TW202309218A - 黏著膜、及積層體 - Google Patents
黏著膜、及積層體 Download PDFInfo
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- TW202309218A TW202309218A TW111122633A TW111122633A TW202309218A TW 202309218 A TW202309218 A TW 202309218A TW 111122633 A TW111122633 A TW 111122633A TW 111122633 A TW111122633 A TW 111122633A TW 202309218 A TW202309218 A TW 202309218A
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- Prior art keywords
- adhesive film
- resin
- polyvinyl acetal
- film
- mass
- Prior art date
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Images
Classifications
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract
本發明之黏著膜包含熱塑性樹脂,且其tanδ之最大峰值溫度為0℃以上52℃以下,20℃之剪切儲存模數為3×10
5Pa以上,且使上述黏著膜1.0 g溶解於異丙醇10 g之情形時之未溶解成分之比率為35質量%以上100質量%以下。
Description
本發明係關於一種黏著膜、及具備黏著膜之積層體。
於液晶顯示器、有機EL顯示器、附帶觸控面板之顯示器等各種顯示器中,為了將表面保護面板、偏光板、附帶觸控感測器之膜、附帶觸控感測器之玻璃等重疊並固定,而廣泛使用有黏著膜。作為黏著膜,就透明性、黏著性等觀點而言,以往廣泛使用有(甲基)丙烯酸系樹脂。又,除(甲基)丙烯酸系樹脂以外,亦正在研究使用聚乙烯縮醛系樹脂。
已知於使用聚乙烯縮醛系樹脂之情形時,例如,如專利文獻1、2中所揭示,使用摻合有一定量以上之塑化劑之塑化聚乙烯縮醛系樹脂。又,亦正在研究於塑化聚乙烯縮醛系樹脂中摻合會藉由光照射而硬化之反應性稀釋劑,以可藉由光照射提升儲存模數。
又,塑化聚乙烯縮醛系樹脂亦被廣泛用作層合玻璃用中間膜。層合玻璃用中間膜例如將2片層合玻璃構件接合而構成層合玻璃。層合玻璃即便受到外部衝擊發生破損,亦少有玻璃碎片分散之情形,較為安全,因此被廣泛用於汽車等車輛、航空器、建築物等之窗玻璃。
進而,近年來,正嘗試向構成窗玻璃等之層合玻璃導入調光膜,以能夠調整透光性等。於導入調光膜之情形時,層合玻璃例如已知如下構成:於2片玻璃板之間配置調光膜,將調光膜與各玻璃板介隔作為層合玻璃用中間之樹脂膜而接合之構成。然後,正研究將含有塑化聚乙烯縮醛系樹脂之黏著膜應用於樹脂膜。
[先前技術文獻]
[專利文獻]
專利文獻1:日本特許第6046811號公報
專利文獻2:日本特許第6116772號公報
[發明所欲解決之課題]
且說,於上述顯示器、層合玻璃等中所使用之含有塑化聚乙烯縮醛系樹脂之黏著膜或層合玻璃用中間膜存在「塑化劑或聚乙烯縮醛系樹脂吸濕,若於高溫高濕下長期使用,則產生白化」之問題。
又,於液晶顯示器等中廣泛用作黏著膜之習知之(甲基)丙烯酸系樹脂膜儘管耐濕熱性較高,不易產生白化之問題,但耐衝擊性不易提升。因此,若在層合玻璃或顯示器用途中使用,則受到外部衝擊而破損時玻璃之碎片飛散而安全性變低,而變得難以用於車例如輛用途。
因此,本發明之課題在於提供一種於包含熱塑性樹脂之黏著膜中,使耐衝擊性及耐濕熱性兩者變得良好。
[解決課題之技術手段]
本發明人等進行積極研究,結果發現,藉由於包含熱塑性樹脂之黏著膜中,使tanδ之最大峰值溫度為特定之溫度範圍內,使剪切儲存模數為一定值以上,且使對於異丙醇之未溶解成分之比例為一定值以下,可解決上述課題,從而完成以下之本發明。
即,本發明提供以下之[1]~[31]。
[1]一種黏著膜,其包含熱塑性樹脂,且
上述黏著膜之tanδ之最大峰值溫度為0℃以上52℃以下,20℃之剪切儲存模數為3×10
5Pa以上,且使上述黏著膜1.0 g溶解於異丙醇10 g之情形時之未溶解成分的比率為35質量%以上100質量%以下。
[2]如上述[1]記載之黏著膜,其不含塑化劑、或者相對於上述熱塑性樹脂100重量份包含未達20重量份之塑化劑。
[3]如上述[1]或[2]記載之黏著膜,其中,上述熱塑性樹脂為聚乙烯縮醛系樹脂。
[4]如上述[3]記載之黏著膜,其中,上述聚乙烯縮醛系樹脂具有以下式(1)所示之聚環氧烷(polyalkylene oxide)結構,
(式(1)中,A
1O為碳數2~6之氧伸烷基,m為平均重複數,為4~200;R
1為碳數1~8之烷基或氫原子;再者,氧伸烷基可為單獨1種,亦可混合存在2種以上;*為與其他基之鍵結位置)
[5]如上述[4]記載之黏著膜,其中,上述聚乙烯縮醛系樹脂以0.1莫耳%以上10莫耳%以下之比率包含上述聚環氧烷結構。
[6]如上述[4]或[5]記載之黏著膜,其中,上述聚環氧烷結構包含氧伸乙基及氧伸丙基之至少任一者。
[7]如上述[6]記載之黏著膜,其中,上述聚環氧烷結構包含氧伸乙基及氧伸丙基兩者,且其等具有無規結構。
[8]如上述[4]至[7]中任一項記載之黏著膜,其中,上述聚環氧烷結構之末端為烷基。
[9]如上述[3]至[8]中任一項記載之黏著膜,其中,上述聚乙烯縮醛系樹脂之縮醛化度為60莫耳%以上。
[10]如上述[4]至[9]中任一項記載之黏著膜,其中,上述聚環氧烷結構係經由單鍵、或醚鍵、酯鍵、醯胺鍵、及可具有該等鍵中之至少任一者之烴基之任一者而連結於主鏈。
[11]如上述[3]至[10]中任一項記載之黏著膜,其中,上述聚乙烯縮醛系樹脂之羥基量為5莫耳%以上35莫耳%以下。
[12]如上述[3]至[11]中任一項記載之黏著膜,其中,上述聚乙烯縮醛系樹脂之乙醯化度為0.01莫耳%以上50莫耳%以下。
[13]如上述[3]至[12]中任一項記載之黏著膜,其中,上述聚乙烯縮醛系樹脂為聚乙烯縮丁醛系樹脂。
[14]如上述[3]至[13]中任一項記載之黏著膜,其中,上述聚乙烯縮醛系樹脂之重量平均分子量(Mw)為50,000以上800,000以下。
[15]如上述[3]至[14]中任一項記載之黏著膜,其中,上述聚乙烯縮醛系樹脂之含量以黏著膜所含有之熱塑性樹脂總量為基準,為50質量%以上100質量%以下。
[16]如上述[1]至[15]中任一項記載之黏著膜,其不含有分子量未達1000之低分子量化合物、或相對於上述熱塑性樹脂100質量份含有未達20質量份之分子量未達1000之低分子量化合物。
[17]如上述[2]至[16]中任一項記載之黏著膜,其中,上述塑化劑為選自由有機酯塑化劑、有機磷系塑化劑、有機醚系塑化劑、及醇系塑化劑所組成之群中之至少1種。
[18]如上述[1]至[17]中任一項記載之黏著膜,其中,上述黏著膜包含選自由二醇與一元性有機酸之酯、及碳數4~12之二元性有機酸與碳數4~10之醇之酯化合物、聚伸烷基二醇(polyalkylene glycol)系塑化劑、及聚氧伸烷基醚(polyoxyalkylene ether)系塑化劑所組成之群中之至少1種作為塑化劑。
[19]如上述[1]至[18]中任一項記載之黏著膜,其厚度為100 μm以上2000 μm以下。
[20]一種積層體,其具備上述[1]至[19]中任一項記載之黏著膜、及一對基材,且於上述一對基材之間配置上述黏著膜。
[21]如上述[20]記載之積層體,其中,上述一對基材均為玻璃。
[22]如上述[20]記載之積層體,其中,上述一對基材之一者為玻璃,另一者為調光膜及偏光膜之任一者。
[23]如上述[20]至[22]中任一項記載之積層體,其中,上述基材構成觸控面板、調光元件、及顯示元件之至少一部分。
[24]如上述[20]至[23]中任一項記載之積層體,其具備配置於上述一對基材之間之中間構件、及配置於各基材與上述中間構件之間之接著用膜,上述接著用膜之至少任一者為上述黏著膜。
[25]如上述[24]記載之積層體,其中,在上述中間構件之接著上述黏著膜之位置處配置無機材料基材、及有機材料基材之至少任一者。
[26]如上述[24]或[25]記載之積層體,其中,上述中間構件為觸控面板及調光元件之任一者。
[27]一種液晶顯示器,其包含上述[20]至[26]中任一項記載之積層體。
[28]一種層合玻璃,其包含上述[20]至[26]中任一項記載之積層體。
[29]一種顯示器,其包含上述[20]至[26]中任一項記載之積層體。
[30]一種上述[1]至[19]中任一項記載之黏著膜之用途,其係用於顯示器。
[31]一種上述[1]至[19]中任一項記載之黏著膜之用途,其係用於層合玻璃。
[發明之效果]
