TW201908128A - 樹脂膜及含有玻璃板之積層體 - Google Patents
樹脂膜及含有玻璃板之積層體 Download PDFInfo
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- TW201908128A TW201908128A TW107125473A TW107125473A TW201908128A TW 201908128 A TW201908128 A TW 201908128A TW 107125473 A TW107125473 A TW 107125473A TW 107125473 A TW107125473 A TW 107125473A TW 201908128 A TW201908128 A TW 201908128A
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Abstract
本發明提供一種可提高隔音性與透明性兩者之樹脂膜。 本發明之樹脂膜具有1層構造或2層以上之構造,且具備含有後述樹脂成分、與萜酚樹脂之第1層,該樹脂成分為熱塑性樹脂、或者由光硬化性化合物或濕氣硬化性化合物硬化所得之硬化物。
Description
本發明係關於一種貼合於玻璃板等其他構件而可適宜地使用之樹脂膜。又,本發明係關於一種使用上述樹脂膜之含有玻璃板之積層體。
已知有於玻璃板貼合有樹脂膜之含有玻璃板之積層體。含有玻璃板之積層體之中,廣泛地使用層合玻璃。
上述層合玻璃即便受到外部衝擊而破損,玻璃碎片之飛散量亦較少而安全性優異。因此,上述層合玻璃係廣泛用於汽車、軌道車輛、航空器、船舶及建築物等。上述層合玻璃藉由在一對玻璃板之間夾入熱塑性樹脂膜而製造。又,除層合玻璃以外,有時亦於玻璃板以外之其他構件貼合熱塑性樹脂膜來使用。
上述層合玻璃所使用之熱塑性樹脂膜例如揭示於下述之專利文獻1、2中。
於下述之專利文獻1中揭示有含有聚乙烯縮醛樹脂、塑化劑、及黏著賦予劑之熱塑性樹脂膜。於專利文獻1之實施例中,使用松香樹脂作為黏著賦予劑。於專利文獻1中,記載有藉由使用黏著賦予劑而可提高隔音性。
於下述之專利文獻2中揭示有含有乙烯-乙酸乙烯酯共聚物、乙烯-(甲基)丙烯酸烷基酯共聚物或聚乙烯縮醛、與氫化聚合松香酯之熱塑性樹脂膜。於專利文獻2中,記載有藉由使用氫化聚合松香酯,可滿足透明性、耐候性、耐水性、接著性及耐衝擊性等性能。 [先前技術文獻] [專利文獻]
[專利文獻1]WO2013/042771A1 [專利文獻2]日本專利特開2015-101530號公報
[發明所欲解決之問題]
先前之熱塑性樹脂膜難以充分地提高隔音性,或難以充分地提高透明性。
先前之熱塑性樹脂膜並非僅難以提高隔音性與透明性中之一者,而是難以提高兩者。
又,如專利文獻1、2所記載般,若使用松香樹脂,則可一定程度地提高隔音性。然而,松香樹脂對於提高隔音性而言存在極限。進而,松香樹脂難以使隔音性與透明性兩者變得良好。若可較使用松香樹脂之情形進一步提高隔音性,則可提供更高品質之含有玻璃板之積層體。
本發明之目的在於提供一種可提高隔音性與透明性兩者之樹脂膜。又,本發明之目的亦在於提供一種使用上述樹脂膜之含有玻璃板之積層體。 [解決問題之技術手段]
根據本發明之廣泛態樣,提供一種樹脂膜,其係具有1層構造或2層以上之構造之樹脂膜,且具備含有後述樹脂成分、與萜酚樹脂之第1層,該樹脂成分為熱塑性樹脂、或者由光硬化性化合物或濕氣硬化性化合物硬化所得之硬化物。
於本發明之樹脂膜之某一特定態樣中,上述第1層中之上述熱塑性樹脂為聚乙烯縮醛樹脂、聚乙酸乙烯酯、或(甲基)丙烯醯基聚合物。
於本發明之樹脂膜之某一特定態樣中,於上述第1層含有上述聚乙烯縮醛樹脂或上述聚乙酸乙烯酯之情形時,上述第1層含有塑化劑。
於本發明之樹脂膜之某一特定態樣中,上述萜酚樹脂之羥值為50 mgKOH/g以上且200 mgKOH/g以下。
於本發明之樹脂膜之某一特定態樣中,於上述第1層中,相對於上述樹脂成分100重量份,上述萜酚樹脂之含量為10重量份以上且150重量份以下。
於本發明之樹脂膜之某一特定態樣中,上述樹脂膜具備含有熱塑性樹脂與塑化劑之第2層,上述第2層係配置於上述第1層之第1表面側。
於本發明之樹脂膜之某一特定態樣中,上述樹脂膜具備含有熱塑性樹脂與塑化劑之第3層,上述第3層係配置於上述第1層之與上述第1表面相反之第2表面側。
於本發明之樹脂膜之某一特定態樣中,上述樹脂膜係貼合於玻璃板而使用之樹脂膜。
根據本發明之廣泛態樣,提供一種含有玻璃板之積層體,其具備第1玻璃板、與上述樹脂膜,且於上述第1玻璃板貼合有上述樹脂膜。
於本發明之含有玻璃板之積層體之某一特定態樣中,上述含有玻璃板之積層體具備:作為第1層合玻璃構件之上述第1玻璃板、上述樹脂膜、及第2層合玻璃構件,於上述第1玻璃板貼合有上述樹脂膜,於上述第2層合玻璃構件貼合有上述樹脂膜,於上述第1玻璃板與上述第2層合玻璃構件之間配置有上述樹脂膜。 [發明之效果]
本發明之樹脂膜具有1層構造或2層以上之構造。本發明之樹脂膜具備含有後述樹脂成分、與萜酚樹脂之第1層,該樹脂成分為熱塑性樹脂、或者由光硬化性化合物或濕氣硬化性化合物硬化所得之硬化物。本發明之樹脂膜由於具備上述構成,故而可提高隔音性與透明性兩者。
以下,對本發明詳細地進行說明。
(樹脂膜) 本發明之樹脂膜具有1層構造或2層以上之構造。
本發明之樹脂膜具備含有後述樹脂成分、與萜酚樹脂之第1層,該樹脂成分為熱塑性樹脂、或者由光硬化性化合物或濕氣硬化性化合物硬化所得之硬化物。
本發明之樹脂膜由於具備上述構成,故而可提高隔音性與透明性兩者。
本發明與使用松香樹脂之情形相比,可相當地提高隔音性。而且,除已得到相當提高之隔音性以外,亦可提高透明性。
本發明之樹脂膜可具有1層之構造,亦可具有2層以上之構造。本發明之樹脂膜可具有2層之構造,亦可具有3層之構造,亦可具有3層以上之構造。本發明之樹脂膜具備第1層。本發明之樹脂膜可為僅具備第1層之單層樹脂膜,亦可為具備第1層與其他層之多層樹脂膜。
上述樹脂膜可具有2層以上之構造,可除第1層以外亦具備第2層。上述樹脂膜較佳為進而具備第2層。於上述樹脂膜具備上述第2層之情形時,於上述第1層之第1表面側配置上述第2層。
上述樹脂膜可具有3層以上之構造,可除第1層及第2層以外亦具備第3層。上述樹脂膜較佳為進而具備第3層。於上述樹脂膜具備上述第2層及上述第3層之情形時,於上述第1層之與上述第1表面相反之第2表面側配置上述第3層。
上述第2層之與上述第1層側相反之表面較佳為供積層層合玻璃構件或玻璃板之表面。上述第1層之與第1表面(上述第2層側之表面)相反之第2表面亦可為供積層層合玻璃構件或玻璃板之表面。上述第3層之與上述第1層側相反之表面較佳為供積層層合玻璃構件或玻璃板之表面。
上述樹脂膜較佳為熱塑性樹脂膜。該熱塑性樹脂膜係於至少一層中含有熱塑性樹脂。
以下,一面參照圖式,一面對本發明之具體實施形態進行說明。
圖1係模式性地表示本發明之第1實施形態之樹脂膜之剖視圖。
圖1所示之樹脂膜11係具有2層以上之構造之多層樹脂膜。樹脂膜11係用以獲得含有玻璃板之積層體。樹脂膜11較佳為層合玻璃用中間膜。樹脂膜11具備:第1層1、第2層2、及第3層3。於第1層1之第1表面1a側配置並積層有第2層2。於第1層1之與第1表面1a相反之第2表面1b側配置並積層有第3層3。第1層1係中間層。第2層2及第3層3分別為保護層,於本實施形態中為表面層。第1層1係配置並夾入於第2層2與第3層3之間。因此,樹脂膜11具有依序積層有第2層2、第1層1、及第3層3之多層構造(第2層2/第1層1/第3層3)。
再者,於第2層2與第1層1之間、及第1層1與第3層3之間亦可分別配置有其他層。第2層2與第1層1、及第1層1與第3層3較佳為分別直接積層。作為其他層,可列舉含有聚對苯二甲酸乙二酯等之層。
圖2係模式性地表示本發明之第2實施形態之樹脂膜之剖視圖。
圖2所示之樹脂膜11A係具有1層構造之單層樹脂膜。樹脂膜11A係第1層。樹脂膜11A係用以獲得含有玻璃板之積層體。樹脂膜11A較佳為層合玻璃用中間膜。
以下,對本發明之樹脂膜、上述第1層、上述第2層及上述第3層之詳細內容、以及本發明之樹脂膜、上述第1層、上述第2層及上述第3層所含有之各成分之詳細內容進行說明。
(熱塑性樹脂、或者使光硬化性化合物或濕氣硬化性化合物硬化所得之硬化物之樹脂成分) 上述樹脂膜含有熱塑性樹脂、或者使光硬化性化合物或濕氣硬化性化合物硬化所得之硬化物之樹脂成分。上述樹脂膜含有上述樹脂成分(熱塑性樹脂、或者使光硬化性化合物或濕氣硬化性化合物硬化所得之硬化物)作為與萜酚樹脂不同之樹脂。上述第1層(包含單層樹脂膜)含有上述樹脂成分(以下,有時記載為樹脂成分(1))。
作為上述樹脂,可列舉熱固性樹脂及熱塑性樹脂。上述樹脂亦可為使光硬化性化合物或濕氣硬化性化合物硬化所得之硬化物。上述使光硬化性化合物或濕氣硬化性化合物硬化所得之硬化物亦有時成為熱塑性樹脂。
