TWI714541B - 黏著片材 - Google Patents
黏著片材 Download PDFInfo
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- TWI714541B TWI714541B TW104139748A TW104139748A TWI714541B TW I714541 B TWI714541 B TW I714541B TW 104139748 A TW104139748 A TW 104139748A TW 104139748 A TW104139748 A TW 104139748A TW I714541 B TWI714541 B TW I714541B
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Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
本發明提供一種可表現較高之經時接著力、且黏著片材與被接著體之間之排氣性良好之黏著片材。根據本發明,提供一種具備膜狀基材、及設置於該膜狀基材之至少一表面之黏著劑層之黏著片材。該黏著片材具備部分地覆蓋上述黏著劑層表面之塗層,藉此該黏著劑層表面具有塗層配置部與塗層非配置部。又,上述黏著劑層表面中之上述塗層非配置部之面積比率為70%以上。進而,上述塗層配置部於自上方觀察上述黏著劑層表面時,具有自該黏著劑層之一端向另一端線狀延伸之部分。並且,上述線狀延伸之部分之寬度為0.1~2mm之範圍內。
Description
本發明係關於一種黏著片材。
本申請案主張基於2014年11月28日提出申請之日本專利申請2014-242183號及2015年8月21日提出申請之日本專利申請2015-164270號之優先權,並將該等申請之全部內容作為參照而併入本說明書中。
通常,黏著劑(亦稱為感壓接著劑,以下相同)於室溫附近之溫度區域呈現柔軟之固體(黏彈性體)之狀態,具有藉由壓力而簡單地接著於被接著體之性質。黏著劑運用此種性質,以於基材之至少一表面設置有黏著劑層之附基材之黏著片材之形態,例如以固定各種物品、或者獲得各種物品之表面保護、或裝飾等所需之外觀等目的而被廣泛利用。作為揭示此種先前技術之文獻,可列舉專利文獻1。
[專利文獻1]日本專利申請公開2000-160117號公報
於先前之黏著片材中,於將黏著片材貼附於被接著體時,存在空氣等流動性雜質殘留於黏著片材與被接著體之間,該雜質成為氣泡等(空氣積存等)而引起外觀品質降低之情形。如上所述之氣泡等在接
著力之降低等對黏著特性造成不良影響之方面亦不理想。以賦予預防此種氣泡等之產生、或去除產生之氣泡等之性質(以下亦稱為「排氣性」)為目的,提出有於黏著劑層之表面部分地積層非黏著性層之技術(專利文獻1)。然而,於專利文獻1所記載之技術中,由於非黏著性層占黏著劑層表面之面積比率較高,因此並未充分應對接著力有降低傾向等對黏著特性之影響。尤其是於貼合後繼續要求較高之接著力之用途中,根據本發明者等人之研究明確並未成為可靠性較高之接著方法。
本發明係鑒於上述情況而提出者,其目的在於提供一種可表現出較高之經時接著力、且黏著片材與被接著體之間之排氣性良好之黏著片材。
根據本發明,提供一種具備膜狀基材、及設置於該膜狀基材之至少一表面之黏著劑層之黏著片材。該黏著片材具備部分地覆蓋上述黏著劑層表面之塗層,藉此,該黏著劑層表面具有塗層配置部與塗層非配置部。又,上述黏著劑層表面中之上述塗層非配置部之面積比率為70%以上。進而,上述塗層配置部於自上方觀察上述黏著劑層表面時,具有自該黏著劑層之一端向另一端線狀延伸之部分。此外,上述線狀延伸之部分之寬度為0.1~2mm之範圍內。
作為一般傾向,黏著片材若其黏著面之面積變小,則接著性與其成正比例而亦會降低。認為即便於將塗層配置於黏著片材之黏著面之情形時,黏著面之露出面積會減少塗層被覆之量,因此表現出同樣之傾向。實際上,於下文所述之實施例中,若黏著劑層表面中之塗層之面積變大,黏著劑層之露出面積減少,則剛貼合後之初期接著力亦會以與其成正比例之方式降低。然而,本發明者等人之研究之結果表明,經時接著力表現出與上述初期接著力不同之傾向。具體而言,於
將塗層部分地配置於黏著劑層表面之構成中,判明於將黏著劑層表面之塗層非配置部之面積比率設為未達70%之情形時,自剛貼合後起難以表現出接著力上升,與上述面積比率為70%以上之情形相比,經時接著力不足之傾向增大(參照下文所述之實施例)。因此,於此處所揭示之技術中,將上述塗層非配置部之面積比率設為70%以上而獲得較高之經時接著力。然而,當然若增大塗層非配置部之面積,則塗層配置部之面積相對變小。因此,對黏著片材與被接著體之間賦予排氣性之塗層本來之作用存在受損之可能性。因此,於此處所揭示之技術中,於自上方觀察黏著劑層表面時,以具有自黏著劑層之一端向另一端線狀延伸之部分之方式配置塗層,且將該線狀延伸之部分之寬度設定為0.1~2mm之範圍內。藉此,於可表現出較高之經時接著力之黏著片材中,可實現良好之排氣性。上述線狀延伸之部分之寬度較佳為設為0.2mm以上(例如0.3mm以上,進而0.5mm以上),又,較佳為設為1.2mm以下(更佳為0.7mm以下,進而較佳為0.4mm以下)。再者,於本說明書中,所謂經時接著力係指自貼合至被接著體起經過24小時以上後之接著力。
於此處所揭示之黏著片材之較佳之一態樣中,於上述黏著劑層表面配置有複數個上述線狀延伸之部分。又,上述複數個線狀延伸之部分中構成一群之複數個線狀延伸之部分係於其寬度方向上隔開間隔而配置,藉此,上述塗層配置部具有條紋狀圖案。藉由以上述方式構成,利用構成條紋狀圖案之複數個線狀延伸之部分,而效率良好地去除會殘留於被接著體表面與黏著面之間之空氣等。
於此處所揭示之黏著片材之較佳之一態樣中,上述塗層配置部包含第1條紋狀圖案部、及以與該第1條紋狀圖案部交叉之方式配置之第2條紋狀圖案部,藉此,上述塗層配置部具有格子狀圖案。藉由以上述方式構成,而效率良好地去除會殘留於被接著體表面與黏著面之
間之空氣等。
於此處所揭示之黏著片材之較佳之一態樣中,於上述塗層配置部中構成一條紋狀圖案之複數個線狀延伸之部分之間隔為1.0~10mm之範圍內。藉由以上述方式構成,而平衡性良好地同時實現較高之經時接著力與排氣性。上述線狀延伸之部分之間隔更佳為1.5~8mm,進而較佳為2.5~5mm。
於此處所揭示之黏著片材之較佳之一態樣中,部分地配置有上述塗層之黏著性表面表現出13N/25mm以上之經過24小時後之180度剝離強度。根據此處所揭示之技術,於設置塗層之構成中,可實現上述之剝離強度。
又,根據本發明,提供一種具備此處所揭示之任一黏著片材、及保護該黏著片材之黏著劑層表面之剝離襯墊之附剝離襯墊之黏著片材。並且,該剝離襯墊之表面中上述黏著劑層側之表面係平滑地形成。藉由以上述方式構成,有黏著特性提高之傾向。又,根據此處所揭示之技術,於採用上述構成,利用剝離襯墊作為塗層轉印用膜之情形時,可實現良好之塗層轉印性。
又,根據本發明,提供一種具備至少一表面為剝離性表面之剝離性支持體之黏著片材用剝離襯墊。於該剝離襯墊之上述剝離性支持體之剝離性表面上設置有可轉印至黏著片材之塗層,藉此,該剝離性表面具有塗層配置部與塗層非配置部。又,上述剝離性表面中之上述塗層非配置部之面積比率為70%以上。進而,上述塗層具有自上述剝離性表面之一端朝向另一端線狀延伸之部分。並且,上述線狀延伸之部分之寬度為0.1~2mm之範圍內。藉由使用此種剝離襯墊將塗層轉印至黏著片材之黏著劑層表面,可較佳地實現高度兼顧較高之經時接著力與良好之排氣性之黏著片材。
1‧‧‧黏著片材
1A‧‧‧黏著性表面
1B‧‧‧非黏著性之表面
2‧‧‧黏著片材
10‧‧‧膜狀基材
20‧‧‧黏著劑層
20A‧‧‧黏著劑層表面
21‧‧‧黏著劑層
22‧‧‧黏著劑層
30‧‧‧塗層
40‧‧‧剝離襯墊
41‧‧‧剝離襯墊
42‧‧‧剝離襯墊
50‧‧‧塗層配置部
51‧‧‧塗層非配置部
60‧‧‧塗層圖案(格子狀圖案)
70‧‧‧第1條紋狀圖案部
75A‧‧‧長條部(線狀延伸之部分)
75B‧‧‧長條部(線狀延伸之部分)
75C‧‧‧長條部(線狀延伸之部分)
80‧‧‧第2條紋狀圖案部
85A‧‧‧長條部(線狀延伸之部分)
85B‧‧‧長條部(線狀延伸之部分)
85C‧‧‧長條部(線狀延伸之部分)
110‧‧‧附塗層之剝離襯墊
120‧‧‧剝離性支持體
120A‧‧‧剝離性表面
W1‧‧‧寬度
W2‧‧‧間隔
圖1係示意性表示一實施形態之黏著片材之俯視圖。
圖2係圖1之II-II線之剖視圖。
圖3係示意性表示一實施形態之附剝離襯墊之黏著片材之剖視圖。
圖4係示意性表示另一實施形態之附剝離襯墊之黏著片材之剖視圖。
圖5係示意性表示一實施形態之黏著片材用剝離襯墊之剖視圖。
