TWI843462B - 低摩擦薄膜及其製造方法、以及成形體 - Google Patents
低摩擦薄膜及其製造方法、以及成形體 Download PDFInfo
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Abstract
本發明係製備一種薄膜,其至少一面之表面的峰度(Rku)為2以上,且前述表面之最大剖面高度(Rt)為1μm以上。前述表面之動摩擦係數可為0.25以下,相對動摩擦係數可為0.3以下。前述薄膜包含由包含硬化性樹脂之硬化性組成物的硬化物所形成之低摩擦層,且該低摩擦層之表面可具有前述範圍的Rku及Rt。前述硬化性樹脂可包含:選自包含具有聚合性基之(甲基)丙烯酸系聚合物、胺基甲酸酯(甲基)丙烯酸酯及聚矽氧(甲基)丙烯酸酯之群組的至少1種。前述硬化性組成物可進一步包含纖維素酯。前述硬化性組成物可不包含微粒。該薄膜即使由種類廣泛的材質形成表面,亦可降低動摩擦係數。
Description
本發明係關於一種用來披覆觸控面板顯示器、家電製品之殼體、建築材料等各種成形體之表面的低摩擦薄膜及其製造方法、成形體及提升該薄膜之滑動性(尤其手指滑動性)之方法。
已知個人電腦(PC)、智慧型手機等的觸控面板顯示器、家電製品之殼體、建築材料等各種成形體之表面,為了防止受到損傷、為了提升觸感,貼附硬塗薄膜、施加硬塗處理作為表面保護層或披覆層之方法。該硬塗薄膜、硬塗層追求以手觸摸時的良好滑動性,然而作為提升滑動性之方法,以往通常藉由施加包含聚矽氧化合物、氟化合物之硬塗處理來提升滑動性。
日本特開2007-264281號公報(專利文獻1)揭示一種硬塗層,其係用於光學積層體之硬塗層,其包含矽系化合物、氟系化合物或此等之混合物作為防污染劑及/或滑動性賦予劑而成,當對前述硬塗層之最表面進行XPS分析時,矽原子之存在率為10%以上,及/或氟原子之存在率為20%以上。
又,WO2008/038714(專利文獻2)揭示一種光學機能薄膜,其具有基材、形成於該基材上之光學機能層、與形成於前述光學機能層上之防污層;該防污層的表面之元素比例為矽元素(Si)與碳元素(C)之比Si/C為0.25~1,氟元素(F)與碳元素(C)之比F/C為0.1~1,液態石蠟接觸角及滑落角為65°以上及15°以下,黑色麥克筆接觸角及滑落角為35°以上及15°以下,且動摩擦係數小於0.15。
然而,此等硬塗層及防污層雖然可以藉由聚矽氧化合物、氟化合物來降低表面之摩擦係數,但是非但不充分,而且手指滑動性會因表面結構之細微差異而大幅不同。又,由於表面成為疏水性,因此不但用途受到限制,而且因為藉由濕式塗布來調平表面,因此難以利用對流現象來控制表面形狀。
[先前技術文獻]
[專利文獻]
專利文獻1 日本特開2007-264281號公報(請求項1)
專利文獻2 WO2008/038714(申請專利範圍第1項)
[發明欲解決之課題]
因此,本發明之目的係提供一種即使由種類廣泛的材質形成表面,亦可降低動摩擦係數之低摩擦薄膜、成形體及其製造方法及提升該薄膜之手指滑動性之方法。
又,本發明之其它目的係提供一種不摻合大量的聚矽氧化合物、氟化合物而可提升滑動性(尤其手指滑動性)之低摩擦薄膜及其製造方法、成形體及提升該薄膜之滑動性(尤其手指滑動性)之方法。
[用以解決課題之手段]
本發明者為了達成前述課題而潛心探討,結果發現藉由調整薄膜表面之峰度(Rku)及最大剖面高度(Rt),即使由種類廣泛的材質形成表面,亦可降低動摩擦係數,而完成本發明。
