TWI813730B - 積層體及環氧樹脂片之製造方法 - Google Patents
積層體及環氧樹脂片之製造方法 Download PDFInfo
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- TWI813730B TWI813730B TW108127529A TW108127529A TWI813730B TW I813730 B TWI813730 B TW I813730B TW 108127529 A TW108127529 A TW 108127529A TW 108127529 A TW108127529 A TW 108127529A TW I813730 B TWI813730 B TW I813730B
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- epoxy resin
- laminated body
- resin sheet
- sheet
- tensile
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Abstract
本發明之積層體係具備環氧樹脂片(A)、與積層於該環氧樹脂片(A)之至少一面之載體片(B)者,該環氧樹脂片(A)於100℃~200℃下之拉伸儲存模數為1.0×104
~6.0×107
Pa,且拉伸伸長率為150%以上,該積層體於100℃~200℃下之拉伸儲存模數為6.0×107
~1.0×1010
Pa,該環氧樹脂片(A)與該載體片(B)之剝離強度為5 N/15 mm以下。
Description
本發明係關於一種積層體及環氧樹脂片之製造方法。
由於環氧樹脂之耐熱性、接著性、耐水性、機械強度及電特性等優異,因此使用於各種領域。尤其於電氣、電子領域中,近年來隨著電氣、電子零件之小型化、精密化、高性能化,對所使用之環氧樹脂要求高度之成形性。最近,亦要求對可撓性或可延展性積層板等更重視柔軟性之用途之適應性。
專利文獻1中揭示有一種特定之高可撓性環氧樹脂,且記載有調配有該環氧樹脂之樹脂組合物提供平衡性良好地具備接著性及電特性並且亦具有較高之可撓性之硬化物。
先前技術文獻
專利文獻
專利文獻1:日本專利特開2005-320477號公報
[發明所欲解決之問題]
若使高可撓性之環氧樹脂硬化物薄膜化而形成為單層片,則該單層片具有伸縮性優異之優點。然而,伸縮性較高同時亦意味著尺寸穩定性較低,因此上述單層片具有操作性較差之觀點。尤其是,若於如卷對卷之連續二次加工步驟中使用伸縮性之單層片,則容易產生伸長、撓曲、皺褶等異常。
本發明係鑒於此種狀況而成者,本發明之課題在於提供一種於二次加工過程中操作性良好(即,產生伸長、撓曲、皺褶等異常得到抑制)之含有環氧樹脂片之積層體、及環氧樹脂片之製造方法。
[解決問題之技術手段]
本發明人等經過潛心研究,結果發現,若使用具有特定構成之積層體,則可容易地解決上述課題,從而完成了本發明。
即,本發明係關於下述之[1]至[13]。
[1]一種積層體,其係具備環氧樹脂片(A)、與積層於該環氧樹脂片(A)之至少一面之載體片(B)者,
該環氧樹脂片(A)於100℃~200℃下之拉伸儲存模數為1.0×104
~6.0×107
Pa,且拉伸伸長率為150%以上,
該積層體於100℃~200℃下之拉伸儲存模數為6.0×107
~1.0×1010
Pa,
該環氧樹脂片(A)與該載體片(B)之剝離強度為5 N/15 mm以下。
[2]如上述[1]所記載之積層體,其中於上述環氧樹脂片(A)之兩面具備上述載體片(B)。
[3]如上述[1]或[2]所記載之積層體,其中上述載體片(B)包含聚酯膜。
[4]如上述[1]至[3]中任一項所記載之積層體,其中上述載體片(B)包含離型層。
[5]如上述[1]至[4]中任一項所記載之積層體,其中上述載體片(B)係包含聚酯膜與聚烯烴膜之2層構成。
[6]如上述[5]所記載之積層體,其中上述載體片(B)中,聚酯膜與聚烯烴膜之層厚比為聚酯膜/聚烯烴膜=0.2~10。
[7]如上述[1]至[6]中任一項所記載之積層體,其中上述環氧樹脂片(A)包含使含有環氧樹脂與脂環式聚胺之環氧樹脂組合物硬化而成之硬化物。
[8]如上述[7]所記載之積層體,其中上述環氧樹脂具有剛性成分與柔軟成分之嵌段結構。
[9]如上述[1]至[8]中任一項所記載之積層體,其厚度為30 μm~1000 μm。
[10]一種積層體,其係將上述載體片(B)自如上述[1]至[9]中任一項所記載之積層體之一面剝離而得。
[11]一種可撓性或可延展性積層板,其使用如上述[1]至[10]中任一項所記載之積層體之環氧樹脂片(A)。
[12]一種環氧樹脂片之製造方法,其包含如下步驟:藉由將上述載體片(B)自如上述[1]至[10]中任一項所記載之積層體剝離,而獲得上述環氧樹脂片(A)。
[13]一種捲繞體,其係於芯體捲繞有具備環氧樹脂片(A)、與積層於該環氧樹脂片(A)之至少一面之載體片(B)之積層體者,
該環氧樹脂片(A)於100℃~200℃下之拉伸儲存模數為1.0×104
~6.0×107
Pa,且拉伸伸長率為150%以上,
該積層體於100℃~200℃下之拉伸儲存模數為6.0×107
~1.0×1010
Pa,
該環氧樹脂片(A)與該載體片(B)之剝離強度為5 N/15 mm以下。
[發明之效果]
若使用本發明之積層體,則可抑制於二次加工過程中環氧樹脂片產生伸長、撓曲、皺褶等異常。又,藉由於加工後將載體片剝離,可於不損害外觀之情況下簡便地獲得伸縮性優異之環氧樹脂片。
以下,基於實施形態例對本發明進行說明。但是,本發明不受以下所說明之實施形態限定。