以下,對本發明之較佳之實施形態進行說明。再者,關於本說明書中特別提及之事項以外且為本發明之實施所必需之事項,業者基於本說明書所記載之關於發明實施之教示及提出申請時之技術常識可理解。本發明可基於本說明書所揭示之內容及該領域中之技術常識而實施。又,於以下之圖式中,存在對發揮相同作用之構件、部位標註相同符號進行說明之情況,亦存在省略或簡化重複之說明之情況。又,為了清楚地說明本發明而將圖式所記載之實施形態模式化,未必準確表示實際作為製品所提供之本發明之黏著片材之尺寸或比例尺。
又,本說明書中之黏著片材之概念包含可稱為膠帶、黏著標籤、黏著膜等者。又,此處所揭示之黏著片材可為輥狀,亦可為單片狀。或可為進一步加工成各種形狀之形態之片材。
圖1係示意性表示一實施形態之黏著片材之俯視圖,圖2係圖1之II-II線之剖視圖。一面參照圖式,一面對該實施形態之黏著片材進行說明。
如圖1、2所示,該實施形態之黏著片材1具有膜狀基材10與黏著劑層20之積層結構。膜狀基材10支持黏著劑層20。於黏著片材1中,黏著劑層20側之表面20A構成黏著性表面1A。黏著片材1之另一表面(膜狀基材10側之表面)1B係非黏著性之表面。
於黏著劑層20之表面20A部分地配置有塗層30。換言之,黏著劑層表面20A由塗層30部分地覆蓋,具有配置有塗層30之塗層配置部50、及未配置塗層30而黏著劑層20露出至表面之塗層非配置部51。該塗層30於黏著片材1貼合於被接著體時,於黏著片材1與被接著體之間成為空氣等通過之通路,而賦予排氣性。再者,塗層30之表面可與黏著劑層表面20A處於同一平面,亦可相對於黏著劑層表面20A而厚度方向之至少一部分突出。
塗層配置部50於自上方觀察黏著劑層表面20A時呈現出特定之圖案(塗層圖案)60。於該實施形態中,塗層配置部50呈現出格子狀圖案60。具體而言,由塗層30形成之格子狀圖案60於自上方觀察黏著劑層表面20A時,包含第1條紋狀圖案部70、及以與第1條紋狀圖案部70交叉之方式配置之第2條紋狀圖案部80。
第1條紋狀圖案部70包含自黏著劑層20之一端向另一端直線狀延伸之複數個長條部(帶狀部分)75A、75B、75C,該等複數個長條部75A、75B、75C於其寬度方向上隔開間隔而平行配置。於該實施形態中,長條部75A、75B、75C係以其長度方向與黏著片材1之寬度方向之端部交叉之角度配置,分別到達黏著劑層20之兩端。再者,於本說明書中,「長條部」係以具有長度方向與寬度方向(與長度方向正交之方向)之部分之含義使用,典型而言,不論直線狀、曲線狀,均為帶狀延伸之部分。長條部可換稱為線狀延伸之部分。
第2條紋狀圖案部80亦與第1條紋狀圖案部70同樣地,包含自黏著劑層20之一端向另一端直線狀延伸之複數個長條部(帶狀部分)85A、85B、85C,該等複數個長條部85A、85B、85C於其寬度方向上隔開間隔而平行配置。於該實施形態中,長條部85A、85B、85C係以其長度方向與黏著片材1之寬度方向之端部交叉之角度配置,分別到達黏著劑層20之兩端。再者,於該實施形態中,長條部75A、
75B、75C、85A、85B、85C為直線狀,但並不限定於此,各長條部可為曲線狀延伸者。於該情形時,複數個長條部可形成之條紋狀圖案可為波狀等。
又,於該實施形態中,第1條紋狀圖案部70與第2條紋狀圖案部80以第1條紋狀圖案部70之長條部75A、75B、75C與第2條紋狀圖案部80之長條部85A、85B、85C大致正交之方式交叉。因此,第1條紋狀圖案部70之長條部75A、75B、75C與第2條紋狀圖案部80之長條部85A、85B、85C部分地重疊。
再者,於本說明書中,所謂格子狀圖案,典型而言係指包含互相交叉之兩個條紋狀圖案部之圖案,不僅包含如本實施形態之斜方格子,而且包含正方格子、三角格子等各種格子形狀。於長條部為直線狀之情形時,兩個條紋狀圖案部之交叉角度(銳角側)可於10度~90度(較佳為45度~90度,典型而言為60度~90度)之範圍內進行設定。又,此處所揭示之格子狀圖案亦包含例如六角格子之類的圖案,該圖案含有包含反覆彎曲之複數個長條部之條紋狀圖案部。該種圖案可為相鄰之長條部彼此以一部分連接而成者。就排氣性之觀點而言,塗層配置部較佳為具有1個或2個以上之條紋狀圖案部。因此,塗層配置部(典型而言為格子狀圖案)可為具有第3條紋狀圖案部者。
塗層配置部50中之各長條部75A、75B、75C、85A、85B、85C之寬度(W1)係於0.1~2mm之範圍內進行設定。藉此,可同時實現較高之經時接著力與良好之排氣性。就提高排氣性之觀點而言,上述長條部之寬度W1較佳為0.2mm以上,更佳為0.3mm以上,進而較佳為0.5mm以上。就接著力或外觀等觀點而言,上述長條部之寬度W1較佳為1.2mm以下,更佳為1.0mm以下,進而較佳為0.7mm以下,尤佳為0.5mm以下,最佳為0.4mm以下。
塗層配置部50中構成第1條紋狀圖案部70之長條部75A、75B、
75C之間隔W2較佳為設定於1.0~10mm之範圍內。藉此,於將長條部之寬度設為上述範圍內之構成中,平衡性良好地同時實現較高之經時接著力與排氣性之傾向得以提高。此處所謂長條部之間隔W2係指於黏著劑層表面存在於相鄰之兩個長條部之間的部分之寬度。就提高經時接著力等觀點而言,上述長條部之間隔W2更佳為1.5mm以上,進而較佳為2.5mm以上。上述長條部之間隔W2可為8mm以下(例如5mm以下,典型而言為3mm以下)左右。構成第2條紋狀圖案部80之長條部85A、85B、85C之間隔亦可根據上述作為長條部75A、75B、75C之間隔W2而例示之範圍內較佳地設定。上述間隔W2較佳為間隔相等。
就平衡性良好地同時實現較高之經時接著力與排氣性之觀點而言,長條部之間距較佳為設為1~20mm之範圍內。上述長條部之間距更佳為1.5mm以上,進而較佳為2mm以上(例如2.5mm以上),且更佳為15mm以下(例如12mm以下),進而較佳為5mm以下。再者,上述間距係指上述長條部之寬度方向之中心線間的距離(間隔)。
如圖3所示,黏著片材1於使用前可為黏著劑層20具有至少黏著劑層表面20A側由成為剝離面之剝離襯墊40保護之構成之附剝離襯墊之黏著片材1之形態。又,或者可為膜狀基材10之背面(與黏著劑層20側之表面為相反側之面)成為剝離面,藉由捲繞黏著片材1使黏著劑層20抵接於該背面,從而黏著劑層20由膜狀基材10之背面保護之構成。此種僅單面具有接著性之單面接著性之黏著片材(單面黏著片材)例如於對與黏著性表面為相反側之表面要求裝飾性、表面保護性等特性之情形時、或用作塗料代替片材之情形時較佳。
又,於此處所揭示之黏著片材為如圖4所示之雙面接著型之附基材之黏著片材(雙面黏著片材)之情形時,黏著片材2可為具有於膜狀基材10之各面(均為非剝離性)分別設置黏著劑層21、22,該等黏著劑
層21、22係至少該黏著劑層側分別由成為剝離面之剝離襯墊41、42保護之構成者。再者,於該黏著片材2中,僅於黏著劑層21之表面部分地配置有塗層30,於黏著劑層22之表面未設置塗層。或並未特別圖示,但雙面黏著片材亦可具有於膜狀基材之各面(均為非剝離性)分別設置黏著劑層,該等中一黏著劑層係雙面由成為剝離面之剝離襯墊保護之構成。此種黏著片材成為藉由捲繞該黏著片材,使另一黏著劑層抵接於剝離襯墊之背面,從而兩個黏著劑層由一個剝離襯墊保護之構成。上述雙面黏著片材例如可較佳地用於接合固定用途等。
<黏著片材之特性等>
此處所揭示之黏著片材之特徵在於:其黏著劑層表面之塗層非配置部之面積比率(亦可為黏著片材之接著面(黏著性表面)中之塗層之面積比率)為70%以上。藉此,可確保較高之經時接著力。上述面積比率較佳為75%以上,更佳為80%以上。就獲得良好之排氣性之觀點而言,上述面積比率較佳為90%以下,更佳為85%以下。
於較佳之一態樣中,黏著片材之黏著性表面(典型而言包含黏著劑層表面與塗層表面)表現出13N/25mm以上之經過24小時後之180度剝離強度(以下亦稱為「經過24小時後之接著力」)。藉由上述黏著片材,可具有良好之空氣等排除性,並且發揮特定以上之經時接著力。上述經過24小時後之接著力較佳為14N/25mm以上(例如16N/25mm以上)。再者,上述經過24小時後之接著力藉由下述方法測定即可。具體而言,對於將黏著片材切割成寬25mm、長100mm之尺寸而得之測定樣品,於23℃、50%RH之環境下,使2kg之輥往返一次而將上述測定樣品之黏著性表面壓合於不鏽鋼板(SUS304BA板)之表面。將其於相同環境下放置24小時後,使用萬能拉伸壓縮試驗機,依照JIS Z 0237:2000,於拉伸速度300mm/min、剝離角度180度之條件下,測定剝離強度(N/25mm)。更具體而言,藉由下文所述之實施例所記載
之方法進行測定。
於較佳之一態樣中,黏著片材係透明性(包含半透明)之黏著片材。於此種黏著片材中,若氣泡等混入至黏著片材與被接著體之間,則隔著黏著片材可視認到該氣泡等而外觀性容易受損。根據此處所揭示之技術,可防止黏著片材與被接著體之間之氣泡等之產生,因此於具有透明性之黏著片材中,可獲得優異之外觀性。具體而言,上述黏著片材可為表現出80%以上(例如90%以上,典型而言為95%以上)之全光線透過率者。又,黏著片材之霧值較佳為10%以下(例如5%以下)。上述全光線透過率及霧值依據JIS K 7136:2000,使用市售之透過率計(例如,商品名「HAZEMETER HM-150」,村上色彩技術研究所公司製造)測定即可。下文所述之膜狀基材之全光線透過率及霧值亦藉由同樣之方法而測定。
