴特徵(或具有碳對碳鍵結，諸如烴鏈結)的部分。當在該聚醯胺中的醯胺鏈結量增加時，於該聚醯胺中之來自醯胺形成單體的重覆單元量增加。在一個具體實例中，該聚醯胺寡聚物或遙爪聚醯胺有至少25重量%，或至少30、40、50，或甚至至少60、70、80、90或95重量%係來自醯胺形成單體的重覆單元，其中該單體亦鑑別為在該重覆單元的二端處形成醯胺鏈結之單體。此等單體包括內醯胺、胺基羧酸、二羧酸及二胺。在一個具體實例中，於該聚醯胺寡聚物或遙爪聚胺中之醯胺鏈結的至少50、65、75、76、80、90或95莫耳百分比係三級醯胺鏈結。
以下列方程式來計算總醯胺鏈結數之三級醯胺鏈結的百分比：
Figure 107130077-A0202-12-0014-2
其中n係單體數目；索引i指為某一單體；wtertN係於單體中在聚合時形成或係三級醯胺鏈結部分的平均氮原子數(注意：形成末端基團的胺在聚合期間不形成醯胺基團，及其量係從wtertN排除)；wtotalN係在單體中於聚合時形成或係三級醯胺鏈結部分的平均氮原子數(注意：形成末端基團的胺在聚合期間不形成醯胺基團，及其量係從wtotalN排除)；及ni係具有索引i的單體之莫耳數。
藉由下列方程式來計算全部含雜原子鏈結(其連接烴鏈結)總數的醯胺鏈結之百分比：
Figure 107130077-A0202-12-0014-3
其中wtotalS係在單體中的平均含雜原子鏈結(連接烴鏈結)數目與在聚醯胺聚合期間從該單體與承載羧酸的單體反應所形成之含雜原子鏈結(其連接烴鏈結)數目的總和；及全部其它變量係如上述所定義。如於本文中所使用，用語「烴鏈結」僅係每個重覆單元的烴部分，其係在重覆單元中從連續碳碳鍵(即，沒有諸如氮或氧的雜原子)形成。此烴部分將係環氧乙烷或環氧丙烷的伸乙基或伸丙基部分、十二烷基內醯胺的十一烷基、乙二胺的伸乙基及己二酸的(CH2)4(或伸丁基)。
在某些具體實例中，該醯胺或三級醯胺形成單體包括二羧酸、二胺、胺基羧酸及內醯胺。合適的二 羧酸有該二羧酸之伸烷基部分係2至36個碳原子的環狀、線性或分枝(選擇性包括芳香族基團)伸烷基，選擇性該二酸的每3或10個碳原子包括最高1個雜原子，更佳為4至36個碳原子(該二酸將比該伸烷基部分多包括2個碳原子)。這些包括脂肪酸二聚物、氫化的二聚物酸、癸二酸等等。
合適的二胺包括含有最高60個碳原子的那些，該二胺選擇性每3或10個碳原子包括一個雜原子(除了該二個氮原子外)，及選擇性包括多種環狀、芳香族或雜環基團，其前提為該胺基團之一或二者係二級胺。
此等二胺包括來自Albermarle的EthacureTM 90(根據推測為N,N’-雙(1,2,2-三甲基丙基)-1,6-己二胺)；來自Dorf Ketal的ClearlinkTM 1000，或來自Huntsman的JefflinkTM 754；N-甲基胺基乙醇；二羥基終端、羥基及胺終端或二胺終端的聚(環氧烷烴)，其中該伸烷基具有2至4個碳原子及具有分子量約40或100至2,000；N,N’-二異丙基-1,6-己二胺、N,N’-二(二級丁基)苯二胺、哌
Figure 107130077-A0202-12-0015-10
、高哌
Figure 107130077-A0202-12-0015-11
及甲基-哌
Figure 107130077-A0202-12-0015-12
。
合適的內醯胺包括在其中有4至12個碳原子之直鏈或分枝伸烷基片段，如此在該內醯胺的氮上沒有取代基之環結構具有總共5至13個碳原子(當其包括羰基時)，及在該內醯胺的氮上之取代基(若該內醯胺係三級醯胺時)係1至8個碳原子的烷基及更想要為1至4個碳原子的烷基。十二烷基內醯胺、經烷基取代的十二烷基內醯胺、己內醯胺、經烷基取代的己內醯胺及具有較 大伸烷基的其它內醯胺係較佳的內醯胺，因為它們提供具有較低Tg值的重覆單元。該胺基羧酸具有與該內醯胺相同的碳原子數目。在某些具體實例中，於該胺基羧酸之胺與羧酸基團間的線性或分枝伸烷基之碳原子數係4至12，及在該胺基團的氮上之取代基(若其係二級胺基團時)係具有1至8個碳原子的烷基，或1或2至4個碳原子的烷基。
