TWI696652B - 覆蓋膜 - Google Patents

覆蓋膜 Download PDF

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TWI696652B
TWI696652B TW108107947A TW108107947A TWI696652B TW I696652 B TWI696652 B TW I696652B TW 108107947 A TW108107947 A TW 108107947A TW 108107947 A TW108107947 A TW 108107947A TW I696652 B TWI696652 B TW I696652B
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hard coat
coat layer
cover film
meth
acrylate
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TW108107947A
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TW202003655A (zh
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松原圭佑
池田拓也
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日商郡是股份有限公司
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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Abstract

本發明一撓曲顯示器用的覆蓋膜，係具備：透明的基材膜、在前述透明的基材膜的至少其中一面所形成之硬塗層；前述硬塗層之厚度為23μm以下，該硬塗層的端面的線粗度為2.5μm以下。

Description

覆蓋膜
本發明係關於一種覆蓋膜以及其製造方法。
近年來，提出了保護智慧型手機等顯示器的表面之各種的覆蓋膜。例如日本特開2003－292828號公報提出了一種覆蓋膜，係具有膜基材及在其表面所形成之硬塗層。
另一方面，近年提出了一種顯示器的表面撓曲(或是彎曲)之撓曲顯示器。這種顯示器由於配置於表面之覆蓋膜亦會撓曲，故要求覆蓋膜具有抗撓曲性。亦即，覆蓋膜撓曲時，尤其需要在硬塗層不產生裂痕。本發明乃是為了解決上述問題而完成，目的在於提供一種撓曲顯示器用的覆蓋膜，可提高抗撓曲性。
第1項：一種撓曲顯示器用的覆蓋膜，具備：透明的基材膜、在前述透明基材膜的至少其中一面所形成之硬塗層；前述硬塗層係厚度為23μm以下；該硬塗層的端面的線粗度Ra為2.5μm以下。
第2項：如第1項所記載之覆蓋膜，其中端面藉由雷射而被切斷。
第3項：如第1項或第2項所記載之覆蓋膜，其中表面鉛筆硬度為3H以上。
第4項：一種覆蓋膜的製造方法，係具備：在透明的基材膜積層23μm以下的厚度的硬塗層，以形成覆蓋膜之步驟；在前述硬塗層上配置保護膜之步驟；將前述覆蓋膜藉由雷射切斷之步驟；該硬塗層的端面的線粗度Ra為2.5μm以下。
第5項：如第4項所記載之覆蓋膜的製造方法，其中藉由前述雷射切斷的速度為50mm／sec至600mm／sec。
根據本發明之覆蓋膜，可提高抗撓曲性。
以下對於本發明之覆蓋膜的一實施形態進行說明。本發明之覆蓋膜係具備：透明的基材膜、積層在該基材膜的至少其中一面之硬塗層。亦即，硬塗層亦可積層於基材膜的兩面。以下對於各構件進行詳細的說明。另外，說明書中以「至」所連接之數值係表示將「至」的前後的數值作為下限值以及上限值而含有之數值範圍。此外，複數的下限值與複數的上限值有個別地記載之情況下，可選擇任意的下限值與上限值，並以「至」連接。