上述第1層較佳為含有熱塑性樹脂(以下,有時記載為熱塑性樹脂(1))、或者含有使光硬化性化合物或濕氣硬化性化合物硬化所得之硬化物(以下,有時記載為硬化物(1))。將熱塑性樹脂(1)及硬化物(1)合併稱為樹脂成分(1)。上述樹脂成分(1)可僅使用1種,亦可將2種以上併用。
上述第1層中之與萜酚樹脂不同之樹脂100重量%中,上述樹脂成分(1)之含量較佳為50重量%以上,更佳為60重量%以上,進而較佳為70重量%以上,尤佳為80重量%以上,最佳為90重量%以上。上述第1層中之與萜酚樹脂不同之樹脂亦可全部為上述樹脂成分(1)。
上述第1層(包含單層樹脂膜)較佳為含有熱塑性樹脂(以下,有時記載為熱塑性樹脂(1))。就有效地提高接著性之觀點而言,上述第2層較佳為含有熱塑性樹脂(以下,有時記載為熱塑性樹脂(2)),更佳為含有聚乙烯縮醛樹脂(以下,有時記載為聚乙烯縮醛樹脂(2))。就有效地提高接著性之觀點而言,上述第3層較佳為含有熱塑性樹脂(以下,有時記載為熱塑性樹脂(3)),更佳為含有聚乙烯縮醛樹脂(以下,有時記載為聚乙烯縮醛樹脂(3))。
上述第2層中之熱塑性樹脂100重量%中,上述聚乙烯縮醛樹脂(2)之含量較佳為50重量%以上,更佳為60重量%以上,進而較佳為70重量%以上,尤佳為80重量%以上,最佳為90重量%以上。上述第2層中之熱塑性樹脂亦可全部為上述聚乙烯縮醛樹脂(2)。
上述第3層中之熱塑性樹脂100重量%中,上述聚乙烯縮醛樹脂(3)之含量較佳為50重量%以上,更佳為60重量%以上,進而較佳為70重量%以上,尤佳為80重量%以上,最佳為90重量%以上。上述第3層中之熱塑性樹脂亦可全部為上述聚乙烯縮醛樹脂(3)。
作為上述熱塑性樹脂,可列舉:聚乙烯縮醛樹脂、聚乙酸乙烯酯、(甲基)丙烯醯基聚合物、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、聚胺基甲酸酯樹脂、聚乙烯樹脂、聚乙酸乙烯酯及聚酯樹脂等。亦可使用該等以外之熱塑性樹脂。
上述樹脂成分(1)較佳為聚乙烯縮醛樹脂、聚乙酸乙烯酯、或(甲基)丙烯醯基聚合物。上述第1層(包含單層樹脂膜)較佳為含有聚乙烯縮醛樹脂(以下,有時記載為聚乙烯縮醛樹脂(1))、聚乙酸乙烯酯(以下,有時記載為聚乙酸乙烯酯(1))、或(甲基)丙烯醯基聚合物(以下,有時記載為(甲基)丙烯醯基聚合物(1))。
就進一步提高隔音性之觀點而言,上述樹脂成分(1)較佳為聚乙酸乙烯酯(1)、或(甲基)丙烯醯基聚合物(1)。就進一步提高隔音性之觀點而言,上述第1層(包含單層樹脂膜)較佳為含有聚乙酸乙烯酯(1)、或(甲基)丙烯醯基聚合物(1)。
上述熱塑性樹脂(1)與上述熱塑性樹脂(2)可相同亦可不同。上述熱塑性樹脂(1)與上述熱塑性樹脂(3)可相同亦可不同。上述聚乙烯縮醛樹脂(1)與上述熱塑性樹脂(2)可相同亦可不同。上述聚乙烯縮醛樹脂(1)與上述熱塑性樹脂(3)可相同亦可不同。上述熱塑性樹脂(2)與上述熱塑性樹脂(3)可相同亦可不同。上述熱塑性樹脂(1)可僅使用1種,亦可將2種以上併用。聚乙烯縮醛樹脂(1)、聚乙酸乙烯酯(1)及(甲基)丙烯醯基聚合物(1)可分別僅使用1種,亦可將2種以上併用。上述熱塑性樹脂(2)及上述熱塑性樹脂(3)可分別僅使用1種,亦可將2種以上併用。
上述聚乙烯縮醛樹脂例如可藉由利用醛使聚乙烯(PVA)縮醛化而製造。上述聚乙烯縮醛樹脂較佳為聚乙烯之縮醛化物。上述聚乙烯例如藉由將聚乙酸乙烯酯皂化而獲得。上述聚乙烯之皂化度一般為70~99.9莫耳%之範圍內。
上述聚乙烯(PVA)之平均聚合度較佳為200以上,更佳為500以上,進而較佳為1500以上,進而更佳為1600以上,且較佳為5000以下,更佳為4000以下,進而較佳為3500以下。若上述平均聚合度為上述下限以上,則含有玻璃板之積層體之耐貫通性進一步變高。若上述平均聚合度為上述上限以下,則樹脂膜之成形變得容易。
上述聚乙烯之平均聚合度係藉由依據JIS K6726「聚乙烯試驗方法」之方法而求出。
上述聚乙烯縮醛樹脂所含之縮醛基之碳數並無特別限定。製造上述聚乙烯縮醛樹脂時所使用之醛並無特別限定。上述聚乙烯縮醛樹脂中之縮醛基之碳數較佳為3~5,更佳為3或4。若上述聚乙烯縮醛樹脂中之縮醛基之碳數為3以上,則樹脂膜之玻璃轉移溫度充分地變低。
上述醛並無特別限定。一般而言,可較佳地使用碳數為1~10之醛。作為上述碳數為1~10之醛,例如可列舉:甲醛、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、正癸醛及苯甲醛等。上述醛較佳為丙醛、正丁醛、異丁醛、正己醛或正戊醛,更佳為丙醛、正丁醛或異丁醛,進而較佳為正丁醛。上述醛可僅使用1種,亦可將2種以上併用。
上述聚乙烯縮醛樹脂之羥基之含有率(羥基量)較佳為10莫耳%以上,更佳為15莫耳%以上,進而較佳為18莫耳%以上,且較佳為40莫耳%以下,更佳為35莫耳%以下。若上述羥基之含有率為上述下限以上,則樹脂膜之接著力進一步變高。又,若上述羥基之含有率為上述上限以下,則樹脂膜之柔軟性變高,樹脂膜之處理變容易。
上述聚乙烯縮醛樹脂(1)之羥基之含有率(羥基量)較佳為10莫耳%以上,更佳為20莫耳%以上,且較佳為28莫耳%以下,更佳為24莫耳%以下。若上述羥基之含有率為上述下限以上,則樹脂膜之機械強度進一步變高。尤其是若上述聚乙烯縮醛樹脂(1)之羥基之含有率為20莫耳%以上,則反應效率較高而生產性優異,又若為28莫耳%以下,則含有玻璃板之積層體之隔音性進一步變高。若上述羥基之含有率為上述上限以下,則樹脂膜之柔軟性變高,樹脂膜之處理變容易。
上述聚乙烯縮醛樹脂(2)及上述聚乙烯縮醛樹脂(3)之羥基之各含有率較佳為25莫耳%以上,更佳為28莫耳%以上,進而較佳為30莫耳%以上。上述聚乙烯縮醛樹脂(2)及上述聚乙烯縮醛樹脂(3)之羥基之各含有率較佳為38莫耳%以下,更佳為37莫耳%以下。若上述羥基之含有率為上述下限以上,則樹脂膜之接著力進一步變高。若上述羥基之含有率為上述上限以下,則樹脂膜之柔軟性變高,樹脂膜之處理變容易。
關於上述聚乙烯縮醛樹脂之羥基之含有率,係以百分率表示用鍵結有羥基之伸乙基量除以主鏈之總伸乙基量而求出之莫耳分率之值。上述鍵結有羥基之伸乙基量例如可依據JIS K6728「聚乙烯縮丁醛試驗方法」進行測定。
上述聚乙烯縮醛樹脂(1)之乙醯化度(乙醯基量)較佳為0.01莫耳%以上,更佳為0.1莫耳%以上,進而較佳為7莫耳%以上,進而更佳為9莫耳%以上,且較佳為30莫耳%以下,更佳為25莫耳%以下。若上述乙醯化度為上述下限以上,則聚乙烯縮醛樹脂與塑化劑之相溶性變高。若上述乙醯化度為上述上限以下,則樹脂膜及含有玻璃板之積層體之耐濕性變高。尤其是若上述聚乙烯縮醛樹脂(1)之乙醯化度為0.1莫耳%以上且25莫耳%以下,則耐貫通性優異。
上述聚乙烯縮醛樹脂(2)及上述聚乙烯縮醛樹脂(3)之各乙醯化度較佳為0.01莫耳%以上,更佳為0.5莫耳%以上,且較佳為10莫耳%以下,更佳為2莫耳%以下。若上述乙醯化度為上述下限以上,則聚乙烯縮醛樹脂與塑化劑之相溶性變高。若上述乙醯化度為上述上限以下,則樹脂膜及含有玻璃板之積層體之耐濕性變高。
上述乙醯化度係以百分率表示用鍵結有乙醯基之伸乙基量除以主鏈之總伸乙基量而求出之莫耳分率之值。上述鍵結有乙醯基之伸乙基量例如可依據JIS K6728「聚乙烯縮丁醛試驗方法」而進行測定。
上述聚乙烯縮醛樹脂(1)之縮醛化度(於聚乙烯縮丁醛樹脂之情形時為丁醛化度)較佳為47莫耳%以上,更佳為60莫耳%以上,且較佳為85莫耳%以下,更佳為80莫耳%以下,進而較佳為75莫耳%以下。若上述縮醛化度為上述下限以上,則聚乙烯縮醛樹脂與塑化劑之相溶性變高。若上述縮醛化度為上述上限以下,則製造聚乙烯縮醛樹脂所需要之反應時間變短。
上述聚乙烯縮醛樹脂(2)及上述聚乙烯縮醛樹脂(3)之各縮醛化度(於聚乙烯縮丁醛樹脂之情形時為丁醛化度)較佳為55莫耳%以上,更佳為60莫耳%以上,且較佳為75莫耳%以下,更佳為71莫耳%以下。若上述縮醛化度為上述下限以上,則聚乙烯縮醛樹脂與塑化劑之相溶性變高。若上述縮醛化度為上述上限以下,則製造聚乙烯縮醛樹脂所需要之反應時間變短。
上述縮醛化度係以如下方式求出。首先,求出自主鏈之總伸乙基量減去鍵結有羥基之伸乙基量、及鍵結有乙醯基之伸乙基量所獲得之值。用所獲得之值除以主鏈之總伸乙基量而求出莫耳分率。以百分率表示該莫耳分率之值為縮醛化度。
再者,上述羥基之含有率(羥基量)、縮醛化度(丁醛化度)及乙醯化度較佳為自藉由依據JIS K6728「聚乙烯縮丁醛試驗方法」之方法所測得之結果算出。但是,亦可使用基於ASTM D1396-92之測定。於聚乙烯縮醛樹脂為聚乙烯縮丁醛樹脂之情形時,上述羥基之含有率(羥基量)、上述縮醛化度(丁醛化度)及上述乙醯化度可自藉由依據JIS K6728「聚乙烯縮丁醛試驗方法」之方法所測得之結果算出。
上述聚乙烯縮醛樹脂(1)較佳為聚乙烯縮丁醛樹脂。上述聚乙烯縮醛樹脂(2)較佳為聚乙烯縮丁醛樹脂。上述聚乙烯縮醛樹脂(3)較佳為聚乙烯縮丁醛樹脂。
