TWI396625B - 多層物件以及製造多層物件的方法 - Google Patents
多層物件以及製造多層物件的方法 Download PDFInfo
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Description
本發明是有關可熱成形之材料、製造可熱成形片材的方法、及由其所製成的物件。
經模內裝飾之熱塑塑膠膜在諸如家用之消費型電子、電器、及印刷之覆蓋物的應用上正獲得廣泛的接受度。這些應用要求諸如清晰度、印刷性、熱成形性、及硬度、以及耐刮性、耐化學品性及耐衝擊性等性質之組合。此組合不能用很多選擇的材料來達成。最普遍之解決方式已是施加官能塗層作為覆蓋層於熱塑塑膠層上,其中塗層提供表面性質,而基礎膜提供整體機械整合性。然而,在塗層改良耐刮性之同時,該塗層減去膜之熱形成性,而此嚴重地限制此種膜之有用的應用。最困難之挑戰之一是耐刮性與熱成形性間之平衡。
因此,在此技藝中仍需要可容易地成形(例如藉由共擠出作用)且提供所要之性質(包括熱成形性及耐刮性)之組合的多層片。
本揭示大致係關於可熱成形之材料、製造可熱成形片材之方法、及由彼所製之物件。在一具體表現中,片材包含:包含丙烯酸系聚合物之覆蓋層;及一基礎層,其中該片材是可熱成形的。基礎層包含環脂族聚酯共聚物及任意地芳族聚碳酸酯。環脂族聚酯共聚物可包含以環脂族聚酯共聚物總重量為基準計大於10重量%之環脂族二醇或酸或其組合。
在一具體表現中,製造物件之方法可以包含:在擠出機中熔化丙烯酸系聚合物;在擠出機中形成熔化的環脂族聚酯共聚物;及共擠出該丙烯酸系聚合物及該環脂族聚酯共聚物以形成一片材。該環脂族聚酯共聚物可包含以環脂族聚酯共聚物總重量為基準計含量大於10重量%之環脂族聚酯。該環脂族聚酯共聚物可以形成基礎層且該丙烯酸系聚合物形成覆蓋層於該基礎層上。
本揭示藉參考以下之本揭示之多種特徵之詳細描述及其中所包括之實例而更容易地了解。
多層物件包含覆蓋層及基礎層。覆蓋層可以是以丙烯酸系聚合物為底質的,諸如以(甲基)丙烯酸甲酯為底質的,例如以聚甲基丙烯酸甲酯(“PMMA”)為底質的,同時基礎層可以是環脂族聚酯共聚物及任意之芳族聚碳酸酯之組合。覆蓋層及基礎層可以被共擠出以形成多層片材。
此種物件之硬度、耐刮性、機械強度及熱可成形性應使這些物件符合諸如清晰度、印刷性、熱成形性、及硬度、以及耐刮性、耐化學品性、及耐衝擊性等性質之所要組合。另外,基礎層無須任何黏合劑或縛層(tie layer)即可黏合至覆蓋層,且在覆蓋層及基礎層間提供實質的流變性匹配,因此改良複合膜之加工性。
在一具體表現中,片材包含:包含丙烯酸系聚合物的覆蓋層;及基礎層,其中該片材是可熱成形的。基礎層包含環脂族聚酯共聚物及任意地芳族聚碳酸酯。環脂族聚酯共聚物可包含以環脂族聚酯共聚物總重量為基準計大於10重量%之環脂族二醇或酸或其組合。覆蓋層可以佔總厚度之1%至50%,且總厚度可以是5密耳(mil)至500密耳。基礎層可以包含25重量%至100重量%之環脂族聚酯及其餘之聚碳酸酯的摻合物;或特別地50重量%至90重量%之環脂族聚酯及其餘之聚碳酸酯的摻合物。片材可以具有大於HB之鉛筆硬度。具有大於HB之鉛筆硬度的片材可以另外具有大於或等於120N/mm之撕裂起始強度及/或5N/mm之撕裂擴展強度,及/或大於40MPa之抗張強度。丙烯酸系聚合物可以是(甲基)丙烯酸烷酯,或特別地聚(甲基)丙烯酸甲酯。基礎層可以包含20重量%至90重量% PCCD,其餘為芳族聚碳酸酯。