＜1.基材膜＞ 本發明之基材膜可以透明的各種的材料來形成，例如以纖維素醯化物、環烯烴聚合物、聚碳酸酯、丙烯酸酯系聚合物、聚酯、聚醯亞胺等來形成。尤其聚醯亞胺抗撓曲強，此外，即使撓曲亦不易起皺，故較佳。此外，該基材膜可根據需要添加各種的添加劑。例如亦可添加塑化劑、抗靜電剤、紫外線吸收劑等各種添加劑。
基材膜的厚度例如較佳為25μm以上300μm以下，更佳為75μm以上250μm以下。若厚度小於25μm，則在硬塗層的表面無法獲得充分的抗刮性，若大於300μm則難以獲得充分的撓曲耐久性。
基材膜在馬氏硬度(Martens hardness)試驗中，較佳為具有200 N／mm2 至600 N／mm2 的硬度，更佳為250 N／mm2 至500 N／mm2 的硬度，更佳為300 N／mm2 至450 N／mm2 的硬度。藉此提高抗刮性。
馬氏硬度可於動態超微小硬度計DUH－211((股份有限公司)島津製作所)來測定。作為壓頭，可以使用稜間夾角115度的三角錐壓頭、壓入深度0.25μm、承載速度0.15mN／sec的條件下來測定。然後，具體的馬氏硬度係藉由以下的式所算出之值。 馬氏硬度［N／mm2 ］＝荷重［μN］／(24.5×(深度最大值hmax(μm)2 )
＜2.硬塗層＞ 再來，對於硬塗層進行說明。硬塗層係含有游離輻射硬化型樹脂、光聚合起始劑等之硬塗層形成用樹脂組成物經硬化者。此外，該組成物亦可根據需要而調配後述之添加劑。
＜2－1.游離輻射硬化型樹脂＞ 所謂游離輻射硬化型樹脂，係包含具有藉由游離輻射(紫外線或是電子射線)而進行高分子化或是交聯反應之自由基聚合性的化合物，例如在結構單元中含有至少1個以上的乙烯性的不飽和鍵之化合物、或是這些的混合物。
作為含有1個不飽和鍵之單官能的化合物而言，可列舉例如：(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸環己酯等。
此外，作為含有2個不飽和鍵之二官能的化合物而言，可列舉例如：乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、壬二醇二(甲基)丙烯酸酯、乙氧基化己二醇二(甲基)丙烯酸酯、丙氧基化己二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、乙氧基化新戊二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、羥基新戊酸新戊二醇二(甲基)丙烯酸酯等二(甲基)丙烯酸酯等。
此外，作為含有3個以上不飽和鍵之多官能化合物而言，可列舉例如：三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、三2－羥乙基異氰酸酯三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯等三(甲基)丙烯酸酯；季戊四醇三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、二三羥甲基丙烷三(甲基)丙烯酸酯等3官能的(甲基)丙烯酸酯化合物；季戊四醇四(甲基)丙烯酸酯、二三羥甲基丙烷四(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二三羥甲基丙烷五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二三羥甲基丙烷六(甲基)丙烯酸酯等3官能以上的多官能(甲基)丙烯酸酯化合物；或是將這些(甲基)丙烯酸酯的一部分以烷基或ε-己內酯來取代之多官能(甲基)丙烯酸酯化合物等(甲基)丙烯酸酯化合物。