在一個具體實例中，想要該聚醯胺寡聚物或遙爪聚醯胺的至少50重量%，或至少60、70、80或90重量%包含來自二酸與二胺之重覆單元，其中該重覆單元的結構係：
Figure 107130077-A0202-12-0016-4
其中Ra係該二羧酸的伸烷基部分及係2至36個碳原子之環狀、線性或分枝(選擇性包括芳香族基團)伸烷基，該二酸每3或10個碳原子選擇性包括最高1個雜原子，更佳為4至36個碳原子(該二酸將比該伸烷基部分多包括2個碳原子)；及Rb係一直接鍵結或2至36或60個碳原子及更佳為2或4至12個碳原子的線性或分枝(選擇性係或包括環狀、雜環或芳香族部分)伸烷基(選擇性每10個碳原子包括最高1或3個雜原子)；及Rc與Rd各別係1至8個碳原子的線性或分枝烷基，更佳為1或2至4個碳原子，或Rc與Rd係連接在一起以形成1至8 個碳原子的單一線性或分枝伸烷基，或選擇性Rc與Rd之一係在碳原子處連接至Rb，更想要為Rc及Rd係1或2至4個碳原子的烷基。
在一個具體實例中，想要該聚醯胺寡聚物或遙爪聚醯胺的至少50重量%，或至少60、70、80或90重量%包含來自內醯胺或胺基羧酸而具有下列結構之重覆單元：
Figure 107130077-A0202-12-0017-5
該重覆單元可依起始劑型式而在衍生自內醯胺或胺基羧酸的寡聚物中有多種定向，其中每個Re各自獨立地係4至12個碳原子的線性或分枝伸烷基及每個Rf各自獨立地係1至8，更想要為1或2至4個碳原子的線性或分枝烷基。
在某些具體實例中，該遙爪聚醯胺多元醇包括具有下列的那些：(i)衍生自聚合單體的重覆單元，其中該等單體係藉由在該重覆單元與選自於羧基或一級或二級胺的末端官能基團間之鏈結連接，其中該遙爪聚醯胺的至少70莫耳百分比精確具有二個相同而選自於由胺基末端基團或羧基末端基團所組成之群的官能基型式之末端官能基團；(ii)聚醯胺片段，其包含至少二個特徵為衍生自胺與羧基的反應之醯胺鏈結，及該聚醯胺片段包含衍生自聚合二或更多種選自於內醯胺、胺基羧酸、 二羧酸及二胺的單體之重覆單元；(iii)其中連接烴型式鏈結的含雜原子鏈結總數之至少10百分比具有醯胺鏈結的特徵；及(iv)其中該醯胺鏈結之至少25百分比具有三級醯胺鏈結的特徵。
在本發明中有用的TPU組成物可選擇性使用鏈伸長劑組分製得。該鏈伸長劑包括雙醇、二胺及其組合。
合適的鏈伸長劑包括相對小的多羥基化合物，例如，具有2至20，或2至12，或2至10個碳原子之低級脂肪族或短鏈二醇。合適的實施例包括乙二醇、二甘醇、丙二醇、二丙二醇、1,4-丁二醇(BDO)、1,6-己二醇(HDO)、1,3-丁二醇、1,5-戊二醇、新戊二醇、十二烷二醇、1,4-環己二甲醇(CHDM)、2,2-雙[4-(2-羥基乙氧基)苯基]丙烷(HEPP)、六伸甲基二醇、庚二醇、壬二醇、十二烷二醇、3-甲基-1,5-戊二醇、乙二胺、丁烷二胺、己二胺、及羥乙基間苯二酚(HER)、及其類似物、和其混合物。在某些具體實例中，該鏈伸長劑包括BDO、HDO、3-甲基-1,5-戊二醇或其組合。在某些具體實例中，該鏈伸長劑包括BDO。可使用其它二醇，諸如芳香族二醇，但是在某些具體實例中，於本文中所描述的TPUs基本上無或甚至完全無此等材料。