上述聚乙酸乙烯酯(1)較佳為含有乙酸乙烯酯、與含有具有氫鍵結性之官能基A1之單體A之聚合性組合物的聚合物。
上述聚乙酸乙烯酯(1)較佳為具有源自乙酸乙烯酯之結構單元、與源自單體A之結構單元。
具有氫鍵結性之官能基A1係羥基、醯胺基、胺基、及羧基。上述羥基亦可為酚性羥基。就有效地提高隔音性之觀點而言,上述官能基A1較佳為羥基或醯胺基,更佳為羥基。
作為單體A,可列舉:具有羥基之單體、具有醯胺基之單體、具有胺基之單體、及具有羧基之單體等。作為上述具有羥基之單體,可列舉3-甲基-3-丁烯-1-醇、乙二醇單乙烯醚、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯及二乙二醇單乙烯醚等。作為上述具有醯胺基之單體,可列舉N,N-二甲胺基丙基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉、N-異丙基(甲基)丙烯醯胺及N-羥基乙基(甲基)丙烯醯胺等。作為上述具有胺基之單體,可列舉N-二烷基胺基烷基(甲基)丙烯醯胺及N,N-二烷基胺基烷基(甲基)丙烯醯胺等。作為上述具有羧基之單體,可列舉琥珀酸2-丙烯醯氧基乙酯及(甲基)丙烯酸等。
就有效地提高隔音性之觀點而言,聚乙酸乙烯酯(1)之重量平均分子量較佳為25萬以上,更佳為30萬以上,進而較佳為40萬以上,尤佳為50萬以上。就有效地提高透明性與隔音性之觀點而言,聚乙酸乙烯酯(1)之重量平均分子量較佳為200萬以下,更佳為170萬以下,進而較佳為120萬以下,尤佳為90萬以下。
上述重量平均分子量係表示藉由凝膠滲透層析法(GPC)所測得之以聚苯乙烯換算計之重量平均分子量。
使上述聚合性組合物聚合而合成上述聚乙酸乙烯酯(1)之方法並無特別限定。作為該合成方法,可列舉溶液聚合法、懸濁聚合法、及UV聚合法等。製造上述聚乙酸乙烯酯(1)之方法亦可為溶液聚合法或懸濁聚合法。製造上述聚乙酸乙烯酯(1)之方法可為溶液聚合法,亦可為溶液聚合法以外之方法,亦可為懸濁聚合法。
就提高樹脂膜之透明性,且於已提高了透明性之樹脂膜中有效地提高隔音性之觀點而言,上述聚乙酸乙烯酯(1)之合成方法較佳為溶液聚合法。於上述聚乙酸乙烯酯(1)之合成方法為懸濁聚合法之情形時,有樹脂膜之霧度(於2片透明玻璃之間夾入有上述樹脂膜之含有玻璃板之積層體的依據JIS K6714所測定之霧度)變高之傾向。於上述聚乙酸乙烯酯(1)之合成方法為溶液聚合法之情形時,樹脂膜之霧度(於2片透明玻璃之間夾入有上述樹脂膜之含有玻璃板之積層體的依據JIS K6714所測定之霧度)變得相當低。霧度之測定所使用之透明玻璃較佳為依據JIS R3202:1996之透明玻璃。
但是,即便上述聚乙酸乙烯酯(1)之合成方法為懸濁聚合法,亦可藉由適當地選擇界面活性劑或分散劑而降低樹脂膜之霧度(於2片透明玻璃之間夾入有上述樹脂膜之含有玻璃板之積層體的依據JIS K6714所測定之霧度)。於藉由懸濁聚合法合成上述聚乙酸乙烯酯(1)之情形時所使用之分散劑就接著性與透明性之觀點而言,較佳為與有機溶劑相溶之高分子分散劑或反應性界面活性劑。若分散劑為高分子,則於積層有樹脂膜時分散劑不易向其他層移動,而可抑制因分散劑於層界面或玻璃界面滲出而產生之層間接著力之降低。作為上述高分子分散劑,可列舉環氧乙烷-環氧丙烷之嵌段共聚物等。作為上述反應性界面活性劑,可列舉下述之聚合性化合物等。
就有效地提高隔音性之觀點而言,上述聚乙酸乙烯酯(1)之全部結構單元100莫耳%中,源自單體A之結構單元之比例較佳為0.1莫耳%以上,更佳為0.2莫耳%以上,進而較佳為0.4莫耳%以上,尤佳為0.5莫耳%以上。就有效地提高隔音性之觀點而言,上述聚乙酸乙烯酯(1)之全部結構單元100莫耳%中,源自單體A之結構單元之比例較佳為40莫耳%以下,更佳為30莫耳%以下。聚乙酸乙烯酯(1)較佳為以該較佳之比例含有源自單體A之結構單元。
於上述聚乙酸乙烯酯(1)中,亦包含乙酸乙烯酯及單體A、與該等化合物以外之聚合性化合物(共聚成分)之共聚物。上述聚合性組合物亦可含有乙酸乙烯酯及單體A以外之聚合性化合物。上述聚合性組合物較佳為含有作為聚合性化合物之乙酸乙烯酯作為主成分。上述聚乙酸乙烯酯(1)之全部結構單元(骨架)100莫耳%中,源自乙酸乙烯酯之結構單元(骨架)之比例較佳為50莫耳%以上,更佳為60莫耳%以上,進而較佳為70莫耳%以上,尤佳為80莫耳%以上,最佳為90莫耳%以上。作為乙酸乙烯酯以外之聚合性化合物,可列舉:(甲基)丙烯酸系化合物、苯乙烯化合物及異戊二烯化合物等。
作為乙酸乙烯酯以外之聚合性化合物,例如可列舉:丙烯酸苄酯、苯乙烯、苯甲酸乙烯酯、苯甲酸烯丙酯、乙氧化鄰苯基苯酚丙烯酸酯、丙烯酸五溴苯基酯及丙烯酸五溴苄酯等。藉由使用該等聚合性化合物,於將上述第1層與其他層或層合玻璃構件積層之情形時,與其他層或層合玻璃構件之折射率調整變得容易,而光學應變得到抑制。
作為乙酸乙烯酯以外之聚合性化合物之其他例,可列舉:聚氧乙烯苯乙烯化丙烯基苯基醚硫酸酯銨、聚氧乙烯壬基丙烯基苯基醚硫酸酯銨、聚氧乙烯-1-(烯丙氧基甲基)烷基醚硫酸酯銨、聚氧乙烯苯乙烯化丙烯基苯基醚、及聚氧乙烯-1-(烯丙氧基甲基)烷基醚等。若使用該等聚合性化合物作為反應性界面活性劑,則即便為懸濁聚合法,亦可獲得透明性較高之樹脂膜。
就進一步有效地提高隔音性之觀點而言,構成上述(甲基)丙烯醯基聚合物(1)之(甲基)丙烯醯基單體較佳為具有環狀醚結構之(甲基)丙烯酸酯、具有芳香環之(甲基)丙烯酸酯、或側鏈之碳數位6以下之非環式(甲基)丙烯酸酯。
作為上述具有環狀醚結構之(甲基)丙烯酸酯,可列舉:(甲基)丙烯酸縮水甘油酯;(3-丙基氧雜環丁烷-3-基)(甲基)丙烯酸甲酯、(3-乙基氧雜環丁烷-3-基)丙烯酸甲酯、(3-丁基氧雜環丁烷-3-基)(甲基)丙烯酸甲酯、(3-乙基氧雜環丁烷-3-基)(甲基)丙烯酸乙酯、(3-乙基氧雜環丁烷-3-基)(甲基)丙烯酸丙酯、(3-乙基氧雜環丁烷-3-基)(甲基)丙烯酸丁酯、(3-乙基氧雜環丁烷-3-基)(甲基)丙烯酸戊酯、(3-乙基氧雜環丁烷-3-基)(甲基)丙烯酸己酯;γ-丁內酯(甲基)丙烯酸酯、(2,2-二甲基-1,3-二氧戊環-4-基)(甲基)丙烯酸甲酯、(2-甲基-2-乙基-1,3-二氧戊環-4-基)(甲基)丙烯酸甲酯、(2-甲基-2-異丁基-1,3-二氧戊環-4-基)(甲基)丙烯酸甲酯、(2-環己基-1,3-二氧戊環-4-基)(甲基)丙烯酸甲酯、環狀三羥甲基丙烷縮甲醛丙烯酸酯、及(甲基)丙烯醯基嗎啉等。就進一步有效地提高隔音性之觀點而言,上述具有環狀醚結構之(甲基)丙烯酸酯較佳為環狀三羥甲基丙烷縮甲醛丙烯酸酯。
作為上述具有芳香環之(甲基)丙烯酸酯,可列舉:丙烯酸苄酯、苯氧基聚乙二醇丙烯酸酯、及丙烯酸羥基苯氧基丙酯等。
作為上述側鏈之碳數為6以下之非環式(甲基)丙烯酸酯,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、及(甲基)丙烯酸丁酯。為了進一步有效地獲得本發明之效果,(甲基)丙烯醯基單體100重量%中,上述側鏈之碳數為6以下之非環式(甲基)丙烯酸酯之調配量較佳為未達20重量%。
藉由使用上述較佳之化合物作為上述(甲基)丙烯醯基單體,隔音性等樹脂膜之特性之平衡性進一步變良好。
作為(甲基)丙烯醯基單體,除上述化合物以外,亦可列舉:二乙二醇單乙醚(甲基)丙烯酸酯、(甲基)丙烯酸異基酯、(甲基)丙烯酸3-甲氧基丁酯、(甲基)丙烯酸環己酯;乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、1,9-壬二醇二丙烯酸酯、聚1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、2,2-雙[4-(甲基丙烯醯氧基乙氧基)苯基]丙烷二(甲基)丙烯酸酯;三羥甲基丙烷三丙烯酸酯、季戊四醇四甲基丙烯酸酯、三(2-丙烯醯氧基乙基)磷酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、及四羥甲基丙烷四(甲基)丙烯酸酯等。上述化合物可僅使用1種,亦可將2種以上併用。
就有效地提高隔音性之觀點而言,(甲基)丙烯醯基聚合物(1)之重量平均分子量較佳為25萬以上,更佳為30萬以上,進而較佳為40萬以上,尤佳為50萬以上。就有效地提高透明性之觀點而言,(甲基)丙烯醯基聚合物(1)之重量平均分子量較佳為200萬以下,更佳為170萬以下,進而較佳為120萬以下,尤佳為90萬以下。
上述重量平均分子量係表示藉由凝膠滲透層析法(GPC)所測得之以聚苯乙烯換算計之重量平均分子量。
合成上述(甲基)丙烯醯基聚合物(1)之方法並無特別限定。作為該合成方法,可列舉:溶液聚合法、懸濁聚合法、及UV聚合法等。製造上述(甲基)丙烯醯基聚合物(1)之方法亦可為溶液聚合法或懸濁聚合法。製造上述(甲基)丙烯醯基聚合物(1)之方法可為溶液聚合法,亦可為溶液聚合法以外之方法,亦可為懸濁聚合法。