在一具體表現中,一種製造物件之方法可以包含:在擠出機中熔化丙烯酸系聚合物;在擠出機中形成熔化的環脂族聚酯共聚物;共擠出該丙烯酸系聚合物及該環脂族聚酯共聚物以形成一片材。該環脂族聚酯共聚物可包含以環脂族聚酯共聚物總重量為基準計含量大於10重量%之環脂族聚酯。該環脂族聚酯共聚物可以形成基礎層且該丙烯酸系聚合物形成覆蓋層於該基礎層上。該片材可以被熱成形環脂族聚酯之式為:
其中R13
及R14
在每次出現時獨立地是芳基、具有2至20個碳原子之脂族或環烷類,其條件是R13
及R14
之至少一者是環脂族基團。環脂族聚酯是一種縮合產物,其中R13
是二醇殘基或其化學同等物之殘基,且R14
是二酸殘基或其化學同等物之殘基。在一具體表現中,R13
及R14
二者是含環烷基之基團。此種聚酯通常含有至少50莫耳%之環脂族二酸及/或環脂族二醇成分,其餘者若存在則是芳族二酸類及/或直鏈脂族二醇類。
在一具體表現中,R13
及R14
是獨立選自以下結構單元之環烷基團:
在一特定具體表現中,二醇是1,4-環己烷二甲醇或其化學同等物。可以使用1,4-環己烷二甲醇之順式或反式異構物的任一者或二者。二醇之化學同等物包括酯類,諸如C1-4
二烷酯、二芳酯及類似者。二酸類之特定非限定性實例包括十氫萘二羧酸類、降烯二羧酸類、雙環辛烷二羧酸類、1,4-環己烷二羧酸或其化學同等物。最特別地,二酸類包括反式-1,4-環己烷二羧酸或其化學同等物。這些二酸類之化學同等物包括C1-4
二烷酯類、二芳酯類、酸酐類、鹽類、醯氯類(acid chlorides)、醯溴類(acid bromides)及類似者。在一具體表現中,化學同等物包含環脂族二酸類之二烷酯類,且最特別地,該酸之二甲酯,諸如1,4-環己烷二羧酸二甲酯。
於環脂族聚酯共聚物中可以存在其他形式之單元,其包括衍生自芳族羧二酸成分及非環脂族二醇或其化學同等物之反應的單元。例示之芳族二羧酸類包括間苯二甲酸、對苯二甲酸、1,2-二(對-羧基苯基)乙烷、4,4-二羧基二苯基醚、4,4-雙苯甲酸、1,4-、1,5-或2,6-萘二羧酸類及包含前述之酸類的至少一者的組合。特定之二羧酸類是對苯二甲酸、間苯二甲酸、及包含二個前述酸類的組合。非環脂族二醇可以是C1-4
烷二醇,例如乙二醇、丙二醇、1,4-丁二醇及類似者及包含前述二醇類之至少一者的組合。
環脂族聚酯共聚物更特別地包含至少50莫耳%之環脂族殘基,更特別地至少70莫耳%之環脂族殘基,其餘為芳族二酸殘基或C1-4
烷二醇殘基。特定之環脂族聚酯是聚(環己烷-1,4-二伸甲基環己烷-1,4-二羧酸酯),也稱為聚(1,4-環己烷-二甲醇-1,4-二羧酸酯)(PCCD)。另一特定的酯類是聚(1,4-伸環己基二伸甲基共伸乙基對苯二甲酸酯)(PCTG),其中多於50莫耳%之酯基團係衍生自1,4-環己烷二甲醇;及聚(伸乙基-共-1,4-伸環己基二伸甲基對苯二甲酸酯),其中多於50莫耳%之酯基團係衍生自乙烯(PETG)。在本文中也預期使用任何以上的聚酯類與少量(例如0.5至5重量%)之衍生自脂族酸之單元及/或衍生自脂族多元醇之單元以形成共聚酯類。脂族多元醇類包括二醇類,諸如聚(乙二醇)或聚(丁二醇)。
芳族聚碳酸酯類之式係為:
其中R1
基團總數之至少60%是芳族有機基團且其餘為脂族、脂環或芳族基團。本文中所用之“聚碳酸酯”一詞包括共聚碳酸酯類,亦即包含二或更多不同之R1