亦即,本發明之薄膜(低摩擦薄膜)係至少一面之表面具有2以上的Rku及1μm以上的Rt。前述表面之動摩擦係數可為0.25以下,相對動摩擦係數可為0.3以下。前述薄膜包含由包含硬化性樹脂之硬化性組成物的硬化物所形成,且配置於最表層之低摩擦層,且該低摩擦層之表面可具有2以上的Rku及1μm以上的Rt。前述硬化性樹脂可包含:選自包含具有聚合性基之(甲基)丙烯酸系聚合物、胺基甲酸酯(甲基)丙烯酸酯及聚矽氧(甲基)丙烯酸酯之群組的至少1種。前述硬化性組成物可進一步包含纖維素酯。前述硬化性組成物可不包含微粒。前述低摩擦薄膜可於由透明樹脂所形成之基材層之上積層有低摩擦層。前述薄膜係表面之矽原子的存在率小於10%,且表面之氟原子的存在率可小於20%。
本發明亦包含一種前述薄膜之製造方法,其包含:使包含硬化性樹脂之硬化性組成物硬化之硬化步驟。又,本發明亦包含一種成形體,其於表面具備前述薄膜。該成形體可為觸控面板顯示器。再者,本發明亦包含一種提升薄膜之手指滑動性之方法,其係藉由將薄膜的至少一面之表面調整為2以上的峰度(Rku)及1μm以上的最大剖面高度(Rt),而提升薄膜之手指滑動性。
[發明之效果]
在本發明中,由於薄膜表面之凹凸結構中的Rku及Rt調整為特定範圍,因此即使由種類廣泛的材質形成薄膜表面,亦可降低動摩擦係數。因此,不摻合大量的聚矽氧化合物、氟化合物而可提升薄膜之滑動性(尤其手指滑動性或觸感)。
[用以實施發明的形態]
[低摩擦薄膜]
本發明之薄膜(低摩擦薄膜)係至少一面之表面的Rku(峰度)為2以上,且由於前述表面的Rt調整為1μm以上,因此於表面形成有峰度及高低差大的凸部。因此,茲推測在本發明之低摩擦薄膜中,當表面與手指等被接觸體接觸時,由於接觸面積小,因此可降低動摩擦係數。具有Rku及Rt調整為前述範圍之凹凸結構的表面亦可形成於雙面,但通常多為形成於與手指接觸之側的單面之情形。
前述表面的Rku(峰度)只要是2以上(例如2~100)即可,例如為2.5~80(例如3~50),較佳為3.2~30(例如3.3~20),進一步較佳為3.5~10(尤其4~5)左右。若Rku過小,則無法降低表面之動摩擦係數,無法提升手指滑動性。
前述表面的Rt(最大剖面高度)只要是1μm以上(例如1~30μm)即可,例如為1.5~20μm(例如2~15μm),較佳為2~10μm(例如2.5~8μm),進一步較佳為3~5μm(尤其3.5~4.5μm)左右。若Rt過小,則無法降低表面之動摩擦係數,無法提升手指滑動性。
此外,在本說明書及申請專利範圍中,Rku及Rt可根據JIS B0601,使用光學式表面粗糙度計等來測定,詳細而言可利用後述的實施例中記載之方法來測定。
前述表面由於具有Rku及Rt調整為前述範圍之凹凸結構,因此動摩擦係數(μk)低,前述表面之動摩擦係數可為0.25以下,例如為0.01~0.23,較佳為0.03~0.2,進一步較佳為0.05~0.15(尤其0.08~0.12)左右。又,相對動摩擦係數可為0.3以下,例如為0.01~0.29,較佳為0.04~0.25,進一步較佳可為0.06~0.19(尤其0.1~0.15)左右。
此外,在本說明書及申請專利範圍中,動摩擦力可使用靜動摩擦測定機來測定,詳細而言可利用後述的實施例所記載之方法來測定。另一方面,相對動摩擦係數係將以相同負載進行測定之薄膜的動摩擦力,除以將玻璃作為檢體而測定之動摩擦力的值,詳細而言可利用後述的實施例所記載之方法來測定。由於該相對動摩擦係數係以與穩定的玻璃表面之動摩擦力的相對值來評價薄膜之摩擦特性,因此為緩和了人工皮膚的隨時間變化所致之誤差的高可靠性評價。
本發明之低摩擦薄膜只要具有至少一面之表面的Rku及Rt調整為前述範圍之凹凸結構即可,薄膜之材質、結構並未特別限定。