此外，上述(甲基)丙烯酸酯化合物可混合胺基甲酸酯系樹脂。作為胺基甲酸酯系樹脂而言，可使用例如胺基甲酸酯(甲基)丙烯酸酯系樹脂。具體而言，可使用例如：季戊四醇三丙烯酸酯六亞甲基二異氰酸酯胺基甲酸酯預聚物、二季戊四醇五丙烯酸酯六亞甲基二異氰酸酯胺基甲酸酯預聚物、季戊四醇三丙烯酸酯甲苯二異氰酸酯胺基甲酸酯預聚物、二季戊四醇五丙烯酸酯、甲苯二異氰酸酯胺基甲酸酯預聚物、季戊四醇三丙烯酸酯異佛酮二異氰酸酯胺基甲酸酯預聚物、二季戊四醇五丙烯酸酯異佛酮二異氰酸酯胺基甲酸酯預聚物等。
胺基甲酸酯系樹脂的分子量較佳為1000至10000，更佳為2000至5000。此外，作為分子量的測定方法而言，可使用GPC法(Gel Permeation Chromatography；膠體滲透層析法)。
此處，相對於含有(甲基)丙烯酸酯化合物與胺基甲酸酯系樹脂之混合物100重量份而言，胺基甲酸酯系樹脂較佳為5重量份至20重量份。其中，胺基甲酸酯系樹脂的分子量較佳為2000至5000。
＜2－2.光聚合起始劑＞ 作為聚合起始劑而言，可列舉例如J.Photochem.Sci.Technol.，2，283(1987).所記載之下列化合物：2,2－二甲氧基－1,2－二苯基乙烷－1－酮等苄甲縮酮類、1－羥基環己基苯基酮、2－羥基－2－甲基－1－苯基丙烷－1－酮等α－羥基酮類；2－甲基－1［4－(甲硫基)苯基］－2－嗎啉基丙烷－1－酮、2－苄基－2－二甲基胺基－1－(4－嗎啉基苯基)丁酮－1等α－胺基酮類；雙(2,6－二甲氧基苯甲醯基)－2,4,4－三甲基戊基氧化膦等雙醯基氧化膦類；2,2'－雙(鄰氯苯基)－4,4',5,5'－四苯基－1,1'－二咪唑、雙(2,4,5－三苯基)咪唑等雙咪唑類；N－苯基甘氨酸等N－芳基甘氨酸類、4,4'－二疊氮查爾酮等有機疊氮類；3,3',4,4'－四(三級丁基過氧羧基)二苯甲酮等有機過氧化物類。
具體而言，可列舉：鐵芳烴錯合物、三鹵代甲基取代S-三嗪、鋶鹽、重氮鹽、鏻鹽、硒鹽、砷鹽、碘鹽等。此外，作為碘鹽而言，可列舉如Macromolecules,10,1307(1977).所記載之化合物，例如：二苯基碘、二甲苯基碘、苯基(對茴香基)碘、雙(間硝基苯基)碘、雙(對三級丁基苯基)碘、雙(對氯苯基)碘等碘的氯化物、溴化物；或者是氟硼酸鹽、六氟磷酸鹽、六氟砷酸鹽、芳香族磺酸鹽等；二苯基苯甲醯甲基鋶(正丁基)三苯基硼酸鹽等鋶有機硼錯合物類。
＜2－3.添加劑＞ 硬塗層形成用樹脂組成物可根據需要而調配添加劑。例如可列舉賦予流平性、表面滑動性、低水接觸角性等之聚矽氧系、氟系的添加劑(例如流平劑)。藉由調配這種添加劑，可提高硬塗層的表面的抗刮性。此外，在光聚合時利用紫外線的情況下，藉由上述之添加劑滲出至空氣界面，可降低氧所致之樹脂的硬化阻礙。因此，即使在低照射強度條件下亦可獲得有效的硬化程度。這些的添加劑的調配量，相對於硬塗層形成用樹脂組成物100重量份，可為0.01重量份至0.5重量份。
＜3.硬塗層的物性＞ 硬塗層的厚度為0.25μm以上23μm以下，在需要鉛筆硬度的情況下的硬塗層的厚度的下限值較佳為6μm以上，更佳為8μm以上。此外，上限值較佳為20μm以下，更佳為14μm以下。此外，尤其在需要撓曲性的情況下的硬塗層的厚度的下限值較佳為0.5μm以上，更佳為0.75μm以上。此外，上限值較佳為1.5μm以下，更佳為1.25μm以下。這是因為若小於0.25μm，則無法獲得充分的抗摩擦性能，此外，若大於23μm則由撓曲性的方面來看並不佳。
硬塗層較佳係在馬氏硬度試驗中具有480 N／mm2 至850 N／mm2 的硬度者，更佳為500 N／mm2 至800 N／mm2 以上的硬度。這是因為若小於480 N／mm2 則如下所說明鉛筆硬度會降低，若大於850 N／mm2 則撓曲性會降低。馬氏硬度可以上述之方法來測定。