根據本發明,於包含熱塑性樹脂之黏著膜中,可使耐衝擊性及耐濕熱性兩者變得良好。
<黏著膜>
本發明之黏著膜包含熱塑性樹脂,且tanδ之最大峰值溫度為0℃以上52℃以下,20℃之剪切儲存模數為3×10
5Pa以上,且使黏著膜1.0 g溶解於異丙醇10 g之情形時之未溶解成分為35質量%以上100質量%以下。
本發明之黏著膜藉由具有以上之構成,可使耐衝擊性及耐濕熱性兩者優異。
以下,對本發明之一實施方式之黏著膜詳細地進行說明。
[tanδ之最大峰值溫度]
本發明中,黏著膜之tanδ之最大峰值溫度為0℃以上52℃以下。若tanδ之最大峰值溫度未達0℃,則有時耐衝擊性未充分提升。因此,當藉由黏著膜進行接著而獲得之積層體受到衝擊時變得容易破損,進而在破損時碎片容易飛散。又,若tanδ之最大峰值溫度高於52℃,則有時樹脂膜之柔軟性變得不充分,而無法使各種樹脂材料、對於無機玻璃之接著性變得良好。另一方面,若tanδ之最大峰值溫度未達0℃,則有時黏著性變得過高而導致操作性降低。
就以上之觀點而言,黏著膜之tanδ之最大峰值溫度較佳為50℃以下,更佳為44℃以下。又,tanδ之最大峰值溫度較佳為5℃以上,更佳為10℃以上,進而較佳為20℃以上。
再者,黏著膜之tanδ之最大峰值溫度可藉由如下方式檢測:使用動態黏彈性測定裝置進行黏彈性測定,讀取根據黏彈性測定之結果所獲得之損耗正切tanδ達到最大值的峰值溫度。
[剪切儲存模數]
本發明之黏著膜於20℃之剪切儲存模數為3×10
5Pa以上。若剪切儲存模數未達3×10
5Pa,則耐衝擊性變低,當藉由黏著膜進行接著而獲得之積層體等受到衝擊時,變得容易破損,又,破損時碎片容易飛散。
就耐衝擊性之觀點而言,上述20℃之剪切儲存模數較佳為1×10
6Pa以上,更佳為5×10
6Pa以上,進而較佳為1×10
7Pa以上,進而更佳為2×10
7Pa以上。
就耐衝擊性之觀點而言,黏著膜於20℃之剪切儲存模數較高為宜,但就平衡性良好地改善其他物性等觀點而言,例如為5×10
9Pa以下,較佳為1×10
9Pa以下,進而較佳為8×10
8Pa以下。
[未溶解成分之比例]
關於本發明之黏著膜,使黏著膜1.0 g溶解於異丙醇10 g之情形時之未溶解成分之比例為35質量%以上100質量%以下。若未溶解成分未達35質量%,則耐濕熱性降低,若長時間在高溫高濕環境下,則有時黏著膜之周邊部產生白化而導致外觀不良等。
就進一步提升耐濕熱性之觀點而言,未溶解成分較佳為45質量%以上,更佳為50質量%以上,進而較佳為60質量%以上。
再者,上述剪切儲存模數、tanδ之最大峰值溫度、及未溶解成分之比率可藉由適當選擇樹脂之種類、樹脂之分子量、有無摻合塑化劑及其含量等來調整。
[熱塑性樹脂]
作為黏著膜所使用之熱塑性樹脂,例如可例舉:(甲基)丙烯酸系樹脂、聚乙烯縮醛系樹脂、聚乙烯醇系樹脂(PVA)、聚胺酯(polyurethane)系樹脂(PU)、乙烯-乙酸乙烯酯共聚物樹脂(EVA)、乙烯-乙酸乙烯酯共聚物皂化物(EVOH)、乙烯-甲基丙烯酸共聚物樹脂、離子聚合物樹脂、異丁烯樹脂、苯乙烯-異戊二烯共聚物樹脂、苯乙烯-丁二烯共聚物樹脂等。
於黏著膜中,熱塑性樹脂可單獨使用1種,亦可併用2種以上。
其中,就謀求兼顧耐濕熱性與耐衝擊性之觀點而言,較佳為聚乙烯縮醛系樹脂、聚胺酯系樹脂(PU)、乙烯-乙酸乙烯酯共聚物樹脂(EVA)、乙烯-乙酸乙烯酯共聚物皂化物(EVOH)、乙烯-甲基丙烯酸共聚物樹脂、離子聚合物樹脂、異丁烯樹脂、苯乙烯-異戊二烯共聚物樹脂、苯乙烯-丁二烯共聚物樹脂。又,上述之中,熱塑性樹脂更佳為聚乙烯縮醛系樹脂。藉由使用聚乙烯縮醛系樹脂,變得容易使耐衝擊性優異。又,容易使對於各種樹脂材料或無機玻璃之接著力變得良好。以下,對熱塑性樹脂所使用之聚乙烯縮醛系樹脂詳細地進行說明。
[聚乙烯縮醛系樹脂]
如上所述,熱塑性樹脂更佳為聚乙烯縮醛系樹脂。聚乙烯縮醛系樹脂可為改質聚乙烯縮醛樹脂,亦可為未改質聚乙烯縮醛樹脂。改質聚乙烯縮醛樹脂如下所示,只要具有除縮醛基、羥基、及乙醯基以外之結構(改質基)即可,較佳為於側鏈具有改質基。改質聚乙烯縮醛樹脂藉由適當變更改質基之種類而疏水性提升,變得容易提升上述未溶解成分之比率。
聚乙烯縮醛系樹脂係藉由利用醛使聚乙烯醇縮醛化,進而視需要與改質劑反應,或進行再乙醯化(re-acetylation)處理而獲得。又,為了獲得改質聚乙烯縮醛樹脂,亦可使用改質聚乙烯醇作為原料聚乙烯醇。
上述除縮醛基、羥基、及乙醯基以外之結構較佳為聚環氧烷結構。本發明中,藉由具有聚環氧烷結構而疏水性提升,上述未溶解成分之比率變高,藉此使得耐濕熱性容易提升。又,變得容易使耐衝擊性、對於樹脂材料之接著性等亦良好。聚環氧烷結構具體而言,如以下之式(1)所示。
A
1O中之氧伸烷基為碳數2~6之氧伸烷基,較佳為碳數2~4之氧伸烷基,更佳為碳數2或3之氧伸烷基。若氧伸烷基之碳數為上述範圍內,則上述未溶解成分之比率變高,耐濕熱性變得容易提升。又,容易使耐衝擊性、對於樹脂材料之接著性等亦變得良好。
氧伸烷基中之伸烷基可為直鏈,亦可具有分支結構。作為氧伸烷基,例如可例舉:氧伸乙基、氧伸丙基、或氧伸丁基,較佳為氧伸乙基、氧伸丙基。氧伸烷基可單獨使用1種,亦可併用2種以上。於併用2種以上之情形時,各氧伸烷基可無規地加成,亦能夠以嵌段加成,但更佳為無規地加成。
聚環氧烷結構中之氧伸烷基較佳為包含氧伸乙基及氧伸丙基之至少任一者,亦較佳為包含氧伸乙基及氧伸丙基兩者。於包含氧伸乙基及氧伸丙基兩者之情形時,其等可構成嵌段結構,但更佳為構成無規結構。
於包含氧伸乙基(EO)及氧伸丙基(PO)之情形時,氧伸丙基相對於氧伸乙基之比(PO/EO)以莫耳比計,例如為1/9以上9/1以下,較佳為2/8以上8/2以下,更佳為3/7以上7/3以下。
式(1)中,m表示氧伸烷基之平均重複數,為4~200,較佳為5~100,更佳為10~80,進而較佳為15~50。
又,R
1中之烷基可為直鏈,亦可具有分支結構。
作為R
1中之烷基,可例舉:甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等分支丁基、正戊基、分支戊基、正己基、分支己基、正庚基、異庚基、3-庚基等分支庚基、正辛基、異辛基、2-乙基己基等分支辛基等。
R
1可為烷基及氫原子之任一者,但較佳為烷基。因此,聚環氧烷結構較佳為末端為烷基。聚環氧烷結構若於末端具有烷基,則疏水性提升,黏著膜之耐濕熱性變得容易進一步提升。烷基之碳數如上所述,只要為碳數1~8即可,但較佳為碳數1~6,更佳為碳數1~4。
上述聚環氧烷結構可經由單鍵連結於主鏈,但較佳為經由單鍵以外之連結基而連結於主鏈。
作為單鍵以外之連結基,可例舉:醚鍵(-O-)、酯鍵(-COO-)、醯胺鍵(-CONR-:R為氫原子或碳數1~4之烷基,較佳為氫原子)、或可具有該等鍵中之至少任一者之烴基。其中,更佳為醚鍵(-O-)、酯鍵(-COO-)、或可具有該等鍵中之至少任一者之烴基。該烴基之碳數並無特別限定,例如為1~10左右即可,較佳為1~4。又,其中,上述聚環氧烷結構更佳為經由醚鍵或-CH
2O-之任一者鍵結於主鏈。聚環氧烷結構藉由經由其等之任一者鍵結於主鏈而容易製造。再者,於-CH
2O-中,氧原子可鍵結於上述聚環氧烷結構。
聚乙烯縮醛系樹脂典型而言,具有縮醛基、羥基、及乙醯基。但是,聚乙烯縮醛系樹脂亦可因為被官能基改質,或進行再乙醯化反應故而不含有羥基。再者,縮醛基、羥基、及乙醯基如下述式(3-1)~式(3-3)所示,為直接或經由氧原子鍵結於主鏈之基,不包含聚環氧烷結構所具有之羥基等。
又,聚乙烯縮醛系樹脂較佳為藉由進行改質,而如上所述,具有上述式(1)所示之聚環氧烷結構。再者,以下,對於具有聚環氧烷結構之聚乙烯縮醛系樹脂,為了與其他聚乙烯縮醛系樹脂區分說明,而有時作為改質聚乙烯縮醛樹脂(A)進行說明。
改質聚乙烯縮醛樹脂(A)之利用聚環氧烷結構(即,式(1)所示之官能基)之改質量較佳為0.1莫耳%以上10莫耳%以下。若使上述改質量為上述範圍內,則tanδ之最大峰值溫度成為適度溫度,且20℃之剪切儲存模數容易變高,耐衝擊性容易提升。又,容易提升對於各種樹脂材料之接著力。進而,藉由設為上述下限值以上,上述未溶解成分之比率變高,耐濕熱性容易變得良好。
就該等觀點而言,利用聚環氧烷結構之改質量較佳為0.2莫耳%以上,更佳為0.3莫耳%以上,進而較佳為0.4莫耳%以上,尤佳為0.5莫耳%以上,又,較佳為8莫耳%以下,更佳為6莫耳%以下,進而較佳為4莫耳%以下。
再者,利用官能基之改質量表示官能基相對於構成聚乙烯縮醛系樹脂之全部乙烯系單體單位之比率。可對於聚乙烯縮醛系樹脂進行質子NMR測定,根據所獲得之光譜而算出改質量。下述之縮醛化度、羥基量、及乙醯化度亦可同樣地進行質子NMR測定,根據所獲得之光譜而算出。
聚乙烯縮醛系樹脂亦可不具有上述聚環氧烷結構。此種聚乙烯縮醛系樹脂可為具有式(1)所示之官能基以外之改質基之改質聚乙烯縮醛樹脂,亦可為未改質聚乙烯縮醛樹脂。即便為未改質聚乙烯縮醛樹脂,藉由再乙醯化反應等而如下述般使羥基量變少,藉此變得容易降低tanδ之最大峰值溫度等,而提升耐衝擊性。