基團的共聚物。在一具體表現中,每一R1
係衍生自下式之雙酚化合物:
其中Ra
及Rb
各自是鹵原子或單價烴基且可以相同或不同;p及q各自獨立是0至4之整數;且Xa
代表下式之基團:
其中Rc
及Rd
個別獨立地代表氫原子或單價直鏈形或環狀烴基且Re
是二價烴基。
雙酚化合物之特定實例包括1,1-雙(4-羥基苯基)甲烷、1,1-雙(4-羥基苯基)乙烷、2,2-雙(4-羥基苯基)丙烷(下文稱為“雙酚A”或“BPA”)、2,2-雙(4-羥基苯基)丁烷、2,2-雙(4-羥基苯基)辛烷、1,1-雙(4-羥基苯基)丙烷、1,1-雙(4-羥基苯基)正丁烷、2,2-雙(4-羥基-1-甲基苯基)丙烷、1,1-雙(4-羥基-第三-丁基苯基)丙烷、3,3-雙(4-羥基苯基)鄰苯二醯亞胺、2-苯基-3,3-雙(4-羥基苯基)鄰苯二醯亞胺(PPPBP)、及1,1-雙(4-羥基-3-甲基苯基)環己烷(DMBPC)。也可以使用包含前述雙酚化合物之至少一者的組合。例如,可以使用包含衍生自雙酚A及1,1-雙(4-羥基-3-甲基苯基)環己烷之單元混合物的共聚物。
在一特定具體表現中,聚碳酸酯是一種衍生自雙酚A的直鏈型均聚物,其中p及q各自為0,且Y1
是異亞丙基。
環脂族聚酯成分及芳族聚碳酸酯成分的相對量隨著特定應用而改變。在一具體表現中,聚酯成分的量是大於10重量%,諸如25重量%至100重量%之量,而其餘者是芳族聚碳酸酯。在其他具體表現中,環脂族聚酯之量是50重量%至90重量%,而其餘者是芳族聚碳酸酯。基礎層組成物是在商業上可從GE Plastics得到之XYLEX。
覆蓋層可以丙烯酸系聚合物為底質,諸如以(甲基)丙烯酸烷酯為底質者,例如聚甲基丙烯酸甲酯(“PMMA”)。以覆蓋層之總重量為基準計,此層可以包含大於或等於50重量%之丙烯酸系聚合物,或特別地大於或等於約70重量%之丙烯酸系聚合物,或更特別地大於或等於約90重量%之丙烯酸系聚合物。其餘可以是任何其他聚合物,其在與丙烯酸系聚合物摻合時獲得具有大於或等於80%透射率的覆蓋層,該透射率係依ASTM D1003-00程序A,例如使用得自BYK-Gardner之HAZE-GUARD DUAL(其使用且累積球狀物(0°/擴散幾何學))而測量,其中光譜敏感性在標準燈D65下符合CIE標準光譜值。
除了以上材料之外,基礎層及/或覆蓋層還可以獨立地包括不同的添加劑,其條件是選擇添加劑以致不會顯著不利地影響所要之層性質,例如熱成形性、耐刮性等。可以使用添加劑之組合。此種添加劑可以在混合各成分以形成每一層之組成物期間的適當時間時被混合。可能的添加劑包括抗氧化劑、阻燃劑、阻滴劑、染料、顏料、著色劑、安定劑(例如熱安定劑、紫外線安定劑等)、小顆粒材料(諸如黏土、雲母及/或滑石)、抗靜電劑、塑化劑、潤滑劑、脫模劑、增白劑、強化用填料(例如玻璃)、及包含前述之至少一者的組合。以包含添加劑之層的總重量為基準計,添加劑之量可以是少於或等於20重量%,或特別地約0.1重量%至約10重量%之添加劑,或更特別地約0.5至約5重量%之添加劑。