關於材質,本發明之低摩擦薄膜由於表面的Rku及Rt調整為前述範圍,因此即使未大量包含聚矽氧化合物及氟化合物,亦可降低動摩擦係數。因此,低摩擦薄膜表面(尤其具有前述範圍的Rku及Rt之表面)的矽原子之存在率可小於10%,較佳為5%以下,進一步較佳可為1%以下。又,低摩擦薄膜表面(尤其具有前述範圍的Rku及Rt之表面)的氟原子之存在率可小於20%,較佳為10%以下,進一步較佳可為1%以下。此外,在本說明書及申請專利範圍中,矽原子及氟原子之存在率可利用使用X射線光電子光譜裝置(XPS)之慣用方法來測定。
關於結構,本發明之低摩擦薄膜例如可為至少一面之表面的Rku及Rt調整為前述範圍之單層薄膜,亦可為包含表面的Rku及Rt調整為前述範圍之低摩擦層的積層體。
(單層薄膜及低摩擦層)
單層薄膜及低摩擦層之材質係如前述般未限定,可選自各種有機材料(熱塑性樹脂、熱硬化性樹脂、光硬化性樹脂等)、無機材料(玻璃、陶瓷、金屬等),但從生產性等的觀點來看,係以包含硬化性樹脂之硬化性組成物的硬化物為較佳。
硬化性樹脂可為熱硬化性樹脂、光硬化性樹脂之任一者,但從生產性等的觀點來看,廣泛使用(甲基)丙烯酸系光硬化性樹脂。又,(甲基)丙烯酸系樹脂由於透明性亦優異,因此可理想地利用作為觸控面板顯示器等光學用途之保護薄膜。
作為(甲基)丙烯酸系光硬化性樹脂,例如可列舉:多官能性(甲基)丙烯酸酯[例如新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等具有2~8左右的聚合性基之(甲基)丙烯酸酯等]、環氧(甲基)丙烯酸酯[具有2以上的(甲基)丙烯醯基之多官能性環氧(甲基)丙烯酸酯]、聚酯(甲基)丙烯酸酯[具有2以上的(甲基)丙烯醯基之多官能性聚酯(甲基)丙烯酸酯]、胺基甲酸酯(甲基)丙烯酸酯[具有2以上的(甲基)丙烯醯基之多官能性胺基甲酸酯(甲基)丙烯酸酯]、聚矽氧(甲基)丙烯酸酯[具有2以上的(甲基)丙烯醯基之多官能性聚矽氧(甲基)丙烯酸酯]、具有聚合性基之(甲基)丙烯酸系聚合物等。此等硬化性樹脂可單獨或組合二種以上來使用。
此等硬化性樹脂之中,係以胺基甲酸酯(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯、具有聚合性基之(甲基)丙烯酸系聚合物為較佳,具有聚合性基之(甲基)丙烯酸系聚合物為特佳。具有聚合性基之(甲基)丙烯酸系聚合物可為於(甲基)丙烯酸系聚合物之羧基的一部分導入聚合性不飽和基之聚合物,例如:於(甲基)丙烯酸-(甲基)丙烯酸酯共聚物之羧基的一部分,使含有環氧基之(甲基)丙烯酸酯(例如丙烯酸3,4-環氧環己烯基甲酯等)之環氧基反應,於側鏈導入聚合性基(光聚合性不飽和基)之(甲基)丙烯酸系聚合物(Daicel-Allnex(股)製「Cyclomer P」)。
具有聚合性基之(甲基)丙烯酸系聚合物係以與胺基甲酸酯(甲基)丙烯酸酯及/或聚矽氧(甲基)丙烯酸酯組合者為較佳,與胺基甲酸酯(甲基)丙烯酸酯及聚矽氧(甲基)丙烯酸酯組合者為特佳。
當組合具有聚合性基之(甲基)丙烯酸系聚合物、與胺基甲酸酯(甲基)丙烯酸酯及/或聚矽氧(甲基)丙烯酸酯時,胺基甲酸酯(甲基)丙烯酸酯之比例係相對於100重量份的具有聚合性基之(甲基)丙烯酸系聚合物而言,例如為10~300重量份,較佳為100~200重量份,進一步較佳為120~180重量份左右。聚矽氧(甲基)丙烯酸酯之比例係相對於100重量份的具有聚合性基之(甲基)丙烯酸系聚合物而言,例如為0.1~10重量份,較佳為0.5~5重量份,進一步較佳為1~3重量份左右。