作為式(1)所示之官能基以外之改質基,可例舉烷基。烷基可為直鏈,亦可具有分支結構。烷基之碳數例如為2~30,較佳為3~24,更佳為5~20,進而較佳為7~18,進而更佳為11~18。烷基可直接鍵結於主鏈,較佳為直接鍵結於構成主鏈之源自乙烯基之結構單元,但較佳為經由醚鍵(-O-)、酯鍵(*-COO-**)、胺酯鍵(urethane bond,*-NHCOO-**)鍵結,更佳為經由酯鍵、或胺酯鍵鍵結。
再者,於酯鍵、胺酯鍵中,「*」及「**」係鍵結於烷基或主鏈之鍵結位置,各鍵中較佳為「*」為鍵結於烷基之鍵結位置,「**」為鍵結於主鏈之鍵結位置。
聚乙烯縮醛系樹脂係具有源自乙烯基之結構單元作為主鏈者,式(1)所示之官能基可為與構成主鏈之源自乙烯基之結構單元鍵結者。因此,聚乙烯縮醛系樹脂較佳為具有以下式(2)所示之結構單元,其中,更佳為具有以下式(2-1)及式(2-2)所示之結構單元之任一者。
式(2)、(2-1)、(2-2)中之A
1O、R
1、m係如上所述,因此省略其等之說明。式(2)中之R
2之碳數例如為1~10,較佳為1~4。R
2之烴基如上所述,可具有酯鍵或醚鍵,但較佳為不具有酯鍵或醚鍵。
聚乙烯縮醛系樹脂典型而言,具有縮醛基、羥基、及乙醯基,即,聚乙烯縮醛系樹脂典型而言,具有以下式(3-1)、式(3-2)及式(3-3)所示之結構單元。因此,改質聚乙烯縮醛樹脂較佳為具有以下之式(3-1)、式(3-2)及式(3-3)所示之結構單元、及上述式(2)所示之結構單元。
但是,於聚乙烯縮醛系樹脂例如為未改質聚乙烯縮醛樹脂等之情形時,如上所述,可不具有羥基,亦可不具有式(3-2)所示之結構單元。即,未改質聚乙烯縮醛樹脂可具有以下之式(3-1)及式(3-3)所示之結構單元,還可進而任意地具有以下式(3-2)所示之結構單元。
聚乙烯縮醛系樹脂如上所述,係利用醛,對聚乙烯醇、或使聚乙烯醇改質而成之改質聚乙烯醇進行縮醛化,其後視需要進行改質而獲得者,作為聚乙烯醇,一般使用鹼化度80~99.8莫耳%之聚乙烯醇。
聚乙烯縮醛系樹脂中所含之縮醛基之碳數並無特別限定,如上述式(3-1)中所示,例如為1~20,但較佳為2~10,更佳為2~6,進而較佳為2、3或4。因此,上述式(3-1)所示之R之碳數較佳為1~9,更佳為1~5,進而較佳為1~3。
作為縮醛基,具體而言,尤佳為縮丁醛基,因此,作為聚乙烯縮醛系樹脂,較佳為聚乙烯縮丁醛系樹脂。聚乙烯縮醛系樹脂之縮醛化度(即,縮醛量)例如為40莫耳%以上90莫耳%以下。又,縮醛化度較佳為60莫耳%以上,更佳為63莫耳%以上,進而較佳為65莫耳%以上。藉由使縮醛化度變高,上述未溶解成分之比率容易變高,耐濕熱性變得容易提升。
又,縮醛化度更佳為88莫耳%以下,進而較佳為85莫耳%以下。藉由使縮醛化度為上述範圍內,而變得容易使羥基量為適度之量,並且含有一定量之式(1)所示之官能基。
再者,所謂縮醛化度,於聚乙烯縮醛系樹脂之縮醛基為乙醯縮醛基(acetoacetal group)之情形時,意味著乙醯縮醛化度,於縮醛基為縮丁醛基之情形時,意味著縮丁醛化度。
又,縮醛化度表示經縮醛化之乙烯醇單位相對於構成聚乙烯縮醛系樹脂之全部乙烯系單體單位的比率。
聚乙烯縮醛系樹脂之羥基量較佳為35莫耳%以下,更佳為33莫耳%以下,進而較佳為30莫耳%以下,進而更佳為25莫耳%以下。若使羥基量為上述上限值以下,則變得容易使tanδ之最大峰值溫度為適宜值,又,容易提升對於聚碳酸酯等極性較低之樹脂材料之接著力。進而,變得容易提升上述未溶解成分之比率。
又,聚乙烯縮醛系樹脂之羥基量可為0莫耳%以上,但於改質聚乙烯縮醛樹脂(A)之情形時,就防止黏著膜變得過於柔軟之觀點而言,可含有一定量之羥基量,例如為5莫耳%以上,較佳為9莫耳%以上,更佳為10莫耳%以上,進而較佳為12莫耳%以上。
又,於聚乙烯縮醛系樹脂例如為未改質聚乙烯縮醛樹脂之情形時,為了降低tanδ之最大峰值溫度,提升對於聚碳酸酯等極性較低之樹脂之接著力,需要減少羥基量。因此,未改質聚乙烯縮醛樹脂之羥基量較佳為15莫耳%以下,更佳為10莫耳%以下,進而較佳為5莫耳%以下,進而更佳為3莫耳%以下,最佳為0莫耳%。
再者,羥基量表示羥基相對於構成聚乙烯縮醛系樹脂之全部乙烯系單體單位的比率。
上述聚乙烯縮醛系樹脂之乙醯化度(乙醯基量)例如為0.01莫耳%以上50莫耳%以下,但於改質聚乙烯縮醛樹脂(A)之情形時,為了使利用式(1)所示之官能基之改質量為一定值以上,使乙醯化度亦為一定值以下為宜。因此,改質聚乙烯縮醛樹脂(A)之乙醯化度較佳為20莫耳%以下,更佳為15莫耳%以下,進而較佳為12莫耳%以下,進而更佳為5莫耳%以下。
又,改質聚乙烯縮醛樹脂(A)之乙醯化度如上所述,例如為0.01莫耳%以上,但較佳為0.1莫耳%以上,更佳為0.3莫耳%以上。
又,就降低羥基量,降低tanδ之最大峰值溫度,提升耐衝擊性、未溶解成分之比率、對於各種樹脂材料之接著力的觀點而言,於未改質聚乙烯縮醛樹脂之情形時,其乙醯化度設為一定值以上為宜,較佳為15莫耳%以上,更佳為25莫耳%以上,進而較佳為30莫耳%以上。又,未改質聚乙烯縮醛樹脂之乙醯化度如上所述,例如為50莫耳%以下,但較佳為45莫耳%以下,進而較佳為42莫耳%以下。
再者,乙醯化度表示乙醯基相對於構成聚乙烯縮醛系樹脂之全部乙烯系單體單位的比率。
聚乙烯縮醛系樹脂之重量平均分子量(Mw)較佳為50,000以上800,000以下。藉由將重量平均分子量調整至上述範圍內,變得容易使剪切儲存模數或tanδ之最大峰值溫度等為所需範圍內,變得容易使耐衝擊性、接著性等變得良好。又,藉由設為上述下限值以上,容易提升未溶解成分之比率。就該等觀點而言,聚乙烯縮醛系樹脂之重量平均分子量(Mw)更佳為100,000以上,進而較佳為120,000以上,進而更佳為150,000以上。又,重量平均分子量(Mw)更佳為600,000以下,進而較佳為500,000以下,進而更佳為400,000以下。
再者,重量平均分子量(Mw)係藉由凝膠滲透層析法來測定。
製造聚乙烯縮醛系樹脂時所使用之醛並無特別限定,例如為碳數1~20之醛,一般而言,可適宜地使用碳數為2~10之醛。上述碳數為2~10之醛並無特別限定,例如可例舉:乙醛、丙醛、正丁醛、異丁醛、正戊醛、2-乙基丁醛、正己醛、正辛醛、正壬醛、正癸醛、苯甲醛等。其中,較佳為乙醛、正丁醛、正己醛、正戊醛等碳數2~6之醛,更佳為碳數2、3、4之醛,進而較佳為正丁醛。該等醛可單獨地使用,亦可併用2種以上。
本發明中所使用之聚乙烯縮醛系樹脂可單獨地使用1種,亦可併用2種以上。
於本發明之黏著膜使用聚乙烯縮醛系樹脂作為熱塑性樹脂之情形時,只要發揮本發明之效果,則亦可具有聚乙烯縮醛系樹脂以外之熱塑性樹脂。但是,聚乙烯縮醛系樹脂為主成分較佳。聚乙烯縮醛系樹脂以外之熱塑性樹脂如上所述。
具體而言,聚乙烯縮醛系樹脂之含量以黏著膜所含有之熱塑性樹脂總量基準計,例如為50質量%以上,較佳為70質量%以上,更佳為90質量%以上,最佳為100質量%。因此,本發明之黏著膜所含有之熱塑性樹脂亦可為僅由聚乙烯縮醛系樹脂所構成者。
(塑化劑)
本發明之黏著膜亦可含有塑化劑。黏著膜藉由含有塑化劑而變得柔軟,可降低黏著膜之tanδ之最大峰值溫度,提升對於聚碳酸酯等各種樹脂材料或無機玻璃等各種被接著體之接著性。但是,本發明之黏著膜較佳為不含有塑化劑,或含有少量之塑化劑。藉由僅含有少量塑化劑或不含有塑化劑,而防止上述未溶解成分之比率降低,耐濕熱性容易變得良好。
又,本發明之黏著膜即便含有少量塑化劑或不含有塑化劑,藉由使用上述特定之熱塑性樹脂,亦能夠使對於聚碳酸酯等各種樹脂材料之接著性變得良好。
黏著膜中之塑化劑之含量相對於黏著膜所包含之熱塑性樹脂100質量份,可未達20質量份。藉由使塑化劑未達20質量份,上述未溶解成分之比率容易變高,耐濕熱性亦變得良好。
就耐濕熱性之觀點而言,塑化劑之上述含量較佳為15質量份以下,更佳為10質量份以下,進而較佳為5質量份以下,進而更佳為1質量份以下。塑化劑之含量之下限為0質量份。
於本發明之樹脂組成物使用改質聚乙烯縮醛樹脂(A)之情形時,可不含有塑化劑,但藉由含有塑化劑,變得容易提升樹脂膜之接著性。另一方面,於樹脂組成物使用未改質聚乙烯縮醛樹脂之情形時,就提升樹脂膜之接著性之觀點而言,含有塑化劑為宜。
作為塑化劑,例如可例舉:有機酯塑化劑、以及有機磷酸酯塑化劑及有機亞磷酸酯塑化劑等有機磷系塑化劑等。又,可例舉:聚伸烷基二醇系塑化劑、聚氧伸烷基醚系塑化劑等有機醚系塑化劑、醇系塑化劑等。
塑化劑可單獨使用1種,亦可併用2種以上。上述之中,較佳為有機酯塑化劑。作為較佳之有機酯塑化劑,可例舉:一元性有機酸酯及多元性有機酸酯等。
作為一元性有機酸酯,可例舉二醇與一元性有機酸之酯。作為二醇,可例舉:各伸烷基單位為碳數2~4、較佳為碳數2或3且伸烷基單位之重複數為2~10、較佳為2~4之聚伸烷基二醇。又,作為二醇,亦可為碳數2~4、較佳為碳數2或3之單伸烷基二醇(即,重複單位為1)。