覆蓋層及基礎層可以藉共擠出作用而形成。例如,使用如圖2中所概略顯示之連續壓延共擠出作用,可以合適地形成多層複合材料。在此方法中,單螺桿擠出機1及2將用於個別層(亦即上層、第二層及任何另外之聚合層)之樹脂熔化物供應於送料方塊3中。塑模4形成熔化之聚合疋狀物,此疋狀物送至3滾筒壓延疊置體5。典型地,壓延疊置體包含2至4個相對轉動之柱狀滾筒,而每一滾筒個別地由金屬(例如鋼)或經橡膠塗覆之金屬所製成。每一滾筒視需要地可被加熱或冷卻。藉塑模所形成之熔化的疋狀物可以連續地在壓延滾筒間被擠壓。疋狀物所拉伸經過之滾筒間之間隙或“夾縫”決定層厚度。也可以從分開之預成形膜形成多層複合材料,該等預成形膜係對應於例如使用經加熱之滾筒及任意之縛層而隨後被層合在一起之聚合層。
多層可以被共擠出以形成不同之覆蓋層對基礎層厚度比例(亦即覆蓋層厚度除以基礎層厚度)。厚度比例可以是1%至50%,或特別地5%至40%,或更特別地10%至25%。通常,片材之總厚度可以高達數毫米,且甚至超過數毫米。更特別地,片材厚度(例如量規厚度)可以是1密耳(25.4微米)至500密耳(1,2700微米),或更特別地是約5密耳(127微米)至約40密耳(1016微米),且更特別地約5密耳(127微米)至約30密耳(762微米)。
以下實例僅是例示的,非限制性的。
使用關於圖2所述之共擠出方法製備不同之覆蓋層組成及膜構成之雙層膜(表2中之樣品1至13)。隨著個別層厚度及膜之總厚度而變化之各樣品的特定處理參數,涵蓋表2中所有實例之處理參數的範圍在表3中給予。據了解:用於擠出這些膜之處理窗不限於在表3中所列者。此實驗之另一目的是要決定是否存在“一種”條件,在此條件下可以製造這些共擠出膜,亦即是否這些膜是可擠出的。表3僅提供一組用於共擠出這些膜的條件。
此實例證明所揭示之物件對於膜內裝飾(IMD)應用之適用性。用於此種應用之膜對於IMD之三種次處理應是可修正的:(a)擠出性-在表面品質與商業上可得之經磨光的作圖膜(例如Lexan 8010膜)相當的狀況下,從所選擇之材料製造膜的能力;(b)成形性-將膜拉伸成不同幾何形狀之能力;及(c)修整性-乾淨地切割膜且不引起裂痕或剝離的能力。
表1含有在表2中所列之膜構造中所用之樹脂的化學描述及來源。
表2評估樣品之以上3種屬性度量:表面品質、熱成形性及修整性。為測量表面品質,10片12英吋×12英吋(30.5公分×30.5公分)尺寸之樣品由3個操作者來檢查以確認任何長度大於2毫米之瑕疵(線條、凹痕、凸起)。對無輔助之眼睛而言,沒有任何此種瑕疵者被認為是“合格的”。並未企圖要測試膜之光學品質;反之要確認任何缺陷,此缺陷引起與膜共擠出作用相關之議題。
為測試成形性,12英吋×12英吋之膜樣品被預熱至140℃,而後被真空成形在配備120℃之陽型形成工具、5mm之最小曲線及10mm最大拉伸之COMET Thermoformer上。在此測試之“合格的”是在方法期間無任何皺摺、發白或撕裂於膜上,如以無輔助之眼睛所決定的。(無輔助之眼睛排除用於放大之光學裝置之使用,但用於正常視力所需之校正鏡片係例外的)。
使用配合的金屬塑模(American Iron and Steel Institute “AISI” Type A2鋼)修整經成形的部份,該金屬塑膜包含硬化之陽型半塑模及陰型半塑模(American Iron and Steel Institute “AISI” Type A2鋼),而陽型半塑模及陰型半塑模之間的間隙為片材厚度之10%;其中該部份在衝擊時對刮刀呈90°角。修整該熱成形之部份在IMD方法中是不可缺少步驟。層間黏合性不良的多層結構體在此步驟期間易於剝離。對此測試為合格者是在此步驟期間無任何可眼見之裂痕及任何可眼見之剝離,且可眼見性係使用無輔助之眼睛者。