為了製備在本發明中有用的TPU組成物，可一起反應三種反應物(多元醇中間體、二異氰酸酯及鏈伸長劑)。可使用任何已知讓三種反應物反應的方法來製得該TPU。在一個具體實例中，該方法係所謂的「單次 (one-shot)」方法，其將全部三種反應物加入擠壓器反應器並進行反應。該二異氰酸酯的當量量對該含羥基組分，也就是說，多元醇中間體與鏈伸長劑二醇的總當量量可係約0.95至約1.10，或約0.96至約1.02，甚至約0.97至約1.005。該胺基甲酸酯觸媒所使用的反應溫度可係約175至約245℃，及在另一個具體實例中，180至220℃。
在另一個具體實例中，該TPU亦可使用預聚物方法製備。在預聚物途徑中，該多元醇中間體通常與過量一當量的一或多種二異氰酸酯反應以形成一具有自由態或未反應的二異氰酸酯在其中之預聚物溶液。該反應通常於合適的胺基甲酸酯觸媒存在下，在溫度約80至約220℃，或約150至約200℃下進行。隨後，以通常等於異氰酸酯末端基團和任何自由態或未反應的二異氰酸酯化合物之當量量加入如上述提到的鏈伸長劑。因此，總二異氰酸酯的整體當量對多元醇中間體與鏈伸長劑的總當量之比率係約0.95至約1.10，或約0.96至約1.02及甚至約0.97至約1.05。該鏈延伸的反應溫度通常係約180至約250℃或約200至約240℃。典型來說，該預聚物途徑可在任何習知裝置中進行，包括擠壓器。在此具體實例中，該多元醇中間體係在該擠壓器之第一部分中與過量的二異氰酸酯反應以形成一預聚物溶液，隨後在下游部分處加入該鏈伸長劑及與該預聚物溶液反應。可使用任何習知的擠壓器，包括裝備有屏障型螺桿(barrier screw)且具有長度對直徑比率至少20及在某些具體實例 中至少25之擠壓器。
在一個具體實例中，於單或雙螺桿擠壓器中混合該等成份，其中該擠壓器在其進料端與其模具端間具有多重加熱區域及多重進料埠。可在一或多個進料埠處加入該等成份及可將從擠壓器的模具端引出之所產生的TPU組成物進行粒化。
根據習知程序及方法及因此如上述提及般來製備多種聚胺基甲酸酯，通常可使用任何型式的聚胺基甲酸酯，其多種特定組分的量、多種反應物比率、加工溫度、其觸媒量、聚合設備諸如多種型式的擠壓器及其類似者全部一般習知，及如由技藝及文獻充分知曉。
對本發明來說，於某些具體實例中，該TPU可以「單次」聚合方法讓該等組分一起反應而製得，其將包括反應物的全部組分一起同步或實質上同步地加入熱擠壓器並反應以形成該TPU。在其它具體實例中，該TPU可藉由首先讓該多異氰酸酯組分與某些部分之多元醇組分反應以形成一預聚物，然後讓該預聚物與剩餘反應物反應以完成反應以產生TPU而完成反應。
可在聚合反應期間存在有一或多種聚合觸媒。通常來說，可使用任何習知觸媒來讓該二異氰酸酯與該多元醇中間體或鏈伸長劑反應。特別能加速在該二異氰酸酯之NCO基團與該多元醇及鏈伸長劑之羥基間的反應之合適觸媒的實施例有先前技術已知的習知三級胺，例如，三乙基胺、二甲基環己基胺、N-甲基嗎福啉、N,N’-二甲基哌
Figure 107130077-A0202-12-0020-13
、2-(二甲基胺基乙氧基)乙醇、二吖雙 環[2.2.2]辛烷及其類似物，及亦特別有有機金屬化合物，諸如鈦酯；鐵化合物，例如，乙醯丙酮酸鐵；錫化合物，例如，二醋酸亞錫、二辛酸亞錫、二月桂酸亞錫、或脂肪族羧酸的二烷基錫鹽，例如，二醋酸二丁基錫、二月桂酸二丁錫及其類似物；或鉍化合物，諸如辛酸鉍、月桂酸鉍及其類似物。該觸媒的通常使用量係每100重量份之多羥基化合物(b)0.0001至0.1重量份。