作為二醇,具體而言,可例舉:乙二醇、二乙二醇、三乙二醇、四乙二醇、丙二醇、二丙二醇、三丙二醇、四丙二醇、丁二醇等。
作為一元性有機酸,可例舉碳數3~10之有機酸,具體而言,可例舉:丁酸、異丁酸、己酸、2-乙基丁酸、庚酸、正辛酸、2-乙基己酸、正壬酸及癸酸等。
作為具體之一元性有機酸,可例舉:三乙二醇二-2-乙基丁酸酯、三乙二醇二-2-乙基己酸酯、三乙二醇二辛酸酯、三乙二醇二正辛酸酯、三乙二醇二正庚酸酯、四乙二醇二正庚酸酯、四乙二醇二-2-乙基己酸酯、二乙二醇二-2-乙基丁酸酯、二乙二醇二-2-乙基己酸酯、二丙二醇二-2-乙基丁酸酯、三乙二醇二-2-乙基戊酸酯、四乙二醇二-2-乙基丁酸酯、二乙二醇二辛酸酯、三乙二醇二正庚酸酯、四乙二醇二正庚酸酯、三乙二醇二-2-乙基丁酸酯、乙二醇二-2-乙基丁酸酯、1,2-丙二醇二-2-乙基丁酸酯、1,3-丙二醇二-2-乙基丁酸酯、1,4-丁二醇二-2-乙基丁酸酯、1,2-丁二醇二-2-乙基丁酸酯等。
又,作為多元性有機酸酯,例如可例舉:己二酸、癸二酸、壬二酸等碳數4~12之二元性有機酸、與碳數4~10之醇之酯化合物。碳數4~10之醇可為直鏈,亦可具有分支結構,亦可具有環狀結構。
具體而言,可例舉:癸二酸二丁酯、壬二酸二辛酯、己二酸二己酯、己二酸二辛酯、己二酸己酯環己酯、己二酸二異壬酯、己二酸庚酯壬酯、二丁基卡必醇己二酸酯、混合型己二酸酯等。又,亦可為油改質癸二酸醇酸等。作為混合型己二酸酯,可例舉:由選自碳數4~9之烷基醇及碳數4~9之環狀醇中之2種以上之醇製作的己二酸酯。
作為上述有機磷系塑化劑,可例舉:磷酸三丁氧基乙酯、磷酸異癸基苯酯及磷酸三異丙酯等磷酸酯等。
作為有機酯塑化劑,並不限定於上述各酯之完全酯,亦可為部分酯。例如可為二醇與一元性有機酸之部分酯,亦可為二元性有機酸與醇之部分酯。具體而言,可例舉三乙二醇-單-2-乙基己酸酯等。
進而,可為甘油等3元以上之醇、與一元性有機酸之部分酯等。作為一元性有機酸,可例舉碳數3~24、較佳為碳數6~18之一元性有機酸。作為3元以上之醇、與一元性有機酸之部分酯之具體例,可例舉:甘油與硬脂酸之單或二酯、甘油與2-乙基己酸之單或二酯等。
作為有機酯塑化劑,上述中,可尤其適宜地使用三乙二醇-二-2-乙基己酸酯(3GO)。
作為聚伸烷基二醇系塑化劑,可例舉聚乙二醇、聚丙二醇、聚(環氧乙烷/環氧丙烷)嵌段共聚物、聚(環氧乙烷/環氧丙烷)無規共聚物、聚四亞甲基二醇等,其中,較佳為聚丙二醇。
聚氧伸烷基醚系塑化劑係一元或多元醇與聚氧伸烷基之醚化合物。
作為具體之聚氧伸烷基醚系塑化劑,例如可例舉:聚氧伸乙基己醚、聚氧伸乙基庚醚、聚氧伸乙基辛醚、聚氧伸乙基-2-乙基己醚、聚氧伸乙基壬醚、聚氧伸乙基癸醚、聚氧伸乙基烯丙醚、聚氧伸丙基烯丙醚、聚氧伸乙基甘油醚、聚氧伸丙基甘油醚、聚氧伸乙基二甘油醚、聚氧伸丙基二甘油醚、聚氧伸烷基新戊四醇醚等。
聚氧伸烷基醚系塑化劑較佳為多元醇與聚氧伸烷基之醚化合物,更佳為甘油或二甘油與聚氧伸烷基之醚化合物,進而較佳為甘油或二甘油與聚氧伸丙基之醚化合物。
作為醇系塑化劑,可例舉:丁二醇、己二醇、三羥甲基丙烷、新戊四醇等各種多元醇。其中,較佳為三羥甲基丙烷。
黏著膜除塑化劑以外,還可適當含有與熱塑性樹脂併用之公知添加劑。即,黏著膜亦可為由聚乙烯縮醛系樹脂等熱塑性樹脂所構成者,但除熱塑性樹脂以外,還可含有視需要摻合之塑化劑、或除塑化劑以外之添加劑。
除塑化劑以外之添加劑具體而言,可例舉:紫外線吸收劑、紅外線吸收劑、抗氧化劑、光穩定劑、接著力調整劑、顏料、染料、螢光增白劑、結晶成核劑等。又,本發明之樹脂組成物亦可被溶劑稀釋而以稀釋液之形態使用。
又,黏著膜較佳為不含有低分子量化合物、或僅含有少量之低分子量化合物。藉由僅含有少量之低分子量化合物或不含有低分子量化合物,而藉由低分子量化合物,使得未溶解成分之比率變低,防止耐濕熱性降低。
再者,低分子量化合物係指分子量未達1000之化合物,可例舉:上述塑化劑、或藉由光照射會硬化之反應性稀釋劑等。作為反應性稀釋劑,例如可例舉:(甲基)丙烯酸系單體或(甲基)丙烯酸系低聚物等(甲基)丙烯酸系反應性稀釋劑;環氧單體、環氧低聚物等環氧系反應性稀釋劑;烷氧基矽烷單體、烷氧基矽烷低聚物等聚矽氧系反應性稀釋劑等。
黏著膜中之低分子量化合物之含量相對於黏著膜所含之熱塑性樹脂100質量份,例如未達20質量份。若減少低分子量化合物之含量,則未溶解成分之比率變高,耐濕熱性變得容易提升。關於低分子量化合物之含量,就耐濕熱性之觀點而言,較佳為15質量份以下,更佳為10質量份以下,進而較佳為5質量份以下,進而更佳為1質量份以下。低分子量化合物之含量之下限為0質量份。
[聚乙烯縮醛系樹脂之製造方法]
本發明之黏著膜中所使用之聚乙烯縮醛系樹脂係藉由「利用醛使聚乙烯醇(亦稱為「原料聚乙烯醇」)縮醛化,其後視需要與改質劑反應,或進行再乙醯化處理」而獲得者。作為原料聚乙烯醇,亦可為未改質聚乙烯醇,於獲得改質聚乙烯縮醛樹脂之情形時,亦可使用改質聚乙烯醇作為原料聚乙烯醇。
例如,於製造具有聚環氧烷結構之改質聚乙烯縮醛樹脂(A)時,較佳為藉由以下之製造方法(1)進行製造。
(製造方法(1))
本製造方法(1)中,首先製造作為原料聚乙烯醇之聚氧伸烷基改質聚乙烯醇。具體而言,可藉由使乙烯酯、與包含具有聚氧伸烷基之乙烯系單體之單體聚合而獲得聚合物後,使聚合物皂化而獲得。皂化時一般使用鹼或酸,但較佳為使用鹼。作為聚氧伸烷基改質聚乙烯醇,可僅使用1種,亦可併用2種以上。
繼而,可利用醛,對上述中所獲得之聚氧伸烷基改質聚乙烯醇進行縮醛化,而獲得改質聚乙烯縮醛樹脂(A)。縮醛化之方法可藉由公知之方法來進行。
作為製造方法(1)中所使用之乙烯酯,可使用乙酸乙烯酯、甲酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、異丁酸乙烯酯、三甲基乙酸乙烯酯、新癸酸(versatic acid)乙烯酯、己酸乙烯酯、辛酸乙烯酯、月桂酸乙烯酯、棕櫚酸乙烯酯、硬脂酸乙烯酯、油酸乙烯酯、苯甲酸乙烯酯等。其中,較佳為乙酸乙烯酯。
又,作為製造方法(1)中所使用之具有聚氧伸烷基之乙烯系單體,具體而言,可例舉以下式(4)所示之化合物。其中,較佳為以下式(4-1)所示之聚氧伸烷基乙烯醚、式(4-2)所示之聚氧伸烷基烯丙醚。
作為具有聚氧伸烷基之乙烯系單體之較佳具體例,可例舉:聚氧伸乙基單乙烯醚、聚氧伸乙基聚氧伸丙基單乙烯醚、聚氧伸丙基單乙烯醚、聚氧伸乙基單烯丙醚、聚氧伸乙基聚氧伸丙基單烯丙醚、聚氧伸丙基單烯丙醚、聚氧伸乙基烷基乙烯醚、聚氧伸乙基聚氧伸丙基烷基乙烯醚、聚氧伸丙基烷基乙烯醚、聚氧伸乙基烷基烯丙醚、聚氧伸乙基聚氧伸丙基烷基烯丙醚、聚氧伸丙基烷基烯丙醚等。
又,於未改質聚乙烯縮醛樹脂之情形時,較佳為藉由以下之製造方法(2)來製造。
(製造方法(2))
於本製造方法(2)中,利用醛使原料聚乙烯醇縮醛化,而獲得聚乙烯縮醛系樹脂(以下,亦稱為原料聚乙烯縮醛系樹脂)。此處,作為原料聚乙烯醇,使用使聚乙烯酯皂化而獲得之未改質聚乙烯醇。繼而,可對於原料聚乙烯縮醛系樹脂,進行再乙醯化處理,而獲得未改質聚乙烯縮醛樹脂。作為再乙醯化處理,可利用先前公知之方法來進行,但只要使用乙酸酐,於吡啶等鹼存在下進行即可。又,再乙醯化處理例如可加熱至50℃以上100℃以下、較佳為70℃以上90℃以下左右來進行。對於聚乙烯縮醛系樹脂,藉由進行再乙醯化處理,而使得羥基量變少,變得容易降低tanδ之最大峰值溫度,使對於聚碳酸酯等各種樹脂材料之接著性變得良好。
又,於側鏈具有烷基之改質聚乙烯縮醛樹脂例如可藉由以下製造方法來製造。
首先,利用醛使原料聚乙烯醇縮醛化,而獲得聚乙烯縮醛系樹脂(以下,亦稱為原料聚乙烯縮醛系樹脂)。此處所使用之原料聚乙烯醇係使聚乙烯酯皂化所獲得者,較佳為未改質聚乙烯醇。
繼而,使具有烷基之改質劑與上述原料聚乙烯縮醛系樹脂反應,向原料聚乙烯縮醛系樹脂導入烷基。作為改質劑,可為具有「與原料聚乙烯縮醛系樹脂所具有之羥基反應而形成胺酯鍵或酯鍵之反應性基」的化合物。具體而言,可例舉:異氰酸正十八烷基酯等烷基之碳數為2~30之異氰酸烷基酯。又,可例舉:碳數3~31之羧酸、或上述羧酸之酸酐、羧酸酯、羧醯鹵化物等羧酸衍生物。作為羧酸衍生物,較佳為2-乙基己醯氯、月桂醯氯、肉豆蔻氯、棕櫚醯氯、硬脂醯氯等羧醯氯(carboxylic chloride)。
本發明之黏著膜不僅指黏著膜單獨體,還廣泛包括於其他構件上進行積層、覆膜等而成為層狀、膜狀之形態的情形,一般而言,稱為片之厚度相對較大者亦稱為黏著膜。黏著膜之厚度並無特別限定,例如為100 μm以上2000 μm以下,較佳為100 μm以上1000 μm以下。又,關於黏著膜,為了提高耐衝擊性,黏著膜之厚度越大越佳,更佳為200 μm以上,進而較佳為300 μm以上。又,就薄型化之觀點而言,黏著膜之厚度更佳為500 μm以下。
本發明之黏著膜可為由單層所構成者。構成單層膜之層可具有如上述黏著膜中所述之組成。即,構成單層膜之層可含有熱塑性樹脂,且不含有塑化劑,或者以如上述之含量含有塑化劑。進而,如上所述,亦可適當摻合添加劑。