[積層體]
本發明之積層體具備環氧樹脂片(A)、與積層於該環氧樹脂片(A)之至少一面之載體片(B),該環氧樹脂片(A)於100℃~200℃下之拉伸儲存模數為1.0×104
~6.0×107
Pa,且拉伸伸長率為150%以上,該積層體於100℃~200℃下之拉伸儲存模數為6.0×107
~1.0×1010
Pa,該環氧樹脂片(A)與該載體片(B)之剝離強度為5 N/15 mm以下。
一般之環氧樹脂片於100℃~200℃下之拉伸儲存模數為0.1 GPa~10 GPa左右,拉伸伸長率為10%左右。因此,本發明中作為對象之環氧樹脂片(A)遠比一般之環氧樹脂片柔軟,可將其視為特殊之環氧樹脂片。
本發明係消除正因為柔軟之環氧樹脂片(A)而產生之課題、即二次加工過程中之操作性(產生伸長、撓曲、皺褶等異常)之問題者。若為具有剛性特性之一般之環氧樹脂片,則二次加工本身本就容易,因此本發明中之問題本身便不會發生。
於本發明中,以藉由對於下述環氧樹脂片(A)之至少一面設置下述載體片(B)而使積層體於100℃~200℃下之拉伸儲存模數成為6.0×107
~1.0×1010
Pa之方式進行調整。藉由積層體具有此種拉伸儲存模數,可抑制二次加工過程中環氧樹脂片產生伸長、撓曲、皺褶等異常,提高操作性。
更詳細而言,若積層體於100℃~200℃下之拉伸儲存模數為上述下限值以上,則即便環氧樹脂片(A)柔軟,亦不僅抑制產生撓曲或皺褶,且例如於對積層體進行沖切加工之情形時,積層體不會黏著於沖切刀,且經沖切之構件之尺寸穩定性亦良好。
又,若積層體於100℃~200℃下之拉伸儲存模數為上述上限值以下,則容易將積層體製成捲繞體(捲筒)形狀,且即便以捲繞體之狀態長期保存後將積層體捲出並進行二次加工時,亦可維持與製造起初同樣之形狀(厚度變動等)及諸特性。
進而,藉由環氧樹脂片(A)與載體片(B)之剝離強度為5 N/15 mm以下,從而於將載體片自環氧樹脂片剝離時,可於不損害環氧樹脂片之剝離面之情況下簡便地獲得伸縮性優異之環氧樹脂片或積層體。
再者,所謂「於100℃~200℃下之拉伸儲存模數為6.0×107
~1.0×1010
Pa」係指於100℃~200℃之全部溫度範圍內,拉伸儲存模數維持在6.0×107
以上且1.0×1010
Pa以下之值。於其他數值範圍之情形時亦同樣地處理。關於積層體之拉伸儲存模數,具體而言可利用實施例中所記載之方法測定。
本發明之積層體於100℃~200℃下之拉伸儲存模數較佳為6.0×107
~5.0×109
Pa,更佳為1.0×108
~1.0×109
Pa。
關於本發明之積層體,藉由將載體片(B)積層於環氧樹脂片(A)之至少一面而將該積層體於100℃~200℃下之拉伸儲存模數設為規定之範圍內,從而可使積層體之耐撓曲性(即,撓曲變化量較小)良好。本發明之積層體之撓曲變化量較佳為7.0 mm以下,更佳為6.0 mm以下,進而較佳為5.0 mm以下。關於積層體之撓曲變化量,具體而言可利用實施例中所記載之方法測定。
關於本發明之積層體,藉由將載體片(B)積層於環氧樹脂片(A)之至少一面而將該積層體於100℃~200℃下之拉伸儲存模數設為規定之範圍內,從而可良好地實現積層體具有耐伸長性。積層體之伸長率較佳為20%以下,更佳為10%以下,進而較佳為2.0%以下。關於積層體之伸長率,具體而言可利用實施例中所記載之方法測定。
本發明之積層體亦可於環氧樹脂片(A)之兩面具備載體片(B),於該情形時,第一載體片(B)與第二載體片(B)相互可相同亦可不同。
本發明之積層體亦可於滿足上述拉伸儲存模數之範圍內具備除環氧樹脂片(A)及載體片(B)以外之層,作為此種層,例如可例示:黏著層、接著層、硬塗層、障壁層等。
本發明之積層體之厚度較佳為30 μm~1000 μm,更佳為50 μm~500 μm,進而較佳為80 μm~400 μm,特佳為100 μm~350 μm。關於積層體之厚度,具體而言可利用實施例中所記載之方法測定。
本發明之積層體之製造方法無特別限制,較佳為包含以下步驟:將環氧樹脂片(A)用之樹脂組合物(以下,亦稱為「環氧樹脂組合物」)塗佈於載體片(B)上,使該環氧樹脂組合物硬化而形成環氧樹脂片(A)。
本發明中所謂「環氧樹脂」之用語可用於硬化前之原料樹脂及硬化後之樹脂(硬化物)兩者。再者,存在因環氧基被硬化反應消耗,導致硬化後之樹脂不具有環氧基(環氧結構)之情形。
又,於製造於環氧樹脂片(A)之兩面具備載體片(B)之積層體之情形時,可列舉以下之製造方法1及製造方法2。
製造方法1:將環氧樹脂組合物塗佈於第一載體片(B)上,使該環氧樹脂組合物硬化而形成環氧樹脂片(A),其後將第二載體片(B)貼合於該環氧樹脂片(A)之與設置有上述第一載體片(B)之面相反之面。
製造方法2:將環氧樹脂組合物塗佈於第一載體片(B)上,並將第二載體片(B)貼合於該環氧樹脂組合物之與設置有上述第一載體片(B)之面相反之面,其後使該環氧樹脂組合物硬化而形成環氧樹脂片(A)。
以下,對本發明之積層體所具備之環氧樹脂片(A)及載體片(B)之詳情進行說明。
<環氧樹脂片(A)>
本發明中,環氧樹脂片(A)係於100℃~200℃下之拉伸儲存模數為1.0×104
~6.0×107
Pa,且拉伸伸長率為150%以上,伸縮性優異之片。
再者,所謂「100℃~200℃下之拉伸儲存模數為1.0×104
~6.0×107
Pa」係指於100℃~200℃之全部溫度範圍內,拉伸儲存模數維持在1.0×104
以上且6.0×107
Pa以下之值。於其他數值範圍之情形時亦同樣地處理。關於環氧樹脂片(A)之拉伸儲存模數及拉伸伸長率,具體而言可利用實施例中所記載之方法測定。
本發明中,環氧樹脂片(A)於100℃~200℃下之拉伸儲存模數較佳為6.0×104