在聚合反應期間，可存在有多種型式的選擇性組分及/或將其併入上述TPU彈性體中以改良加工及其它性質。這些添加劑包括但不限於抗氧化劑，諸如酚型式、有機亞磷酸鹽、膦及亞膦酸鹽、位阻胺、有機胺、有機硫化合物、內酯及羥胺化合物；滅菌劑、殺黴菌劑、抗微生物劑、相容劑、電耗散或抗靜電添加劑；充填劑及補強劑，諸如二氧化鈦、氧化鋁、黏土及碳黑；阻燃劑，諸如磷酸鹽、經鹵化的材料及苯磺酸烷酯的金屬鹽；衝擊改質劑，諸如甲基丙烯酸酯-丁二烯-苯乙烯(「MBS」)及甲基丙烯酸甲酯丙烯酸丁酯(「MBA」)；脫模劑，諸如蠟、脂肪及油；顏料及著色劑、塑化劑、聚合物；流變改質劑，諸如單胺、聚醯胺蠟、聚矽氧及聚矽氧烷；滑動添加劑(slip additives)，諸如石蠟、烴聚烯烴及/或氟化的聚烯烴；及UV安定劑，其可係位阻胺光安定劑(HALS)及/或UV光吸收劑(UVA)型式。可使用其它添加劑來提高該TPU組成物或摻合產物之性能。上述全部添加劑可以這些物質常用的有效量使用。
可在該TPU樹脂之製備時或在製得該TPU 樹脂後將這些額外添加劑併入組分中或併入反應混合物中。在另一種方法中，可將全部材料與該TPU樹脂混合，然後熔化；或可將其直接併入該TPU樹脂之熔融物中。可根據想要授予本發明的複合積層體之性質由一般熟悉此技藝之人士來選擇添加劑。
在本發明的一個具體實例中，使用來製得用於複合積層體之TPU薄膜的TPU組成物包括一或多種選自於下列的添加劑：抗氧化劑、滅菌劑、殺黴菌劑、抗微生物劑、相容劑、電耗散或抗靜電添加劑、充填劑及補強劑、阻燃劑、衝擊改質劑；脫模劑諸如蠟、脂肪及油；顏料及著色劑、塑化劑、聚合物、流變改質劑、滑動添加劑及UV安定劑。在一個特別的具體實例中，本發明的TPU組成物包括UV安定劑，特別是，一或多種位阻胺光安定劑(HALS)及/或UV光吸收劑(UVA)型式。
熱塑性聚胺基甲酸酯薄膜
本發明的組成物及其任何摻合物可形成單層或多層薄膜。這些薄膜可藉由任何在技藝中已知的習知技術形成，包括擠出、共擠出、擠壓塗佈法、積層、吹出、熱成形及鑄塑或其任何組合。該薄膜可藉由平膜或管式法獲得，其可接著在薄膜平面中於單軸方向上或於二個互相垂直的方向上進行定向。該一或多層薄膜可在橫軸及/或縱軸方向上定向至相同或不同程度。此定向可於各別層匯集在一起前或後進行。典型來說，該薄膜係在機器方向(MD)上以最高15之比率，較佳為在5至7間，及在橫軸方向(TD)上以最高15之比率，較佳為7至 9進行定向。但是，在另一個具體實例中，該薄膜係在MD及TD方向二者上定向至相同程度。
在本發明中有用的薄膜其厚度可變化，例如，厚度1微米至5000微米，例如，1微米至4000微米、1微米至3000微米、1微米至2000微米或甚至1微米至1000微米可合適。
在另一個具體實例中，可藉由電暈處理、電子束照射、γ照射或微波照射來修改一或多層。在較佳具體實例中，藉由電暈處理來修改該表面層之一或二者。
現在轉看至圖式，圖1及圖3闡明用以製備複合積層體結構的先前技術方法。在圖1中，使用含單向安排的纖維之預浸體層1來形成積層體結構10。該積層體結構10隨處可包括1至10層，例如，1至6層或單向纖維預浸體。該積層體結構10的表面11典型將包括表面缺陷，其需要施加諸如補土的充填劑及隨後噴砂以提供一可進行塗裝的表面。將補土施加至頂層及對該補土層噴沙2以產生準備好塗裝的表面。在該經噴沙的補土層2上施加底塗層3，然後施加塗裝的頂塗層以提供想要的裝飾效果，而產生一完整的碳積層體結構。圖3闡明第二先前技術方法，其使用至少一層具有單向纖維的預浸體14及一具有編織纖維的預浸體12。將這些預浸體層積層在一起，例如，該積層體可包括1至10層，例如，1至6層具有單向纖維的預浸體，及1至10層，例如，1至6層具有編織纖維的預浸體。在圖3闡明的實施例中，將一UV塗層16然後一透明塗層18施加至 該積層體。該塗佈層可需要額外加工諸如拋光，以提供最後有用的複合積層體結構。