就提高樹脂膜之透明性,且於已提高了透明性之樹脂膜中有效地提高隔音性之觀點而言,上述(甲基)丙烯醯基聚合物(1)之合成方法較佳為溶液聚合法。於上述(甲基)丙烯醯基聚合物(1)之合成方法為懸濁聚合法之情形時,有樹脂膜之霧度(於2片透明玻璃之間夾入有上述樹脂膜之含有玻璃板之積層體的依據JIS K6714所測定之霧度)變高之傾向。於上述(甲基)丙烯醯基聚合物(1)之合成方法為溶液聚合法之情形時,樹脂膜之霧度(於2片透明玻璃之間夾入有上述樹脂膜之含有玻璃板之積層體的依據JIS K6714所測定之霧度)變得相當低。
但是,即便上述(甲基)丙烯醯基聚合物(1)之合成方法為懸濁聚合法,亦可藉由適當地選擇界面活性劑或分散劑而降低樹脂膜之霧度(於2片透明玻璃之間夾入有上述樹脂膜之含有玻璃板之積層體的依據JIS K6714所測定之霧度)。於藉由懸濁聚合法合成上述(甲基)丙烯醯基聚合物(1)之情形時所使用之分散劑就接著性之觀點而言,較佳為與有機溶劑相溶之高分子分散劑或反應性界面活性劑。若分散劑為高分子,則於積層有樹脂膜時分散劑不易向其他層移動,而可抑制因分散劑於層界面或玻璃界面滲出而產生之層間接著力之降低。作為上述高分子分散劑,可列舉:環氧乙烷-環氧丙烷之嵌段共聚物等。
上述(甲基)丙烯醯基聚合物(1)亦可含有(甲基)丙烯醯基單體以外之聚合性化合物作為構成成分。上述(甲基)丙烯醯基聚合物(1)較佳為含有(甲基)丙烯醯基單體作為主成分。上述(甲基)丙烯醯基聚合物(1)之全部結構單元(骨架)100莫耳%中,源自(甲基)丙烯醯基單體之結構單元(骨架)之比例較佳為50莫耳%以上,更佳為60莫耳%以上,進而較佳為70莫耳%以上,尤佳為80莫耳%以上,最佳為90莫耳%以上。
作為(甲基)丙烯醯基單體以外之聚合性化合物,例如可列舉:乙酸乙烯酯、苯乙烯化合物、苯乙烯、異戊二烯化合物、苯甲酸乙烯酯及苯甲酸烯丙酯等。藉由使用該等聚合性化合物,於將上述第1層與其他層或層合玻璃構件積層之情形時,與其他層或層合玻璃構件之折射率調整變得容易,而光學應變得到抑制。
作為(甲基)丙烯醯基單體以外之聚合性化合物之其他例,可列舉:聚氧乙烯苯乙烯化丙烯基苯基醚硫酸酯銨、聚氧乙烯壬基丙烯基苯基醚硫酸酯銨、聚氧乙烯-1-(烯丙氧基甲基)烷基醚硫酸酯銨、聚氧乙烯苯乙烯化丙烯基苯基醚、及聚氧乙烯-1-(烯丙氧基甲基)烷基醚等。若使用該等聚合性化合物作為反應性界面活性劑,則即便為懸濁聚合法,亦可獲得透明性較高之樹脂膜。
(塑化劑) 上述樹脂膜較佳為含有塑化劑。上述第1層(包含單層樹脂膜)較佳為含有塑化劑(以下,有時記載為塑化劑(1))。上述第2層較佳為含有塑化劑(以下,有時記載為塑化劑(2))。上述第3層較佳為含有塑化劑(以下,有時記載為塑化劑(3))。藉由使用塑化劑,又藉由併用聚乙烯縮醛樹脂與塑化劑,而耐貫通性進一步優異,包含聚乙烯縮醛樹脂與塑化劑之層之對於層合玻璃構件或其他層之接著力適度地變高。上述塑化劑並無特別限定。上述塑化劑(1)、上述塑化劑(2)、及上述塑化劑(3)可相同亦可不同。上述塑化劑(1)、上述塑化劑(2)及上述塑化劑(3)可分別僅使用1種,亦可將2種以上併用。
就有效地發揮本發明之效果之觀點而言,於上述第1層含有聚乙烯縮醛樹脂或聚乙酸乙烯酯之情形時,上述第1層較佳為含有塑化劑。就有效地發揮本發明之效果之觀點而言,於上述第1層含有聚乙烯縮醛樹脂之情形時,上述第1層較佳為含有塑化劑。就有效地發揮本發明之效果之觀點而言,於上述第1層含有聚乙酸乙烯酯之情形時,上述第1層較佳為含有塑化劑。就有效地發揮本發明之效果之觀點而言,於上述第1層含有(甲基)丙烯醯基聚合物之情形時,上述第1層較佳為含有塑化劑。於上述第1層含有(甲基)丙烯醯基聚合物之情形時,上述第1層亦可不含有塑化劑。
作為上述塑化劑,可列舉:一元有機酸酯及多元有機酸酯等有機酯塑化劑、以及有機磷酸塑化劑及有機亞磷酸塑化劑等有機磷酸塑化劑等。較佳為有機酯塑化劑。上述塑化劑較佳為液狀塑化劑。
作為上述一元有機酸酯,可列舉:藉由二醇與一元有機酸之反應而獲得之二醇酯等。作為上述二醇,可列舉:三乙二醇、四乙二醇及三丙二醇等。作為上述一元有機酸,可列舉: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。
作為上述多元有機酸酯,可列舉:多元有機酸、與具有碳數4~10之直鏈或支鏈結構之醇之酯化合物等。作為上述多元有機酸,可列舉:己二酸、癸二酸及壬二酸等。
作為上述有機酯塑化劑,可列舉:三乙二醇二(2-乙基丙酸酯)、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、壬二酸二丁酯、壬二酸二辛酯、二丁基卡必醇己二酸酯、乙二醇二(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)、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、馬來酸二丁酯、己二酸雙(2-丁氧基乙酯)、己二酸二丁酯、己二酸二異丁酯、己二酸2,2-丁氧基乙氧基乙酯、苯甲酸二醇酯、己二酸1,3-丁二醇聚酯、己二酸二己酯、己二酸二辛酯、己二酸己酯環己酯、己二酸庚酯與己二酸壬酯之混合物、己二酸二異壬酯、己二酸二異癸酯、己二酸庚酯壬酯、檸檬酸三丁酯、乙醯檸檬酸三丁酯、碳酸二乙酯、癸二酸二丁酯、油改性癸二酸醇酸、及磷酸酯與己二酸酯之混合物等。亦可使用該等以外之有機酯塑化劑。亦可使用上述之己二酸酯以外之其他己二酸酯。
作為上述有機磷酸塑化劑,可列舉:磷酸三丁氧基乙酯、磷酸異癸酯苯酯及磷酸三異丙酯等。
上述塑化劑較佳為下述式(1)所表示之二酯塑化劑。
[化1]
上述式(1)中,R1及R2分別表示碳數2~10之有機基,R3表示伸乙基、伸異丙基或伸正丙基,p表示3~10之整數。上述式(1)中之R1及R2分別較佳為碳數5~10之有機基,更佳為碳數6~10之有機基。
上述塑化劑較佳為含有三乙二醇二(2-乙基己酸酯)(3GO)、三乙二醇二(2-乙基丁酸酯)(3GH)或三乙二醇二(2-乙基丙酸酯)。上述塑化劑更佳為含有三乙二醇二(2-乙基己酸酯)或三乙二醇二(2-乙基丁酸酯)。上述塑化劑進而較佳為含有三乙二醇二(2-乙基己酸酯)。
於上述第1層含有上述聚乙酸乙烯酯(1)之情形時,上述第1層較佳為含有己二酸酯作為上述塑化劑,尤佳為含有己二酸雙(2-丁氧基乙酯)、或己二酸二丁酯作為上述塑化劑。
於上述第1層含有上述(甲基)丙烯醯基聚合物(1)之情形時,上述第1層較佳為含有有機酯塑化劑作為上述塑化劑。
於上述第2層中,將相對於上述熱塑性樹脂(2)100重量份(於熱塑性樹脂(2)為聚乙烯縮醛樹脂(2)之情形時,聚乙烯縮醛樹脂(2)100重量份)之上述塑化劑(2)之含量設為含量(2)。於上述第3層中,將相對於上述熱塑性樹脂(3)100重量份(於熱塑性樹脂(3)為聚乙烯縮醛樹脂(3)之情形時,聚乙烯縮醛樹脂(3)100重量份)之上述塑化劑(3)之含量設為含量(3)。上述含量(2)及上述含量(3)分別較佳為10重量份以上,更佳為15重量份以上,且較佳為40重量份以下,更佳為35重量份以下。若上述含量(2)及上述含量(3)為上述下限以上,則樹脂膜之柔軟性變高,樹脂膜之處理變容易。若上述含量(2)及上述含量(3)為上述上限以下,則彎曲剛度進一步變高。
於上述第1層中,將相對於上述樹脂成分(1)100重量份之上述塑化劑(1)之含量設為含量(1)。上述含量(1)較佳為1重量份以上,更佳為5重量份以上,進而較佳為10重量份以上,進而更佳為20重量份以上,且較佳為90重量份以下,更佳為85重量份以下,進而較佳為80重量份以下。若上述含量(1)為上述下限以上,則樹脂膜之柔軟性變高,樹脂膜之操作變容易。若上述含量(1)為上述上限以下,則含有玻璃板之積層體之耐貫通性進一步變高。
於上述第1層中,將相對於上述聚乙烯縮醛樹脂(1)100重量份之上述塑化劑(1)之含量設為含量(1a)。上述含量(1a)較佳為1重量份以上,更佳為2重量份以上,進而較佳為3重量份以上,進而更佳為5重量份以上,且較佳為90重量份以下,更佳為85重量份以下,進而較佳為80重量份以下。若上述含量(1a)為上述下限以上,則樹脂膜之柔軟性變高,樹脂膜之處理變容易。若上述含量(1a)為上述上限以下,則含有玻璃板之積層體之耐貫通性進一步變高。
於上述第1層中,將相對於上述聚乙酸乙烯酯(1)100重量份之上述塑化劑(1)之含量設為含量(1b)。上述含量(1b)較佳為30重量份以上,更佳為50重量份以上,進而較佳為55重量份以上,尤佳為60重量份以上,且較佳為100重量份以下,更佳為90重量份以下,進而較佳為85重量份以下,尤佳為80重量份以下。若上述含量(1b)為上述下限以上,則樹脂膜之柔軟性變高,樹脂膜之處理變容易。若上述含量(1b)為上述上限以下,則含有玻璃板之積層體之耐貫通性進一步變高。