~1.0×107
Pa,更佳為4.0×105
~9.0×106
Pa。
本發明中,環氧樹脂片(A)之拉伸伸長率為150%以上,較佳為200%以上,更佳為300%以上。關於上限值,較佳為500%以下。
本發明中,環氧樹脂片(A)之厚度通常為10 μm~500 μm,較佳為20 μm~200 μm,更佳為30 μm~150 μm,進而較佳為50 μm~140 μm。環氧樹脂片(A)之厚度(平均厚度)係利用測微計測定,根據該等測定值之算術平均而求出。
環氧樹脂片(A)之厚度之變動率越小,則厚度越均勻,因此較佳。環氧樹脂片(A)之厚度之變動率較佳為±20%以下,更佳為±10%以下。
再者,關於環氧樹脂片(A)之厚度之變動率,具體而言可利用實施例中所記載之方法測定。
本發明中,環氧樹脂片(A)係一種片狀之成形體,其包含使環氧樹脂組合物硬化而成之硬化物。此處所謂「硬化」係指藉由熱及/或光等,刻意地使環氧樹脂組合物中之環氧樹脂硬化。再者,此處所謂「刻意地」,亦包含例如因將硬化前之環氧樹脂片(A)長期保管,而憑藉由熱或光所產生之經時影響,逐漸地使環氧樹脂硬化之類的情形。
環氧樹脂片(A)可藉由使環氧樹脂組合物以調整為特定厚度之片狀之狀態進行硬化而製造。或者,可藉由使由環氧樹脂組合物獲得之半硬化物成形為特定厚度之片狀,並且進而使其硬化,從而製造環氧樹脂片(A)。
環氧樹脂組合物之硬化方法根據環氧樹脂組合物中之調配成分或調配量、調配物之形狀(例如片之厚度)而不同,通常可列舉於23~200℃下加熱5分鐘~24小時之條件。該加熱就減少硬化不良之觀點而言,較佳為以於23~160℃下實施5分鐘~24小時之一次加熱、與於較一次加熱溫度高40~177℃之80~200℃下實施5分鐘~24小時之二次加熱之兩段加熱,以及進而於高於二次加熱溫度之100~200℃下實施5分鐘~24小時之三次加熱之三段處理而進行。
當將硬化物製成半硬化物時,只要藉由加熱等以形狀得到保持之程度進行環氧樹脂組合物之硬化反應即可。於環氧樹脂組合物含有溶劑之情形時,利用加熱、減壓、風乾等方法去除大部分溶劑,亦可於半硬化物中殘留5質量%以下之溶劑。
再者,關於本發明之積層體,即便環氧樹脂片(A)為半硬化之狀態,但只要於100℃~200℃下之拉伸儲存模數及拉伸伸長率為上述範圍內,則其亦包含於本發明之積層體。若環氧樹脂片(A)為半硬化之狀態,則存在容易製成捲繞體,或二次加工性變得良好之情形。
以下,對於本發明中適宜地使用之環氧樹脂組合物(以下,亦稱為「環氧樹脂組合物(a)」)詳細地進行說明。但是,本發明中所使用之環氧樹脂組合物並不限定於環氧樹脂組合物(a)。
(1.環氧樹脂組合物(a))
環氧樹脂組合物(a)較佳為含有具有剛性成分與柔軟成分之嵌段結構之環氧樹脂(以下,稱為「環氧樹脂(α)」)。此處,剛性成分較佳為包含具有芳香族性之環結構、例如含有多個苯環、萘環、蒽環、芘環等縮合芳香環結構、或聯苯酚環、鉸鏈結構、茀環等芳香環結構之結構;或包含吡咯環、噻吩環等雜環式結構。柔軟成分較佳為含有脂肪族烴,例如碳數1~8之伸烷基、乙二醇基、丙二醇基、丁二醇基。藉由含有此種環氧樹脂(α),能夠對硬化物賦予柔軟性。再者,關於環氧樹脂組合物(a),亦可未必剛性成分與柔軟成分兩者具有環氧基或者源自環氧基之結構。即,只要至少剛性成分及柔軟成分中之任一者具有環氧基或者源自環氧基之結構即可。就具有耐熱性、機械強度等環氧樹脂原本之特性並且賦予柔軟性之觀點而言,較佳為僅剛性成分與柔軟成分中之任一者具有環氧基或者源自環氧基之結構。
環氧樹脂組合物(a)至少包含環氧樹脂(α)與硬化劑,亦可視需要適當調配環氧樹脂(α)以外之其他環氧化合物、硬化促進劑、其他成分等。
再者,環氧樹脂組合物(a)可僅含有1種環氧樹脂(α),亦可含有2種以上。又,作為環氧樹脂組合物(a)所含有之硬化劑,可使用通常為人所知之全部環氧樹脂硬化劑。環氧樹脂組合物(a)可僅含有1種硬化劑,亦可含有2種以上。
(1-1.環氧樹脂(α))
作為環氧樹脂(α),無特別限定,具體而言,例如可列舉:雙酚F與1,6-己二醇二縮水甘油醚之共聚物、1,6-己二醇與雙酚F二縮水甘油醚之共聚物、雙酚F與1,4-丁二醇二縮水甘油醚之共聚物、1,4-丁二醇與雙酚F二縮水甘油醚之共聚物、雙酚A與1,6-己二醇二縮水甘油醚之共聚物、1,6-己二醇與雙酚A二縮水甘油醚之共聚物、雙酚A與1,4-丁二醇二縮水甘油醚之共聚物、1,4-丁二醇與雙酚A二縮水甘油醚之共聚物、四甲基聯苯酚與1,6-己二醇二縮水甘油醚之共聚物、1,6-己二醇與四甲基聯苯酚二縮水甘油醚之共聚物、四甲基聯苯酚與1,4-丁二醇二縮水甘油醚之共聚物、1,4-丁二醇與四甲基聯苯酚二縮水甘油醚之共聚物、聯苯酚與1,6-己二醇二縮水甘油醚之共聚物、1,6-己二醇與聯苯酚二縮水甘油醚之共聚物、聯苯酚與1,4-丁二醇二縮水甘油醚之共聚物、1,4-丁二醇與聯苯酚二縮水甘油醚之共聚物、1,4-萘二酚與1,6-己二醇二縮水甘油醚之共聚物、1,6-己二醇與1,4-萘二酚二縮水甘油醚之共聚物、1,4-萘二酚與1,4-丁二醇二縮水甘油醚之共聚物、1,4-丁二醇與1,4-萘二酚二縮水甘油醚之共聚物、1,6-萘二酚與1,6-己二醇二縮水甘油醚之共聚物、1,6-己二醇與1,6-萘二酚二縮水甘油醚之共聚物、1,6-萘二酚與1,4-丁二醇二縮水甘油醚之共聚物、1,4-丁二醇與1,6-萘二酚二縮水甘油醚之共聚物等。
該等可單獨使用1種,亦可以任意之組合及比率混合2種以上使用。該等之中,就柔軟性之觀點而言,環氧樹脂(α)較佳為雙酚F與1,6-己二醇二縮水甘油醚之共聚物。
(1-2.硬化劑)