為了即使在硬塗層的膜厚較薄的情況下亦可以表現高的表面硬度，硬塗層需要與基材膜的馬氏硬度相當。由該觀點來看，馬氏硬度的比(硬塗的馬氏硬度／基材膜的馬氏硬度)較佳為0.8至3.8，更佳為0.9至3.0，更佳為1.0至2.5。
此外，硬塗層較佳為在JIS(Japanese Industrial Standards；日本工業規格)5600－5－4(1999)所規定之表面鉛筆硬度試驗中為3H以上。
此外，如上述由膜基材以及硬塗層所形成之覆蓋膜，較佳係根據圓筒形心軸法(JISK5600－5－1)使其撓曲之後，硬塗層在直徑為12mm以上的圓筒處不產生裂痕。
＜4.覆蓋膜的製造方法＞ 本發明之覆蓋膜的製造方法雖沒有特別限定，但例如在上述基材膜塗布硬塗層形成用樹脂組成物，使其乾燥之後，藉由光聚合使其硬化，可獲得覆蓋膜。
作為硬塗層形成用樹脂組成物對基材膜之塗布方法而言，可採用例如：輥塗布機、逆輥塗布機、凹版塗布機、刀塗布機、棒塗布機等公知的方法。
使塗布後之硬塗層形成用樹脂組成物乾燥的方法沒有特別限定。可列舉例如將塗布有硬塗層形成用樹脂組成物之基材膜通過乾燥器內之方法。此時的乾燥溫度較佳為例如40℃至100℃。
此外，該塗膜的硬化較佳係使用紫外線作為游離輻射源，可利用高壓汞燈、低壓汞燈、超高壓汞燈、金屬鹵素燈、碳弧、氙弧等光源。
＜5.覆蓋膜的切斷(修整)＞ 如上述的方式所製造之覆蓋膜，在切出期望的大小之後使用。覆蓋膜的切斷可藉由雷射或者是切割機來進行，但本發明人發現，因切斷所產生之硬塗層的端面的線粗度若大，則對上述之撓曲性能(抗撓曲性)帶來影響。
由該觀點來看，以上述的方式切斷後之硬塗層的端面的線粗度中之算術平均粗度Ra較佳為2.5μm以下，更佳為2.0μm以下，尤佳為1.5μm以下。
此外，端面的線粗度Ra如圖1所示，係指至少沿著覆蓋膜的撓曲方向之端面的線粗度。另外，撓曲方向通常為覆蓋膜的長邊方向的情況較多，但也可能為短邊方向。在長邊方向和短邊方向皆撓曲的情況下，撓曲較大的方向作為撓曲方向。由該觀點來看，與撓曲方向正交之方向的端面的線粗度Ra亦成為上述結果更佳。線粗度Ra的測定例如可以下列的方式來進行。
亦即，將雷射顯微鏡中物鏡的倍率設為150倍，並觀察切斷之硬塗層的端面(平行於撓曲方向之端面)。此時，以測定長度為70μm以上的條件下測定不同5點(大約等間隔的5點)的線粗度Ra，算出其平均。另外，線粗度Ra較佳係算出5點的平均，但例如測定困難的情況下，亦可為5點以下之數的平均、或是測定點設為1點。
另外，為了降低硬塗層的端面的線粗度Ra，較佳係以雷射進行切斷。此外，若線粗度Ra低，則可縮小在覆蓋膜的端部產生之毛邊。另外，雷射切斷速度沒有特別限定，例如可設為50mm／sec至600mm／sec。
此外，以雷射進行切斷的情況下，為了保護硬塗層不受切斷時產生的煙之影響，較佳係將保護片貼附在硬塗層並進行切斷。保護片可使用例如在以PET(聚對苯二甲酸乙二酯；polyethylene terephthalate)等樹脂材料所形成之基材塗布有黏著層者。然後，將黏著層貼附在硬塗層，進行雷射切斷。
＜6.特徵＞ 藉由本實施形態之覆蓋膜，可使硬塗層的端面的線粗度Ra為2.5μm以下，故提高撓曲性能。因此，可適合用作為撓曲顯示器用的覆蓋膜。 [實施例]
再來，對於本發明的實施例進行說明。然而本發明並不限定於以下的實施例。
＜1.實施例以及比較例的製作＞ 以下對於實施例1～6以及比較例1～6之覆蓋膜的製作進行說明。
首先，作為基材膜，準備100μm厚的PET膜(東麗股份有限公司製U48)。再來，準備含有(甲基)丙烯酸酯化合物之硬塗塗料(荒川化學股份有限公司製Beamset 907)作為硬塗層形成用樹脂組成物。然後，使用線棒塗布機將該硬塗層形成用樹脂組成物塗敷在基材膜其中一面。之後，將硬塗層形成用樹脂組成物在80℃以2分鐘至5分鐘的熱處理使稀釋溶劑乾燥之後，使用UV(Ultraviolet；紫外線)照射裝置(賀利氏股份有限公司製)以200mJ／cm2的積算光量使其硬化，並形成硬塗層。硬塗層的厚度為12μm。