又,本發明之黏著膜亦可為2層以上之多層膜。多層膜只要膜整體之組成如上述黏著膜中所述即可,但各層(以下,亦稱為「第1層」)可具有如上述黏著膜中所述之組成。即,各第1層可如上述黏著膜中所述,包含熱塑性樹脂,且不含有塑化劑,或者以如上所述之含量含有塑化劑。進而,亦可如上所述,適當摻合添加劑。多層膜之各第1層中之熱塑性樹脂、塑化劑、及添加劑之詳情、及各成分之含量之詳情係如上述黏著膜中所述。但是,作為含量基準之熱塑性樹脂係各第1層所含有之熱塑性樹脂。多層膜中,各第1層可為相同組成,亦可為不同組成。
又,多層膜亦可為上述第1層、與第1層以外之層(以下,亦稱為「第2層」)的積層體。具體而言,例如可例舉:第1層/第2層/第1層之3層結構等。
再者,於本發明之黏著膜為2層以上之多層膜之情形時,較佳為各層分別為上述黏著膜中所述之組成。
[黏著膜之製造方法]
本發明之黏著膜可藉由「利用公知之方法將包含聚乙烯縮醛系樹脂等熱塑性樹脂之樹脂組成物成形為膜狀」來製造。樹脂組成物可至少包含以上述方式製造之聚乙烯縮醛系樹脂等熱塑性樹脂,並視需要添加塑化劑、添加劑等來製備。又,樹脂組成物亦可適當於溶劑中進行稀釋來使用。
更具體而言,關於單層之黏著膜,可將樹脂組成物塗佈於脫模片等支持體上,或者使之流入至模框中,視需要適當進行加熱、乾燥而成形為膜狀,亦可藉由擠製成形、加壓成形等而成形為膜狀。
又,如上所述,於使原料聚乙烯縮醛系樹脂與改質劑反應而獲得聚乙烯縮醛系樹脂之情形時,亦可以如下方式成形。即,亦可將包含原料聚乙烯縮醛系樹脂、改質劑、及其他視需要摻合之塑化劑等添加劑之組成物塗佈於剝離片等支持體上,或者使之流入至模框,其後進行加熱,藉此使改質劑與原料聚乙烯縮醛系樹脂反應並且成形為膜狀。
進而,於黏著膜為多層膜之情形時,可準備構成各層之樹脂組成物,由構成其各層之樹脂組成物獲得多層膜之各層。於多層結構之情形時,可將各層適當重疊而獲得,亦可藉由共擠製等而成形多層結構。
本發明之黏著膜可用於各種用途,並無特別限定,較佳為用於各種顯示器用途、層合玻璃用途等。顯示器較佳為車載用,但並無特別限定。又,顯示器可例舉液晶顯示器、有機EL顯示器等,其中較佳為液晶顯示器。
層合玻璃係用於汽車、電車等車輛、船舶、飛行器等各種交通工具;或者高樓、公寓、獨立住宅、大廳、體育館等各種建築物;或者切削、研磨等機床、挖掘機或起重機等建設機械等的窗玻璃,其中,較佳為汽車等車輛用途。本發明之黏著膜由於耐衝擊性較高,使得下述之積層體等不易產生破損,又,即便產生破損,其碎片亦不易飛散,故而適宜用於車載用顯示器或車輛用窗玻璃。
再者,應用本發明之黏著膜之層合玻璃及顯示器可具備下述積層體。
<積層體>
本發明之黏著膜較佳為與有機材料基材、無機材料基材等基材一同使用而用作積層體之一部分,但並無特別限定。本發明之積層體具體而言,可具備:上述黏著膜、及選自無機材料基材與有機材料基材之至少任一者之基材。又,黏著膜較佳為以接著於無機材料基材、及有機材料基材之至少任一者之方式進行配置。再者,黏著膜可提升對於各種樹脂材料之接著力,因此,可藉由配置在接著於有機材料基材之位置處,而以高接著力接著於基材。
作為有機材料基材,可例舉有機樹脂板、樹脂膜等。有機樹脂板亦被稱為有機玻璃板。作為有機樹脂板,並無特別限定,可例舉:聚碳酸酯板、聚甲基丙烯酸甲酯板等(甲基)丙烯酸板、丙烯腈苯乙烯共聚物板、丙烯腈丁二烯苯乙烯共聚物板、聚對苯二甲酸乙二酯板等聚酯板、氟系樹脂板、聚氯乙烯板、氯化聚氯乙烯板、聚丙烯板、聚苯乙烯板、聚碸板、環氧樹脂板、酚樹脂板、不飽和聚酯樹脂板、聚醯亞胺樹脂板等各種有機玻璃板。有機樹脂板亦可適當進行表面處理等。
上述之中,就透明性、耐衝擊性優異之方面而言,較佳為聚碳酸酯板,就透明性較高,耐候性、機械強度優異之方面而言,較佳為(甲基)丙烯酸板,其中,更佳為聚碳酸酯板。
有機樹脂板之厚度並無特別限定,較佳為0.1 mm以上,進而較佳為0.4 mm以上,又,較佳為5.0 mm以下,進而較佳為3.0 mm以下。
樹脂膜並無特別限定,可例舉:(甲基)丙烯酸樹脂膜、聚碳酸酯膜、聚對苯二甲酸乙二酯(PET)膜、聚萘二甲酸乙二酯(PEN)膜等聚酯樹脂膜、聚乙烯膜、聚丙烯膜等聚烯烴樹脂膜、環狀聚烯烴(COP)膜、三乙醯纖維素(TAC)膜、聚醚碸(PES)樹脂膜、聚醯亞胺樹脂膜等。又,亦可於樹脂膜之表面設置表面層,該表面層「以(甲基)丙烯酸系樹脂等所構成」之由硬塗層等所構成。
樹脂膜可由1層單層所構成,亦可為積層有2層以上者。
又,有機材料基材亦可為包含上述樹脂膜之功能膜。作為功能膜,可例舉偏光膜(偏光板)、調光膜等。偏光膜及調光膜之構成如下所述。
積層體中之樹脂膜或功能膜之厚度並無特別限定,較佳為30 μm以上,進而較佳為50 μm以上,又,較佳為500 μm以下,進而較佳為450 μm以下。
再者,將厚度相對較大,柔軟性較低,一般無法彎折者稱為有機樹脂板,另一方面,將厚度相對較小,一般能夠彎折者大致稱為樹脂膜,其等並未得到明確區分。
作為無機材料基材,可例舉無機玻璃板。無機玻璃板並無特別限定,例如可例舉:浮法平板玻璃、強化玻璃、著色玻璃、拋光板玻璃、壓花玻璃、夾網平板玻璃、夾線平板玻璃、紫外線吸收板玻璃、紅外線反射板玻璃、紅外線吸收板玻璃、綠色玻璃等各種玻璃板。無機玻璃亦可進行表面處理等。無機玻璃之厚度並無特別限定,較佳為0.1 mm以上,進而較佳為1.0 mm以上,又,較佳為5.0 mm以下,進而較佳為3.0 mm以下。
有機材料基材、或無機材料基材亦可為適當附有電極、感測器等者。電極係由積層於上述各基材之導電層所構成。
作為感測器,可例舉觸控感測器。觸控感測器係感測手指、觸控筆、其他物體接近或接觸基材之觸控輸入的感測器,係由積層於上述基材之導電層所構成。觸控感測器會因手指、觸控筆、其他物體接近或接觸基材而使導電層產生靜電電容、電流、電壓等電性變化,根據該電性變化來感測觸控輸入。
導電層並無特別限定,只要為先前公知之具有透明性之電極材料,則可無特別限定地使用,例如可例舉:銦錫氧化物(ITO)導電膜、氧化錫導電膜、氧化鋅導電膜、高分子導電膜等。
又,積層有電極、感測器等導電層之有機材料基材(尤其是膜)亦可在設置有導電層之面之相反側面上形成上述硬塗層。與設置有導電層之面相反側之面通常為與黏著膜之接著面,但本發明之黏著膜對於設置有硬塗層之面亦容易具有良好之接著力。
本發明之黏著膜較佳為用以接合一對基材,但並無特別限定。因此,本發明之積層體具體而言,具備上述黏著膜、及一對基材,可將黏著膜配置於一對基材之間。並且,一對基材較佳為介隔黏著膜接合。
此處,一對基材較佳為兩者為玻璃。作為玻璃,可為無機玻璃板,亦可為有機玻璃板。
又,一對基材亦可一者為玻璃而另一者為膜。於該情形時,作為玻璃,可為無機玻璃板,亦可為有機玻璃板。又,膜亦可為樹脂膜,但較佳為偏光膜(偏光板)、調光膜等功能膜。
本發明之黏著片由於耐衝擊性較高,故而即便用以接合玻璃彼此、或者玻璃與其他構件,玻璃亦不易破損,又,即便於玻璃破損之情形時其碎片亦不易飛散,而安全性等得到提高。
積層體並無特別限定,較佳為具備選自無機材料基材及有機材料基材中之一對基材、以及配置於該等一對基材之間之接著用膜,並且具有3層以上之多層結構。
於此種多層結構中,接著用膜例如可接著於一對基材之兩者,藉此介隔接著用膜將一對基材接合。於該情形時,接著用膜可為上述本發明之黏著膜。
又,積層體亦可具有於上述一對基材之間進而配置其他中間構件之結構,於此種結構中,可於各基材與中間構件之間配置接著用膜,具有5層以上之多層結構。此處,接著用膜可接著於各基材與中間構件,藉此可介隔接著用膜將基材與中間構件接合。又,於以上說明之5層以上之多層結構中,基材與中間構件之間之接著用膜為樹脂膜,只要至少一者為本發明之黏著膜即可,但較佳為兩者為本發明之黏著膜。
中間構件可具有上述無機材料基材及有機材料基材之至少任一者,可於接著本發明之黏著膜之位置處配置無機材料基材及有機材料基材之至少任一者。
以上說明之積層體只要構成顯示器、層合玻璃等即可,但並不限定於其等。又,如下所述,中間構件亦可為觸控面板或調光元件等,但並不限定於其等。又,上述無機材料基材或有機材料基材只要構成觸控面板、調光元件、構成顯示器之顯示元件等之一部分即可。
本發明之積層體例如可藉由準備接著用膜,介隔準備好之接著用膜將各構件進行壓接來製造。例如可藉由依序重疊基材、接著用膜、及基材並將其等進行壓接來製造。又,於設置中間構件之情形時,可藉由依序重疊基材、接著用膜、中間構件、接著用膜及基材並將其等進行壓接來製造。
壓接並無特別限定,但較佳為一面加熱一面壓接。又,在以相對較低之壓力及溫度進行暫時接著後,相較於暫時壓接之情形提高壓力、溫度或該等兩者來進行正式接著。
繼而,參照圖式對積層體之具體例進行說明。圖1係表示第1實施方式之積層體。於第1實施方式中,將積層體30A應用於附帶觸控面板之顯示器。附帶觸控面板之顯示器較佳為車載用顯示器。本實施方式之積層體30A具備顯示元件31、表面保護面板32、及配置於顯示元件31與表面保護面板32之間之觸控面板33,且於觸控面板33與顯示元件31之間、及表面保護面板32與觸控面板33之間分別配置接著用膜34A、34B。