表2導致以下結論:(1)共擠出膜顯出顯著之硬度改良,即使10%之覆蓋層使硬度升至H;(2)雖然增加覆蓋層厚度改良鉛筆硬度,這卻使膜變脆,如由修整效能所見的(樣品4,雖然其顯現出4H之鉛筆硬度,其在修整方法期間破裂,且因此不適於IMD);(3)在基礎層中聚酯使膜IMD溫和(100% PC於基礎層中使該層與覆蓋層之共擠出具挑戰性。在10%覆蓋層厚度下(樣品6),膜不能被擠出,雖然在較高之覆蓋層對基礎層比例下膜確實被共擠出(樣品5),膜不能通過修整測試,其中在覆蓋層及基礎層間有剝離;(4)依照聚酯之形式,聚酯與PC之摻合可能是有用的,例如以基礎層總重量為基準計,0%至20%或更多之重量比例,以例如促進共擠出作用。雖然100%PCTG作為基礎層是可擠出的,PCCD與PC摻合以使擠出成為可行。因此,若利用PCCD,基礎層可以包含20重量%至90重量% PCCD,或特別地30重量%至80重量% PCCD,或更特別地40重量%至60重量% PCCD,其餘為PC。另外,覆蓋層厚度可以是1%至50%,或特別地5%至40%,或更特別地10%至30%,且更特別地15%至25%。
此實例證明多層膜之硬度及耐刮性。二樣品依照表4中所列之膜及樹脂組成而製備。這些樣品製備方式與實例1者相同。樣品14基本上是單層膜,其被包括於此比較中以凸顯由覆蓋層所產生之效能改良。
此二樣品與商業上用於作圖應用之樣品比較:一種雙層共擠出聚碳酸酯膜。覆蓋層是PC共聚物,同時基礎層是PC(特別是Lexan ML 9735,商業上可得自SABIC Innovative Plastics,Pittsfield,MA)(樣品17)(已知為1HD00,商業上可得自SABIC Innovative Plastics);單層聚碳酸酯(樣品18)聚碳酸酯(Lexan 8010,商業上可得自SABIC Innovative Plastics);及包含可固化矽石塗層於聚碳酸酯基礎上之經塗覆的碳酸酯膜(樣品19)(特別地Lexan 8010)(已知為HP92S,商業上可得自SABIC Innovative Plastics),在商業上皆可得自SABIC Innovative Plastics。必須注意:HP92S是不可成形之經塗覆膜。
測試所有樣品之硬度,亦即依照ASTM D3363-05之鉛筆硬度。樣品15及16二者具有2H之鉛筆硬度,但樣品(17、18、19)分別具有1H、2H及HB之較低硬度。樣品14具有2B之硬度,此凸顯覆蓋層之重要性。
也使用Erichsen Scratch Tester Type 413(其符合ISO 1518),以測試樣品之耐刮性。施加2牛頓(N)及4N之力至半徑0.01毫米(mm)之圓錐形尖筆,此在該部份表面上造成凹陷。凹陷程度隨後藉Dektak 6M輪廓計來測量且係報告成由凹陷底部至樣品表面所測得之凹陷高度。再次,樣品15及16優於比較性樣品。樣品15及16分別具有1.15微米(μm)及1.25μm之刮痕深度。比較性實例分別具有1.4μm、2.86μm及2.95μm之刮痕深度。無任何覆蓋層之樣品(樣品14)具有3.02μm之刮痕深度。