硬化性組成物除了前述硬化性樹脂以外,可進一步包含纖維素酯。作為纖維素酯,例如可列舉:纖維素二乙酸酯、纖維素三乙酸酯等纖維素乙酸酯;纖維素丙酸酯、纖維素丁酸酯、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等纖維素C
2-6醯化物等。此等纖維素酯可單獨或組合二種以上來使用。此等之中,係以纖維素二乙酸酯、纖維素三乙酸酯、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等纖維素C
2-4醯化物為較佳,纖維素乙酸酯丙酸酯等纖維素乙酸酯C
3-4醯化物為特佳。纖維素酯之比例係相對於100重量份的硬化性樹脂而言,例如為0.1~30重量份,較佳為0.5~20重量份,進一步較佳為1~10重量份(尤其2~5重量份)左右。
硬化性組成物除了前述硬化性樹脂以外,可進一步包含微粒。作為微粒,例如可列舉:二氧化矽粒子、二氧化鈦粒子、二氧化鋯粒子、氧化鋁粒子等無機微粒、(甲基)丙烯酸系單體與苯乙烯系單體之共聚物粒子、交聯(甲基)丙烯酸系聚合物粒子、交聯苯乙烯系樹脂粒子等有機微粒等。此等微粒可單獨或組合二種以上來使用。此等之中,廣泛使用交聯(甲基)丙烯酸系聚合物粒子等。微粒之平均粒徑例如為1~30μm,較佳為10~30μm,進一步較佳為15~25μm左右。微粒之比例係相對於100重量份的硬化性樹脂而言,例如為0.1~10重量份,較佳為0.2~5重量份,進一步較佳為0.3~3重量份(尤其0.4~1重量份)左右。
此外,在本發明中,當硬化性樹脂[尤其具有聚合性基之(甲基)丙烯酸系聚合物、與胺基甲酸酯(甲基)丙烯酸酯及/或聚矽氧(甲基)丙烯酸酯之組合]與纖維素酯組合時,可不使用微粒而形成具有前述範圍的Rku及Rt,且動摩擦係數低的表面。
硬化性組成物除了前述硬化性樹脂以外,可包含慣用的添加劑,例如:聚合起始劑、安定劑(抗氧化劑、紫外線吸收劑等)、界面活性劑、水溶性高分子、填充劑、交聯劑、偶合劑、著色劑、阻燃劑、潤滑劑、蠟、防腐劑、黏度調整劑、增黏劑、調平劑、消泡劑等。此等添加劑可單獨或組合二種以上來使用。
當硬化性組成物為光硬化性組成物時,光硬化性組成物可包含光聚合起始劑作為聚合起始劑。作為光聚合起始劑,例如可例示:苯乙酮類或苯丙酮類、二苯乙二酮類、安息香類、二苯基酮類、噻噸酮類、醯基膦氧化物類等。光聚合起始劑可包含慣用的光增感劑、光聚合促進劑(例如三級胺類等)。光聚合起始劑之比例係相對於100重量份的光硬化性樹脂而言,例如為0.1~10重量份,較佳為0.5~5重量份,進一步較佳為1~3重量份左右。
硬化前之硬化性組成物可進一步包含溶媒。作為溶媒,例如可例示:酮類、醚類、烴類、酯類、水、醇類、賽路蘇類、賽路蘇乙酸酯類、亞碸類、醯胺類等。又,溶媒可為混合溶媒。此等溶媒之中,係以包含酮類(丙酮、甲基乙基酮、甲基異丁基酮、環己酮等)者為較佳,酮類與醇類(乙醇、異丙醇、丁醇、環己醇等)之混合溶媒為特佳。溶媒之比例係相對於100重量份的硬化性樹脂而言,例如為30~300重量份,較佳為50~250重量份,進一步較佳為100~200重量份左右。
單層薄膜及低摩擦層之平均厚度分別例如為1~30μm,較佳為3~20μm,進一步較佳為5~15μm(尤其8~10μm)左右。此外,在本說明書及申請專利範圍中,單層薄膜及低摩擦層之平均厚度可利用後述的實施例中記載之方法來測定。
(積層體)
當低摩擦薄膜為積層體時,只要前述低摩擦層配置於最表面即可,積層結構並未特別限定,但從生產性、處理性等的觀點來看,係以於基材層之上積層有低摩擦層之結構(基材層與積層於該基材層之一面的低摩擦層之積層體)為較佳。