圖2闡明根據本發明的一個具體實例之用來製造複合積層體結構的方法。在此具體實例中，提供含單向安排纖維的預浸體層1及熱塑性聚胺基甲酸酯(TPU)薄膜5。該TPU薄膜5可係透明或經著色。該複合物結構可包括1至10層，例如，1至6層含單向安排纖維的預浸體。在一個具體實例中，若使用多層含單向安排纖維的預浸體時，可將每層預浸體配置成該一層的纖維係與毗連層之纖維垂直。對該等預浸體層及TPU薄膜施加熱及或壓力，諸如藉由熱成形或積層方法來形成該複合積層體結構。除了該預浸體層及TPU薄膜的樹脂外，不需要額外的黏著劑。在此積層體結構的表面上之TPU薄膜5係準備好進行直接塗裝而不需進一步加工以產生最後有用的複合積層體結構。
圖4闡明根據本發明的另一個具體實例之用來製造複合積層體結構的方法。在此具體實例中，提供含單向安排纖維的預浸體層14、含編織纖維的預浸體層12及熱塑性聚胺基甲酸酯(TPU)薄膜15。該TPU薄膜15可係透明或經著色。諸如藉由熱成形或積層方法施加熱及/或壓力以將該等層黏附在一起。除了在該預浸體層及TPU薄膜中之樹脂外，不需要額外的黏著劑。
在本文描述的積層體中，例如，於圖式中所闡明的那些，該TPU薄膜層可包含二層TPU薄膜。在此具體實例中，該TPU薄膜層可包含第一相對較軟層及第 二相對較硬層。例如，該第一層可具有硬度約55Shore A至95Shore A，例如，55Shore A至90Shore A；同時該第二層具有硬度約95Shore A至85Shore D，例如，95Shore A至60Shore D。在一個具體實例中，該第一層可具有厚度約1微米至約250微米，例如，1微米至約100微米，同時該第二層具有厚度約100微米至約5000微米，例如，約100微米至約4000微米，或甚至約100微米至約3000微米，或甚至約250微米至約2500微米，或甚至約500微米至約1000微米。該二層可進行共擠壓，其中該底層(配置成與該預浸體毗連)係相對較軟、較薄的層，及該頂(表面)層係相對較硬、較厚的層。
在圖2闡明的複合積層體之一個具體實例中，該TPU可包含一包括芳香族多異氰酸酯且具有硬度60Shore D以上之TPU組成物。此芳香族TPU組成物將係在如上所述的二層TPU薄膜中之頂(表面)層。此芳香族TPU組成物可係透明或經著色。
在圖4闡明的複合積層體之一個具體實例中，該TPU可包含一包含聚己內酯多元醇且具有硬度80Shore A至85Shore D，例如，60Shore D至80Shore D之TPU組成物。此聚己內酯基底的熱塑性聚胺基甲酸酯組成物將係在如上所述的二層TPU薄膜中之頂層。該聚己內酯TPU組成物可係透明或經著色。
在本發明中，該使用作為表面層之經著色或呈色的TPU組成物可藉由已知方法著色，包括直接將顏料加入至該TPU組成物或使用可加入至該TPU組成物而 不會影響該TPU之其它有益性質之經著色的TPU母料。
可調配該使用來製得圖2及4所闡明的具體實例之薄膜的TPU組成物以提供多種對該複合積層體有益的性質，諸如對水、溶劑、UV光、天氣、磨損、腐蝕之抗性，和在技藝中已知之任何其它有用的性質。在一個具體實例中，於本發明的複合積層體中所使用之TPU組成物係透明或實質上透明。在其它具體實例中，該TPU薄膜可具有加入的顏料或顏色以對該積層體提供裝飾表面。這些性質可直接從TPU層獲得而不需要額外加工該複合積層體結構及施加額外的塗佈層。
為了製得本發明的複合積層體，堆疊想要之數量的預浸體層及將TPU薄膜配置在該預浸體層堆疊之頂表面上。將該已安排的積層體材料放置在諸如壓力鍋或熱成形加壓機之容器中，及該溫度係設定成從約100℉向上跳躍至約350℉，例如，200℉至325℉。在某些具體實例中，該方法可花一小時或更多來完成，但是其它方法可在數分鐘內提供完成的複合積層體產物。本發明的複合積層體可形成模具，或可形成如為平坦的積層體薄片，然後切割其以用於特別應用。