此處所揭示之黏著片材(包含黏著劑層與基材,但不含剝離襯墊)之總厚度並無特別限定,大致設為2~1000μm之範圍較為適當,較佳為5~500μm(例如10~300μm,典型而言為30~100μm)。總厚度受到限制之黏著片材可成為於應用該黏著片材之製品之小型化、輕量化、省資源化等方面有利者。
<膜狀基材>
作為此處所揭示之膜狀基材,例如可使用樹脂膜、紙、布、橡膠膜、發泡體膜、金屬箔、該等之複合體或積層體等。其中,就貼附性或外觀性之觀點而言,較佳為含有樹脂膜層。就尺寸穩定性、厚度精度、加工性、拉伸強度等觀點而言,含有樹脂膜層亦有利。作為樹脂膜之例,可列舉:聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物等聚烯烴系樹脂膜;聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等聚酯系樹脂膜;氯乙烯系樹脂膜;乙酸乙烯酯系樹脂膜;聚醯亞胺系樹脂膜;聚醯胺系樹脂膜;氟系樹脂膜;塞璐芬
(cellophane)等。作為較佳例,可列舉由PE、PP、PET形成之樹脂膜。樹脂膜中更佳為聚酯膜,其中進而較佳為PET膜。膜狀基材可為單層結構,亦可具有兩層或三層以上之多層結構。
於較佳之一態樣中,膜狀基材係具備發泡體膜之基材(含發泡體之基材)。藉此,可對黏著片材賦予減震功能。此處,所謂發泡體膜係指具備具有氣泡(氣泡結構)之部分之膜狀結構體。含發泡體之基材可為含有發泡體膜之單層結構體,亦可為兩層以上之多層結構中之至少一層含有發泡體膜(發泡體層)之多層結構體。作為含發泡體之基材之構成例,可列舉積層發泡體膜(發泡體層)與非發泡體膜(非發泡體層)而成之複合基材。所謂非發泡體膜(非發泡體層)係指未進行用以製成發泡體之刻意處理(例如氣泡導入處理)之膜狀結構體,指實質上不具有氣泡結構之膜。作為非發泡體膜之典型例,可列舉發泡倍率未達1.1倍(例如未達1.05倍,典型而言為未達1.01倍)之樹脂膜(例如PET等聚酯系樹脂膜)。於膜狀基材含有兩層以上之發泡體層之情形時,該等發泡體層之材質或結構可相同,亦可不同。又,於發泡體膜具有含有發泡體層之多層結構之情形時,就提高層間密接性之觀點而言,亦可於各層之間配置接著層。
上述發泡體膜之平均氣泡直徑並無特別限定,通常為10μm~200μm較為適當,較佳為20μm~180μm,進而較佳為30μm~150μm。藉由將平均氣泡直徑設為10μm以上,有減震性提高之傾向。另一方面,藉由將平均氣泡直徑設為200μm以下,有操作性或防水性(止水性)提高之傾向。
發泡體膜之平均氣泡直徑(μm)可藉由使用市售之低真空掃描電子顯微鏡掃描發泡體剖面之放大圖像並進行圖像解析而求出。解析之氣泡數設為10~20個左右即可。作為低真空掃描電子顯微鏡,例如可使用Hitachi High-Tech Science Systems公司製造之商品名「S-3400N型
掃描電子顯微鏡」。
上述發泡體膜之密度(視密度)並無特別限定,通常設為0.01g/cm3以上較為適當,較佳為0.01~0.7g/cm3,進而較佳為0.02~0.5g/cm3。藉由將密度設為0.01g/cm3以上,有發泡體膜之強度(進而黏著片材之強度)提高、耐衝擊性或操作性提高之傾向。另一方面,藉由將密度設為0.7g/cm3以下,有柔軟性不會過度降低、階差追隨性提高之傾向。
發泡體膜之密度(視密度)係依據JIS K 7222:1999所記載之方法而測定。具體而言,將發泡體膜沖裁為100mm×100mm之尺寸而製作試樣,並測定該試樣之尺寸。又,使用測定端子之直徑為20mm之1/100針盤量規測定試樣之厚度。根據該等值算出發泡體膜試樣之體積。又,藉由最小刻度0.01g以上之上皿天平測定上述試樣之重量。根據該等值可求出發泡體膜之視密度(g/cm3)。
上述發泡體膜之50%壓縮荷重並無特別限定。就耐衝擊性之觀點而言,發泡體膜表現出0.1N/cm2以上之50%壓縮荷重較為適當。藉由50%壓縮荷重為特定值以上,例如即便於發泡體膜厚度較薄(例如100μm左右之厚度)之情形時,亦可於被壓縮時表現出充分之阻力(被壓縮時欲回彈之力),而保持良好之耐衝擊性。上述50%壓縮荷重較佳為0.2N/cm2以上,更佳為0.5N/cm2以上。又,就平衡性良好地同時實現柔軟性與耐衝擊性之觀點而言,上述50%壓縮荷重為8N/cm2以下較為適當,較佳為6N/cm2以下,更佳為3N/cm2以下。
發泡體膜之50%壓縮荷重(硬度)係依據JIS K 6767:1999而測定。具體而言,將發泡體膜裁切為100mm×100mm,以總厚度成為2mm以上之方式進行積層,以其作為測定樣品。於室溫條件下,使用壓縮試驗機,對上述測定樣品以10mm/min之速度進行壓縮,於壓縮率達到50%時(相對於初始厚度,厚度被壓縮至50%之時間點),記錄
保持10秒後之值(反彈應力:N/cm2)作為50%壓縮荷重。關於其他條件(例如夾具或計算方法等),依據JIS K 6767:1999即可。
此處所揭示之構成發泡膜之發泡體之氣泡結構並無特別限制。作為氣泡結構,可為連續氣泡結構、獨立氣泡結構、半連續半獨立氣泡結構之任一種。就減震性之觀點而言,較佳為連續氣泡結構、半連續半獨立氣泡結構。
發泡體膜之材質並無特別限制。典型而言,發泡體膜可由含有聚合物成分(例如熱塑性聚合物)之材料形成。通常較佳為由塑膠材料之發泡體(塑膠發泡體)形成之發泡體膜。用以形成塑膠發泡體之塑膠材料(為包含橡膠材料之含義)並無特別限制,可自公知之塑膠材料中適當進行選擇。塑膠材料(典型而言為熱塑性聚合物)可單獨使用一種,或可適當組合兩種以上而使用。再者,以下存在將膜狀基材或發泡體膜所含之聚合物成分之主成分(典型而言,含有超過50重量%之成分)稱為「基礎聚合物」之情況。
作為發泡體之具體例,可列舉:PE製發泡體、PP製發泡體等聚烯烴製樹脂發泡體;PET製發泡體、聚萘二甲酸乙二酯製發泡體、聚對苯二甲酸丁二酯製發泡體等聚酯系樹脂製發泡體;聚氯乙烯製發泡體等聚氯乙烯系樹脂製發泡體;乙酸乙烯酯系樹脂製發泡體;丙烯酸系樹脂製發泡體;聚苯硫醚樹脂製發泡體;聚醯胺(尼龍)樹脂製發泡體、全芳香族聚醯胺(芳族聚醯胺)樹脂製發泡體等醯胺系樹脂製發泡體;聚醯亞胺系樹脂製發泡體;聚醚醚酮(PEEK)製發泡體;聚苯乙烯製發泡體等苯乙烯系樹脂製發泡體;聚胺基甲酸酯樹脂製發泡體等胺基甲酸酯系樹脂製發泡體等。又,作為發泡體,亦可使用聚氯丁二烯橡膠製發泡體等橡膠系樹脂製發泡體。
於較佳之一態樣中,使用丙烯酸系樹脂發泡體(丙烯酸系樹脂製發泡體)作為發泡體。此處,所謂丙烯酸系樹脂發泡體係指含有丙烯
酸系聚合物作為基礎聚合物之發泡體。本說明書中之丙烯酸系聚合物之定義如下文所述。作為構成丙烯酸系聚合物之(甲基)丙烯酸烷基酯,可較佳地使用具有碳原子數1~20(較佳為1~8,典型而言為1~4)之鏈狀烷基之(甲基)丙烯酸烷基酯之一種或兩種以上。作為(甲基)丙烯酸烷基酯之較佳例,可列舉丙烯酸乙酯、丙烯酸正丁酯及丙烯酸2-乙基己酯。作為主單體之(甲基)丙烯酸烷基酯之量設為丙烯酸系聚合物之全部單體成分中之70重量%以上較為適當,較佳為75重量%以上(例如80重量%以上)。又,上述(甲基)丙烯酸烷基酯之量為全部單體成分中之98重量%以下較為適當,較佳為97重量%以下(例如96重量%以下)。
與作為主單體之(甲基)丙烯酸烷基酯具有共聚合性之副單體可於在丙烯酸系聚合物中導入交聯點、或提高丙烯酸系聚合物之凝聚力之方面發揮作用。作為副單體,例如可使用含羧基之單體、含羥基之單體、含酸酐基之單體、含醯胺基之單體、含胺基之單體、含氰基之單體、具有含氮原子環之單體等含官能基之單體之一種或兩種以上。又,副單體可為乙酸乙烯酯等乙烯酯系單體、苯乙烯等芳香族乙烯化合物、含磺酸基之單體、含磷酸基之單體等。上述副單體之量設為丙烯酸系聚合物之全部單體成分中之0.5重量%以上較為適當,較佳為1重量%以上。又,副單體之量為全部單體成分中之30重量%以下較為適當,較佳為10重量%以下。
於使用乳液型之樹脂組合物,採用攪拌等以機械方式混入空氣等氣體之發泡方法形成發泡體之情形時,較佳為於構成丙烯酸系聚合物之單體成分中含有含氮原子之單體作為副單體。藉此,可發揮如下作用:於發泡時容易產生氣泡,又,於形成發泡體時(典型而言,上述樹脂組合物之乾燥時),上述組合物之黏度上升,容易將氣泡保持於發泡體內。
作為上述含氮原子之單體,例如可列舉:丙烯腈、甲基丙烯腈等含氰基之單體;N-乙烯基-2-吡咯啶酮等含內醯胺環之單體;(甲基)丙烯醯胺、N-羥基乙基(甲基)丙烯醯胺、N-羥甲基丙烯醯胺、N,N-二甲基丙烯醯胺、N,N-二乙基丙烯醯胺、二丙酮丙烯醯胺等含醯胺基之單體等。該等可單獨使用一種,或可組合兩種以上而使用。其中,較佳為丙烯腈等含氰基之單體、N-乙烯基-2-吡咯啶酮等含內醯胺環之單體。
上述含氮原子之單體之量設為丙烯酸系聚合物之全部單體成分中之2重量%以上較為適當,較佳為3重量%以上(例如4重量%以上)。又,上述含氮原子之單體之量為全部單體成分中之30重量%以下較為適當,較佳為25重量%以下(例如20重量%以下)。