表面保護面板32較佳為有機樹脂板或無機玻璃板之任一者,但較佳為無機玻璃板。
又,作為顯示元件31,可例舉有機EL顯示元件、液晶顯示元件。顯示元件31較佳為於其表面側之最外面設置有偏光板(偏光膜)。再者,表面側之最外面係指表面保護面板側之最外面,其相反側亦稱為背面側。
偏光板(偏光膜)一般而言具有於聚乙烯醇樹脂膜等偏光元件之兩面設置有保護膜之構成。保護膜由上述樹脂膜所構成,較佳為PET膜、COP膜、或TAC膜之任一者。再者,亦可於保護膜之表面設置由(甲基)丙烯酸系樹脂等所構成之硬塗層作為基材之表面層。又,顯示元件31即便在其表面側之面未設置有偏光板之情形時,亦可在表面側之最外面設置保護膜。因此,於任一情形時,顯示元件31之表面側之最表面均由有機材料基材所構成。
觸控面板33可由附帶觸控感測器之無機玻璃、有機樹脂板、或樹脂膜之任一者所構成,但較佳為附帶觸控感測器之無機玻璃或樹脂膜。
又,於觸控面板33中,無機玻璃、有機樹脂板、或樹脂膜亦可其等中之2者以上積層而為多層結構體。於此情形時,於觸控面板33中,可於無機玻璃、有機樹脂板、或樹脂膜之任一者上附帶觸控感測器。
又,觸控面板33亦可於表面側之最表面、背面側之最表面之任一面上配置由樹脂膜所構成之保護膜。因此,觸控面板33與接著用膜34A、34B之接著面成為無機玻璃、有機玻璃、及樹脂膜之任一者。
接著用膜34A、34B係分別接著於顯示元件31及觸控面板33、觸控面板33及表面保護面板32,而將其等接合者。接著用膜34A、34B中之任一者可為上述本發明之黏著膜,較佳為兩者均為本發明之黏著膜。
本發明之黏著膜不僅對於無機材料基材具有高接著力,對於各種樹脂材料(即,有機材料基材)亦具有高接著力。因此,顯示元件33、表面保護面板32、及觸控面板33與接著用膜34A、34B之接著面有時由有機材料基材所構成,但即便於此種情形時,亦能夠以高接著力使顯示元件31與觸控面板33、及表面保護面板32與觸控面板33接合。
又,本發明之黏著膜由於耐衝擊性較高,故而即便於附帶觸控面板之顯示器為車載用顯示器之情形時,亦可防止因附帶觸控面板之顯示器破損而產生巨大傷害。進而,由於耐濕熱性良好,故而積層體能夠於高溫高濕環境下長期使用。
圖2係表示第2實施方式之積層體。第2實施方式之積層體亦應用於顯示器,但積層體30B省略觸控面板33,因此,積層體30B具備:顯示元件31、表面保護面板32、及配置於其等間之接著用膜34。
顯示元件31、及表面保護面板32之詳情係如第1實施方式中所述。
本實施方式中,接著用膜34由本發明之黏著膜所構成。接著用膜34(黏著膜)係接著於顯示元件31及表面保護面板32,將其等接合,因此,與第1實施方式同樣地,顯示元件31與表面保護面板32以高接著力接合。又,黏著膜由於耐衝擊性及耐濕熱性較高,故而即便將積層體30B應用於車載用顯示器,亦不易因顯示器破損而產生巨大傷害,又,亦能夠於高溫高濕下長期使用。
再者,於第2實施方式中,表面保護面板32亦可為OGS(one glass solution,單片玻璃方案)面板,於表面保護面板32上亦可設置觸控感測器等感測器。因此,表面保護面板32亦可由附帶感測器之無機玻璃等所構成。
圖3係表示第3實施方式之積層體。第3實施方式之積層體30C係應用於附帶調光功能之層合玻璃。本實施方式之積層體30C具備:一對層合玻璃構件(基材)41、42、及配置於一對層合玻璃構件41、42之間之調光元件43,於一層合玻璃構件41與調光元件43之間、及另一層合玻璃構件42與調光元件43之間分別配置接著用膜34A、34B。
層合玻璃構件41、42可為無機玻璃板、有機樹脂板之任一者,其等之詳情如上述中所說明。
調光元件43較佳為具備2片樹脂膜、及配置於2片樹脂膜之間之調光層的調光膜。因此,調光元件43之與接著用膜34A、34B之接著面為樹脂材料。
作為調光元件43所具備之樹脂膜,可例舉:PET膜、PEN膜等聚酯樹脂膜、(甲基)丙烯酸樹脂膜、TAC膜、PES樹脂膜、聚醯亞胺樹脂膜等。其中,就操作性等觀點而言,較佳為聚酯樹脂膜,其中,更佳為PET膜。
又,2片樹脂膜分別於調光層側之面設置構成電極之導電層。
調光層係藉由切換對2片樹脂膜之導電層間施加電壓及不施加電壓而使得可見光透過率產生變化者。調光層可由聚合物分散型液晶(PDLC)等液晶層所構成。又,調光膜亦可為SPD(Suspended Particle Device,懸浮粒子裝置)膜、電致變色膜、電泳膜裝置等。因此,調光層可為包含樹脂基質及分散於樹脂基質中之光調整懸浮液之SPD層,亦可為電致變色材料層。又,亦可為具備電泳粒子、及使電泳粒子分散之分散劑的電泳層等。
本實施方式中,接著用膜34A、34B亦分別接著於層合玻璃構件41及調光元件43、以及層合玻璃構件42及調光元件43而將其等接合。接著用膜34A、34B為樹脂膜,其中任一者可為上述本發明之黏著膜,但較佳為兩者均為本發明之黏著膜。
本發明之黏著膜不僅對於無機材料基材具有高接著力,對於各種樹脂材料亦具有高接著力,因此能夠以高接著力將層合玻璃構件41、42、與調光元件43接合。
又,本發明之黏著膜由於耐衝擊性及耐濕熱性較高,故而即便於將第3實施方式之層合玻璃用於車輛用窗玻璃之情形時,亦可防止因破損而產生巨大傷害,又,亦能夠於高溫高濕下長期使用。
圖4係表示第4實施方式之積層體。本實施方式之積層體30D係應用於層合玻璃。本實施方式之積層體30D具備一對層合玻璃構件41、42、及配置於一對層合玻璃構件41、42之間之接著用膜34,接著用膜34可由上述本發明之黏著膜所構成。
一對層合玻璃構件41、42係如第3實施方式中所說明。接著用膜34(黏著膜)係接著於層合玻璃構件41、42兩者而將其等接合,因此能夠以高接著力接合層合玻璃構件41、42。
又,本發明之黏著膜由於耐衝擊性及耐濕熱性較高,故而即便於將第4實施方式之層合玻璃用於車輛用窗玻璃之情形時,亦可防止因破損而產生巨大傷害,又,亦能夠於高溫高濕下長期使用。
[實施例]
藉由實施例對本發明進一步詳細地進行說明,但本發明並不受該等例任何限定。再者,本發明之各物性值之測定方法、及評價方法如以下所示。
<重量平均分子量(Mw)>
使黏著膜溶解於四氫呋喃中至0.05重量%之濃度,使用注射器過濾器(Merck公司製造,Millex-LH 0.45 μm)進行過濾後,使用凝膠滲透層析法(Waters公司製造,e2690)來測定分子量。重量平均分子量(Mw)係使用藉由單分散聚苯乙烯標準試樣所製作之分子量校正曲線而算出。又,管柱使用Shodex GPC KF-806L(昭和電工公司製造),析出液使用四氫呋喃。
<剪切儲存模數、及tanδ之最大峰值溫度>
將實施例、比較例中所獲得之黏著膜切成長度10 mm、寬度5 mm,使用動態黏彈性測定裝置(IT計測控制股份有限公司製造,商品名「DVA-200」),於以下之測定條件下測定黏彈性,檢測20℃剪切儲存模數(G')。
又,讀取根據黏彈性測定之結果所獲得之損耗正切tanδ之峰值溫度。於-50~150℃之溫度範圍內將上述峰值溫度中tanδ達到最大值之峰值溫度作為tanδ之最大峰值溫度。
(測定條件)
變形方式:剪切模式、測定溫度:-50℃~200℃、升溫速度:5℃/分鐘、測定頻率:1 Hz、應變:1%
<改質量、縮醛化度、乙醯化度、及羥基量>
使聚乙烯縮醛系樹脂溶解於氯仿-d中,使用1H-NMR(核磁共振譜)進行測定,並對各單元之莫耳比進行分析,藉此求出。
<未溶解成分之比率>
於異丙醇10.0 g中浸漬各實施例、比較例之黏著膜1.0 g,利用混合旋轉器(製品名「Mix rotor variable VMR-5R」,AS ONE公司製造)以50 rpm、15℃振盪48小時。其後,將未溶解成分取至200網目之金屬絲網上,於110℃加熱1小時以進行乾燥。當將乾燥後之未溶解成分之重量設為W1,將黏著膜浸漬於異丙醇之前之重量設為W2時,藉由以下之式求出未溶解成分之比率。
未溶解成分(質量%)=W1/W2×100
<耐濕熱性評價>
將各實施例、比較例中所獲得之黏著膜切割成縱11.0 cm×橫11.0 cm之大小。準備2片玻璃板(透明浮法玻璃,縱10 cm×橫10 cm×厚度2.5 mm)作為一對層合玻璃構件。於2片玻璃板之間插入黏著膜,於10分鐘、80℃及施加100 kPa之壓力之條件下進行暫時壓接。其後,歷時10分鐘加壓至1.3 MPa,及歷時30分鐘加熱至140℃,其後,於1.3 MPa・140℃之條件下壓接20分鐘。繼而,於1.3 MPa之加壓條件下歷時40分鐘降溫至32℃,其後進而歷時10分鐘使加壓條件成為0 MPa,而獲得層合玻璃。於玻璃端部伸出之黏著膜被切掉。
將所獲得之層合玻璃於23℃、50%環境下放置2週後,將層合玻璃垂直地置於調整至50℃、95%RH之恆溫恆濕槽中並保持12週。12週後,取出層合玻璃,測定層合玻璃之外緣之邊及角部的白化距離,使用最大之白化距離並按照以下評價基準進行評價。