基材層之材質並未特別限定,可選自各種有機材料(熱塑性樹脂、熱硬化性樹脂、光硬化性樹脂等)、無機材料(玻璃、陶瓷、金屬等),但當利用作為觸控面板顯示器等光學用途之保護薄膜時,係以透明材料為較佳。
作為透明材料,例如可列舉:玻璃等無機材料;纖維素酯、聚酯、聚醯胺、聚醯亞胺、聚碳酸酯、(甲基)丙烯酸系聚合物等有機材料等。此等之中,廣泛使用纖維素酯、聚酯等。
作為纖維素酯,可列舉:纖維素三乙酸酯(TAC)等纖維素乙酸酯、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等纖維素乙酸酯C
3-4醯化物等。作為聚酯,可列舉:聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)等聚伸烷基芳酯等。
此等之中,從機械特性、透明性等之平衡優異的觀點來看,係以PET、PEN等聚C
2-4伸烷基C
8-12芳酯為較佳。
由聚酯所形成之基材層可為單軸或雙軸延伸薄膜,但從低雙折射率且光學上各向同性優異的觀點來看,可為未延伸薄膜。
基材層可經過表面處理(例如電暈放電處理、火焰處理、電漿處理、臭氧、紫外線照射處理等),亦可具有易接著層。
基材層之平均厚度可為10μm以上,例如為12~500μm,較佳為20~300μm,進一步較佳為30~200μm左右。
(黏著層)
本發明之低摩擦薄膜可於形成有具有前述範圍的Rku及Rt之凹凸結構的表面之背面(單層薄膜中的低摩擦薄膜之背面、基材層之表面等)之至少一部分形成有黏著層。前述於背面形成有黏著層之低摩擦薄膜亦可使用作為智慧型手機、平板PC等之觸控面板顯示器中的保護薄膜。
黏著層係由慣用的透明黏著劑所形成。作為黏著劑,例如可例示:橡膠系黏著劑、丙烯酸系黏著劑、烯烴系黏著劑(改性烯烴系黏著劑等)、聚矽氧系黏著劑等。此等黏著劑可單獨或組合二種以上來使用。此等黏著劑之中,從光學特性、再製性等的觀點來看,係以聚矽氧系黏著劑為較佳。
黏著層之平均厚度例如為1~150μm,較佳為10~100μm,進一步較佳為20~70μm(尤其25~50μm)左右。
黏著層可形成於背面全體、形成於背面之一部分(例如周圍部)之任一者。再者,當形成於周圍部時,基於提升用來貼附的處理性之目的,可於低摩擦薄膜之周圍部形成框狀構件(例如於周圍部積層塑膠薄片),而於框狀構件形成黏著層。
[低摩擦薄膜之製造方法]
本發明之低摩擦薄膜之製造方法,只要是可於表面形成調整為前述範圍的Rku及Rt之凹凸結構的方法,則未特別限定,可因應低摩擦薄膜之材質而適當選擇。作為具體的製造方法,例如可列舉:包含使包含硬化性樹脂之硬化性組成物硬化之硬化步驟的方法(例如使包含微粒之硬化性組成物的微粒突出而硬化之方法;使包含可相分離的樹脂成分之硬化性組成物的前述樹脂成分相分離後硬化之方法等);使用於表面具有凹凸結構之模具來轉印之方法;藉由切削加工來形成凹凸結構之方法(例如利用雷射等之切削加工等);藉由研磨來形成凹凸結構之方法(例如噴砂法、珠擊法等);藉由蝕刻來形成凹凸結構之方法等。
此等方法之中,從能以高生產性來製造表面之凹凸結構調整為前述範圍的Rku及Rt之低摩擦薄膜的觀點來看,係以包含使包含硬化性樹脂之硬化性組成物硬化之硬化步驟的方法為較佳,例如可為於支撐體(當低摩擦薄膜為積層體時,為構成低摩擦薄膜之前述基材層)之上塗布液狀的硬化性組成物並乾燥後,使其硬化之方法。
作為塗布方法,可列舉慣用的方法,例如:輥塗機、氣刀塗布機、刮刀塗布機、棒式塗布機(rod coater)、逆塗機、刮棒塗布機(bar coater)、缺角輪塗布機、浸軋塗布機(dip-squeeze coater)、模塗機、凹版塗布機、微凹版塗布機、絲網塗布機等塗布機法、浸漬法、噴塗法、旋塗法等。此等方法之中,廣泛使用刮棒塗布機法、凹版塗布機法等。此外,只要有必要,亦可連續多次來塗布塗布液。