於上述第1層中,將相對於上述(甲基)丙烯醯基聚合物(1)100重量份之上述塑化劑(1)之含量設為含量(1c)。上述含量(1c)可為0重量份以上(包括未含有),亦可超過0重量份,較佳為15重量份以上,更佳為20重量份以上,且較佳為60重量份以下,更佳為50重量份以下。若上述含量(1c)為上述下限以上,則樹脂膜之柔軟性變高,樹脂膜之處理變容易。若上述含量(1c)為上述上限以下,則含有玻璃板之積層體之耐貫通性進一步變高。
於上述樹脂膜為2層以上之情形時,為了提高含有玻璃板之積層體之隔音性,上述含量(1)較佳為多於上述含量(2),上述含量(1)較佳為多於上述含量(3)。
就進一步提高含有玻璃板之積層體之隔音性之觀點而言,上述含量(2)與上述含量(1)之差之絕對值、以及上述含量(3)與上述含量(1)之差之絕對值分別較佳為10重量份以上,更佳為15重量份以上,進而較佳為20重量份以上。上述含量(2)與上述含量(1)之差之絕對值、以及上述含量(3)與上述含量(1)之差之絕對值分別較佳為80重量份以下,更佳為75重量份以下,進而較佳為70重量份以下。
(萜酚樹脂) 上述樹脂膜含有萜酚樹脂。上述第1層(包含單層樹脂膜)含有萜酚樹脂。上述萜酚樹脂可僅使用1種,亦可將2種以上併用。
上述萜酚樹脂之羥值較佳為50 mgKOH/g以上,更佳為70 mgKOH/g以上,且較佳為200 mgKOH/g以下,更佳為180 mgKOH/g以下。若上述羥值為上述下限以上及上述上限以下,則隔音性及透明性進一步變高。
上述羥值係依據JIS K0070:1992「化學製品之酸值、皂化值、酯值、碘值、羥值及不皂化物之試驗方法」所記載之測定方法所測定。
於上述第1層中,相對於上述樹脂成分(1)100重量份,上述萜酚樹脂之含量較佳為10重量份以上,更佳為20重量份以上,進而較佳為30重量份以上,且較佳為150重量份以下,更佳為100重量份以下。若上述萜酚樹脂之含量為上述下限以上,則隔音性進一步變高。若上述萜酚樹脂之含量為上述上限以下,則透明性進一步變高。
於上述第1層中,相對於上述熱塑性樹脂(1)100重量份,上述萜酚樹脂之含量較佳為10重量份以上,更佳為20重量份以上,進而較佳為30重量份以上,且較佳為150重量份以下,更佳為100重量份以下。若上述萜酚樹脂之含量為上述下限以上,則隔音性進一步變高。若上述萜酚樹脂之含量為上述上限以下,則透明性進一步變高。
於上述第1層中,相對於上述聚乙烯縮醛樹脂(1)100重量份,上述萜酚樹脂之含量較佳為10重量份以上,更佳為20重量份以上,進而較佳為30重量份以上,且較佳為150重量份以下,更佳為100重量份以下。若上述萜酚樹脂之含量為上述下限以上,則隔音性進一步變高。若上述萜酚樹脂之含量為上述上限以下,則透明性進一步變高。
於上述第1層中,相對於上述聚乙酸乙烯酯(1)100重量份,上述萜酚樹脂之含量較佳為10重量份以上,更佳為20重量份以上,進而較佳為30重量份以上,且較佳為150重量份以下,更佳為100重量份以下。若上述萜酚樹脂之含量為上述下限以上,則隔音性進一步變高。若上述萜酚樹脂之含量為上述上限以下,則透明性進一步變高。
於上述第1層中,相對於上述(甲基)丙烯醯基聚合物(1)100重量份,上述萜酚樹脂之含量較佳為10重量份以上,更佳為20重量份以上,進而較佳為30重量份以上,且較佳為150重量份以下,更佳為100重量份以下。若上述萜酚樹脂之含量為上述下限以上,則隔音性進一步變高。若上述萜酚樹脂之含量為上述上限以下,則透明性進一步變高。
(隔熱性物質) 上述樹脂膜較佳為含有隔熱性物質(隔熱性化合物)。上述第1層(包含單層樹脂膜)較佳為含有隔熱性物質。上述第2層較佳為含有隔熱性物質。上述第3層較佳為含有隔熱性物質。上述隔熱性物質可僅使用1種,亦可將2種以上併用。
上述隔熱性物質較佳為含有酞菁化合物、萘酚菁化合物或蒽酞菁化合物(以下,有時將該等記載為成分X),或者含有隔熱粒子。於該情形時,亦可含有上述成分X與上述隔熱粒子兩者。
成分X: 上述樹脂膜較佳為含有作為酞菁化合物、萘酚菁化合物或蒽酞菁化合物之成分X。上述第1層(包含單層樹脂膜)較佳為含有上述成分X。上述第2層較佳為含有上述成分X。上述第3層較佳為含有上述成分X。上述成分X係隔熱性物質。上述成分X可僅使用1種,亦可將2種以上併用。
上述成分X並無特別限定。作為成分X,可使用先前公知之酞菁化合物、萘酚菁化合物及蒽酞菁化合物。
就進一步提高樹脂膜及含有玻璃板之積層體之隔熱性之觀點而言,上述成分X較佳為酞菁、酞菁之衍生物、萘酚菁或萘酚菁之衍生物,更佳為酞菁或酞菁之衍生物。
含有上述成分X之層(第1層、第2層或第3層)100重量%中,上述成分X之含量較佳為0.001重量%以上,更佳為0.005重量%以上,進而較佳為0.01重量%以上,尤佳為0.02重量%以上。含有上述成分X之層(第1層、第2層或第3層)100重量%中,上述成分X之含量較佳為0.2重量%以下,更佳為0.1重量%以下,進而較佳為0.05重量%以下,尤佳為0.04重量%以下。若上述成分X之含量為上述下限以上及上述上限以下,則隔熱性充分地變高,且可見光透過率充分地變高。例如可使可見光透過率成為70%以上。
隔熱粒子: 上述樹脂膜較佳為含有隔熱粒子。上述第1層(包含單層樹脂膜)較佳為含有上述隔熱粒子。上述第2層較佳為含有上述隔熱粒子。上述第3層較佳為含有上述隔熱粒子。上述隔熱粒子為隔熱性物質。藉由使用隔熱粒子,可有效地遮斷紅外線(熱線)。上述隔熱粒子可僅使用1種,亦可將2種以上併用。
就進一步提高含有玻璃板之積層體之隔熱性之觀點而言,上述隔熱粒子更佳為金屬氧化物粒子。上述隔熱粒子較佳為藉由金屬之氧化物所形成之粒子(金屬氧化物粒子)。
作為上述隔熱粒子之具體例,可列舉:摻鋁氧化錫粒子、摻銦氧化錫粒子、摻銻氧化錫粒子(ATO粒子)、摻鎵氧化鋅粒子(GZO粒子)、摻銦氧化鋅粒子(IZO粒子)、摻鋁氧化鋅粒子(AZO粒子)、摻鈮氧化鈦粒子、摻鈉氧化鎢粒子、摻銫氧化鎢粒子、摻鉈氧化鎢粒子、摻銣氧化鎢粒子、摻錫氧化銦粒子(ITO粒子)、摻錫氧化鋅粒子、摻矽氧化鋅粒子等金屬氧化物粒子、或六硼化鑭(LaB6
)粒子等。亦可使用該等以外之隔熱粒子。就熱線之遮蔽功能較高而言,較佳為金屬氧化物粒子,更佳為ATO粒子、GZO粒子、IZO粒子、ITO粒子或氧化鎢粒子,尤佳為ITO粒子或氧化鎢粒子。尤其是就熱線之遮蔽功能較高,且容易獲取而言,較佳為摻錫氧化銦粒子(ITO粒子),亦較佳為氧化鎢粒子。
就進一步提高樹脂膜及含有玻璃板之積層體之隔熱性之觀點而言,氧化鎢粒子較佳為摻金屬氧化鎢粒子。上述「氧化鎢粒子」包括摻金屬氧化鎢粒子。作為上述摻金屬氧化鎢粒子,具體而言,可列舉:摻鈉氧化鎢粒子、摻銫氧化鎢粒子、摻鉈氧化鎢粒子及摻銣氧化鎢粒子等。
含有上述隔熱粒子之層(第1層、第2層或第3層)100重量%中,上述隔熱粒子之含量較佳為0.01重量%以上,更佳為0.1重量%以上,進而較佳為1重量%以上,尤佳為1.5重量%以上。含有上述隔熱粒子之層(第1層、第2層或第3層)100重量%中,上述隔熱粒子之含量較佳為6重量%以下,更佳為5.5重量%以下,進而較佳為4重量%以下,尤佳為3.5重量%以下,最佳為3重量%以下。若上述隔熱粒子之含量為上述下限以上及上述上限以下,則隔熱性充分地變高,且可見光透過率充分地變高。
(金屬鹽) 上述樹脂膜較佳為含有鹼金屬鹽、鹼土金屬鹽或鎂鹽(以下,有時將該等記載為金屬鹽M)。上述第1層(包含單層樹脂膜)較佳為含有上述金屬鹽M。上述第2層較佳為含有上述金屬鹽M。上述第3層較佳為含有上述金屬鹽M。藉由使用上述金屬鹽M,而變得容易控制樹脂膜與層合玻璃構件之接著性或樹脂膜中之各層間之接著性。上述金屬鹽M可僅使用1種,亦可將2種以上併用。
上述金屬鹽M較佳為含有Li、Na、K、Rb、Cs、Mg、Ca、Sr或Ba。樹脂膜中所含有之金屬鹽較佳為含有K或Mg。
又,上述金屬鹽M更佳為碳數2~16之有機酸之鹼金屬鹽、碳數2~16之有機酸之鹼土金屬鹽或碳數2~16之有機酸之鎂鹽,進而較佳為碳數2~16之羧酸鎂鹽或碳數2~16之羧酸鉀鹽。
作為上述碳數2~16之羧酸鎂鹽及上述碳數2~16之羧酸鉀鹽,可列舉:乙酸鎂、乙酸鉀、丙酸鎂、丙酸鉀、2-乙基丁酸鎂、2-乙基丁酸鉀、2-乙基己酸鎂及2-乙基己酸鉀等。
含有上述金屬鹽M之層(第1層、第2層或第3層)中之Mg及K之含量之合計較佳為5 ppm以上,更佳為10 ppm以上,進而較佳為20 ppm以上。含有上述金屬鹽M之層(第1層、第2層或第3層)中之Mg及K之含量之合計較佳為300 ppm以下,更佳為250 ppm以下,進而較佳為200 ppm以下。若Mg及K之含量之合計為上述下限以上及上述上限以下,則可進一步良好地控制樹脂膜與層合玻璃構件之接著性或樹脂膜中之各層間之接著性。
(紫外線遮蔽劑) 上述樹脂膜亦可含有紫外線遮蔽劑。上述第1層(包含單層樹脂膜)亦可含有紫外線遮蔽劑。上述第2層較佳為含有紫外線遮蔽劑。上述第3層較佳為含有紫外線遮蔽劑。藉由使用紫外線遮蔽劑,即便長期使用樹脂膜及含有玻璃板之積層體,可見光透過率亦難以進一步降低。上述紫外線遮蔽劑可僅使用1種,亦可將2種以上併用。