獲得丙烯酸系聚合物之方法並無特別限定,可適當採用溶液聚合法、乳液聚合法、塊狀聚合法、懸浮聚合法、活性能量線聚合法(例如UV(ultraviolet,紫外線)聚合法)等已知作為丙烯酸系聚合物之合成方法之各種聚合方法。例如,使單體混合物溶解或分散於適當之聚合溶劑(甲苯、乙酸乙酯、水等)中,使用偶氮系聚合起始劑或過氧化物系起始劑等聚合起始劑進行聚合操作,藉此可獲得所需之丙烯酸系聚合物。就起泡性或環境方面而言,可較佳地使用藉由乳液聚合法獲得之丙烯酸系樹脂發泡體(乳液型丙烯酸系樹脂發泡體)。
就提高凝聚力之觀點而言,丙烯酸系樹脂發泡體形成用組合物較佳為含有交聯劑。交聯劑之種類並無特別限制,可適當選擇各種交聯劑之一種或兩種以上而使用。作為交聯劑之較佳例,可列舉異氰酸酯系交聯劑、環氧系交聯劑、唑啉系交聯劑、碳二醯亞胺系交聯劑、三聚氰胺系交聯劑、金屬氧化物系交聯劑。其中,較佳為唑啉系交聯劑。交聯劑之使用量並無特別限制,相對於丙烯酸系聚合物100重量份而自大致10重量份以下(例如大致0.005~10重量份,較佳
為大致0.01~5重量份)之範圍中選擇較為適當。
於其他較佳之一態樣中,使用聚烯烴系樹脂發泡體(聚烯烴製樹脂發泡體)作為發泡體。作為構成上述聚烯烴系發泡體之塑膠材料,可無特別限定地使用公知或慣用之各種聚烯烴系樹脂。例如可列舉:低密度聚乙烯(LDPE)、直鏈狀低密度聚乙烯(LLDPE)、高密度聚乙烯(HDPE)、茂金屬觸媒系直鏈狀低密度聚乙烯等聚乙烯、聚丙烯、乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物等。此種聚烯烴系樹脂可單獨使用一種,或可適當組合兩種以上而使用。
作為此處所揭示之技術中之發泡體膜之較佳例,就耐衝擊性或防水性等觀點而言,可列舉實質上含有聚乙烯系樹脂之發泡體之聚乙烯系發泡體膜、實質上含有聚丙烯系樹脂之發泡體之聚丙烯系發泡體膜等。此處,所謂聚乙烯系樹脂係指以乙烯作為主單體(即,單體中之主成分)之樹脂,除了HDPE、LDPE、LLDPE等以外,可包含乙烯之共聚合比率超過50重量%之乙烯-丙烯共聚物或乙烯-乙酸乙烯酯共聚物等。同樣地,所謂聚丙烯系樹脂係指以丙烯作為主單體之樹脂。作為此處所揭示之技術中之發泡體膜,可較佳地採用聚丙烯系發泡體膜。
發泡體膜之發泡方法並無特別限定,可根據目的或操作性等單獨或組合採用化學方法、物理方法等方法。就污染性等觀點而言,較佳為物理發泡法。具體而言,可列舉:於膜形成材料中預先含有烴等低沸點化合物或熱膨脹微小球等發泡劑而由該發泡劑形成氣泡之發泡方法;以機械方式混入空氣等氣體之發泡方法;利用水等溶劑之去除之溶劑去除發泡法、利用超臨界流體之發泡法等。又例如,亦可較佳地採用於加壓條件下向發泡體膜形成用聚合物中注入惰性氣體(例如二氧化氧)並將其減壓,藉此形成發泡體膜之方法。藉由該方法,容易將平均氣泡直徑限制為特定以下,且容易將發泡體膜低密度化。
藉由採用如上所述之發泡方法,而製作發泡體膜。發泡體膜之形成並無特別限制,例如,於採用以機械方式混入空氣等氣體之發泡方法之情形時,其後,將含有氣泡之樹脂組合物(例如乳液型樹脂組合物)塗附於基材或剝離紙等上並加以乾燥,藉此可獲得發泡體膜。就氣泡穩定性等觀點而言,乾燥較佳為包括50℃以上且未達125℃之預乾燥步驟、及125℃~200℃之正式乾燥步驟。或亦可使用軋光機或擠出機、傳送帶流延法等連續形成膜狀之發泡體,亦可採用以分批方式將發泡體形成材料之混練物發泡成形之方法。於形成發泡體膜時,可藉由切片加工去除表層部分,以成為所需之厚度、發泡特性之方式進行調整。
於上述發泡體膜可含有之熱塑性聚合物(例如聚烯烴系聚合物)中可含有於常溫下表現作為橡膠之性質、於高溫下表現熱塑性之熱塑性彈性體。就柔軟性或追隨性之觀點而言,例如可使用如下熱塑性彈性體中之一種或兩種以上:乙烯-丙烯共聚物、乙烯-丙烯-二烯共聚物、乙烯-乙酸乙烯酯共聚物、聚丁烯、聚異丁烯、氯化聚乙烯等烯烴系彈性體;苯乙烯-丁二烯-苯乙烯共聚物等苯乙烯系彈性體;熱塑性聚酯系彈性體;熱塑性聚胺基甲酸酯系彈性體;熱塑性丙烯酸系彈性體等,其中,可較佳地使用玻璃轉移溫度為室溫以下(例如20℃以下)之熱塑性彈性體。上述發泡體膜中之熱塑性彈性體之含有比率較佳為設為發泡體膜中之熱塑性聚合物之大致10~90重量%(例如20~80重量%)左右。
就氣泡形成氣體之混入性或氣泡之穩定性之觀點而言,發泡體膜形成材料(例如乳液型丙烯酸系樹脂組合物)中可使用例如陰離子性界面活性劑、陽離子性界面活性劑、非離子性界面活性劑、兩性界面活性劑等各種界面活性劑作為起泡劑。亦可使用烴系或氟系之界面活性劑。其中,就氣泡直徑之微細化或氣泡穩定性之觀點而言,較佳為
陰離子系界面活性劑,更佳為硬脂酸銨等脂肪酸銨(典型而言為高級脂肪酸銨)系界面活性劑。上述界面活性劑可單獨使用一種,或可組合使用兩種以上。上述界面活性劑之含量較佳為相對於發泡體膜之基礎聚合物100重量份,設為0.1~10重量份(例如0.5~8重量份)左右。再者,本說明書中之起泡劑中不僅含有表現起泡作用之劑,而且含有將氣泡直徑微細化之氣泡直徑調整劑、或整泡劑等氣泡穩定劑。
於發泡體膜形成材料為水性分散液(例如丙烯酸乳液)之情形時,較佳為使用聚矽氧系化合物作為上述起泡劑。藉此,有壓縮後之厚度回覆性(回覆之程度或速度)提高之傾向。作為聚矽氧系化合物,較佳為矽氧烷鍵為2000個以下之聚矽氧系化合物。作為聚矽氧系化合物,例如,可列舉聚矽氧油、改性聚矽氧油、聚矽氧樹脂等。其中,較佳為二甲基聚矽氧油、甲基苯基聚矽氧油。作為聚矽氧系化合物,亦可使用聚矽氧改性聚合物(例如,聚矽氧改性丙烯酸系聚合物、聚矽氧改性胺基甲酸酯系聚合物等)。該等可單獨使用一種,或可組合兩種以上而使用。聚矽氧系化合物之含量較佳為相對於發泡體膜之基礎聚合物100重量份,設為0.01~5重量份(例如0.05~4重量份,典型而言為0.1~3重量份)左右。
又,就氣泡穩定性、成膜性提高之觀點而言,發泡體膜形成材料(例如乳液型丙烯酸系樹脂組合物)亦可含有增黏劑。作為增黏劑,並無特別限制,例如,可列舉丙烯酸系增黏劑、胺基甲酸酯系增黏劑、聚乙烯醇系增黏劑等。其中,較佳為聚丙烯酸系增黏劑、胺基甲酸酯系增黏劑。增黏劑之含量較佳為相對於發泡體膜之基礎聚合物100重量份,設為0.1~10重量份(例如0.1~5重量份)左右。
於使用含發泡體之基材作為上述膜狀基材之情形時,發泡體膜較佳為含有例如金屬氫氧化物(例如氫氧化鎂)等氣泡成核劑。藉此,有發泡體膜中之平均氣泡直徑之調整變得容易,容易獲得所需之減震
性或柔軟性等之傾向。氣泡成核劑可為金屬氧化物、複合氧化物、金屬碳酸鹽、金屬硫酸鹽等。氣泡成核劑之含量較佳為相對於發泡體膜之基礎聚合物100重量份,設為0.5~125重量份(例如1~120重量份)左右。
於使用含發泡體之基材作為上述膜狀基材之情形時,就抑制氣泡形成時氣體成分自發泡體透過之觀點而言,發泡體膜較佳為含有脂肪醯胺等氣體透過抑制劑。更佳為脂肪醯胺具有雙醯胺結構。氣體透過抑制劑亦可為脂肪酸金屬鹽。氣體透過抑制劑之含量較佳為相對於發泡體膜之基礎聚合物100重量份,設為0.5~10重量份(例如0.7~8重量份,典型而言為1~6重量份)左右。
為了使膜形成材料具有所需之流動性而改善柔軟性等特性,上述膜狀基材(例如發泡體膜)亦可含有軟化劑。又,藉由使發泡體膜含有軟化劑,可較佳地調節膜延伸性或發泡倍率等特性。例如,可較佳地使用液態石蠟、石蠟、微晶石蠟、聚乙烯石蠟等烴系軟化劑、或硬脂酸單甘油酯等酯系軟化劑、脂肪酸系軟化劑之一種或兩種以上。軟化劑之含量較佳為相對於膜狀基材(例如發泡體膜)之基礎聚合物100重量份,設為0.5~50重量份(例如0.8~40重量份,典型而言為1~30重量份)左右。
又,於使用乳液型丙烯酸系樹脂發泡體之情形時,為了防止與發泡體膜鄰接之金屬構件之腐蝕,亦可含有任意之防銹劑。作為防銹劑,較佳為含唑環之化合物。藉由使用含唑環之化合物,可以較高之水準同時實現防金屬腐蝕性及對被接著體之密接性。其中,較佳為唑環與苯環等芳香環形成縮合環之化合物,尤佳為苯并三唑系化合物、苯并噻唑系化合物。防銹劑之含量較佳為相對於發泡體膜之基礎聚合物100重量份,設為0.2~5重量份(例如0.3~2重量份)左右。
於較佳之一態樣中,膜狀基材具有透明性(包含半透明)。於具備
此種膜狀基材之黏著片材中,若氣泡等混入至黏著片材與被接著體之間,則隔著黏著片材可視認到該氣泡等而外觀性容易受損。根據此處所揭示之技術,可防止黏著片材與被接著體之間之氣泡等之產生,因此於具備透明性基材之構成中,可獲得優異之外觀性。具體而言,上述膜狀基材可為表現出80%以上(例如90%以上,典型而言為95%以上)之全光線透過率者。又,膜狀基材之霧值較佳為10%以下(例如5%以下)。
為了賦予所需之設計性或光學特性,上述膜狀基材(例如樹脂膜)可含有各種著色劑(例如顏料)而被著色為黑色、白色及其他顏色。作為黑色系著色劑,較佳為碳黑。又,亦可採用藉由印刷等於膜狀基材之至少一表面(單面或雙面)積層一層或兩層以上之著色層(例如黑色層或白色層)之方法。