在(表5至7)中所產生之數據係在重負荷下產生。在另一例子中,使用Nano Indenter XP,MTS Systems,施加範圍為0至50毫牛頓(mN)之垂直負荷,以進行微刮動測試(輕負荷)。刮動速度是50微米每秒{μm/s)。使用標準Berkovich鑽石壓痕器(具有10奈米(nm)半徑之尖端),其從邊緣移動經過材料。圖1是此一刮痕之說明及顯出圍繞此刮痕之構造的相關測量之橫截輪廓。以下報告是在負荷達25mN之時間點的輪廓的瞬間深度(期間深度)。這獲得材料之軟度/硬度之量度。在製造了整個刮痕時(負荷達50mN),沿著此刮痕已發現一些經阻擋的材料,這些材料使刮痕深度減少。刮痕之深度及寬度在如上之相同點上再次地被測量。這是“後深度(depth after)”。此舉獲得材料之恢復(“寬容(forgiveness)”)的量度。
表5另外強調由於雙層構造所得之耐刮性改良(樣品14對15/16)。樣品15及16比樣品18及18不僅效能要好,彼也與經塗覆之比較性樣品HP92S(樣品19)相當。這是不能預測的,因為會預測:塗層因其交聯會在此種輕負荷下更具抗性。
除了耐刮性及硬度之外,機械強韌度也是用於IMD應用之因素;例如膜應對破裂及撕裂具抗性。表6報告:分別使用ASTM D1004-03、D1938-02及ASTM D882所測量之撕裂起始強度及撕裂擴展強度,其單位為牛頓/毫米(N/mm)。
由表6證明:在先前實例中所見之經改良的耐刮性及硬度並不損及物件之機械性。
在本文中所揭示之範圍是包括性的且是可組合的(例如“高達約25重量%,或更特別地約5重量%至約20重量%的範圍包括“約5重量%至約25重量%”等範圍之端點及其間所有之值)。“組合”包括摻合物、混合物、衍生物、合膠、反應產物等。另外,“第一”、“第二”等詞在本文中並不指明任何順序、份量或重要性,而是用來區分各元素,且“一(a)”在本文中並不指明份量之限制,而是指明至少一種所指稱之項目的存在與量相關使用之修飾語“約”包括所述之值且具有上下文所指明之意義(例如包括與特定量之測量有關的誤差程度。在本文中所用之接尾字“類(s)”企圖包括彼所修飾之詞的單數及多數,藉此包含該詞之一或多者(例如著色劑類包括一或多種著色劑)。在整個說明書中指稱之“一個具體表現”、“另一具體表現”、“一具體表現”等意指與該具體表現相關描述之特別元素(例如特性、結構及/或特徵)被包括在本文所述之至少一具體表現中,且可以存在或不存在於其他具體表現中。此外,據了解:所描述之元素在多種具體表現中可用任何適合方式組合。如本文中所用,“(甲基)丙烯酸酯”一詞涵蓋丙烯酸酯及甲基丙烯酸酯。使用標準命名法描述化合物。例如,未被任何所指明之基團取代之位置被了解是使其價數被所指之鍵結或氫原子所填充。非介於二字母或二符號間之破折號(“-“)用來指明取代基之連接點。例如,-CHO是經由羰基之碳來連接。
所有引用之專利、專利申請案及其他參考資料整體以參照方式被倂入本文。然而,若在本申請案中之一詞與所併入之參考資料中的詞有牴觸或衝突時,則本申請案中之該詞比所合倂之參考資料中的該具衝突性之詞有優先地位。
雖然本發明已參考例示之具體表現來描述,精於此技藝者將了解:多種改變可以進行且同等物可以代替其元素而不偏離本發明之範圍。此外,可以進行很多修正以使特定條件或材料適應本發明之教導而不偏離其實質範圍。因此,企圖使本發明不限制於所揭示之作為實施本發明所認定之最佳模式的特定具體表現,但本發明將包括在所附之申請專利範圍內的所有具體表現。
1...單螺桿擠出機
2...單螺桿擠出機
3...送料方塊
4...塑模