上述紫外線遮蔽劑包括紫外線吸收劑。上述紫外線遮蔽劑較佳為紫外線吸收劑。
作為上述紫外線遮蔽劑,例如可列舉:含有金屬原子之紫外線遮蔽劑、含有金屬氧化物之紫外線遮蔽劑、具有苯并三唑結構之紫外線遮蔽劑(苯并三唑化合物)、具有二苯甲酮結構之紫外線遮蔽劑(二苯甲酮化合物)、具有三結構之紫外線遮蔽劑(三化合物)、具有丙二酸酯結構之紫外線遮蔽劑(丙二酸酯化合物)、具有草醯替苯胺結構之紫外線遮蔽劑(草醯替苯胺化合物)及具有苯甲酸酯結構之紫外線遮蔽劑(苯甲酸酯化合物)等。
作為上述含有金屬原子之紫外線遮蔽劑,例如可列舉:鉑粒子、鉑粒子之表面經二氧化矽被覆之粒子、鈀粒子及鈀粒子之表面經二氧化矽被覆之粒子等。紫外線遮蔽劑較佳為不為隔熱粒子。
上述紫外線遮蔽劑較佳為具有苯并三唑結構之紫外線遮蔽劑、具有二苯甲酮結構之紫外線遮蔽劑、具有三結構之紫外線遮蔽劑或具有苯甲酸酯結構之紫外線遮蔽劑。上述紫外線遮蔽劑較佳為具有苯并三唑結構之紫外線遮蔽劑或具有二苯甲酮結構之紫外線遮蔽劑。上述紫外線遮蔽劑較佳為具有苯并三唑結構之紫外線遮蔽劑。
作為上述含有金屬氧化物之紫外線遮蔽劑,例如可列舉:氧化鋅、氧化鈦及氧化鈰等。進而,關於上述含有金屬氧化物之紫外線遮蔽劑,亦可表面經被覆。作為上述含有金屬氧化物之紫外線遮蔽劑之表面之被覆材料,可列舉:絕緣性金屬氧化物、水解性有機矽化合物及矽酮化合物等。
作為上述具有苯并三唑結構之紫外線遮蔽劑,例如可列舉:2-(2'-羥基-5'-甲基苯基)苯并三唑(BASF公司製造之「Tinuvin P」)、2-(2'-羥基-3',5'-二第三丁基苯基)苯并三唑(BASF公司製造之「Tinuvin 320」)、2-(2'-羥基-3'-第三丁基-5-甲基苯基)-5-氯苯并三唑(BASF公司製造之「Tinuvin 326」)、及2-(2'-羥基-3',5'-二戊基苯基)苯并三唑(BASF公司製造之「Tinuvin 328」)等。就吸收紫外線之性能優異之方面而言,上述紫外線遮蔽劑較佳為具有含有鹵素原子之苯并三唑結構之紫外線遮蔽劑,更佳為具有含有氯原子之苯并三唑結構之紫外線遮蔽劑。
作為上述具有二苯甲酮結構之紫外線遮蔽劑,例如可列舉:辛苯酮(BASF公司製造之「Chimassorb 81」)等。
作為上述具有三結構之紫外線遮蔽劑,例如可列舉:ADEKA公司製造之「LA-F70」及2-(4,6-二苯基-1,3,5-三-2-基)-5-[(己基)氧基]-苯酚(BASF公司製造之「Tinuvin 1577FF」)等。
作為上述具有丙二酸酯結構之紫外線遮蔽劑,可列舉:2-(對甲氧基亞苄基)丙二酸二甲酯、2,2-(1,4-伸苯基二亞甲基)雙丙二酸四乙酯、2-(對甲氧基亞苄基)-雙(1,2,2,6,6-五甲基4-哌啶基)丙二酸酯等。
作為上述具有丙二酸酯結構之紫外線遮蔽劑之市售品,可列舉:Hostavin B-CAP、Hostavin PR-25、Hostavin PR-31(均為Clariant公司製造)。
作為上述具有草醯替苯胺結構之紫外線遮蔽劑,可列舉:N-(2-乙基苯基)-N'-(2-乙氧基-5-第三丁基苯基)草醯二胺、N-(2-乙基苯基)-N'-(2-乙氧基-苯基)草醯二胺、2-乙基-2'-乙氧基-草醯替苯胺(Clariant公司製造之「Sanduvor VSU」)等具有取代於氮原子上之芳基等之草醯二胺類。
作為上述具有苯甲酸酯結構之紫外線遮蔽劑,例如可列舉:2,4-二第三丁基苯基-3,5-二第三丁基-4-羥基苯甲酸酯(BASF公司製造「Tinuvin 120」)等。
含有上述紫外線遮蔽劑之層(第1層、第2層或第3層)100重量%中,上述紫外線遮蔽劑之含量較佳為0.1重量%以上,更佳為0.2重量%以上,進而較佳為0.3重量%以上,尤佳為0.5重量%以上。含有上述紫外線遮蔽劑之層(第1層、第2層或第3層)100重量%中,上述紫外線遮蔽劑之含量較佳為2.5重量%以下,更佳為2重量%以下,進而較佳為1重量%以下,尤佳為0.8重量%以下。若上述紫外線遮蔽劑之含量為上述下限以上及上述上限以下,則經過一段時間後之可見光透過率之降低得到進一步抑制。尤其是於含有上述紫外線遮蔽劑之層100重量%中,藉由使上述紫外線遮蔽劑之含量為0.2重量%以上,可顯著地抑制樹脂膜及含有玻璃板之積層體之經過一段時間後之可見光透過率之降低。
(抗氧化劑) 上述樹脂膜較佳為含有抗氧化劑。上述第1層(包含單層樹脂膜)較佳為含有抗氧化劑。上述第2層較佳為含有抗氧化劑。上述第3層較佳為含有抗氧化劑。上述抗氧化劑可僅使用1種,亦可將2種以上併用。
作為上述抗氧化劑,可列舉:酚系抗氧化劑、硫系抗氧化劑及磷系抗氧化劑等。上述酚系抗氧化劑係具有苯酚骨架之抗氧化劑。上述硫系抗氧化劑係含有硫原子之抗氧化劑。上述磷系抗氧化劑係含有磷原子之抗氧化劑。
上述抗氧化劑較佳為酚系抗氧化劑或磷系抗氧化劑。
作為上述酚系抗氧化劑,可列舉:2,6-二第三丁基對甲酚(BHT)、丁基羥基苯甲醚(BHA)、2,6-二第三丁基-4-乙基苯酚、β-(3,5-二第三丁基-4-羥基苯基)丙酸硬脂酯、2,2'-亞甲基雙(4-甲基-6-丁基苯酚)、2,2'-亞甲基雙(4-乙基-6-第三丁基苯酚)、4,4'-亞丁基-雙(3-甲基-6-第三丁基苯酚)、1,1,3-三(2-甲基羥基-5-第三丁基苯基)丁烷、四[亞甲基-3-(3',5'-丁基-4-羥基苯基)丙酸酯]甲烷、1,3,3-三(2-甲基-4-羥基-5-第三丁基苯酚)丁烷、1,3,5-三甲基-2,4,6-三(3,5-二第三丁基-4-羥基苄基)苯、雙(3,3'-第三丁基苯酚)丁酸二醇酯及雙(3-第三丁基-4-羥基-5-甲基苯丙酸)乙二酯雙(氧化乙烯)等。可適宜地使用該等抗氧化劑中之1種或2種以上。
作為上述磷系抗氧化劑,可列舉:亞磷酸三癸酯、亞磷酸三(十三烷基)酯、亞磷酸三苯酯、亞磷酸三(壬基苯基)酯、二亞磷酸雙(十三烷基酯)季戊四醇酯、二亞磷酸雙(癸酯)季戊四醇酯、亞磷酸三(2,4-二第三丁基苯基)酯、亞磷酸雙(2,4-二第三丁基-6-甲基苯基)酯乙酯、及2,2'-亞甲基雙(4,6-二第三丁基-1-苯氧基)(2-乙基己氧基)磷等。可適宜地使用該等抗氧化劑中之1種或2種以上。
作為上述抗氧化劑之市售品,例如可列舉:BASF公司製造之「IRGANOX 245」、BASF公司製造之「IRGAFOS 168」、BASF公司製造之「IRGAFOS 38」、住友化學工業公司製造之「Sumilizer BHT」、堺化學工業公司製造之「H-BHT」、以及BASF公司製造之「IRGANOX 1010」等。
上述樹脂膜100重量%中或含有抗氧化劑之層(第1層、第2層或第3層)100重量%中,上述抗氧化劑之含量較佳為0.1重量%以上。於該情形時,可持續長期維持樹脂膜及含有玻璃板之積層體之較高可見光透過率。
(其他成分) 上述樹脂膜、上述第1層、上述第2層及上述第3層亦可分別視需要含有其他成分。作為上述其他成分,可列舉:含有矽、鋁或鈦之偶合劑、分散劑、界面活性劑、阻燃劑、抗靜電劑、填料、顏料、染料、接著力調整劑、耐濕劑、螢光增白劑及紅外線吸收劑等。上述其他成分可僅使用1種,亦可將2種以上併用。
為了將剪切儲存模數控制為較佳之範圍,樹脂膜、第1層、第2層及第3層亦可含有填料。作為上述填料,可列舉:碳酸鈣粒子、及二氧化矽粒子等。就有效地提高彎曲剛度,且有效地抑制透明性之降低之觀點而言,較佳為二氧化矽粒子。
含有填料之層(第1層、第2層或第3層)100重量%中,上述填料之含量較佳為1重量%以上,更佳為5重量%以上,進而較佳為10重量%以上,且較佳為60重量%以下,更佳為50重量%以下。
(樹脂膜之其他詳細內容) 上述樹脂膜較佳為貼合於玻璃板而使用之樹脂膜。
上述樹脂膜之厚度並無特別限定。就實用方面之觀點、以及充分地提高含有玻璃板之積層體之耐貫通性及彎曲剛度之觀點而言,樹脂膜之厚度較佳為0.1 mm以上,更佳為0.25 mm以上,且較佳為3 mm以下,更佳為1.5 mm以下。若樹脂膜之厚度為上述下限以上,則含有玻璃板之積層體之耐貫通性及彎曲剛度進一步變高。若樹脂膜之厚度為上述上限以下,則樹脂膜之透明性進一步變良好。
上述樹脂膜可為厚度均一之樹脂膜,亦可為厚度產生變化之樹脂膜。上述樹脂膜之剖面形狀可為矩形,亦可為楔形。
本發明之樹脂膜之製造方法並無特別限定。作為本發明之樹脂膜之製造方法,於單層樹脂膜之情形時,可列舉使用擠出機將樹脂組合物擠出之方法。作為本發明之樹脂膜之製造方法,於多層樹脂膜之情形時,例如可列舉:使用用以形成各層之各樹脂組合物分別形成各層後,將所獲得之各層進行積層之方法;以及使用擠出機將用以形成各層之各樹脂組合物進行共擠出,藉此將各層進行積層之方法等。就適於連續之生產而言,較佳為進行擠出成形之製造方法。