所謂本發明中所使用之硬化劑係指有助於上述環氧樹脂(α)之交聯基間之交聯反應之物質。作為硬化劑,無特別限制,可使用通常為人所知之全部環氧樹脂硬化劑。例如可列舉:酚系硬化劑、脂肪族胺、聚醚胺、脂環式胺、芳香族胺等胺系硬化劑、酸酐系硬化劑、醯胺系硬化劑、三級胺、咪唑及其衍生物、有機膦類、鏻鹽、四苯基硼鹽、有機酸二醯肼、鹵化硼胺錯合物、聚硫醇系硬化劑、異氰酸酯系硬化劑、嵌段異氰酸酯系硬化劑等。就高透明性及著色較少之觀點而言,作為硬化劑,較佳為具有脂環式結構之硬化劑。
作為具有脂環式結構之硬化劑,只要為具有脂環式結構,且有助於環氧樹脂之環氧基間之交聯反應及/或擴鏈反應之物質即可,無特別限制,例如可列舉脂環式聚胺、脂環式酸酐等。更具體而言,可列舉:1,4-二氮雜雙環-2,2,2-辛烷、1,8-二氮雜雙環-5,4,0-十一碳-7-烯、N,N'-二甲基哌𠯤、N-胺基乙基哌𠯤、䓝二胺、異佛爾酮二胺、六亞甲基四胺、亞甲基雙環己胺、1,3-雙胺基甲基環己烷、降𦯉烯二胺、1,2-二胺基環己烷、及將該等脂環式聚胺進行環氧改性或環氧乙烷改性、二聚酸改性、曼尼希改性、麥可加成、硫脲縮合、酮亞胺化而成之改性脂環式聚胺、或六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐等。
該等之中,較佳為脂環式聚胺,其中特佳為異佛爾酮二胺、六亞甲基四胺、亞甲基雙環己胺、1,3-雙胺基甲基環己烷、降𦯉烯二胺、1,2-二胺基環己烷、及其等之改性物。
具有脂環式結構之硬化劑亦可使用市售品,例如可使用三菱化學股份有限公司製造之「jERCURE 113」、「jERCURE ST-14」、新日本理化股份有限公司製造之「RIKACID MH-700」等。
關於環氧樹脂組合物(a)中之硬化劑之含量(於使用具有脂環式結構之硬化劑以外之其他硬化劑之情形時,係具有脂環式結構之硬化劑與其他硬化劑之合計含量),較佳為相對於環氧樹脂(α)(於含有環氧樹脂(α)以外之下述其他環氧化合物之情形時,係環氧樹脂(α)與其他環氧樹脂之合計含量)100質量份為0.1~100質量份。又,更佳為80質量份以下,進而較佳為60質量份以下,特佳為40質量份以下。
(1-3.其他環氧化合物)
於環氧樹脂組合物(a)含有環氧樹脂(α)以外之其他環氧化合物之情形時,作為其他環氧化合物,例如可列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、聯苯型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等縮水甘油醚型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、線性脂肪族環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂等各種環氧樹脂之1種或2種以上。
於環氧樹脂組合物(a)含有環氧樹脂(α)與其他環氧化合物之情形時,環氧樹脂組合物中之作為固形物成分之全部環氧成分中之其他環氧化合物之比率較佳為5質量%以上,更佳為10質量%以上,另一方面,較佳為95質量%以下,更佳為90質量%以下。藉由使其他環氧化合物之比率為上述下限值以上,可充分地獲得由調配有其他環氧化合物產生之物性提高效果。另一方面,藉由使其他環氧化合物之比率為上述上限值以下,可充分地獲得由環氧樹脂(α)帶來之柔軟性、可撓性提高效果。
本發明中,所謂「固形物成分」係指除溶媒以外之成分,不僅包含固體之環氧樹脂以及環氧化合物,亦包含半固形或黏稠之液狀物。又,所謂「全部環氧成分」係指環氧樹脂(α)與上述其他環氧化合物之合計。
(1-4.溶劑)
於形成塗膜時等操作時,為了適度地調整環氧樹脂組合物之黏度,亦可於環氧樹脂組合物(a)中調配溶劑而加以稀釋。環氧樹脂組合物(a)中,溶劑用於確保環氧樹脂組合物之成形時之操作性、作業性,其使用量無特別限制。再者,本發明中,根據其使用形態區別使用所謂「溶劑」之用語與所謂「溶媒」之用語,可分別獨立地使用同類者亦可使用不同類者。
作為環氧樹脂組合物(a)所能夠含有之溶劑,例如可列舉:丙酮、甲基乙基酮、甲苯、二甲苯、甲基異丁基酮、乙酸乙酯、乙二醇單甲醚、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、甲醇、乙醇等,該等溶劑亦能夠適當作為2種或2種以上之混合溶劑使用。
(1-5.其他成分)
環氧樹脂組合物(a)中,除以上所列舉之成分以外,還可含有其他成分。其他成分可根據環氧樹脂組合物所需之物性適當組合使用。
例如,為了提高使所獲得之硬化物之硬化收縮率下降之效果、使熱膨脹率下降之效果等各種特性,可於環氧樹脂組合物(a)中調配無機填充材,而實現於電氣、電子領域、尤其是液狀半導體密封材之應用擴展。為了賦予韌性,亦可含有膠粒、丙烯酸系粒子等有機填充材。
可使用之無機填充材有粉末狀之補強劑或填充材,例如為氧化鋁、氧化鎂等金屬氧化物、碳酸鈣、碳酸鎂等金屬碳酸鹽、矽藻土粉、鹼性矽酸鎂、煅燒黏土、微粉末矽石、熔融矽石、沸石等矽化合物、氫氧化鋁等金屬氫氧化物,此外還有高嶺土、雲母、石英粉末、石墨、碳黑、奈米碳管、二硫化鉬、氮化硼、氮化鋁等。
於添加無機填充材之情形時,需要確保該環氧樹脂片層與其積層體之拉伸儲存模數為上述範圍內。該等無機填充材之添加量相對於環氧樹脂(環氧樹脂(α)與視需要使用之其他環氧化合物之合計,以下同樣)與硬化劑之總和之100質量份較佳為900質量份以下。另一方面,其下限無特別限定,較佳為1.0質量份以上。
進而,亦可調配纖維質之補強劑或填充材。例如可列舉:玻璃纖維、陶瓷纖維、瀝青碳纖維、氧化鋁纖維、碳化矽纖維、硼纖維、芳香族聚醯胺纖維、纖維素奈米纖維、纖維素奈米結晶等。又,亦可使用有機纖維、無機纖維之布或者不織布。進而,該等無機填充材、纖維、布、不織布亦可使用對該等之表面利用矽烷偶合劑、鈦酸酯系偶合劑、鋁酸鹽系偶合劑或者底塗處理等進行表面處理者。