AA:白化距離未達5 mm
A:白化距離為5 mm以上且未達12 mm
B:白化距離為12 mm以上
<耐衝擊評價>
將所獲得之黏著膜切割成縱31.0 cm×橫31.0 cm之大小。準備2片玻璃板(透明浮法玻璃,縱30.5 cm×橫30.5 cm×厚度1.0 mm)作為一對層合玻璃構件。於2片玻璃板之間插入黏著膜,於10分鐘、80℃、及施加100 kPa之壓力之條件下進行暫時壓接。其後,歷時10分鐘加壓至1.3 MPa,並歷時30分鐘加熱至140℃,繼而,於20分鐘、1.3 MPa・140℃之條件下進行壓接。其後,於1.3 MPa之加壓條件下,歷時40分鐘降溫至32℃,其後,進而歷時10分鐘將加壓條件設為0 MPa,而獲得層合玻璃。於玻璃端部伸出之黏著膜被切掉。
將所獲得之層合玻璃之表面溫度調整至23℃。繼而,針對6片層合玻璃,分別使質量227 g及直徑38 mm之鋼球自5.0 m之高度處掉落至層合玻璃之中心部分。首先,確認鋼球是否貫通層合玻璃。對於未貫通之層合玻璃,測定來自衝擊面之相反側之剝離碎片的總重量,對於耐衝擊性,按照以下評價基準進行評價。
A:剝離碎片之總重量未達10 g
B:剝離碎片之總重量為10 g以上,或鋼球貫通層合玻璃
(實施例1)
[環氧乙烷改質聚乙烯醇之合成]
準備表1所記載之烯丙醚單體(1)。烯丙醚單體(1)係式(4-2)所示之化合物,A
1O為氧伸乙基(EO),其平均重複數、及末端基(R
1)如表1所示。
向附帶攪拌機、溫度計、滴液漏斗及回流冷凝器之燒瓶中添加乙酸乙烯酯834質量份、烯丙醚單體(1)147質量份、及甲醇20質量份,將系統內氮氣置換後,將溫度升溫至52℃。於將溫度維持為52℃之狀態下,向該系統添加2,2-偶氮二異丁腈0.5質量份,使聚合開始。聚合開始後歷時5小時終止聚合。利用烘箱進行加熱,將未反應之單體及甲醇去除後,製備共聚物之40質量%甲醇溶液。
將所獲得之共聚物之甲醇溶液100質量份於40℃進行攪拌,並且添加3質量%之NaOH甲醇溶液7.4質量份,充分混合後進行放置。2小時後,將固化之聚合物利用粉碎機進行粉碎,利用甲醇洗淨後,進行乾燥而獲得聚合物粉末(環氧乙烷改質聚乙烯醇)。
[聚乙烯縮丁醛(PVB1)之製備]
將所獲得之聚合物粉末280 g添加至純水2100 g中,於90℃之溫度下攪拌約2小時而使之溶解。將該溶液冷卻至40℃,添加濃度35質量%之鹽酸160質量份及正丁醛150質量份,將液溫降低至20℃,保持溫度,進行縮醛化反應,使反應產物析出。其後,使液溫成為40℃,保持3小時而使反應結束,藉由常規方法進行中和、水洗及乾燥,而獲得聚乙烯縮醛系樹脂(PVB1)之白色粉末。
[黏著膜之製作]
將所獲得之聚乙烯縮醛系樹脂(PVB1)於溫度160℃、壓力20 MPa進行加壓成形,而獲得厚度380 μm之黏著膜。針對所獲得之黏著膜,測定tanδ之最大峰值溫度、20℃及85℃之剪切儲存模數(G')、及未溶解成分之比率,又,評價耐衝擊性及耐濕熱性。
(實施例2、3)
相對於100質量份之PVB1,以表3記載之量混合塑化劑(三乙二醇-二-2-乙基己酸酯:3GO),而獲得樹脂組成物,使用所獲得之樹脂組成物,利用與實施例1相同之方法進行加壓成形,而製作黏著膜。針對所獲得之黏著膜,以與實施例1相同之方式測定物性,且進行評價。
(實施例4)
添加烯丙醚單體(1)、及甲醇後,使系統內之溫度上升至60℃,於60℃添加2,2-偶氮二異丁腈而進行聚合,除此以外,以與實施例1相同之方式實施,而獲得PVB2,使用PVB2,以與實施例1相同之方式製作黏著膜。針對所獲得之黏著膜,以與實施例1相同之方式測定物性,且進行評價。
(實施例5)
除將所使用之烯丙醚單體變更為烯丙醚單體(2),且變更為乙酸乙烯酯794質量份、烯丙醚單體(2)186質量份、及甲醇20質量份、2,2-偶氮二異丁腈0.5質量份以外,以與實施例1相同之方式實施,而獲得PVB3,使用PVB3,以與實施例1相同之方式製作黏著膜。針對所獲得之黏著膜,以與實施例1相同之方式測定物性,且進行評價。
再者,烯丙醚單體(2)係式(4-2)所示之化合物,A
1O混合存在氧伸丙基(PO)與氧伸乙基(EO),其平均重複數、及末端基(R
1)如表1所示。
(實施例6)
將所使用之烯丙醚單體變更為烯丙醚單體(3),且變更為乙酸乙烯酯572質量份、烯丙醚單體(3)143質量份、及甲醇286質量份、2,2-偶氮二異丁腈0.7質量份。進而,於添加烯丙醚單體(3)及甲醇後,使系統內之溫度上升至60℃,於60℃添加2,2-偶氮二異丁腈而進行聚合,除此以外,以與實施例1相同之方式實施,而獲得PVB4,使用PVB4,以與實施例1相同之方式製作黏著膜。針對所獲得之黏著膜,以與實施例1相同之方式測定物性,且進行評價。
再者,烯丙醚單體(3)係式(4-2)所示之化合物,A
1O混合存在氧伸丙基(PO)與氧伸乙基(EO),其平均重複數、及末端基(R
1)如表1所示。
(實施例7)
除將所使用之烯丙醚單體(1)變更為74質量份以外,以與實施例1相同之方式實施,而獲得PVB7,使用PVB7,並將塑化劑變更為數量平均分子量為1000之聚丙二醇(「PPG1000」,富士膠片和光純藥公司製造,以下有時稱為「PPG1000」),除此以外,以與實施例3相同之方式製作黏著膜。針對所獲得之黏著膜,以與實施例1相同之方式測定物性,且進行評價。
(實施例8)
除使用PVB7並使塑化劑為數量平均分子量為700之聚氧伸丙基二甘油醚(「UnilubeDGP-700」,日油股份有限公司製造,以下有時稱為「DGP700」)以外,以與實施例3相同之方式製作黏著膜。針對所獲得之黏著膜,以與實施例1相同之方式測定物性,且進行評價。
(實施例9)
除使用PVB7並使塑化劑為數量平均分子量為1000之聚氧伸丙基甘油醚(「UNIOLTG-1000R」,日油股份有限公司製造,以下有時稱為「TG1000R」)以外,以與實施例3相同之方式製作黏著膜。針對所獲得之黏著膜,以與實施例1相同之方式測定物性,且進行評價。
(比較例1)
使用作為未改質聚乙烯縮丁醛之PVB5作為要使用之聚乙烯縮醛系樹脂,且相對於100質量份之PVB5,混合40質量份之塑化劑(3GO),而獲得樹脂組成物,使用所獲得之樹脂組成物,利用與實施例1相同之方法進行加壓成形,而獲得黏著膜。針對所獲得之黏著膜,以與實施例1相同之方式測定物性,且進行評價。
(比較例2)
使用作為未改質聚乙烯縮丁醛之PVB6作為要使用之聚乙烯縮醛系樹脂,且相對於100質量份之PVB6,混合25質量份之塑化劑(3GO),而獲得樹脂組成物,使用所獲得之樹脂組成物,利用與實施例1相同之方法進行加壓成形,而獲得黏著膜。針對所獲得之黏著膜,以與實施例1相同之方式評價。
(比較例3)
使用作為未改質聚乙烯縮丁醛之PVB5作為要使用之聚乙烯縮醛系樹脂。相對於100質量份之PVB5,混合30質量份之塑化劑(3GO)、10質量份之反應性稀釋劑(三羥甲基丙烷三丙烯酸酯:TMPA)、及作為光聚合起始劑之二苯基酮(BP)0.1質量份,而獲得樹脂組成物,使用所獲得之樹脂組成物,利用與實施例1相同之方法進行加壓成形,而獲得黏著膜。
又,對於黏著膜,使用超高壓水銀燈,照射4000 mJ/cm
2之365 nm波長之光。光照射後,測定剪切儲存模數(G')、tanδ之最大峰值溫度、及未溶解成分之比率。
進而,於耐衝擊性及耐濕熱性之評價中,使用比較例3中所製作之黏著膜,如上述各評價方法中所述來製造積層體,對於該積層體,使用超高壓水銀燈,照射4000 mJ/cm
2之365 nm波長之光。其後,評價耐衝擊性及耐濕熱性。
(比較例4)
使用作為未改質聚乙烯縮丁醛之PVB6作為聚乙烯縮醛系樹脂。相對於100質量份之PVB6,混合13質量份之塑化劑(3GO)、4質量份之反應性稀釋劑(TMPA)、及作為光聚合起始劑之二苯基酮0.04質量份,而獲得樹脂組成物,使用所獲得之樹脂組成物,利用與實施例1相同之方法進行加壓成形,而獲得黏著膜。又,對於黏著膜,使用超高壓水銀燈,照射4000 mJ/cm
2之365 nm波長之光。於光照射後測定剪切儲存模數(G')、tanδ之最大峰值溫度、及未溶解成分之比率。且評價耐衝擊性及耐濕熱性。
進而,於耐衝擊性及耐濕熱性之評價中,使用比較例4中所製作之黏著膜,如上述各評價方法中所述來製造層合玻璃,對於該層合玻璃,使用超高壓水銀燈,照射4000 mJ/cm
2之365 nm波長之光。其後,評價耐衝擊性及耐濕熱性。
(比較例5)
將以表3所示之單體比使單體聚合而獲得之(甲基)丙烯酸系聚合物(Ac1)100質量份以固形物成分量達到45質量%之方式利用乙酸乙酯進行稀釋,以固形物成分基準計,添加異氰酸酯系交聯劑(Nippon Polyurethane公司製造之「Coronate L-45」,固形物成分量45質量%)1質量份,而獲得樹脂組成物。於脫模PET膜之脫模處理面上以乾燥後之厚度達到150 μm之方式塗佈所獲得之樹脂組成物,於80℃進行15分鐘乾燥,而獲得黏著膜。針對所獲得之黏著膜,於23℃進行5天熟化後,以與實施例1相同之方式評價。
