TWI389955B - 具有可印刷無光澤表面之熱塑性物件 - Google Patents

具有可印刷無光澤表面之熱塑性物件 Download PDF

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TWI389955B
TWI389955B TW94117496A TW94117496A TWI389955B TW I389955 B TWI389955 B TW I389955B TW 94117496 A TW94117496 A TW 94117496A TW 94117496 A TW94117496 A TW 94117496A TW I389955 B TWI389955 B TW I389955B
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Description

具有可印刷無光澤表面之熱塑性物件
本發明係關於具有可印刷無光澤表面之熱塑性物件。特別地，係藉由將具有特定顆粒大小及顆粒大小分佈之無機顆粒(特別為矽石顆粒)摻入該熱塑性物質內以得到可印刷無光澤表面。
熱塑性物質可用以製備許多物件，因為其可以很容易模製成各種形狀，其可形成硬且耐久物件，且具有以競爭成本供設計及製造使用之優異撓性。
對許多應用而言，控制聚合物物件之光澤程度很重要。就某些聚合物材料(例如，丙烯酸系物)而言，可以很容易得到高光澤物件，但是更難得到一旦進行後續處理(例如，熱成形)時仍可保有其光澤程度之低光澤或無光澤物件。通常其它性質，例如，表面粗度及機械靭性，會藉由該消光方法明顯地改變。
一種得到無光澤熱塑性物件之方法包括，例如，藉由噴砂或表面圖案製法，將圖案以機械壓花在物件上。雖然藉由該方法所製成之物件具有低光澤表面，但是典型上一旦進行續後處理(例如，熱成形或在基材上層合)時，並不能維持其光澤程度。
另一種得到無光澤飾面之方法包括將塗料或油漆沉積在物件上。該塗料調配物中之消光劑可以使該物件具有低光澤表面。然而，因為需要固化及乾燥該塗層，所以該方法不具成本效益。
又另一方法係藉由添加具有合適大小及折射率之無機或有機顆粒以進行該熱塑性樹脂之改質。如歐洲專利EP 1022115、美國專利第5,346,954號、及日本專利JP 2001081266中所述，有機顆粒業經使用以減少熱塑性物質之表面上之光澤。雖然使用有機聚合物顆粒可產生無光澤飾面，但是該等顆粒很難產生，因此很昂貴。而且，有機聚合物細粉末之處理比一些矽石粉末之處理更可能產生塵爆之條件。
無機填料亦業經使用以將無光澤飾面併在熱塑性物件上。遺憾地，這些無機顆粒(例如，硫酸鋇、碳酸鈣、二氧化鈦、矽石等)通常很難均勻分散在聚合物基質材料內。其亦傾向於可重大減少該聚合物之光透射，且不會產生所欲表面織構。此外，該等填料顆粒有惡化該聚合物之物理性質之傾向。
有時候將藉由乳化聚合法製成之共聚物細顆粒(亦即，小於15微米)添加入塑膠基質內以產生供顯示器及光面板應用使用之光擴散作用，例如，美國專利第5,346,954號。然而，該產物類型傾向於會軟化該聚合物基質，且不能產生終端用戶通常較喜歡之織構表面。
美國專利第4,906,676號描述矽石或玻璃顆粒在熱塑性物質內產生光學作用之用途。該等顆粒經矽烷化合物進行表面處理以使該表面具疏水性，並藉以改良該顆粒在該熱塑性基質內之可分散性。
在熱塑性物質上產生無光澤表面之現有方法之缺點包括：機械性質(例如，韌性)之一般損失；及表面粗度之引進。在某些應用上，例如，書寫或印刷至物件上，粗度對影像轉移有害。藉由選用平均直徑<10微米之顆粒，可以使這兩問題之嚴重性減至最輕。美國專利第6,524,694號及專利申請案系號第20030175499號描述無機顆粒(例如，氮化硼及矽酸鹽)在擠製性熱塑性物質之用途。然而，為了得到良好分散性，需要分散劑，及自0.01至15重量%之低填充量。分散劑之存在可降低該熱塑性物質之機械性質。
直徑<1微米之無機顆粒(例如，微米尺寸化之矽石)通常會由於沉積物之累積而導致該熔體處理設備之積垢。因此，為了得到低光澤及夠低之粗度，需要最佳範圍之平均顆粒直徑。
有需要一種可得到低光澤、可印刷性、及低遷移性或"析出現象(plate－out)"之有利平衡之方法，且該方法不需要附加分散劑或顆粒表面塗料(其會增加費用，並可不利地影響該熱塑性物質之機械性質)。目前，在本行並沒有可以成功地使用在一步驟方法並提供取代噴砂玻璃材料所需之性質及外觀之塑膠產物。
令人驚訝地，業經發現添加顆粒大小自2至20微米，且具有窄顆粒大小分佈之無機鹼性礬土矽石顆粒可產生無光澤飾面，不會有表面粗度之問題。此等材料之熔態處理或成形(擠製法、層合法、熱成形法)可產生具有低光澤外觀之可印刷物件(薄膜、薄片、層合物)。使用具有本發明之顆粒大小及顆粒大小分佈之矽石顆粒可以容許顆粒之較高填充量，不需要表面處理法或附加分散劑。