較佳為於上述第2層與上述第3層中含有相同之聚乙烯縮醛樹脂。於該情形時,樹脂膜之製造效率優異。就樹脂膜之製造效率優異之方面而言,更佳為於上述第2層與上述第3層中含有相同之聚乙烯縮醛樹脂及相同之塑化劑。就樹脂膜之製造效率優異之方面而言,進而較佳為上述第2層與上述第3層由相同之樹脂組合物所形成。
上述樹脂膜較佳為於兩側之表面中之至少一表面具有凹凸形狀。上述樹脂膜更佳為於兩側之表面具有凹凸形狀。作為形成上述凹凸形狀之方法,並無特別限定,例如可列舉:模唇壓紋法、壓紋輥法、砑光輥法、及異形擠出法等。就可定量地形成作為一定之凹凸花紋之大量凹凸形狀之壓紋的方面而言,較佳為壓紋輥法。
(含有玻璃板之積層體) 圖3係模式性地表示使用圖1所示之樹脂膜之含有玻璃板之積層體之一例的剖視圖。
圖3所示之含有玻璃板之積層體31具備:第1層合玻璃構件21、第2層合玻璃構件22、及樹脂膜11。樹脂膜11係配置並夾入於第1層合玻璃構件21與第2層合玻璃構件22之間。
於樹脂膜11之第1表面11a積層有第1層合玻璃構件21。於樹脂膜11之與第1表面11a相反之第2表面11b積層有第2層合玻璃構件22。於第2層2之外側表面2a積層有第1層合玻璃構件21。於第3層3之外側表面3a積層有第2層合玻璃構件22。
圖4係模式性地表示使用圖2所示之樹脂膜之含有玻璃板之積層體之一例的剖視圖。
圖4所示之含有玻璃板之積層體31A具備:第1層合玻璃構件21、第2層合玻璃構件22、及樹脂膜11A。樹脂膜11A係配置並夾入於第1層合玻璃構件21與第2層合玻璃構件22之間。
於樹脂膜11A之第1表面11a積層有第1層合玻璃構件21。於樹脂膜11A之與第1表面11a相反之第2表面11b積層有第2層合玻璃構件22。
如上所述,本發明之含有玻璃板之積層體只要具備第1玻璃板、與本發明之樹脂膜即可。上述樹脂膜較佳為配置於上述第1層合玻璃構件(第1玻璃板)與上述第2層合玻璃構件之間。
本發明之含有玻璃板之積層體較佳為於上述第1玻璃板貼合有上述樹脂膜。本發明之含有玻璃板之積層體較佳為於上述第1玻璃板貼合有上述樹脂膜,於上述第2層合玻璃構件貼合有上述樹脂膜。
上述第1層合玻璃構件較佳為第1玻璃板。上述第2層合玻璃構件較佳為第2玻璃板。
作為上述層合玻璃構件,可列舉玻璃板及PET(聚對苯二甲酸乙二酯)膜等。含有玻璃板之積層體不僅包含於2片玻璃板之間夾入有樹脂膜之層合玻璃,亦包含於玻璃板與PET膜等之間夾入有樹脂膜之層合玻璃。上述含有玻璃板之積層體係具備玻璃板之積層體,較佳為使用至少1片玻璃板。上述第1層合玻璃構件及上述第2層合玻璃構件分別為玻璃板或PET膜,且上述層合玻璃較佳為具備玻璃板作為上述第1層合玻璃構件及上述第2層合玻璃構件中之至少一者。
作為上述玻璃板,可列舉無機玻璃及有機玻璃。作為上述無機玻璃,可列舉:浮法板玻璃、熱線吸收板玻璃、熱線反射板玻璃、拋光板玻璃、壓花板玻璃、夾絲板玻璃等。上述有機玻璃係代替無機玻璃之合成樹脂玻璃。作為上述有機玻璃,可列舉聚碳酸酯板及聚(甲基)丙烯酸系樹脂板等。作為上述聚(甲基)丙烯酸系樹脂板,可列舉聚(甲基)丙烯酸甲酯板等。
上述層合玻璃構件之厚度較佳為1 mm以上,且較佳為5 mm以下,更佳為3 mm以下。又,於上述層合玻璃構件為玻璃板之情形時,該玻璃板之厚度較佳為0.5 mm以上,更佳為0.7 mm以上。於上述層合玻璃構件為玻璃板之情形時,該玻璃板之厚度較佳為5 mm以下,更佳為3 mm以下,進而較佳為2.3 mm以下,進而更佳為2.1 mm以下,進而更佳為2.0 mm以下,進而更佳為1.8 mm以下,尤佳為1.6 mm以下,最佳為1.4 mm以下。於上述層合玻璃構件為強化玻璃之情形時,上述玻璃板之厚度可為0.5 mm以上,亦可為0.7 mm以上。於上述層合玻璃構件為強化玻璃之情形時,上述玻璃板之厚度較佳為1 mm以下,更佳為0.7 mm以下。於上述層合玻璃構件為PET膜之情形時,該PET膜之厚度較佳為0.03 mm以上,且較佳為0.5 mm以下。
上述含有玻璃板之積層體之製造方法並無特別限定。例如,於上述第1層合玻璃構件與上述第2層合玻璃構件之間夾入樹脂膜,通過按壓輥、或放入至橡膠袋中進行減壓抽吸,而將殘留於上述第1層合玻璃構件、上述第2層合玻璃構件及樹脂膜之間之空氣進行脫氣。其後,於約70~110℃下進行預接著而獲得積層體。繼而,將積層體放入至高壓釜中,或進行加壓,而於約120~150℃及1~1.5 MPa之壓力下進行壓接。如此,可獲得含有玻璃板之積層體。於製造上述含有玻璃板之積層體時,亦可將第1層、第2層及第3層進行積層。
上述樹脂膜及上述含有玻璃板之積層體可用於汽車、軌道車輛、航空器、船舶及建築物等。上述樹脂膜及上述含有玻璃板之積層體亦可用於該等用途以外。上述樹脂膜及上述含有玻璃板之積層體較佳為車輛用或建築用之樹脂膜及含有玻璃板之積層體,更佳為車輛用之樹脂膜及含有玻璃板之積層體。上述樹脂膜及上述含有玻璃板之積層體可用於汽車之風擋、側窗玻璃、後窗玻璃或天窗玻璃等。上述樹脂膜及上述含有玻璃板之積層體可適宜地用於汽車。上述樹脂膜可用於獲得汽車之含有玻璃板之積層體。
於使用上述層合玻璃時,於上述建築物或上述車輛中,可以上述第1層合玻璃構件位於上述外部空間側,且上述第2層合玻璃構件位於上述內部空間側之方式將上述層合玻璃安裝於上述開口部。上述層合玻璃可以安裝至上述開口部之狀態使用。
於上述汽車之含有玻璃板之積層體中,於車外側與車內側層合玻璃構件之厚度亦可不同。車外側之層合玻璃構件之厚度較佳為0.5 mm以上,更佳為0.7 mm以上,進而較佳為1.0 mm以上,尤佳為1.5 mm以上。車外側之層合玻璃構件之厚度較佳為5 mm以下,更佳為3 mm以下,進而較佳為2.3 mm以下,進而更佳為2.1 mm以下,進而更佳為2.0 mm以下,進而更佳為1.8 mm以下,尤佳為1.6 mm以下。車內側之層合玻璃構件之厚度較佳為0.5 mm以上,更佳為0.7 mm以上。車內側之層合玻璃構件之厚度較佳為3 mm以下,更佳為2.3 mm以下,進而較佳為2.1 mm以下,進而更佳為2.0 mm以下,進而更佳為1.8 mm以下,進而更佳為1.6 mm以下,進而更佳為1.4 mm以下,尤佳為1.0 mm以下,最佳為0.7 mm以下。
於以下列舉實施例及比較例而對本發明進一步詳細地進行說明。本發明並不僅限定於該等實施例。
準備以下之材料。
(實施例1) 用以形成樹脂膜(第1層)之組合物之製作: 調配以下之成分,而獲得用以形成樹脂膜之組合物。
聚乙烯縮醛樹脂(平均聚合度3000,使用正丁基醛,羥基之含有率20莫耳%,乙醯化度14.5莫耳%,縮醛化度65.5莫耳%)100重量份 三乙二醇二(2-乙基己酸酯)(3GO)50重量份 萜酚樹脂(Yasuhara Chemical公司製造之「N125」)40重量份 所獲得之樹脂膜中金屬元素濃度(Mg濃度)成為70 ppm之量之Mg混合物(2-乙基丁酸鎂與乙酸鎂之50:50(重量比)混合物) 所獲得之樹脂膜中成為0.2重量%之量之紫外線遮蔽劑(2-(2-羥基-3-第三丁基-5-甲基苯基)-5-氯苯并三唑) 所獲得之樹脂膜中成為0.2重量%之量之抗氧化劑(2,6-二-第三丁基-對甲酚)
樹脂膜之製作: 使用擠出機將用以形成樹脂膜之組合物擠出,藉此製作樹脂膜(厚度800 μm)。
層合玻璃之製作: 將所獲得之樹脂膜切割成縱30 cm×橫2.5 cm之大小。作為第1層合玻璃構件及第2層合玻璃構件,準備2個玻璃板(透明玻璃,縱30 cm×橫2.5 cm×厚度2.5 mm)。於2片玻璃板之間夾入樹脂膜而獲得積層體。將該積層體放入至橡膠袋內,於2.6 kPa之真空度下進行20分鐘脫氣後,以經脫氣之狀態移至烘箱內,進而於90℃下保持30分鐘,進行真空加壓,將積層體進行預壓接。於高壓釜中於135℃及壓力1.2 MPa之條件下,將經預壓接之積層體進行20分鐘壓接,而獲得層合玻璃。
(實施例2) 進行以下之變更,除此以外,以與實施例1相同之方式獲得樹脂膜及層合玻璃。
將聚乙烯縮醛樹脂變更為聚乙烯縮醛樹脂(平均聚合度3000,使用正丁基醛,羥基之含有率20.5莫耳%,乙醯化度7莫耳%,縮醛化度72.5莫耳%) 將3GO之調配量變更為60重量份 將萜酚樹脂40重量份變更為萜酚樹脂(Yasuhara Chemical公司製造之「G125」)50重量份
(實施例3) 進行以下之變更,除此以外,以與實施例1相同之方式獲得樹脂膜及層合玻璃。
將聚乙烯縮醛樹脂變更為聚乙烯縮醛樹脂(平均聚合度2500,使用正丁基醛,羥基之含有率24莫耳%,乙醯化度12.5莫耳%,縮醛化度63.5莫耳%) 將3GO之調配量變更為70重量份 將萜酚樹脂40重量份變更為萜酚樹脂(Yasuhara Chemical公司製造之「POLYSTAR NH」)70重量份
(比較例1) 進行以下之變更,除此以外,以與實施例1相同之方式獲得樹脂膜及層合玻璃。
將聚乙烯縮醛樹脂變更為聚乙烯縮醛樹脂(平均聚合度2500,使用正丁基醛,羥基之含有率24莫耳%,乙醯化度12.5莫耳%,縮醛化度63.5莫耳%) 將萜酚樹脂40重量份變更為松香樹脂(荒川化學公司製造之「D160」)70重量份