可視需要而進一步於上述膜狀基材(例如樹脂膜基材或發泡體膜基材)中調配填充劑(無機填充劑、有機填充劑等)、防老化劑、抗氧化劑、紫外線吸收劑、抗靜電劑、潤滑劑、塑化劑等各種添加劑。
於黏著片材為單面黏著片材之情形時,膜狀基材之表面中與設置黏著劑層之面為相反側之表面(背面)較佳為平滑地形成。由於上述平滑表面可成為黏著片材之外表面,因此於將具有該平滑表面之黏著片材用作例如裝飾片材或表面保護片材之情形時,可賦予更良好之外觀性(設計性)。於較佳之一態樣中,就黏著特性、外觀性(設計性)之觀點而言,膜狀基材之背面之算術平均表面粗糙度可為1μm以下(例如大致為0.05~0.75μm,典型而言大致為0.1~0.5μm)。再者,於本說明書中,算術平均表面粗糙度可使用通常之表面粗糙度測定裝置(例如,Veeco公司製造之非接觸三維表面形狀測定裝置,型式「Wyko NT-3300」)進行測定。
又,於捲繞單面黏著片材而使黏著劑層之表面抵接於膜狀基材
之背面之情形時,可視需要對該膜狀基材之背面(與設置黏著劑層之面為相反側之面)實施藉由聚矽氧系、長鏈烷基系、氟系等剝離處理劑進行之剝離處理。藉由實施剝離處理,可獲得使將黏著片材捲繞成輥狀而成之捲繞體之回捲變得容易等效果。另一方面,以提高基材與黏著劑層之密接性等為目的,亦可對上述膜狀基材之黏著劑層側表面實施電暈放電處理、底塗劑之塗附等先前公知之表面處理。
膜狀基材之厚度並無特別限定,可根據目的適當進行選擇。通常,上述厚度通常設為1μm以上(例如2~500μm左右)較為適當,較佳為設為5~500μm(例如10~200μm,典型而言為15~100μm)左右。對膜狀基材之厚度進行限制就黏著片材之薄膜化、小型化、輕量化、省資源化等方面而言有利。
於膜狀基材含有發泡體膜之情形時,含發泡體之基材(例如發泡體膜基材)之厚度可根據黏著片材之強度或柔軟性、使用目的等而適當設定。就減震性等觀點而言,將含發泡體之基材之厚度設為30μm以上較為適當,較佳為50μm以上,更佳為60μm以上(例如80μm以上)。就黏著片材之薄膜化、小型化、輕量化、省資源化等觀點而言,通常將含發泡體之基材之厚度設為1mm以下較為適當。藉由使用此處所揭示之發泡體膜,即便上述厚度為350μm以下(更佳為250μm以下,例如180μm以下)左右,亦可發揮優異之減震功能。再者,含發泡體之基材中之發泡體膜(可為發泡體層)之厚度亦可自上述作為含發泡體之基材之厚度而例示之範圍中較佳地選定。
<黏著劑層>
典型而言,此處所揭示之黏著劑層係指含有於室溫附近之溫度區域呈現柔軟之固體(黏彈性體)之狀態、具有藉由壓力而簡單地接著於被接著體之性質之材料(黏著劑)之層。此處所謂之黏著劑如「C.A.Dahlquist,“Adhesion:Fundamental and Practice”,McLaren & Sons,
(1966)P.143」所定義般,通常為具有滿足複拉伸彈性模數E*(1Hz)<107dyne/cm2之性質之材料(典型而言,於25℃下具有上述性質之材料)。
此處所揭示之黏著劑層可含有黏著劑之領域公知之丙烯酸系聚合物、橡膠系聚合物、聚酯系聚合物、胺基甲酸酯系聚合物、聚醚系聚合物、聚矽氧系聚合物、聚醯胺系聚合物、氟系聚合物等之一種或兩種以上作為基礎聚合物。就黏著特性(例如剝離強度或耐反斥性)或分子設計等觀點而言,可較佳地採用丙烯酸系聚合物。換言之,黏著劑層較佳為含有丙烯酸系聚合物作為基礎聚合物之丙烯酸系黏著劑層。再者,所謂黏著劑之「基礎聚合物」係指該黏著劑所含之聚合物成分之主成分(典型而言,含有超過50重量%之成分)。
作為上述丙烯酸系聚合物,較佳為例如含有(甲基)丙烯酸烷基酯作為主單體、進而可含有與該主單體具有共聚合性之副單體之單體原料之聚合物。此處所謂主單體係指上述單體原料中占單體組成超過50重量%之成分。
作為(甲基)丙烯酸烷基酯,例如可較佳地使用下述式(1)所表示之化合物。
CH2=C(R1)COOR2 (1)
此處,上述式(1)中之R1為氫原子或甲基。又,R2為碳原子數1~20之鏈狀烷基(以下有時將此種碳原子數之範圍表示為「C1-20」)。就黏著劑之儲存模數等觀點而言,較佳為R2為C1-12(例如C2-10,典型而言為C4-8)之鏈狀烷基之(甲基)丙烯酸烷基酯。上述R2為C1-20之鏈狀烷基之(甲基)丙烯酸烷基酯可單獨使用一種,或可組合使用兩種以上。作為較佳之(甲基)丙烯酸烷基酯,可列舉丙烯酸正丁酯及丙烯酸2-乙基己酯。
與作為主單體之(甲基)丙烯酸烷基酯具有共聚合性之副單體可於
在丙烯酸系聚合物中導入交聯點、或提高丙烯酸系聚合物之凝聚力之方面發揮作用。作為副單體,例如可使用含羧基之單體、含羥基之單體、含酸酐基之單體、含醯胺基之單體、含胺基之單體、具有含氮原子環之單體等含官能基之單體之一種或兩種以上。又,副單體可為乙酸乙烯酯等乙烯酯系單體、苯乙烯等芳香族乙烯化合物、含磺酸基之單體、含磷酸基之單體等。例如,就提高凝聚力之觀點而言,較佳為作為上述副單體而使含羧基之單體、含羥基之單體共聚合而成之丙烯酸系聚合物。作為含羧基之單體之較佳例,可列舉丙烯酸、甲基丙烯酸。作為含羥基之單體之較佳例,可列舉丙烯酸2-羥基乙酯或丙烯酸4-羥基丁酯。
上述副單體之量設為丙烯酸系聚合物之全部單體成分中之0.5重量%以上較為適當,較佳為1重量%以上。又,副單體之量為全部單體成分中之30重量%以下較為適當,較佳為10重量%以下(例如5重量%以下)。於使含羧基之單體與丙烯酸系聚合物共聚合之情形時,就同時實現黏著力與凝聚力之觀點而言,含羧基之單體之含量較佳為於丙烯酸系聚合物之合成所使用之全部單體成分中大致為0.1~10重量%(例如0.2~8重量%,典型而言為0.5~5重量%)之範圍內。於使含羥基之單體與丙烯酸系聚合物共聚合之情形時,就同時實現黏著力與凝聚力之觀點而言,含羥基之單體之含量較佳為於丙烯酸系聚合物之合成所使用之全部單體成分中大致為0.001~10重量%(例如0.01~5重量%,典型而言為0.02~2重量%)之範圍內。又,於作為上述副單體而使乙酸乙烯酯等乙烯酯系單體共聚合之情形時,上述乙烯酯系單體之含量較佳為於丙烯酸系聚合物之合成所使用之全部單體成分中大致設為30重量%以下(典型而言為0.01~30重量%、例如0.1~10重量%)。
獲得丙烯酸系聚合物之方法並無特別限定,可適當採用溶液聚合法、乳化聚合法、塊狀聚合法、懸浮聚合法等已知作為丙烯酸系聚
合物之合成方法之各種聚合方法。亦可採用照射UV等進行之活性能量線照射聚合。例如,使單體混合物溶解或分散於適當之聚合溶劑(甲苯、乙酸乙酯、水等)中,使用偶氮系聚合起始劑或過氧化物系起始劑等聚合起始劑進行聚合操作,藉此可獲得所需之丙烯酸系聚合物。
就平衡性良好地同時實現黏著力與凝聚力之觀點而言,此處所揭示之丙烯酸系聚合物之重量平均分子量(Mw)較佳為處於10×104以上且100×104以下之範圍內。藉由Mw為20×104以上且70×104以下(例如30×104以上且50×104以下)之丙烯酸系聚合物,可實現更良好之結果。再者,於本說明書中,所謂Mw係指藉由GPC(凝膠滲透層析法)獲得之標準聚苯乙烯換算之值。
就提高凝聚力之觀點而言,黏著劑組合物較佳為含有交聯劑。交聯劑之種類並無特別限制,可適當選擇使用先前公知之交聯劑之一種或兩種以上。作為交聯劑之較佳例,可列舉異氰酸酯系交聯劑、環氧系交聯劑。交聯劑之使用量並無特別限制,例如,可相對於丙烯酸系聚合物100重量份而自大致10重量份以下(例如大致0.005~10重量份,較佳為大致0.01~5重量份)之範圍中選擇。
此處所揭示之黏著劑層可為含有黏著賦予劑之組成。作為黏著賦予劑,並無特別限制,例如可使用松脂系黏著賦予樹脂、萜系黏著賦予樹脂、烴系黏著賦予樹脂、環氧系黏著賦予樹脂、聚醯胺系黏著賦予樹脂、彈性體系黏著賦予樹脂、酚系黏著賦予樹脂、酮系黏著賦予樹脂等各種黏著賦予樹脂。此種黏著賦予樹脂可單獨使用一種,或可組合兩種以上而使用。
黏著賦予樹脂之軟化點(軟化溫度)較佳為大致60℃以上(較佳為大致80℃以上,典型而言為100℃以上)。藉此,可實現接著力更高之黏著片材。黏著賦予樹脂之軟化點之上限並無特別限制,可設為大致
180℃以下(例如大致140℃以下)。再者,此處所謂之黏著賦予樹脂之軟化點係作為藉由JIS K5902:2006及JIS K2207:2006之任一者所規定之軟化點試驗方法(環球法)測定獲得之值而定義。
黏著賦予劑之使用量並無特別限制,可根據目標黏著性能(接著力等)適當進行設定。例如,較佳為以固形物成分基準計,相對於基礎聚合物(較佳為丙烯酸系聚合物)100重量份而以大致10~100重量份(更佳為20~80重量份,進而較佳為30~60重量份)之比率使用黏著賦予劑。
上述黏著劑組合物可視需要而含有調平劑、交聯助劑、塑化劑、軟化劑、填充劑、抗靜電劑、防老化劑、紫外線吸收劑、抗氧化劑、光穩定劑等黏著劑組合物之領域內通常之各種添加劑。關於此種各種添加劑,根據慣例使用先前公知者即可。