乾燥溫度例如為30~120℃,較佳為50~110℃,進一步較佳為60~100℃(尤其70~90℃)左右。乾燥時間例如為0.1~10分鐘,較佳為0.3~5分鐘,進一步較佳為0.5~3分鐘左右。
硬化方法只要是因應硬化性樹脂之種類而賦予活性光線(紫外線、電子束等)、熱等之方法即可,光硬化性樹脂之情形,光照射可因應光硬化樹脂等之種類來選擇,通常可利用紫外線、電子束等。泛用的曝光源通常為紫外線照射裝置。
作為光源,例如紫外線之情形可利用:Deep UV燈、低壓水銀燈、高壓水銀燈、超高壓水銀燈、鹵素燈、雷射光源(氦-鎘雷射、準分子雷射等光源)等。照射光量(照射能量)係因塗膜之厚度而異,例如為10~10000mJ/cm
2,較佳為20~5000mJ/cm
2,進一步較佳為30~3000mJ/cm
2左右。只要有必要,亦可在惰性氣體環境中進行光照射。
在使這樣的硬化性組成物硬化之方法中,作為形成表面的Rku及Rt調整為前述範圍之凹凸結構的方法,可列舉:於前述硬化性組成物摻合微粒,使微粒突出而硬化之方法(利用微粒之方法);於前述硬化性組成物摻合可相分離的樹脂成分,使該樹脂成分相分離後硬化之方法(利用相分離之方法)等。
在利用微粒之方法中,可在微粒從表面突出之狀態下,使硬化性組成物硬化,藉此於表面形成凹凸結構。
在利用相分離之方法中,可在由包含可相分離的樹脂成分及溶媒之組成物的液相,藉由乾燥等來蒸發或去除溶媒之過程中,隨著組成物之濃縮,發生因旋節分解(濕式旋節分解)所致之相分離,形成相間距離較規則的表面凹凸結構(相分離結構)。作為利用相分離之方法,亦可利用例如:日本特開2007-187746、日本特開2008-225195、日本特開2009-267775、日本特開2011-175601、日本特開2014-85371號公報中記載之方法等。作為可相分離的樹脂成分之組合,係以具有聚合性基之(甲基)丙烯酸系聚合物、胺基甲酸酯(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯、與纖維素酯之組合為較佳。
[實施例]
以下根據實施例來更詳細地說明本發明,惟本發明並不限定於此等實施例。實施例及比較例所使用之原料係如下述,並利用以下方法來評價所得之低摩擦薄膜。
[原料]
具有聚合性基之丙烯酸系聚合物A:Daicel-Allnex(股)製「KRM 8713B」
具有聚合性基之丙烯酸系聚合物B:Daicel-Allnex(股)製「Cyclomer P」
丙烯酸系聚合物:Taisei Fine Chemical(股)製「8KX-078」
胺基甲酸酯改性共聚聚酯樹脂:東洋紡(股)製「Vylon(註冊商標)UR-3200」
纖維素乙酸酯丙酸酯:Eastman公司製「CAP-482-20」,乙醯基化度=2.5%,丙醯基化度=46%,聚苯乙烯換算數量平均分子量75000
胺基甲酸酯丙烯酸酯:新中村化學工業(股)製「UA-53H」
聚矽氧丙烯酸酯:Daicel-Allnex(股)製「EBECRYL 1360」
PMMA珠粒A:積水化學工業(股)製「SSX-115」,平均粒徑15μm
PMMA珠粒B:積水化學工業(股)製「SSX-110」,平均粒徑10μm
含有奈米二氧化矽之丙烯酸系紫外線(UV)硬化性化合物:JSR(股)製「Z7501」
光起始劑A:BASF Japan(股)製「Irgacure 184」
光起始劑B:BASF Japan(股)製「Irgacure 907」