進而,環氧樹脂組合物(a)中亦可視需要調配有偶合劑、塑化劑、稀釋劑、可撓性賦予劑、分散劑、濕潤劑、著色劑、顏料、紫外線吸收劑、受阻胺系光穩定劑等光穩定劑、抗氧化劑、消泡劑、離型劑、流動性調整劑等。其等之調配量相對於環氧樹脂與硬化劑之總和之100質量份,較佳為20質量份以下。另一方面,其下限無特別限定,較佳為0.1質量份以上。
進而,為了改善最終之塗膜中之樹脂之性質,環氧樹脂組合物(a)中亦可視需要調配有各種硬化性單體、低聚物及合成樹脂。例如可列舉:氰酸酯樹脂、丙烯酸系樹脂、矽酮樹脂、聚酯樹脂等之1種或2種以上之組合。該等樹脂類之調配比率相對於不損及環氧樹脂組合物(a)之原本性質之範圍之量、即環氧樹脂與硬化劑之總和之100質量份,較佳為50質量份以下。另一方面,其下限無特別限定,較佳為1.0質量份以上。
本發明之環氧樹脂片(A)較佳為包含使含有環氧樹脂與脂環式聚胺之環氧樹脂組合物(a)硬化而成之硬化物。
<載體片(B)>
本發明中,載體片(B)係積層體於100℃~200℃下之拉伸儲存模數成為6.0×107
~1.0×1010
Pa,且環氧樹脂片(A)與載體片(B)之剝離強度成為5 N/15 mm以下者。
再者,關於環氧樹脂片(A)與載體片(B)之剝離強度,具體而言可利用實施例中記載之方法測定。
本發明中,環氧樹脂片(A)與載體片(B)之剝離強度為5 N/15 mm以下,較佳為3 N/15 mm以下,更佳為1 N/15 mm以下。關於下限值,較佳為0.03 N/15 mm以上。
本發明中,載體片(B)之厚度通常為20 μm~500 μm,較佳為30 μm~300 μm,更佳為50 μm~150 μm,進而較佳為55 μm~120 μm。載體片(B)之厚度(平均厚度)係利用測微計測定,根據該等測定值之算術平均而求出。
此處,於本發明之積層體為於環氧樹脂片(A)之兩面具備載體片(B)之積層體之情形時,該載體片(B)之厚度係指各片之厚度。
本發明中,作為載體片(B),可自成為上述特性者中適當地選擇使用,以紙、塑膠、金屬等為原料之較薄之片狀者中,只要拉伸儲存模數與剝離強度為上述範圍者即可。尤其是就經濟且容易加工,又,容易廢棄或再利用之觀點而言,使用紙或塑膠等之片。若為紙,則可使用道林紙、牛皮紙、玻璃紙、羊皮紙、及砑光牛皮紙等表面經矽酮塗佈處理者。進而,就透明性之觀點而言,較佳為塑膠。若為塑膠,則可使用聚乙烯或聚丙烯、聚對苯二甲酸乙二酯、聚碳酸酯、聚萘二甲酸乙二酯、聚醯亞胺等。對該等之表面塗佈矽酮樹脂離型劑等,調整剝離強度。又,就外觀之觀點而言,載體片(B)較佳為包含聚酯膜,只要不超出本發明之主旨,上述樹脂膜可為單層構成亦可為2層以上之多層構成。例如,上述樹脂膜就剝離性或抑制構成下述離型層之成分之轉印之觀點而言,載體片(B)較佳為包含聚酯膜與聚烯烴膜之2層構成。藉由設為具有聚酯膜與聚烯烴膜之2層構成,且使聚烯烴膜側與環氧樹脂片(A)接觸,從而容易將環氧樹脂片(A)與載體片(B)之剝離強度調整為5 N/15 mm以下。
於該情形時,載體片(B)中,聚酯膜與聚烯烴膜之層厚比較佳為聚酯膜/聚烯烴膜=0.2~10,更佳為0.3~5,進而較佳為0.5~3。
於該情形時,成為如下構成:聚酯膜存在於積層片之最表面,具有難接著性之聚烯烴膜與環氧樹脂片(A)接觸。亦可於聚烯烴膜之表面塗佈離型劑而使用。
構成上述聚酯膜之聚酯較佳為使芳香族二羧酸與脂肪族二醇進行縮聚而獲得者,可為包含1種芳香族二羧酸與1種脂肪族二醇之聚酯,亦可為使1種以上之其他成分共聚而成之共聚聚酯。作為芳香族二羧酸,可列舉:對苯二甲酸、2,6-萘二甲酸等;作為脂肪族二醇,可列舉:乙二醇、二乙二醇、1,4-環己烷二甲醇等。作為具代表性之聚酯,可例示聚對苯二甲酸乙二酯等。另一方面,作為用作共聚聚酯之成分之二羧酸,可列舉:間苯二甲酸、鄰苯二甲酸、對苯二甲酸、2,6-萘二甲酸、癸二酸;作為二醇成分,可列舉:乙二醇、二乙二醇、丙二醇、丁二醇、1,4-環己烷二甲醇、新戊二醇等。又,亦可使用對羥基苯甲酸等羥基羧酸。
聚酯膜可為無延伸膜亦可為延伸膜,就機械強度之觀點而言,較佳為延伸膜,更佳為雙軸延伸膜。又,亦可對聚酯膜預先實施電暈處理、電漿處理等表面處理。
作為上述聚烯烴膜,可使用聚乙烯膜或聚丙烯膜、聚4-甲基-1-戊烯、聚1-丁烯等先前公知之膜。就剝離性及低成本之觀點而言,進而較佳為聚乙烯膜,特佳為低密度聚乙烯。
又,亦可對聚烯烴膜預先實施電暈處理、電漿處理等表面處理。
又,載體片(B)亦可為除包含樹脂膜以外,進而包含離型層作為與環氧樹脂片(A)接觸側之最表面層之結構。藉由載體片(B)除樹脂膜以外進而包含離型層,而容易將環氧樹脂片(A)與載體片(B)之剝離強度調整為5 N/15 mm以下。
離型層之構成成分無特別限制,亦可含有矽酮化合物、氟化合物、蠟類、界面活性劑等。就價格與離型性之平衡性良好之面而言,較佳為使用矽酮化合物。
進而,為了調整離型層之剝離性,亦可併用剝離控制劑。
作為可獲取之包含聚酯膜與離型層之載體片(B)之市售品,可列舉Teijin Film Solutions股份有限公司製造之「Purex A31」或三菱化學股份有限公司製造之「MRF-38」。
本發明之環氧樹脂片(A)或積層體之製造方法可包含如下步驟:藉由將上述載體片(B)自本發明之積層體剝離,而獲得上述環氧樹脂片(A)或上述積層體。即,本發明之積層體較佳為自積層體之至少一面剝離載體片(B)而得者。又,本發明之環氧樹脂片(A)較佳為將載體片(B)自積層體剝離而得者。