本發明一目的為提供無光澤或低光澤飾面在熱塑性物件上，且不具有高表面粗度。該表面應該摸起來很平滑。
本發明另一目的為提供可印刷表面在熱塑性物件上。
本發明另一目的為提供一種使熱塑性物質及自該熱塑性物質形成之物件具有可印刷性及低光澤表面之有效一步驟方法。
根據本發明較佳具體實施例之原則，可藉由具有無光澤，可印刷表面之熱塑性物件(其包含自15至30重量%之無機顆粒)而達成本發明該等目的。該顆粒之平均顆粒大小較佳介於2與20微米之間。
本發明係關於具有可印刷無光澤表面之熱塑性物件。可藉由將具有特定顆粒大小及顆粒大小分佈之無機矽石顆粒摻入該熱塑性物質以得到可印刷無光澤表面。
該熱塑性基質可以是任何熱塑性物質，其包括但不限於：ABS三聚物、ASA共聚物、聚碳酸酯、聚酯、PETG、MBS共聚物、HIPS、丙烯腈/丙烯酸酯共聚物、聚苯乙烯、SAN、MMA/S、丙烯腈/甲基丙烯酸甲酯共聚物、抗衝擊改質性聚烯烴、PVC、抗衝擊改質性PVC、亞胺化丙烯酸系聚合物、氟聚合物、聚偏二氟乙烯(PVDF)、PVDF－丙烯酸系聚合物摻合物、丙烯酸系聚合物或抗衝擊改質性丙烯酸系聚合物。較佳熱塑性物質為丙烯酸系物(其包括抗衝擊改質性丙烯酸系物)、及丙烯酸系共聚物。更特佳為聚甲基丙烯酸甲酯聚合物及共聚物。
可用於本發明之無機顆粒之中顆粒大小為自2至20微米，較佳自2至12微米，且最佳自3至8微米。已發現超過20微米之顆粒大小會產生如此粗糙以致很難印刷之表面。可藉由分餾不同大小之顆粒，並稱重各餾份以評估該等消光劑顆粒之顆粒大小分佈。第95百分位數之顆粒大小為低於95重量%該等顆粒之大小。為了使表面粗度減至最小，該消光劑之第95百分位數顆粒大小應該小於40微米，較佳小於30微米，且最佳小於15微米。
有用之無機顆粒包括但不限於：硫酸鈣、滑石、矽酸鹽、矽石、雲母、鈦酸鹽、金屬硫酸鹽、金屬碳酸鹽、金屬氧化物、硼化物、氮化硼、陶瓷、及其混合物。較佳無機顆粒包括矽石、礬土、滑石、金屬碳酸鹽或其混合物。較佳無機顆粒為鹼性礬土矽石。在一具體實施例中，鹼性礬土矽石顆粒為此等平均直徑為4，第95百分位數之顆粒大小分佈為13微米之無機顆粒。
該等無機顆粒以自15至30重量%存在於該熱塑性物件中。該等無機顆粒更佳以自16至23重量%存在。當顆粒之存在量低於15重量%時，該熱塑性物質之光澤度太高。
可藉由本技藝已知之方法(例如，模製法、吹氣模製法、擠製法、共擠製法、熔態鑄造擠製法、層合法、熱成形法)以形成本發明之熱塑性物件。該物件可以是薄片、薄膜、層合物、棒狀物、圓錐體或其它形狀之熱塑性物質。該熱塑性物質可以具多層或單層。
可藉由本技藝已知之方法添加該等顆粒至該熱塑性物質內。其包括於擠製或模製線路之任何進料口添加該等顆粒。於該擠製方法期間添加無機顆粒可提供易於控制及低成本方法。其亦可以以低成本將一產物轉變化另一產物。可藉由該方法之紊流以均勻方式將該等顆粒混入該熱塑性物質內。或者，於接近該聚合方法結束時或其後，使該等顆粒與該熱塑性物質混合。然後使該等顆粒與熱塑性物質形成小粒，其可作為擠製法或模製法之原料。不需要使用如本技藝所需之分散劑，即可添加該等顆粒至該熱塑性物質內。可藉由在該擠製法內之混合步驟及剪應力之合適分配以得到均質性。
除該熱塑性物質及無機顆粒外，可以在擠製及/或模製之前或期間，添加其它一般添加劑至該熱塑性組合物內。這些添加劑包括脫模劑、抗衝擊改質劑、潤滑劑、染料及著色劑。雖然添加來改良該熱塑性物質之加工性之該脫模劑及潤滑劑亦可作為分散劑，但是為了確保該等無機顆粒之良好混合及分散，該脫模劑及潤滑劑並非必要。
本發明該熱塑性物質具有低光澤、低表面粗度、良好透光率、及良好可加工性。此等熱塑性物質之用途包括物件(例如，薄膜、薄片、共擠製薄片、模製物件)之製造。這些物件可進行後續製程，例如，印刷、裝飾、壓花、層合等。
可藉由以下實例例証本發明之較佳具體實施例。熟悉本技藝者可瞭解文中所述該等具體實施例以外之小變異並未違反本發明之精神及範圍。
實例
使用表1所述之組份及比例以製備聚合物樹脂之調配物。如表2所述，用於該等實例之消光劑之中顆粒大小稍有不同，而顆粒大小分佈更明顯不同。使用可得到均勻混合物之條件，藉由熔態擠製法以混合該等組份。藉由熔態擠製法，在拋光滾輪或拋光滾輪群上將所形成樹脂轉化成厚度為0.003"之薄膜。評估該等薄膜試樣之光澤值及表面粗度。使用BYK Gardner Micro－Haze Plus光澤計測定光澤值。
雖然為了得到具有低粗度之表面，文獻主張具有平均顆粒大小在1至10微米範圍內之消光劑較佳，但是一般消光劑具有寬顆粒大小分佈。因此，該等顆粒之顯著餾份(>5重量%)大於15微米。實例1至5之薄膜顯示一些如表3所摘述之光澤及粗度性質。就例如，印刷至薄膜上之應用而言，低粗度及低表面光澤為所欲(於60度形貌下，光澤值較佳<23)。使用具有窄顆粒大小分佈之消光劑(#1鹼性礬土矽石)可產生具有低靭性及低光澤之薄膜。