5...滾筒壓延疊置體
圖1是藉輪廓負荷所產生之刮痕橫截面說明。
圖2是例示之共擠出系統的概圖。
Claims (13)
- 一種片材,其包含:包含丙烯酸系聚合物之覆蓋層,其中該覆蓋層佔總厚度之1%至50%,且該總厚度是0.127毫米(5密耳(mil))至12.7毫米(500密耳);及包含環脂族聚酯共聚物及芳族聚碳酸酯之基礎層,其中該環脂族聚酯共聚物為聚(1,4-伸環己基二伸甲基共伸乙基對苯二甲酸酯),其中大於50莫耳%的酯基係衍生自1,4-環己烷二甲醇;其中該覆蓋層及該基礎層是以共擠出所形成的;且其中該片材是可熱成形的。
- 如申請專利範圍第1項之片材,其中該基礎層包含一種摻合物,該摻合物包含20重量%至100重量%之環脂族聚酯,其餘為聚碳酸酯。
- 如申請專利範圍第2項之片材,其中該摻合物包含50重量%至90重量%之環脂族聚酯,其餘為聚碳酸酯。
- 如申請專利範圍第1至3項中任一項之片材,其中該片材具有大於HB之鉛筆硬度。
- 如申請專利範圍第1至3項中任一項之片材,其中該片材具有大於或等於120 N/mm之撕裂起始強度。
- 如申請專利範圍第1至3項中任一項之片材,其 中該片材具有5 N/mm以上之撕裂擴展強度。
- 如申請專利範圍第1至3項中任一項之片材,其中該片材具有大於40 MPa之抗張強度。
- 如申請專利範圍第1至3項中任一項之片材,其中該丙烯酸系聚合物是聚(甲基)丙烯酸烷酯。
- 如申請專利範圍第1至3項中任一項之片材,其中該覆蓋層是聚(甲基)丙烯酸甲酯。
- 一種製造物件之方法,其包含:在擠出機中熔化丙烯酸系聚合物;在擠出機中形成熔化的環脂族聚酯共聚物及芳族聚碳酸酯,其中該環脂族聚酯共聚物為聚(1,4-伸環己基二伸甲基共伸乙基對苯二甲酸酯),其中大於50莫耳%的酯基係衍生自1,4-環己烷二甲醇;共擠出該丙烯酸系聚合物及該熔化的環脂族聚酯共聚物和芳族聚碳酸酯以形成一片材,其中該熔化的環脂族聚酯共聚物及芳族聚碳酸酯形成基礎層且該丙烯酸系聚合物形成覆蓋層於該基礎層上;其中該覆蓋層佔總厚度之1%至50%,且該總厚度是0.127毫米(5密耳(mil))至12.7毫米(500密耳)。
- 如申請專利範圍第10項之方法,其另外包含將該片材熱成形。
- 如申請專利範圍第10或11項之方法,其中該丙烯酸系聚合物包含聚(甲基)丙烯酸烷酯。
- 如申請專利範圍第10或11項之方法,其中該聚 (甲基)丙烯酸烷酯包含聚(甲基)丙烯酸甲酯。
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- 2009-01-21 WO PCT/US2009/031470 patent/WO2009097199A1/en active Application Filing
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US20110189449A1 (en) | 2011-08-04 |
EP2237949B1 (en) | 2012-10-31 |
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US20090191403A1 (en) | 2009-07-30 |
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