根據本發明所製得的複合積層體結構可在各種各樣的應用中找到用途。該等應用包括現在已知或未來發展將在多種工業中使用複合積層體結構之任何應用，除了別的應用不講以外，其包括但不限於：航空太空應用，例如，機身、引擎和內部及外部組件；能源應用，例如，風力機葉片及支架；汽車應用，例如，引擎 蓋、天棚、保險桿、鏡子、儀表板、內裝飾板和外部及內部組件；曝露至高壓的容器，例如，槽及航空機身；混凝土結構應用，例如，補強柱；運動及休閒應用，例如，鞋底、保護裝備、滑雪裝備、自行車車架、安全設備諸如安全帽或墊；越野車；船隻應用，諸如船或水上摩托車；電子應用。
1‧‧‧含單向安排的纖維之半固化片層
5‧‧‧TPU薄膜
10‧‧‧積層體結構

Claims (13)

  1. 一種積層體物件，其包含：單向纖維預浸體；編織纖維預浸體；及熱塑性聚胺基甲酸酯薄膜，其中該熱塑性聚胺基甲酸酯薄膜係擠出薄膜，其包含多元醇組分、異氰酸酯組分及選擇性鏈伸長劑組分之反應產物；其中該熱塑性聚胺基甲酸酯薄膜係黏附至該單向纖維預浸體或該編織纖維預浸體，但不使用額外的黏著劑；且其中該熱塑性聚胺基甲酸酯薄膜包含二層熱塑性聚胺基甲酸酯薄膜，其包含具有硬度55A至95A的底部熱塑性聚胺基甲酸酯層及具有硬度95A至85D的頂端熱塑性聚胺基甲酸酯層。
  2. 如請求項1之積層體物件，其中該單向纖維預浸體及該編織纖維預浸體包含碳纖維。
  3. 如請求項1或2之積層體物件，其中該單向纖維預浸體及該編織纖維預浸體包含環氧樹脂。
  4. 如請求項1或2之積層體物件，其中該頂端熱塑性聚胺基甲酸酯層包含聚己內酯多元醇。
  5. 如請求項1或2之積層體物件，其中該底部熱塑性聚胺基甲酸酯層具有薄膜厚度1微米至250微米，及該頂端熱塑性聚胺基甲酸酯層具有薄膜厚度250微米至5000微米。
  6. 一種積層體物件，其包含： 第一單向纖維預浸體；第二單向纖維預浸體；其中該第一單向纖維預浸體及該第二單向纖維預浸體係配置成彼此毗連，如此該第一單向纖維預浸體的纖維係與該第二單向纖維預浸體的纖維呈垂直；二層熱塑性聚胺基甲酸酯薄膜，其包含具有硬度55A至95A的底部熱塑性聚胺基甲酸酯層及具有硬度95A至85D的頂端熱塑性聚胺基甲酸酯層。
  7. 如請求項6之積層體物件，其中該底部熱塑性聚胺基甲酸酯層具有薄膜厚度1微米至250微米，及該頂端熱塑性聚胺基甲酸酯層具有薄膜厚度250微米至5000微米。
  8. 如請求項6或7之積層體物件，其中該頂端熱塑性聚胺基甲酸酯層包含芳香族多異氰酸酯。
  9. 一種製造複合積層體結構的方法，其包含：提供二層擠出薄膜，其中該薄膜包含一熱塑性聚胺基甲酸酯組成物，其包含多元醇組分、異氰酸酯組分及選擇性鏈伸長劑組分之反應產物，且該二層擠出薄膜包含具有硬度55A至95A的底層及具有硬度95A至85D的頂層；提供至少一片預浸體薄片；堆疊該擠出薄膜與至少一片預浸體薄片；及施加熱以讓該擠出薄膜與該預浸體薄片黏合在一起。
  10. 如請求項9之方法，其中該提供至少一片預浸體薄片 的步驟包含：提供一或多片單向纖維預浸體。
  11. 如請求項9或10之方法，其中該提供至少一片預浸體薄片的步驟包含：提供一或多片編織纖維預浸體。
  12. 如請求項9或10之方法，其中該底層具有薄膜厚度1微米至250微米及該頂層具有薄膜厚度250微米至5000微米。
  13. 如請求項9或10的方法，更包含：將該堆疊的擠出薄膜與至少一片預浸體薄片放置在模具及壓力鍋中。
TW107130077A 2017-08-29 2018-08-29 含熱塑性聚胺基甲酸酯薄膜層之複合積層體及製造複合積層體結構的方法 TWI798251B (zh)

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