＜2.抗撓曲性評價試驗＞ 由上述的方式製作之實施例以及比較例，一邊改變速度等條件一邊使用雷射切割裝置(GCC社製SpiritGX　30W)切出2.5×10cm、以及5×10cm的試樣片。此時，在硬塗層的表面貼附保護片，並在其上以雷射進行切出。保護片為積層有厚度為5μm的黏著層且厚度為100μm的PET膜，並將黏著層貼附在硬塗層。
此外，雷射的輸出功率為30W，將其設為50％進行切出。此外，雷射切割的速度係將100％設為2m／sec，將其調整至5％至15％並進行切出。
進而作為比較例，亦準備了以切割機所進行切出之試樣片。
然後，測定沿著切出之試樣片的長邊之端面的硬塗層的線粗度Ra。測定方法係如上述實施形態所示。此外，測定沿著試樣片的長邊之端面的毛邊的長度。毛邊係如圖2所示之長度。另外，毛邊的測定之中，測定試樣的長邊的端部的長邊方向的中心的厚度、以及試樣的中央的厚度，並將該差設為毛邊的長度。另外，雖然測定了一對的長邊的雙方，但作為測定值而言係採用長的一方。
隨後，對於以上述的方式準備之各試樣片，根據圓筒形心軸法(JISK5600－5－1)，沿著長邊使其撓曲之後，以目視觀察是否在硬塗層產生裂痕。所使用之圓筒的直徑為12mm至22mm，每2mm進行一次試驗。此時，在基材膜，圓筒係沿著未形成硬塗層之面進行測定。然後，不產生裂痕之圓筒的最大直徑作為試驗結果。結果如以下的表1所示。
[表1]
Figure 108107947-A0304-0001
＜3.馬氏硬度以及鉛筆硬度評價試驗＞ 對於上述實施例1～6以及比較例1～6的硬塗層，基於JIS－K5600－5－4進行表面鉛筆硬度試驗。亦即，在硬塗層的表面依序使用施加了750g的荷重之硬度2H至5H的鉛筆(三菱UNI)，進行試驗。然後，以目視來評價硬塗層的表面的刮痕所致之外觀的變化。結果皆為4H。
此外，實施例1～6以及比較例1～6之硬塗層的馬氏硬度皆為770N／m2 。該馬氏硬度係在玻璃板上塗布硬塗層形成用樹脂組成物並以如上述之方式形成硬塗層來測定。
＜4.考察＞ 如上所述，在抗撓曲性評價試驗中，端面的線粗度大於2.5μm之比較例1～6不產生裂痕之圓筒的最大直徑皆大於實施例1～6。因此，可知若試樣片的端面的線粗度大，則撓曲性能惡化。該傾向即使試樣片的尺寸改變亦相同，若端面的線粗度大於2.5μm，則撓曲性能惡化。然而，可知若試樣片的尺寸亦大，則實施例以及比較例之撓曲性能皆變得略低。此外，可知若端面的線粗度小，則在端部產生之毛邊亦變小。綜上所述，實施例之覆蓋膜即使在具有曲率半徑小的曲面之撓曲顯示器之中亦可適當地使用。
圖1A為說明撓曲方向與線粗度之覆蓋膜的平面圖。 圖1B為圖1A的側視圖。 圖2為說明毛邊的測定之圖。
無。

Claims (5)

  1. 一種撓曲顯示器用的覆蓋膜，具備： 透明的基材膜； 在前述透明的基材膜的至少其中一面所形成之硬塗層； 前述硬塗層之厚度為23μm以下； 該硬塗層的端面的線粗度Ra為2.5μm以下。
  2. 如請求項1所記載之覆蓋膜，其中端面藉由雷射而被切斷。
  3. 如請求項1或2所記載之覆蓋膜，其中表面鉛筆硬度為3H以上。
  4. 一種覆蓋膜的製造方法，係具備：在透明的基材膜積層厚度為23μm以下的硬塗層，以形成覆蓋膜之步驟； 在前述硬塗層上配置保護膜之步驟； 將前述覆蓋膜藉由雷射切斷之步驟； 該硬塗層的端面的線粗度Ra為2.5μm以下。
  5. 如請求項4所記載之覆蓋膜的製造方法，其中藉由前述雷射切斷的速度為50mm／sec至600mm／sec。
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