此處所揭示之黏著劑層可為由水系、溶劑型、熱熔型、活性能量線硬化型等黏著劑組合物所形成之黏著劑層。所謂水系黏著劑組合物係指於以水作為主成分之溶劑(水系溶劑)中含有黏著劑(黏著劑層形成成分)之形態之黏著劑組合物,典型而言,包括被稱為水分散型黏著劑組合物(黏著劑之至少一部分分散於水中之形態之組合物)等者。又,所謂溶劑型黏著劑組合物係指於有機溶劑中含有黏著劑之形態之黏著劑組合物。就降低環境負荷之觀點而言,可較佳地使用水系黏著劑組合物,就黏著特性等觀點而言,可較佳地使用溶劑型黏著劑組合物。
此處所揭示之黏著劑層可藉由先前公知之方法形成。例如,可較佳地採用藉由對基材直接賦予(典型而言為塗附)黏著劑組合物並加以乾燥而形成黏著劑層之方法(直接法)。又,亦可採用藉由對具有剝離性之表面(剝離面)賦予黏著劑組合物並加以乾燥而於該表面上形成黏著劑層、並將該黏著劑層轉印至基材之方法(轉印法)。作為上述剝
離面,可利用剝離襯墊之表面、或經剝離處理之基材背面等。
黏著劑組合物之塗附例如可使用凹版輥式塗佈機、逆輥塗佈機、接觸輥塗佈機、浸漬輥塗佈機、模嘴塗佈機、棒式塗佈機、刮刀塗佈機、噴霧塗佈機等公知或慣用之塗佈機進行。或亦可藉由含浸或淋幕式塗佈法等塗附黏著劑組合物。
就促進交聯反應、提高製造效率等觀點而言,黏著劑組合物之乾燥較佳為於加熱下進行。乾燥溫度例如可設為40~150℃左右,通常較佳為設為60~130℃左右。將黏著劑組合物乾燥後,進而,可以調整黏著劑層內之成分轉移、進行交聯反應、緩和會存在於基材或黏著劑層內之應變等為目的而進行熟化。
此處所揭示之黏著劑層之厚度並無特別限定,可根據目的適當選擇。通常就乾燥效率等生產性或接著特性等觀點而言,設為0.5~200μm左右較為適當,較佳為設為2~200μm(例如5~100μm,典型而言為10~50μm)左右。限制黏著劑層之厚度就黏著片材之薄膜化、小型化、輕量化、省資源化等方面而言有利。於此處所揭示之技術以基材之雙面具備黏著劑層之雙面黏著片材之形態而實施之情形時,各黏著劑層之厚度可相同,亦可不同。
<塗層>
部分地覆蓋黏著劑層表面之塗層為可賦予排氣性者即可,只要處於該範圍,則並無特別限制。作為塗層材料之較佳例,可列舉樹脂材料。就外觀性之觀點而言,較佳為由透明或半透明之樹脂材料所形成之塗層。
作為可構成塗層之樹脂材料,例如可列舉:聚胺基甲酸酯系樹脂、酚系樹脂、環氧系樹脂、聚醯胺系樹脂、脲三聚氰胺系樹脂、聚矽氧系樹脂、聚矽氮烷系樹脂、氟系樹脂、苯氧基樹脂、甲基丙烯酸系樹脂、丙烯酸系樹脂、丙烯酸-胺基甲酸酯系樹脂、丙烯酸-苯乙烯
系樹脂、聚芳酯樹脂、聚酯系樹脂、聚烯烴系樹脂、聚苯乙烯系樹脂、聚氯乙烯、氯乙烯-乙酸乙烯酯共聚物、聚乙酸乙烯酯、聚偏二氯乙烯、聚碳酸酯、纖維素類、聚縮醛等。該等樹脂可為選自熱硬化型樹脂、紫外線硬化型樹脂、電子束硬化型樹脂、二液混合型樹脂等各種類型之樹脂中之一種或兩種以上之樹脂。
此處所揭示之塗層可視需要而含有填充劑、防老化劑、抗氧化劑、紫外線吸收劑、交聯劑、潤滑劑、著色劑(顏料、染料等)、抗靜電劑、流動性調整劑(搖變性劑、增黏劑等)、造膜助劑等各種添加劑。
塗層較佳為非黏著性或弱黏著性。藉此,可較佳地實現良好之排氣性。此處,所謂塗層為非黏著性或弱黏著性係指塗層之180度剝離強度未達3N/25mm(典型而言未達1N/25mm,包含接著力過低而無法測定之情形)。具體而言,塗層之180度剝離強度係藉由下述方法測定。即,對於將於黏著劑層表面之整個面配置有塗層之黏著片材切割成寬25mm、長100mm之尺寸而得之測定樣品,於23℃、50%RH之環境下,使2kg之輥往返一次而將上述測定樣品之塗層表面壓合於不鏽鋼板(SUS304BA板)之表面(於未接著之情形時,於該時間點視為非黏著性),將其於相同環境下放置30分鐘後,使用萬能拉伸壓縮試驗機,依照JIS Z 0237:2000,於拉伸速度300mm/min、剝離角度180度之條件下,測定剝離強度(N/25mm)。
於黏著劑層表面配置塗層之方法並無特別限定。例如,可採用如下方法。具體而言,視需要將塗層形成用組合物溶解或分散於適當之溶劑中等而進行製備。繼而,採用公知或慣用之各種印刷處理方法中適當之方法,將該組合物賦予至剝離性支持體(亦稱為「塗層轉印用膜」,典型而言為剝離襯墊)之剝離性表面並使其硬化。然後,使形成有塗層之剝離性支持體表面抵接於黏著劑層表面,將塗層轉印至黏
著劑層表面。由此,可將塗層部分地配置於黏著劑層表面。例如,藉由採用平版印刷、絲網印刷、凸版印刷、柔版印刷、凹版印刷、噴墨印刷等方法,可較佳地形成格子狀圖案等所需之塗層圖案。就排氣性之觀點而言,更佳為凹版印刷。或亦可藉由對黏著劑層表面賦予直接塗層形成用組合物,利用例如紫外線硬化等方法使其硬化,從而於黏著劑層表面部分地配置塗層。
塗層之厚度以可獲得所需之排氣性之方式設計即可,並無特別限定,就同時實現排氣性與外觀性之觀點而言,較佳為設為黏著劑層之厚度之一半以下(例如1/3以下,典型而言為1/5以下)。具體而言,就排氣性之觀點而言,塗層之厚度較佳為設為0.1μm以上(例如0.5μm以上,典型而言為1μm以上)。又,就外觀性之觀點而言,塗層之厚度較佳為設為10μm以下,更佳為設為5μm以下(例如3μm以下,典型而言為2μm以下)。再者,塗層之厚度可藉由利用穿透式電子顯微鏡(TEM)觀察黏著片材之剖面而掌握。
此處所揭示之技術可以上述具備保護黏著片材之黏著性表面之剝離襯墊的附剝離襯墊之黏著片材之形態較佳地實施。作為剝離襯墊,可使用慣用之剝離紙等,並無特別限定。例如可使用於PET等樹脂膜或紙等襯墊基材之表面具有剝離處理層之剝離襯墊、或者含有氟系聚合物(聚四氟乙烯等)或聚烯烴系樹脂(PE、PP等)之低接著性材料之剝離襯墊等。上述剝離處理層例如可為藉由聚矽氧系、長鏈烷基系、氟系、硫化鉬等剝離處理劑對上述襯墊基材進行表面處理所形成者。
於較佳之一態樣中,上述剝離襯墊(剝離膜)之剝離性表面(與黏著片材之黏著性表面相接之側之面)係平滑地形成。於在此種剝離襯墊之剝離性表面部分地形成塗層,並且使黏著劑層之表面抵接於部分地形成有該塗層之剝離襯墊表面而將塗層轉印至黏著劑層表面之情形
時(於該情形時,剝離襯墊亦成為塗層轉印用膜(剝離膜)),可實現良好之塗層轉印性。又,藉由將剝離襯墊之平滑表面轉印至黏著劑層表面,黏著特性亦有提高之傾向。又,藉由於如上所述之剝離襯墊之剝離性表面部分地形成塗層,進而以覆蓋該塗層之方式於形成有該塗層之剝離性表面上形成黏著劑層,亦可獲得與上述同樣之效果。於該情形時,所形成之黏著劑層係被轉印至膜狀基材之表面。就如上所述之理由而言,上述剝離襯墊之剝離性表面之算術平均表面粗糙度較佳為1μm以下(例如大致為0.05~0.75μm,典型而言大致為0.1~0.5μm)。
又,此處所揭示之黏著片材之製作所使用之剝離襯墊如圖5所示,可為具備具有剝離性表面120A之剝離性支持體120之附塗層之剝離襯墊110。剝離性支持體120可為襯墊基材之至少一表面具有剝離處理層者,亦可為含有低接著性材料之支持體。於該剝離性支持體120之剝離性表面120A上設置可轉印至黏著片材之塗層30。即,塗層30係藉由黏著劑之黏著力等,以可分離之狀態配置於剝離性表面120A上。藉由使用此種表面具有可轉印之塗層30之剝離襯墊110,可較佳地製作此處所揭示之黏著片材。設置於剝離性支持體之剝離性表面上之塗層之構成(形狀、配置狀態、配置關係、尺寸、圖案等)與上述之部分地覆蓋黏著片材之黏著劑層表面之塗層之構成基本相同,故而上述剝離性表面上之塗層配置部及塗層非配置部之構成或相對關係(包含塗層非配置部之面積比率)亦與上述黏著劑層表面之塗層配置部及塗層非配置部之構成或相對關係(包含塗層非配置部之面積比率)基本相同,因此省略說明。
剝離襯墊之厚度(總厚度)並無特別限定,就剝離作業性或操作性、強度等觀點而言,較佳為設為10~500μm(例如15~100μm)左右。
此處所揭示之黏著片材如上述般,於貼附於被接著體時,可高
效率地防止與被接著體之間產生氣泡等。因此,於藉由人工作業之貼附(手動貼附)、或使用自動貼附機等之貼附(自動貼附)之任一貼附方法中,貼附性均提高。例如,於藉由手動貼附進行貼附之情形時,由於可降低對個人能力之依賴程度,因此可獲得貼附效率或貼附品質之提高、穩定化等優點。又,於藉由自動貼附進行貼附之情形時,可實現減少氣泡之混入等貼附不良、或減少重新貼附作業。因此,於手動貼附、自動貼附之任一情形時,均可實現貼附效率或品質之提高、品質之穩定化等,藉此,使用黏著片材所構築之物品之生產性或品質亦提高。此處所揭示之技術就可實現更均勻之貼附之方面而言,作為使用自動貼附機貼附之態樣之黏著片材尤佳。
又,於黏著片材與被接著體之間,不僅貼附時,而且貼附後隨著時間經過而存在產生氣泡等之情形。典型而言,於貼附黏著片材後在相對高溫(例如35℃以上)環境下保管、使用等情形時,上述氣泡等會產生於黏著片材與被接著體之間,而引起外觀性之降低。例如,夏季之工廠內或室外、電子機器內部等容易成為如上所述之高溫狀態。根據此處所揭示之技術,即便用於暴露於如上所述之高溫環境下之用途,亦可防止氣泡等之產生。