聚對苯二甲酸乙二酯(PET)薄膜:三菱樹脂(股)製「Diafoil」。
[低摩擦層之厚度]
使用光學式膜厚計,測定任意的10處,算出平均值。
[表面形狀]
根據JIS B0601,使用光學式表面粗糙度計(Hitachi High-Tech Science(股)製「VertScan R5500G」),在掃描範圍2.5mm平方,掃描次數2次之條件下,測定最大剖面高度(Rt)及凹凸之峰度(Rku)。
[動摩擦係數及相對動摩擦係數]
使用靜動摩擦測定機(Trinity-Lab(股)製「Handy Tribomaster TL201Ts」),在測定條件(負載20g重,速度25mm/秒)下測定動摩擦力(動摩擦係數)。使用於5mm厚的海綿薄片(Cemedine公司製「縫隙用膠帶N-1」)貼附人工皮膚(Beaulax公司製「Bio Skin」)之接觸器作為接觸器。相對動摩擦係數係藉由將測定對象的薄膜之動摩擦力,除以將玻璃(鈉鈣玻璃)作為檢體而測定之動摩擦力來求出。
[手指滑動性]
手指滑動性之評價係藉由使用25μm厚度的Optical Clear Adhesive(OCA)薄膜,準備將所得之低摩擦薄膜的基材層側貼附於壓克力板者,以操作智慧型手機的感覺,使食指滑動於薄膜上(低摩擦層之表面)來進行。根據下述5階段的基準,對20位受試者聽取評價結果。
1分:手指難以滑動,且在操作途中也會卡住。
2分:開始滑動時有卡住,且滑出後之摩擦感大。
3分:開始滑動時有卡住,且滑出後之摩擦感小。
4分:開始滑動時有稍微卡住,但在操作中未感到摩擦感。
5分:開始滑動時沒有卡住,且在操作中未感到摩擦感。
實施例1
將216重量份的具有聚合性基之丙烯酸系聚合物A、1重量份的PMMA珠粒A、1重量份的光起始劑A、1重量份的光起始劑B溶解於117重量份的甲基乙基酮。使用線棒#14將該溶液流延於PET薄膜上後,在100℃的烘箱內放置1分鐘,使溶媒蒸發而形成厚度約12μm的低摩擦層。接著,對低摩擦層照射來自高壓水銀燈之紫外線約5秒鐘(照射累積光量約100mJ/cm
2)以進行UV硬化處理,得到低摩擦薄膜。
實施例2
將50重量份的具有聚合性基之丙烯酸系聚合物B、4重量份的纖維素乙酸酯丙酸酯、76重量份的胺基甲酸酯丙烯酸酯、1重量份的聚矽氧丙烯酸酯、1重量份的光起始劑A、1重量份的光起始劑B溶解於176重量份的甲基乙基酮與28重量份的1-丁醇之混合溶媒。使用線棒#18將該溶液流延於PET薄膜上後,在80℃的烘箱內放置1分鐘,使溶媒蒸發而形成厚度約9μm的低摩擦層。接著,對低摩擦層照射來自高壓水銀燈之紫外線約5秒鐘(照射累積光量約100mJ/cm
2)以進行UV硬化處理,得到低摩擦薄膜。
比較例1
將216重量份的具有聚合性基之丙烯酸系聚合物A、1重量份的PMMA珠粒B、1重量份的光起始劑A、1重量份的光起始劑B溶解於117重量份的甲基乙基酮。使用線棒#14將該溶液流延於PET薄膜上後,在100℃的烘箱內放置1分鐘,使溶媒蒸發而形成厚度約8μm的低摩擦層。接著,對低摩擦層照射來自高壓水銀燈之紫外線約5秒鐘(照射累積光量約100mJ/cm
2)以進行UV硬化處理,得到低摩擦薄膜。
比較例2
將34.2重量份的丙烯酸系聚合物、20重量份的胺基甲酸酯改性共聚聚酯樹脂、166.3重量份的含有奈米二氧化矽之丙烯酸系UV硬化性化合物、0.2重量份的聚矽氧丙烯酸酯、1重量份的光起始劑A、1重量份的光起始劑B溶解於179重量份的甲基乙基酮。使用線棒#16將該溶液流延於PET薄膜上後,在80℃的烘箱內放置1分鐘,使溶媒蒸發而形成厚度約5μm的低摩擦層。接著,對低摩擦層照射來自高壓水銀燈之紫外線約5秒鐘(照射累積光量約100mJ/cm