Claims (5)

  1. 一種具有無光澤可印刷表面之熱塑性物件，其包含至少一種熱塑性樹脂及基於該表面層重量計自15至30重量%之無機顆粒的摻合物，其中該等顆粒具有自2至12微米之平均顆粒大小，且具一顆粒大小分佈，其中第95百分位數顆粒大小係小於15微米；且其中該熱塑性樹脂選自以下所組成之群組：丙烯腈-丁二烯-苯乙烯(acrylonitrile butadiene styrene,ABS)三聚物、丙烯腈-苯乙烯-丙烯酸酯(acrylonitrile-styrene-acrylate,ASA)三聚物、聚碳酸酯、聚酯、經二元醇改質之聚對苯二甲酸乙二酯(polyethylene terephthalate glycol-modified,PETG)、甲基丙烯酸甲酯-丁二烯-苯乙烯(methylmethacrylate-butadiene-styrene,MBS)共聚物、高抗衝擊性聚苯乙烯(high impact polystyrene,HIPS)、丙烯腈/丙烯酸酯共聚物、聚苯乙烯、苯乙烯丙烯腈(styrene acrylonitrile,SAN)、甲基丙烯酸甲酯-苯乙烯(methylmethacrylate-styrene,MMA/S)、丙烯腈/甲基丙烯酸甲酯共聚物、抗衝擊改質性聚烯烴、聚氯乙烯(polyvinyl chloride,PVC)、抗衝擊改質性PVC、亞胺化丙烯酸系聚合物、氟聚合物、聚偏二氟乙烯(polyvinylidenefluoride,PVDF)、PVDF-丙烯酸系聚合物摻合物、(甲基)丙烯酸系聚合物及抗衝擊改質性丙烯酸系聚合物。
  2. 如請求項1之熱塑性物件，其中該熱塑性樹脂為包含甲基丙烯酸甲酯之均聚物或共聚物。
  3. 如請求項1之熱塑性物件，其中該等無機顆粒選自由矽石、滑石、礬土、金屬碳酸鹽及其混合物所組成之群組。
  4. 如請求項1之熱塑性物件，其中該等無機顆粒為鹼鋁矽酸鹽。
  5. 如請求項1之熱塑性物件，其中該等無機顆粒具有自3至8微米之平均顆粒大小。
TW94117496A 2004-05-28 2005-05-27 具有可印刷無光澤表面之熱塑性物件 TWI389955B (zh)

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