由於利用該製造方法所獲得之環氧樹脂片(A)或積層體之表面外觀未受損,因此亦可適宜地使用於如電氣、電子領域之類的要求精密度之用途。例如,可使用於重視柔軟性之可撓性或可延展性積層板。
作為可撓性或可延展性積層板,例如可列舉積層有銅箔等金屬箔之印刷配線板等。作為印刷配線板之製造方法,例如可例示以下之方法:於環氧樹脂片(A)之一面或兩面重疊銅箔,使用真空加壓機等進行熱壓成型,製作銅箔積層板,藉由蝕刻加工形成配線圖案,從而獲得印刷配線板。又,可列舉使用導電膏作為配線圖案之印刷配線板等。進而,可例示如下方法:於環氧樹脂片(A)之一面或兩面,利用網版印刷法、噴墨印刷法等公知之方法塗佈導電膏,形成配線圖案,從而獲得印刷配線板。上述導電膏較佳為具有可撓性、可延展性。
藉由於上述印刷配線板安裝各種電子元件,能夠獲得可撓性或可延展性裝置。
此外,環氧樹脂片(A)或積層體亦可作為電子、電氣構件用途,使用於以緩衝材、黏著片、伸縮膠帶、壓力感測器為代表之各種感測器基板等。
黏著片可用作填充材,該填充材填充液晶顯示器(LCD)、電漿顯示器(PDP)、電致發光顯示器(ELD)等圖像顯示面板、與配置於其使用狀態之前面側(視認側)之保護面板或觸控面板等面板構件間之空隙。
此外,亦可應用於包含電子、電氣構件用途以外之領域在內之各種工業用緩衝材、黏著片、接著片、伸縮膠帶、密封用片、耐熱絕緣片、耐熱導電性片、玻璃替代物、保護膜、醫療用片、農業用片、建築用片等。
[捲繞體]
本發明之捲繞體係於芯體捲繞有具備環氧樹脂片(A)、與積層於該環氧樹脂片(A)之至少一面之載體片(B)之積層體者,該環氧樹脂片(A)於100℃~200℃下之拉伸儲存模數為1.0×104
~6.0×107
Pa,且拉伸伸長率為150%以上,該積層體於100℃~200℃下之拉伸儲存模數為6.0×107
~1.0×1010
Pa,該環氧樹脂片(A)與該載體片(B)之剝離強度為5 N/15 mm以下。又,較佳之態樣與上述本發明之積層體之情形同樣。
如上所述,一般之環氧樹脂片於100℃~200℃下之拉伸儲存模數為0.1 GPa~10 GPa左右,拉伸伸長率為10%左右,但具有此種特性之環氧樹脂片過硬,本就有製成捲繞體時產生皺褶或裂紋等異常之虞。本發明之捲繞體如上所述較為柔軟。藉由使用環氧樹脂片(A),可適宜地製成捲繞體。
又,關於本發明之捲繞體,藉由積層體具有特定之拉伸儲存模數及拉伸伸長率,於將捲繞體捲出使用時,操作性(產生伸長、撓曲、皺褶等異常)變得良好。
本發明之捲繞體中,積層體之長度較佳為10 m以上,更佳為20 m以上。藉由積層體之長度為10 m以上,例如於用作可撓性或可延展性積層板之情形時,能夠連續地生產電子構件,連續製膜性優異。再者,上述長度之上限無特別限定,較佳為1000 m以下。
本發明之捲繞體中,積層體之厚度之變動率較佳為20%以下,更佳為15%以下,進而較佳為10%以下,進而更佳為5.0%以下。藉由積層體之厚度之變動率為20%以下,而實現積層體之厚度均勻且厚度之變動得到抑制之捲繞體。藉此,能夠生產性良好地製造捲繞體作為可撓性或可延展性積層板用途。再者,積層體之厚度之變動率越小越佳,其下限為0%以上。
<芯體>
芯體係使用於積層體之捲取之圓柱形狀之捲芯。作為芯體之素材,例如可列舉:紙、樹脂含浸紙、丙烯腈/丁二烯/苯乙烯共聚物(ABS樹脂)、纖維強化塑膠(FRP)、酚系樹脂、含有無機物之樹脂等。芯體亦可使用接著劑。
作為芯體之素材,無特別限定,就熱膨脹係數較小,硬度較高,相對於濕度之膨潤性較低,且捲繞性優異之觀點而言,較佳為塑膠、熱硬化性樹脂等。
於芯體之素材為紙之情形時,尤其是藉由樹脂等將其表面被覆,而容易獲得所需之特性。
就表面平滑性之觀點而言,芯體較佳為樹脂含浸紙之管。
芯體之外徑較佳為10 mm以上2,000 mm以下,更佳為15 mm以上1,900 mm以下,進而較佳為20 mm以上1,700 mm以下。藉由使芯體之外徑為10 mm以上,積層體容易受到芯體品質之影響,因此於本實施形態中尤為有用。
實施例
以下,基於實施例,更具體地對本發明進行說明,但本發明不受以下之實施例任何限定。再者,以下之實施例中之各種製造條件或評價結果之值具有作為本發明之實施態樣中之上限或下限之較佳值之含義,較佳之範圍亦可為上述上限或下限之值與下述實施例之值或實施例彼此之值之組合所規定之範圍。以下,「份」均表示「質量份」。
[各種分析、評價、測定方法]
以下之各種物性以及特性之分析、評價、測定方法如下所述。
(1)拉伸儲存模數
利用JIS K7244法中所記載之動態黏彈性測定法,使用動態黏彈性測定裝置(IT計測控制股份有限公司製造之「DVA-200」),以頻率1 Hz、升溫速度3℃/分鐘、兩端固定拉伸模式之測定條件進行測定,求出於100℃、150℃、200℃下之儲存模數E'。
(2)拉伸伸長率
依據JIS K7161於23℃、50%之環境下,於拉伸試驗中以試驗速度200 mm/min對評價用樣品進行拉伸試驗,測定斷裂時之伸長。
(3)剝離強度
將積層體切割成長度250 mm、寬度15 mm,製成試片,使用萬能材料試驗機(島津製作所製造之「AGS-X」),以試驗速度50 mm/min對環氧樹脂片(A)層與載體片(B)層之界面進行T型剝離試驗,將位移為30 mm~60 mm間之剝離力之平均值作為剝離強度。
(4)耐撓曲性<固定端自重撓曲測定>
將積層體切割成25 mm×300 mm之短條狀,製成試片,將距離兩側各50 mm長度之部分放置於水平之桌台端部,施加負重。將標線間距離150 mm部分以懸空之狀態於24℃之環境下放置5分鐘,測定中央部之自然撓曲之端部與水平面之距離。將試片中央部與固定水平面之距離設為撓曲變化量,如下述般對耐撓曲性進行評價。