2)以進行UV硬化處理,得到低摩擦薄膜。
比較例3
市售的智慧型手機用保護薄片之PM-A15FLGM(ElECOM公司製)在包裝上被譽為「終極的手指滑動薄膜」、「超級平滑薄膜」,因此採用作為手指滑動性佳的薄膜之比較例。
比較例4
市售的智慧型手機用保護薄片之PM-A15FLST(ElECOM公司製)亦在包裝上被譽為「手指滑動性流暢」、「超級平滑薄膜」,因此採用作為手指滑動性佳的薄膜之比較例。
將評價實施例及比較例所得之低摩擦薄膜的特性之結果示於表1。
表1
項目 | 實施例 | 比較例 | ||||
1 | 2 | 1 | 2 | 3 | 4 | |
最大剖面高度Rt(μm) | 2.47 | 3.94 | 0.73 | 1.72 | 0.47 | 0.47 |
峰度Rku | 45.89 | 4.48 | 25.53 | 1.80 | 3.46 | 3.69 |
動摩擦係數 | 0.22 | 0.10 | >1.00 | 0.40 | 0.29 | 0.27 |
相對動摩擦係數 | 0.28 | 0.13 | >1.27 | 0.51 | 0.37 | 0.34 |
手指滑動性 | 4 | 5 | 1 | 2 | 3 | 3 |
如表1之結果所明示,實施例之低摩擦薄膜係動摩擦係數及相對動摩擦係數低且手指滑動性優異。另一方面,如比較例1、3、4般只有峰度為高數值者,無法提高手指滑動性。再者,即使如比較例2般只有最大剖面高度高者,其手指滑動性亦不如實施例。
[產業上利用之可能性]
本發明之低摩擦薄膜可利用作為用來披覆個人電腦(平板PC等)、智慧型手機等中的觸控面板顯示器、家電製品之殼體、建築材料等各種成形體之表面的表面保護或披覆薄膜,尤其藉由於以手接觸並操作處賦予低摩擦性,就提高觸感之薄膜而言為有用。
無
無
無。
Claims (10)
- 一種薄膜,其包含低摩擦層,該低摩擦層係由包含硬化性樹脂之硬化性組成物的硬化物所形成且配置於最表層,且此低摩擦層之表面具有2以上的峰度(Rku)及1μm以上的最大剖面高度(Rt),其中該硬化性樹脂包含:具有聚合性基之(甲基)丙烯酸系聚合物、與選自由胺基甲酸酯(甲基)丙烯酸酯及聚矽氧(甲基)丙烯酸酯組成之群組的至少1種,於該硬化性樹脂包含該胺基甲酸酯(甲基)丙烯酸酯時,該胺基甲酸酯(甲基)丙烯酸酯之比例係相對於100重量份的該具有聚合性基之(甲基)丙烯酸系聚合物而言為10~300重量份,於該硬化性樹脂包含該聚矽氧(甲基)丙烯酸酯時,該聚矽氧(甲基)丙烯酸酯之比例係相對於100重量份的該具有聚合性基之(甲基)丙烯酸系聚合物而言為0.1~10重量份。
- 如請求項1之薄膜,其中表面之動摩擦係數為0.25以下。
- 如請求項1之薄膜,其中表面之相對動摩擦係數為0.3以下。
- 如請求項1至3中任一項之薄膜,其中硬化性組成物進一步包含纖維素酯。
- 如請求項1至3中任一項之薄膜,其中硬化性組成物不包含微粒。
- 如請求項1至3中任一項之薄膜,其中於由透明樹脂所形成之基材層之上積層有低摩擦層。
- 如請求項1至3中任一項薄膜,其中表面之矽原子的存在率小於10%,且表面之氟原子的存在率小於20%。
- 一種薄膜之製造方法,其係如請求項1至7中任一項之薄膜之製造方法,其包含:使包含硬化性樹脂之硬化性組成物硬化之硬化步驟。
- 一種成形體,其於表面具備如請求項1至7中任一項之薄膜。
- 如請求項9之成形體,其為觸控面板顯示器。
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