(比較例6)
除將(甲基)丙烯酸系聚合物(Ac1)變更為(甲基)丙烯酸系聚合物(Ac2)以外,以與比較例5相同之方式實施。
將實施例中用作原料之烯丙醚單體(1)~(3)示於以下表1。
[表1]
烯丙醚單體 | (1) | (2) | (3) | ||
分子量 | 1500 | 2000 | 2500 | ||
結構 | A 1O之種類 | EO | EO | EO | |
- | PO | PO | |||
PO/EO(mol) | 100 | 50/50 | 50/50 | ||
末端(R 1) | 氫原子 | 氫原子 | 丁基 | ||
平均重複單位數 | EO | 33 | 19 | 23 | |
PO | - | 19 | 23 | ||
將實施例及比較例中所使用之PVB1~PVB7示於以下之表2。
[表2]
PVB1 | PVB2 | PVB3 | PVB4 | PVB5 | PVB6 | FVB7 | |||
聚乙烯縮醛系樹脂 | 乙醯基 | 含有率(mol%) | 3.1 | 1.8 | 1.2 | 1.8 | 1 | 1 | 0.8 |
羥基 | 含有率(mol%) | 14.5 | 15.0 | 23.1 | 21.8 | 32 | 31 | 20.4 | |
縮醛 | 含有率(mol%) | 80.5 | 81.7 | 73.7 | 73.7 | 67 | 68 | 77.8 | |
種類 | 縮丁醛 | 縮丁醛 | 縮丁醛 | 縮丁醛 | 縮丁醛 | 縮丁醛 | 縮丁醛 | ||
環氧烷結構 | 含有率(mol%) | 1.9 | 1.5 | 2.0 | 2.7 | - | - | 1.0 | |
種類 | EO | EO | EO/PO | EO/PO | - | - | EO | ||
末端(R 1) | 氫原子 | 氫原子 | 氫原子 | 丁基 | - | - | 氫原子 | ||
平均重複單位數(EO) | 33 | 33 | 19 | 23 | - | - | 33 | ||
平均重複單位數(PO) | - | - | 19 | 23 | - | - | - |
將比較例中所使用之(甲基)丙烯酸系聚合物示於以下之表3。
[表3]
Ac1 | Ac2 | |||
(甲基)丙烯酸系聚合物 | 單體 (質量%) | 丙烯酸正丁酯 | 65 | 25 |
甲基丙烯酸甲酯 | 26 | - | ||
丙烯酸乙酯 | 4 | - | ||
丙烯酸羥基乙酯 | 1 | - | ||
丙烯酸2-乙基己酯 | - | 32 | ||
丙烯酸異丁酯 | - | 27 | ||
丙烯酸4-羥基丁酯 | - | 15 | ||
丙烯酸 | 4 | 1 |
將各實施例、比較例之實施條件、物性及評價結果示於表4。
[表4]
※1 表示相對於熱塑性樹脂100質量份之質量份。
※2 表示相對於反應性稀釋劑100質量份之質量份。
實施例1 | 實施例2 | 實施例3 | 實施例4 | 實施例5 | 實施例6 | 實施例7 | 實施例8 | 實施例9 | 比較例1 | 比較例2 | 比較例3 | 比較例4 | 比較例5 | 比較例6 | ||
樹脂 | 種類 | PVB1 | PVB1 | PVB1 | PVB2 | PVB3 | PVB4 | PVB7 | PVB7 | PVB7 | PVB5 | PVB6 | PVB5 | PVB6 | Ac1 | Ac2 |
分子量Mw(×10^4) | 26 | 26 | 26 | 25 | 37 | 30 | 16 | 16 | 16 | 36 | 19 | 36 | 19 | 65 | 70 | |
塑化劑 | 3GO(質量份※1) | - | 10 | 15 | - | - | - | - | - | - | 40 | 25 | 30 | 13 | - | - |
PPG1000(質量份※1) | - | - | - | - | - | - | 16 | - | - | - | - | - | - | - | - | |
DGP700(質量份※1) | - | - | - | - | - | - | - | 16 | - | - | - | - | - | - | - | |
TG1000R(質量份※1) | - | - | - | - | - | - | - | - | 16 | - | - | - | - | - | - | |
反應性稀釋劑 | TMPA(質量份※1) | - | - | - | - | - | - | - | - | - | - | - | 10 | 4 | - | - |
光聚合起始劑 | BP(質量份※2) | - | - | - | - | - | - | - | - | - | - | - | 1 | 1 | - | - |
交聯劑 | Coronate L-45(質量份※1) | - | - | - | - | - | - | - | - | - | - | - | - | - | 1 | 1 |
膜厚 | μm | 380 | 380 | 380 | 380 | 380 | 380 | 380 | 380 | 380 | 380 | 200 | 200 | 200 | 150 | 150 |
tanδ 最大峰值溫度 | ℃ | 49.2 | 32.1 | 25.2 | 51.2 | 43.2 | 41.2 | 25.5 | 29.3 | 32.2 | 26 | 31 | 38 光照射後 | 43 光照射後 | 5 | -3 |
G'@20 oC | 10 7Pa | 5.9 | 3.9 | 0.9 | 9.0 | 5.9 | 5.3 | 1.0 | 2.7 | 4.1 | 1.5 | 3.5 | 4.6 光照射後 | 2.8 光照射後 | 0.02 | 0.006 |
未溶解成分 | (質量%) | 97.1 | 87.9 | 83.5 | 50.2 | 65.3 | 93.1 | 77.2 | 70.6 | 70.7 | 24.1 | 4.0 | 15.3 | 12.1 | 95.1 | 92.2 |
耐衝擊性 | A | A | A | A | A | A | A | A | A | A | A | A | A | B | B | |
耐濕熱 | A | A | A | A | A | AA | A | A | A | B | B | B | B | AA | AA |
以上之各實施例之黏著膜藉由使用特定之熱塑性樹脂,而使得tanδ之最大峰值溫度為特定範圍內,且20℃之剪切儲存模數較高,未溶解成分之比率亦較高,因此使得耐衝擊性及耐濕熱性兩者變得良好。
與此相對,於比較例1~4中,儘管tanδ之最大峰值溫度為特定範圍內,20℃之剪切儲存模數較高,但未溶解成分之比率較低,因此無法使耐濕熱性變得良好。又,於比較例5、6中,20℃之剪切儲存模數(G')較低,因此耐衝擊性並不充分。
30A,30B,30C,30D:積層體
31:顯示元件
32:表面保護面板
33:觸控面板
34,34A,34B:接著用膜(黏著膜)
41,42:層合玻璃構件
43:調光元件(調光膜)
[圖1]係表示第1實施方式之積層體之剖視圖。
[圖2]係表示第2實施方式之積層體之剖視圖。
[圖3]係表示第3實施方式之積層體之剖視圖。
[圖4]係表示第4實施方式之積層體之剖視圖。
Claims (14)
- 一種黏著膜,其包含熱塑性樹脂,且 上述黏著膜之tanδ之最大峰值溫度為0℃以上52℃以下,20℃之剪切儲存模數為3×10 5Pa以上,且使上述黏著膜1.0 g溶解於異丙醇10 g之情形時之未溶解成分的比率為35質量%以上100質量%以下。
- 如請求項1之黏著膜,其不含塑化劑,或者相對於上述熱塑性樹脂100重量份包含未達20重量份之塑化劑。
- 如請求項1或2之黏著膜,其中,上述熱塑性樹脂為聚乙烯縮醛系樹脂。
- 如請求項4之黏著膜,其中,上述聚乙烯縮醛系樹脂以0.1莫耳%以上10莫耳%以下之比率包含上述聚環氧烷結構。
- 如請求項4或5之黏著膜,其中,上述聚環氧烷結構包含氧伸乙基及氧伸丙基之至少任一者。
- 如請求項6之黏著膜,其中,上述聚環氧烷結構包含氧伸乙基及氧伸丙基兩者,且其等具有無規結構。
- 如請求項4至7中任一項之黏著膜,其中,上述聚環氧烷結構之末端為烷基。
- 如請求項3至8中任一項之黏著膜,其中,上述聚乙烯縮醛系樹脂之縮醛化度為60莫耳%以上。
- 一種積層體,其具備請求項1至9中任一項之黏著膜、及一對基材,且上述黏著膜配置於上述一對基材之間。
- 如請求項10之積層體,其中,上述一對基材均為玻璃。
- 如請求項10之積層體,其中,上述一對基材之一者為玻璃,另一者為調光膜及偏光膜之任一者。
- 一種液晶顯示器,其包含請求項10至12中任一項之積層體。
- 一種層合玻璃,其包含請求項10至12中任一項之積層體。
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