此處所揭示之黏著片材可活用如上所述之特徵,而較佳地用於貼附於各種物品之表面之用途。於較佳之一態樣中,可用作各種裝飾片材或表面保護片材、柔版印刷等之印刷板之固定片材、遮光片材等。例如,作為車輛之外裝或貼附於住宅建材等之裝飾片材(典型而言為塗裝代替片材)較佳。又,於電視等電子機器之內部,例如作為以提高底板外表面之平滑性之目的、或覆蓋各種構件表面之螺絲孔等不均勻部分之目的而使用之被覆片材亦較佳。藉由使用此種被覆片材,可實現被接著體外表面之外觀不均之減少或尺寸精度之均勻化。又,亦可較佳地用作重視外觀性之電池組之外裝片材。
又,此處所揭示之黏著片材即便於厚度較薄地構成之情形時,亦可防止貼附後之外觀品質之降低,並且維持良好之黏著特性。因此,可較佳地應用於要求厚度薄化或輕量化,且期待省資源化之用途(例如可攜式電子機器用途)。具體而言,可較佳地應用於可攜式電子機器(例如,行動電話、智慧型手機、平板型電腦、筆記型電腦等)之表面保護片材、上述可攜式電子機器之液晶顯示裝置中之接合固定用途、保護上述可攜式電子機器之顯示部之保護面板(透鏡)固定用途、行動電話之關鍵模組構件固定用途等。於使用上述可攜式電子機器之情形時,黏著片材可為根據目的等而具有框狀(邊框狀)、帶狀(條狀)等形狀者。再者,於本說明書中,所謂「可攜式」僅為可攜帶並不充分,其意指具有個人(標準成人)可相對容易地搬運之級別之攜帶性。
藉由本說明書所揭示之事項包括以下者。
(1)一種黏著片材,其具備膜狀基材、及設置於該膜狀基材之至少一表面之黏著劑層,且具備部分地覆蓋上述黏著劑層表面之塗層,藉此,該黏著劑層表面具有塗層配置部與塗層非配置部,上述黏著劑層表面中之上述塗層非配置部之面積比率為70%以上,上述塗層配置部於自上方觀察上述黏著劑層表面時,具有自該黏著劑層之一端向另一端線狀延伸之部分,上述線狀延伸之部分之寬度為0.1~2mm之範圍內。
(2)如上述(1)所記載之黏著片材,其中於上述黏著劑層表面配置有複數個上述線狀延伸之部分,且上述複數個線狀延伸之部分中構成一群之複數個線狀延伸之部分係於其寬度方向上隔開間隔而配置,藉此,上述塗層配置部具有條紋狀圖案。
(3)如上述(2)所記載之黏著片材,其中上述塗層配置部包含第1條紋狀圖案部、及以與該第1條紋狀圖案部交叉之方式配置之第2條紋狀圖案部,藉此,上述塗層配置部具有格子狀圖案。
(4)如上述(2)或(3)所記載之黏著片材,其中於上述塗層配置部中構成一條紋狀圖案之複數個線狀延伸之部分之間隔為1.0~10mm之範圍內。
(5)如上述(1)至(4)中任一項記載之黏著片材,其中部分地配置有上述塗層之黏著性表面表現出13N/25mm以上之經過24小時後之180度剝離強度。
(6)如上述(1)至(5)中任一項記載之黏著片材,其中上述黏著劑層以超過該黏著劑層所含之聚合物成分之50重量%之比率含有丙烯酸系聚合物,上述丙烯酸系聚合物以超過50重量%之比率含有式(1):CH2=C(R1)COOR2 (1)
(上述式(1)中之R1為氫原子或甲基;又,R2為碳原子數1~20之鏈狀烷基)所表示之(甲基)丙烯酸烷基酯作為單體成分。
(7)如上述(6)所記載之黏著片材,其中上述(甲基)丙烯酸烷基酯為丙烯酸正丁酯及/或丙烯酸2-乙基己酯。
(8)如上述(6)或(7)中任一項記載之黏著片材,其中上述丙烯酸系聚合物係作為副單體而使含羧基之單體及/或含羥基之單體共聚合而成之丙烯酸系聚合物。
(9)如上述(6)至(8)中任一項記載之黏著片材,其中上述丙烯酸系聚合物係使選自由丙烯酸、甲基丙烯酸、丙烯酸2-羥基乙酯及丙烯酸4-羥基丁酯所組成之群中之至少一種副單體共聚合而成之丙烯酸系聚合物。
(10)如上述(6)至(9)中任一項記載之黏著片材,其中於上述丙烯
酸系聚合物中共聚合有含羧基之單體,且上述含羧基之單體之共聚合比率於上述丙烯酸系聚合物之合成所使用之全部單體成分中為0.1~10重量%。
(11)如上述(6)至(10)中任一項記載之黏著片材,其中於上述丙烯酸系聚合物中共聚合有含羥基之單體,且上述含羥基之單體之共聚合比率於上述丙烯酸系聚合物之合成所使用之全部單體成分中為0.001~10重量%。
(12)如上述(6)至(11)中任一項記載之黏著片材,其中上述黏著劑層含有異氰酸酯系交聯劑及/或環氧系交聯劑。
(13)如上述(6)至(12)中任一項記載之黏著片材,其中上述黏著劑層以相對於上述丙烯酸系聚合物100重量份為30~60重量份之比率含有軟化點為100℃~140℃之黏著賦予樹脂,且上述黏著賦予樹脂係選自由松脂系黏著賦予樹脂、萜系黏著賦予樹脂及烴系黏著賦予樹脂所組成之群中之至少一種。
(14)如上述(1)至(13)中任一項記載之黏著片材,其中上述塗層含有透明樹脂。
(15)如上述(1)至(14)中任一項記載之黏著片材,其中上述塗層含有選自由聚胺基甲酸酯系樹脂、酚系樹脂、環氧系樹脂、聚醯胺系樹脂、脲三聚氰胺系樹脂、聚矽氧系樹脂、聚矽氮烷系樹脂、氟系樹脂、苯氧基樹脂、甲基丙烯酸系樹脂、丙烯酸系樹脂、丙烯酸-胺基甲酸酯系樹脂、丙烯酸-苯乙烯系樹脂、聚芳酯樹脂、聚酯系樹脂、聚烯烴系樹脂、聚苯乙烯系樹脂、聚氯乙烯、氯乙烯-乙酸乙烯酯共聚物、聚乙酸乙烯酯、聚偏二氯乙烯、聚碳酸酯、纖維素類及聚縮醛所組成之群中之至少一種樹脂。
(16)如上述(1)至(15)中任一項記載之黏著片材,其中上述塗層係聚胺基甲酸酯系樹脂。
(17)如上述(1)至(16)中任一項記載之黏著片材,其中上述塗層係二液混合硬化型之聚胺基甲酸酯系樹脂。
(18)如上述(1)至(17)中任一項記載之黏著片材,其中上述膜狀基材係聚烯烴系樹脂膜、聚酯系樹脂膜、氯乙烯系樹脂膜、乙酸乙烯酯系樹脂膜、聚醯亞胺系樹脂膜、聚醯胺系樹脂膜、氟系樹脂膜或塞璐芬膜。
(19)如上述(1)至(18)中任一項記載之黏著片材,其中上述膜狀基材係聚酯膜。
(20)如上述(1)至(19)中任一項記載之黏著片材,其中上述膜狀基材係聚對苯二甲酸乙二酯膜。
(21)如上述(1)至(20)中任一項記載之黏著片材,其中上述膜狀基材表現出80%以上之全光線透過率。
(22)如上述(1)至(17)中任一項記載之黏著片材,其中上述膜狀基材係發泡體膜。
(23)如上述(22)所記載之黏著片材,其中上述發泡體膜之平均氣泡直徑為10~200μm,密度為0.01~0.7g/cm3。
(24)如上述(22)或(23)所記載之黏著片材,其中上述發泡體膜係丙烯酸系樹脂發泡體或聚烯烴系樹脂發泡體。
(25)一種附剝離襯墊之黏著片材,其具備如上述(1)至(24)中任一項記載之黏著片材、及保護該黏著片材之黏著面之剝離襯墊,且上述剝離襯墊之表面中上述黏著面側之表面係平滑地形成。
(26)一種剝離襯墊,其係具備至少一表面為剝離性表面之剝離性支持體之黏著片材用剝離襯墊,且於上述剝離性支持體之剝離性表面上設置有可轉印至黏著片材之塗層,藉此,該剝離性表面具有塗層配置部與塗層非配置部,上述剝離性表面中之上述塗層非配置部之面積比率為70%以上,
上述塗層具有自上述剝離性表面之一端朝向另一端線狀延伸之部分,上述線狀延伸之部分之寬度為0.1~2mm之範圍內。
以下,對與本發明相關之若干實施例進行說明,但無意將本發明限定於如實施例所示者。再者,於以下之說明中,只要無特別聲明,則「份」及「%」為重量基準。
≪實驗1≫
<例1A>
(黏著劑組合物之製備)
於具備攪拌機、溫度計、氮氣導入管、回流冷凝器、滴加漏斗之反應容器中加入丙烯酸正丁酯70份、丙烯酸2-乙基己酯30份、丙烯酸3份、丙烯酸4-羥基丁酯0.05份、作為聚合起始劑之偶氮二異丁腈0.08份、及作為聚合溶劑之甲苯,於60℃下溶液聚合6小時而獲得丙烯酸系聚合物之甲苯溶液(黏度28Pa‧s,固形物成分40%)。所得之丙烯酸系聚合物之Mw約為44萬。
相對於上述甲苯溶液所含之丙烯酸系聚合物100份而添加作為黏著賦予樹脂之聚合松脂季戊四醇酯(荒川化學工業公司製造,商品名「Pensel D-125」,軟化點125℃)30份後,添加異氰酸酯系交聯劑(Nippon Polyurethane Industry公司製造,商品名「Coronate L」)3份並加以混合,從而製備丙烯酸系黏著劑組合物。
(塗層之形成)
藉由凹版印刷對厚度75μm之剝離膜(Fujiko公司製造,商品名「FMN-75WD(C1-CA1)」)之剝離性表面賦予塗層形成材料(胺基甲酸酯系:2液混合硬化型油墨),而形成具有格子狀圖案之塗層(塗附厚度1.5μm,透明)。
(黏著片材之製作)
準備厚度75μm之PET膜基材(商品名「Lumirror」,Toray公司製造),將上述黏著劑組合物以乾燥後之厚度成為15μm之方式塗附於該PET基材之電暈放電處理面,於100℃下乾燥3分鐘,而於PET膜基材之單面形成黏著劑層。
使上述獲得之塗層形成剝離膜之塗層形成面抵接於上述黏著劑層之表面,而將塗層轉印至黏著劑層表面。剝離膜係直接用於保護黏著劑層表面。由此製作本例之黏著片材。於該黏著片材之黏著劑層表面形成有如圖1所示之包含塗層之格子狀圖案,塗層配置部之長條部之寬度(線寬)為2mm,間隔為8mm。
<例1B>
將塗層配置部之長條部之間隔變更為13mm,除此以外,以與例1A同樣之方式製作本例之黏著片材。
<例1C>
除了不形成塗層以外,以與例1A同樣之方式製作本例之黏著片材。