再者,撓曲變化量之值較小相當於例如當對積層體進行如沖切加工般之二次加工時,經沖切之積層體之彎曲(翹曲)得到了抑制。
A:撓曲變化量之絕對值為0 mm以上5.0 mm以下
B:撓曲變化量之絕對值超過5.0 mm且7.0 mm以下
C:撓曲變化量之絕對值超過7.0 mm
(5)耐伸長性
將積層體切割成12.5 mm×200 mm之短條狀,製成試片樣品。
使用拉伸試驗機,以標線間距離100 mm、試驗速度200 mm/min對上述樣品進行拉伸試驗。求出負重為50 N時之各樣品之伸長率。以如下基準進行評價。
再者,伸長率之值較低相當於例如對積層體進行如沖切加工般之二次加工時,經沖切之積層體之尺寸穩定性良好。
A:伸長率為0%以上2.0%以下
B:伸長率超過2.0%且20%以下
C:伸長率超過20%
(6)環氧樹脂片(A)之外觀評價
切出10 cm見方尺寸之積層體,將單側之載體片(B)自積層體剝離,對此時手觸感之易剝離性、及將載體片剝離後環氧樹脂片(A)之表面狀態,以下述之指標進行評價。
A:未感受到阻力且非常容易地剝離。10 cm見方尺寸之環氧樹脂片之表面整體與至少一面附有載體片之積層體之狀態相比,藉由目視無法確認到光澤度以外之變化。環氧樹脂片之表面平滑之載體片之面被充分地轉印,且平滑。
B:未感受到阻力且容易剝離。藉由目視無法確認到10 cm見方尺寸之環氧樹脂片之表面整體有類似劃痕者。
C:雖稍感受到阻力,但剝離。藉由目視可確認到於10 cm見方尺寸之環氧樹脂片之表面有「鋸」狀之線。
D:阻力非常大。藉由目視可確認到於10 cm見方尺寸之環氧樹脂片出現表面白化或凹凸等。
(7)積層體之厚度、及捲繞體中之積層體之厚度之變動率
積層體之厚度係藉由自積層體之端部於寬度方向上以100 mm間隔測定厚度,算出其平均值而求出。
又,捲繞體中之積層體之厚度之變動率設為由下式所算出之數值之最大值,如下述般進行評價。再者,捲繞體使用經熱處理者,捲繞體中之積層體之厚度係於自捲筒最表層以2 m間隔之5處位置自積層體之端部於寬度方向上以100 mm間隔測定厚度,算出其平均值。
積層體之厚度之變動率[%]=100×|(積層體之厚度之最大值或最小值)-(積層體之厚度)|/(積層體之厚度)
A:積層體之厚度之變動率為0%以上10%以下
B:積層體之厚度之變動率超過10%且20%以下
C:積層體之厚度之變動率超過20%
(8)連續製膜性
連續製膜性係根據製造捲繞體時可連續地捲取採取之積層體之長度,如下述般進行評價。再者,捲取時,於積層體大量地產生皺褶之時點,判斷為無法捲取採取。
A:積層體之長度為20 m以上
B:積層體之長度為10 m以上且未達20 m
C:積層體之長度未達10 m
實施例及比較例中,如下述般製作環氧樹脂片(A)、積層體、及捲繞體。
<環氧樹脂片(A)之使用材料>
(環氧樹脂(α))
向具備攪拌機、滴液漏斗及溫度計之容量1 L之玻璃製燒瓶中加入預先加熱至45℃之1,6-己二醇141.8質量份、三氟化硼乙醚0.51質量份,並加熱至80℃。以不會成為85℃以上之方式歷時滴加表氯醇244.3質量份。一面保持在80~85℃一面進行1小時熟化,其後冷卻至45℃。向其中添加22質量%氫氧化鈉水溶液528.0質量份,於45℃下劇烈攪拌4小時。冷卻至室溫,將水相分離去除,於減壓下進行加熱,去除未反應之表氯醇、水,獲得粗1,6-己二醇二縮水甘油醚283.6質量份。
該粗1,6-己二醇二縮水甘油醚藉由利用Oldershaw型蒸餾塔(15段)進行蒸餾純化,將壓力1300 Pa、170~190℃之滯留份作為主要滯留份,而獲得127.6質量份之利用氣相層析法測得之二縮水甘油體純度為97質量%、全氯量為0.15質量%、環氧當量為116 g/eq之1,6-己二醇二縮水甘油醚。
將上述1,6-己二醇二縮水甘油醚100質量份、雙酚F(酚性羥基當量:100 g/eq)69.3質量份、乙基三苯基碘化鏻(30質量%甲基溶纖劑溶液)0.13質量份放入至耐壓反應容器中,於氮氣氛圍下,以165~170℃進行5小時聚合反應,藉此獲得環氧當量為1,000 g/eq、數量平均分子量為3,000之雙酚F與1,6-己二醇縮水甘油醚之共聚物。
(硬化劑)
脂環式聚胺(三菱化學股份有限公司製造之「jERCUREST-14」)
<載體片(B)>
載體片(1):OPP(Oriented Polypropylene,定向聚丙烯)/PET(Polyethylene Terephthalate,聚對苯二甲酸乙二酯)膜(將厚度50 μm之未改性系聚丙烯(定向聚丙烯:OPP)膜與厚度50 μm之雙軸延伸聚對苯二甲酸乙二酯(PET)膜貼合而成之2種雙層膜)
載體片(2):LDPE(Low Density Polyethylene,低密度聚乙烯)/PET膜(將厚度50 μm之低密度聚乙烯(LDPE)膜與厚度50 μm之雙軸延伸聚對苯二甲酸乙二酯膜貼合而成之2種雙層膜)
載體片(3):Purex A31(Teijin Film Solutions股份有限公司製造,單面塗佈有矽酮之PET膜,厚度100 μm)
載體片(4):Stretchlon 800(Airtech公司製造,尼龍系膜,厚度50 μm)
載體片(5):DIAFOIL T100(三菱化學股份有限公司製造,無塗佈PET膜,厚度100 μm)
載體片(6):DIAFOIL MRF-75(三菱化學股份有限公司製造,單面塗佈有矽酮之PET膜,厚度75 μm)
<實施例1~2、比較例1~2>
以表1所示之比率向環氧樹脂(α)調配硬化劑,製備可撓性環氧樹脂組合物,將該環氧樹脂組合物夾入於表1所示之2片載體片(B)之間,調整為所需之厚度,於40℃下進行16小時熱處理,進而於80℃下進行6小時熱處理,獲得實施例1~2、比較例1~2之伸縮性環氧樹脂片之積層體。將積層體之評價示於表1。
如實施例1、2所示,於載體片(B)為2層之情形時,PET層成為積層體之最外表面,烯烴系之層與伸縮性環氧樹脂片層接觸。
<實施例3>
將實施例1之硬化條件變更為於40℃下進行16小時熱處理,進而於80℃下進行3小時熱處理,從而獲得伸縮性環氧樹脂片之積層體。將積層體之評價示於表1。該環氧樹脂片為半硬化之狀態。
<實施例4>
以表1所示之比率向環氧樹脂(α)調配硬化劑,製備可撓性環氧樹脂組合物,將該環氧樹脂組合物塗佈於表1所示之載體片(B)之一面(烯烴系之層),調整為所需之厚度,於40℃下進行16小時熱處理,進而於80℃下進行6小時熱處理,從而獲得實施例4之伸縮性環氧樹脂片之積層體。將積層體之評價示於表1。
[表1]
<實施例5及6>
除將環氧樹脂片(A)之厚度分別變更為80 μm、200 μm以外,與實施例1同樣地獲得伸縮性環氧樹脂片之積層體。將積層體之評價示於表2。
<實施例7>
除變更為表2所示之載體片(B)以外,與實施例1同樣地獲得伸縮性環氧樹脂片之積層體。將積層體之評價示於表2。
[表2]
<實施例8>
將於表1所示之2片載體片(B)之間夾入有實施例1之環氧樹脂組合物之積層體於紙製之芯體(外徑:12.7 cm)上捲取50 m,進行與實施例1同樣之熱處理,從而獲得捲繞體。將捲繞體之評價示於表3。
<實施例9及10>
除分別使用實施例5及6中所獲得之積層體以外,與實施例8同樣地獲得捲繞體。將捲繞體之評價示於表3。
[表3]
可知實施例1~4中所獲得之伸縮性環氧樹脂片之積層體之耐伸長性、耐撓曲性優異,因此二次加工過程中之操作性良好(即,皺褶、伸長、撓曲等異常得到抑制)。進而,當剝離載體層時,環氧樹脂片表面外觀亦未受損,因此該環氧樹脂片亦可實用性地使用。又,本發明之積層體由於可連續地製膜,因此可簡便地獲得捲繞體。
Claims (13)
- 一種積層體,其係具備環氧樹脂片(A)、與積層於該環氧樹脂片(A)之至少一面之載體片(B)者,該環氧樹脂片(A)於100℃~200℃下之拉伸儲存模數為1.0×104~6.0×107Pa,且拉伸伸長率為150%以上,該積層體於100℃~200℃下之拉伸儲存模數為6.0×107~1.0×1010Pa,該環氧樹脂片(A)與該載體片(B)之剝離強度為5N/15mm以下,以上之各種物性以及特性之分析、評價、測定方法如下所述:拉伸儲存模數:利用JIS K7244法中所記載之動態黏彈性測定法,使用動態黏彈性測定裝置(IT計測控制股份有限公司製造之「DVA-200」),以頻率1Hz、升溫速度3℃/分鐘、兩端固定拉伸模式之測定條件進行測定;拉伸伸長率:依據JIS K7161於23℃、50%之環境下,於拉伸試驗中以試驗速度200mm/min對評價用樣品進行拉伸試驗,測定斷裂時之伸長;剝離強度:將積層體切割成長度250mm、寬度15mm,製成試片,使用萬能材料試驗機(島津製作所製造之「AGS-X」),以試驗速度50mm/min對環氧樹脂片(A)層與載體片(B)層之界面進行T型剝離試驗,將位移為30mm~60mm間之剝離力之平均值作為剝離強度。
- 如請求項1之積層體,其中於上述環氧樹脂片(A)之兩面具備上述載 體片(B)。
- 如請求項1或2之積層體,其中上述載體片(B)包含聚酯膜。
- 如請求項1或2之積層體,其中上述載體片(B)包含離型層。
- 如請求項1或2之積層體,其中上述載體片(B)係包含聚酯膜與聚烯烴膜之2層構成。
- 如請求項5之積層體,其中上述載體片(B)中,聚酯膜與聚烯烴膜之層厚比為聚酯膜/聚烯烴膜=0.2~10。
- 如請求項1或2之積層體,其中上述環氧樹脂片(A)包含使含有環氧樹脂與脂環式聚胺之環氧樹脂組合物硬化而成之硬化物。
- 如請求項7之積層體,其中上述環氧樹脂具有剛性成分與柔軟成分之嵌段結構。
- 如請求項1或2之積層體,其厚度為30μm~1000μm。
- 一種積層體,其係將上述載體片(B)自如請求項2至9中任一項之積層體之一面剝離而得。
- 一種可撓性或可延展性積層板,其使用如請求項1至10中任一項之積層體之環氧樹脂片(A)。
- 一種環氧樹脂片之製造方法,其包含如下步驟:藉由將上述載體片(B)自如請求項1至9中任一項之積層體剝離,而獲得上述環氧樹脂片(A)。
- 一種捲繞體,其係於芯體捲繞有具備環氧樹脂片(A)、與積層於該環氧樹脂片(A)之至少一面之載體片(B)之積層體者,該環氧樹脂片(A)於100℃~200℃下之拉伸儲存模數為1.0×104~6.0×107Pa,且拉伸伸長率為150%以上,該積層體於100℃~200℃下之拉伸儲存模數為6.0×107~1.0×1010Pa,該環氧樹脂片(A)與該載體片(B)之剝離強度為5N/15mm以下,以上之各種物性以及特性之分析、評價、測定方法如下所述:拉伸儲存模數:利用JIS K7244法中所記載之動態黏彈性測定法,使用動態黏彈性測定裝置(IT計測控制股份有限公司製造之「DVA-200」),以頻率1Hz、升溫速度3℃/分鐘、兩端固定拉伸模式之測定條件進行測定;拉伸伸長率:依據JIS K7161於23℃、50%之環境下,於拉伸試驗中以試驗速度200mm/min對評價用樣品進行拉伸試驗,測定斷裂時之伸長;剝離強度:將積層體切割成長度250mm、寬度15mm,製成試片,使用萬能材料試驗機(島津製作所製造之「AGS-X」),以試驗速度50 mm/min對環氧樹脂片(A)層與載體片(B)層之界面進行T型剝離試驗,將位移為30mm~60mm間之剝離力之平均值作為剝離強度。
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