[180度剝離強度]
對於各例之黏著片材,評價對SUS180度剝離強度(接著力)。具體而言,對於將黏著片材切割成寬25mm、長100mm之尺寸而得之測定樣品,於23℃、50%RH之環境下,使2kg之輥往返一次而將上述測定樣品之黏著性表面壓合於不鏽鋼板(SUS304BA板)之表面。將其於相同環境下放置30分鐘、24小時或72小時後,使用萬能拉伸壓縮試驗機,依照JIS Z 0237:2000,於拉伸速度300mm/min、剝離角度180度之條件下,測定剝離強度(N/25mm)。測定係對各例及各條件(壓合後經過時間)各進行3次,採用其平均值。又,將塗層非配置部之面積比率為100%之例1C之180度剝離強度值設為100%,以相對值(%)表示例1A、1B之180度剝離強度值,對伴隨塗層非配置部之面積減少之接著
力之降低程度進行評價。將結果與塗層非配置部之面積比率(%)一併示於表1。
如表1所示,若塗層之面積變大,黏著劑層之露出面積減少,則貼合至被接著體經過30分鐘後之初期接著力以與其成正比例之方式降低。另一方面,關於貼合至被接著體經過24小時或72小時後之經時接著力,於塗層非配置部之面積比率為64%之例1A中,並未引起經時性之接著力上升,如初期接著力之正比例關係崩潰,表現出顯著低於根據塗層非配置部之面積比率為75%之例1B、或塗層非配置部之面積比率為100%之例1C中之結果所預想之值的值。根據該結果可知,於在黏著劑層表面部分地配置有塗層之構成中,為了獲得較高之經時接著力,塗層非配置部之面積比率必須為70%以上。
≪實驗2≫
<例2A~例2J>
將塗層配置部之長條部之寬度(mm)及間隔(mm)設定為如表2所示之值,藉由與例1A同樣之方法製作各例之黏著片材。將對各例所測定之經過24小時後之180度剝離強度(N/25mm)示於表2。其測定方法如上所述。再者,例2A、例2I、例2J分別具有與例1B、例1A、例1C相同之構成。
[排氣性]
對於各例之黏著片材,以目視觀察貼附於透明被接著體之平滑表面時之排氣性,按照下述之4個等級進行評價。將結果示於表2。
A:表現出優異之排氣性,於黏著片材與被接著體之間未殘存氣泡。
B:黏著片材與被接著體之間之氣泡以相對較快之速度排出,未殘存氣泡。
C:黏著片材與被接著體之間之氣泡相對較緩慢地排出,未殘存氣泡。
D:於黏著片材與被接著體之間殘存有氣泡。
如表2所示,黏著劑層表面中之塗層非配置部之面積比率為70%以上、塗層配置部之長條部之寬度為0.1~2mm之範圍內之例2A~例2H之黏著片材表現出較高之經時接著力(經過24小時後之180度剝離強度),黏著片材與被接著體之間之排氣性良好。進而,例2C~例2H之黏著片材於貼合至被接著體後,於自被接著體側及黏著片材側觀察時難以視認到塗層,外觀性優異。例2C~例2G之黏著片材之外觀性優異,且平衡性良好地同時實現較高之經時接著力與排氣性。其中,例2E、例2F、例2G之外觀性尤其優異。另一方面,於塗層非配置部之面積比率未達70%之例2I中,與例2A~例2H相比表現出較低之經時接
著力。又,於未配置塗層之例2J中,於黏著片材與被接著體之間殘存有氣泡。
以上已對本發明之具體例進行詳細說明,但該等僅為例示,並不限定申請專利之範圍。申請專利之範圍所記載之技術包括對以上所例示之具體例進行各種變形、變更而得者。
1‧‧‧黏著片材
1A‧‧‧黏著性表面
20‧‧‧黏著劑層
20A‧‧‧黏著劑層表面
30‧‧‧塗層
50‧‧‧塗層配置部
51‧‧‧塗層非配置部
60‧‧‧塗層圖案(格子狀圖案)
70‧‧‧第1條紋狀圖案部
75A‧‧‧長條部(線狀延伸之部分)
75B‧‧‧長條部(線狀延伸之部分)
75C‧‧‧長條部(線狀延伸之部分)
80‧‧‧第2條紋狀圖案部
85A‧‧‧長條部(線狀延伸之部分)
85B‧‧‧長條部(線狀延伸之部分)
85C‧‧‧長條部(線狀延伸之部分)
W1‧‧‧寬度
W2‧‧‧間隔
Claims (3)
- 一種黏著片材,其具備膜狀基材、及設置於該膜狀基材之至少一表面之黏著劑層,並且具備部分地覆蓋上述黏著劑層表面之塗層,藉此該黏著劑層表面具有塗層配置部與塗層非配置部,上述黏著劑層表面中之上述塗層非配置部之面積比率為70%以上,上述塗層配置部於自上方觀察上述黏著劑層表面時,具有自該黏著劑層之一端向另一端線狀延伸之部分,且部分地配置有上述塗層之黏著性表面表現出13N/25mm以上之經過24小時後之180度剝離強度,於上述黏著劑層表面配置有複數個上述線狀延伸之部分,上述複數個線狀延伸之部分中構成一群之複數個線狀延伸之部分係於其寬度方向上隔開間隔而配置,藉此上述塗層配置部具有條紋狀圖案,上述塗層配置部包含第1條紋狀圖案部、及以與該第1條紋狀圖案部交叉之方式配置之第2條紋狀圖案部,藉此上述塗層配置部具有格子狀圖案,於上述塗層配置部中構成一條紋狀圖案之複數個線狀延伸之部分之寬度為0.1~0.7mm,間隔為1.0~10mm,間距為1~20mm,上述黏著劑層包含基礎聚合物與黏著賦予樹脂,上述黏著賦予樹脂包含選自松脂系黏著賦予樹脂、萜系黏著賦予樹脂、烴系黏著賦予樹脂、環氧系黏著賦予樹脂、聚醯胺系黏著賦予樹脂、彈性體系黏著賦予樹脂、酚系黏著賦予樹脂及酮系黏著賦 予樹脂所組成之群中之至少一種,上述黏著賦予樹脂之含量係相對於上述基礎聚合物100重量份為10~100重量份,上述基礎聚合物係使選自由丙烯酸、甲基丙烯酸、丙烯酸2-羥基乙酯及丙烯酸4-羥基丁酯所組成之群中之至少一種副單體共聚合而成之丙烯酸系聚合物。
- 如請求項1之黏著片材,其中上述黏著劑層表面中之上述塗層非配置部之面積比率為80%以上。
- 一種附剝離襯墊之黏著片材,其具備如請求項1或2之黏著片材、及保護該黏著片材之黏著面之剝離襯墊,並且上述剝離襯墊之表面中上述黏著面側之表面係平滑地形成。
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- 2015-11-27 US US15/529,634 patent/US20170267897A1/en not_active Abandoned
- 2015-11-27 CN CN201580064276.9A patent/CN107001869B/zh active Active
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- 2015-11-27 KR KR1020177011803A patent/KR102506412B1/ko active IP Right Grant
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TW201625757A (zh) | 2016-07-16 |
CN107001870A (zh) | 2017-08-01 |
KR102506412B1 (ko) | 2023-03-07 |
US20170267897A1 (en) | 2017-09-21 |
CN107001870B (zh) | 2021-07-06 |
CN107001871A (zh) | 2017-08-01 |
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CN107001869B (zh) | 2021-07-23 |
JP6664167B2 (ja) | 2020-03-13 |
CN113637419A (zh) | 2021-11-12 |
CN107001869A (zh) | 2017-08-01 |
JP2016108533A (ja) | 2016-06-20 |
JP2016108534A (ja) | 2016-06-20 |
KR102506413B1 (ko) | 2023-03-07 |
CN107001871B (zh) | 2020-11-10 |
US20170335142A1 (en) | 2017-11-23 |
KR102463777B1 (ko) | 2022-11-07 |
KR20170088833A (ko) | 2017-08-02 |
KR20170090411A (ko) | 2017-08-07 |
JP2016108532A (ja) | 2016-06-20 |
TW201625758A (zh) | 2016-07-16 |
JP6664166B2 (ja) | 2020-03-13 |
JP6679239B2 (ja) | 2020-04-15 |
TW201632597A (zh) | 2016-09-16 |
KR20170092541A (ko) | 2017-08-11 |
TWI682984B (zh) | 2020-01-21 |
TWI682983B (zh) | 2020-01-21 |
US20170260425A1 (en) | 2017-09-14 |
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