(比較例2) 進行以下之變更,除此以外,以與實施例1相同之方式獲得樹脂膜及層合玻璃。
將聚乙烯縮醛樹脂變更為聚乙烯縮醛樹脂(平均聚合度3000,使用正丁基醛,羥基之含有率20.5莫耳%,乙醯化度7莫耳%,縮醛化度72.5莫耳%) 將3GO之調配量變更為60重量份 將萜酚樹脂40重量份變更為松香樹脂(荒川化學公司製造之「D125」)50重量份
(比較例3) 進行以下之變更,除此以外,以與實施例1相同之方式獲得樹脂膜及層合玻璃。
將聚乙烯縮醛樹脂變更為聚乙烯縮醛樹脂(平均聚合度3000,使用正丁基醛,羥基之含有率24莫耳%,乙醯化度12.5莫耳%,縮醛化度63.5莫耳%) 將3GO之調配量變更為70重量份 將萜酚樹脂40重量份以不進行調配之方式進行變更
(實施例4) 聚乙酸乙烯酯之製作: 準備具備回流冷卻器、滴液漏斗、溫度計及氮氣導入口之玻璃製聚合容器。於該聚合容器內加入乙酸乙烯酯單體100重量份、乙二醇單乙烯醚(HEVE)1.0重量份、及甲醇3.8重量份,進行加熱及攪拌並對聚合容器內進行氮氣置換。繼而,將上述聚合容器內之溫度設為60℃,歷時4小時滴加作為聚合起始劑之過氧化新癸酸第三丁酯0.02重量份、乙酸乙烯酯單體150重量份、及乙二醇單乙烯醚(HEVE)1.5重量份,於滴加結束後進行1小時聚合,而獲得含有聚乙酸乙烯酯之溶液。使該溶液於110℃之烘箱中乾燥3小時,藉此獲得聚乙酸乙烯酯。於聚乙酸乙烯酯中,源自HEVE之結構單元之比例為0.2莫耳%。聚乙酸乙烯酯之重量平均分子量為699000。
進行以下之變更,除此以外,以與實施例1相同之方式獲得樹脂膜及層合玻璃。
將聚乙烯縮醛樹脂變更為所獲得之聚乙酸乙烯酯 將3GO 50重量份變更為己二酸雙(2-丁氧基乙酯)(D931)40重量份 將萜酚樹脂40重量份變更為萜酚樹脂(Yasuhara Chemical公司製造之「POLYSTAR NH」)30重量份
(實施例5) (甲基)丙烯醯基聚合物之製作: 準備具備回流冷卻器、溫度計及氮氣導入口之玻璃製聚合容器。於該聚合容器內放入以下之成分,進行加熱及攪拌,並對聚合容器內進行氮氣置換。
離子交換水230重量份 聚氧乙烯苯乙烯化丙烯基苯基醚硫酸酯銨(第一工業製藥公司製造之「AR-30」)0.1重量份 環氧乙烷-環氧丙烷共聚物(明成化學工業公司製造之「EP-10」)0.005重量份
繼而,將上述聚合容器內設為60℃,添加以下之成分,進行6小時聚合而獲得粒子狀之(甲基)丙烯醯基聚合物(1)。
過氧化新癸酸第三丁酯(聚合起始劑)0.08重量份 丙烯酸苄酯(大阪有機化學工業公司製造,Viscoat#160)(BzA)5重量份 (2-甲基-2-乙基-1,3-二氧戊環-4-基)丙烯酸甲酯(大阪有機化學工業公司製造)(MEDOL-10)10重量份 丙烯酸羥基丙酯(大阪有機化學工業公司製造)(HPA)15重量份 丙烯酸異基酯(日本觸媒公司製造,IBOA)70重量份
進行以下之變更,除此以外,以與實施例1相同之方式獲得樹脂膜及層合玻璃。
將聚乙烯縮醛樹脂變更為所獲得之(甲基)丙烯醯基聚合物 將3GO之調配量變更為40重量份 將萜酚樹脂40重量份變更為萜酚樹脂(Yasuhara Chemical公司製造之「POLYSTAR NH」)20重量份
(單層樹脂膜之評價) (1)隔音性(低溫側之tanδ之波峰之最大值) 將所獲得之樹脂膜裁切成直徑8 mm之圓形。對於該樹脂膜,使用黏彈性裝置(Rheometrics公司製造之「ARES」)並藉由剪切法,於應變1%及頻率1 Hz之條件下,以升溫速度5℃/min進行動態黏彈性測定。測定出現在最低溫側之損耗正切之最大值(極大值)。
(2)透明性(霧度值) 對於所獲得之層合玻璃,使用霧度計(東京電色公司製造之「TC-HIIIDPK」),依據JIS K6714測定霧度值。
將詳細內容及結果示於下述之表1。再者,於表1中,Mg混合物、紫外線遮蔽劑及抗氧化劑之調配量係省略。
[表1]
(實施例6) 用以形成第1層之組合物: 準備實施例1中所獲得之用以形成第1層之組合物。
用以形成第2層及第3層之組合物之製作: 調配以下之成分,獲得用以形成第2層及第3層之組合物。
聚乙烯縮醛樹脂(平均聚合度1700,使用正丁基醛,羥基之含有率30.7莫耳%,乙醯化度0.8莫耳%,縮醛化度68.5莫耳%)100重量份 三乙二醇二(2-乙基己酸酯)(3GO)37.5重量份 所獲得之樹脂膜中金屬元素濃度(Mg濃度)成為70 ppm之量之Mg混合物(2-乙基丁酸鎂與乙酸鎂之50:50(重量比)混合物) 所獲得之樹脂膜中成為0.2重量%之量之紫外線遮蔽劑(2-(2-羥基-3-第三丁基-5-甲基苯基)-5-氯苯并三唑) 所獲得之樹脂膜中成為0.2重量%之量之抗氧化劑(2,6-二-第三丁基-對甲酚)
樹脂膜之製作: 使用共擠出機將用以形成第1層之組合物、與用以形成第2層及第3層之組合物進行共擠出,藉此製作具有第2層(厚度350 μm)/第1層(厚度100 μm)/第3層(厚度350 μm)之積層構造之樹脂膜(厚度800 μm)。
使用所獲得之樹脂膜,除此以外,以與實施例1相同之方式獲得層合玻璃。
(實施例7~10及比較例4~6) 進行以下之變更,除此以外,以與實施例6相同之方式獲得樹脂膜及層合玻璃。
實施例7:將用以形成第1層之組合物變更為實施例2中所獲得之用以形成第1層之組合物。將用以形成第2、3層之組合物中之聚乙烯縮醛樹脂之種類及塑化劑之調配量如表2所示般變更。將第2、3層之厚度如表2所示般變更。 實施例8:將用以形成第1層之組合物變更為實施例3中所獲得之用以形成第1層之組合物。將用以形成第2、3層之組合物中之聚乙烯縮醛樹脂之種類及塑化劑之調配量如表2所示般變更。將第2、3層之厚度如表2所示般變更。 實施例9:將用以形成第1層之組合物變更為實施例4中所獲得之用以形成第1層之組合物。將用以形成第2、3層之組合物中之聚乙烯縮醛樹脂之種類及塑化劑之種類、調配量如表2所示般變更。將第2、3層之厚度如表2所示般變更。 實施例10:將用以形成第1層之組合物變更為實施例5中所獲得之用以形成第1層之組合物。將用以形成第2、3層之組合物中之聚乙烯縮醛樹脂之種類及塑化劑之調配量如表2所示般變更。將第2、3層之厚度如表2所示般變更。 比較例4:將用以形成第1層之組合物變更為比較例1中所獲得之用以形成第1層之組合物。 比較例5:將用以形成第1層之組合物變更為比較例2中所獲得之用以形成第1層之組合物。 比較例6:將用以形成第1層之組合物變更為比較例3中所獲得之用以形成第1層之組合物。將用以形成第2、3層之組合物中之聚乙烯縮醛樹脂之種類及塑化劑之調配量如表2所示般變更。將第2、3層之厚度如表2所示般變更。
(多層樹脂膜之評價) 對於多層樹脂膜,進行與單層樹脂膜相同之評價。實施例6~10之樹脂膜具備具有與實施例1~5相同之組成之第1層。因此,實施例6~10之樹脂膜與比較例4~6之樹脂膜相比,隔音性及透明性優異。
除上述之評價以外,進行以下之評價。
(3)隔音性(20℃下之一次損耗係數) 藉由阻尼試驗用之振動產生機(振研公司製造之「加振機G21-005D」)對實施例7~10及比較例6中所獲得之層合玻璃進行加振。利用機械阻抗測定裝置(RION公司製造之「XG-81」)將自此獲得之振動特性放大,藉由FFT頻譜分析儀((RION公司製造之「FFT Analyzer SA-01A2」)對振動圖譜進行分析。
將詳細內容及結果示於下述之表2中。再者,於表2中,Mg混合物、紫外線遮蔽劑及抗氧化劑之調配量係省略。
[表2]
1‧‧‧第1層
1a‧‧‧第1表面
1b‧‧‧第2表面
2‧‧‧第2層
2a‧‧‧外側之表面
3‧‧‧第3層
3a‧‧‧外側之表面
11‧‧‧樹脂膜
11A‧‧‧樹脂膜(第1層)
11a‧‧‧第1表面
11b‧‧‧第2表面
21‧‧‧第1層合玻璃構件
22‧‧‧第2層合玻璃構件
31‧‧‧含有玻璃板之積層體
31A‧‧‧含有玻璃板之積層體
圖1係模式性地表示本發明之第1實施形態之樹脂膜之剖視圖。 圖2係模式性地表示本發明之第2實施形態之樹脂膜之剖視圖。 圖3係模式性地表示使用圖1所示之樹脂膜之含有玻璃板之積層體之一例的剖視圖。 圖4係模式性地表示使用圖2所示之樹脂膜之含有玻璃板之積層體之一例的剖視圖。
Claims (10)
- 一種樹脂膜,其係具有1層構造或2層以上之構造者,且 具備含有後述樹脂成分、與萜酚樹脂之第1層,該樹脂成分為熱塑性樹脂、或者由光硬化性化合物或濕氣硬化性化合物硬化所得之硬化物。
- 如請求項1之樹脂膜,其中上述第1層中之上述樹脂成分為聚乙烯縮醛樹脂、聚乙酸乙烯酯、或(甲基)丙烯醯基聚合物。
- 如請求項2之樹脂膜,其中於上述第1層含有上述聚乙烯縮醛樹脂或上述聚乙酸乙烯酯之情形時,上述第1層含有塑化劑。
- 如請求項1至3中任一項之樹脂膜,其中上述萜酚樹脂之羥值為50 mgKOH/g以上且200 mgKOH/g以下。
- 如請求項1至3中任一項之樹脂膜,其中於上述第1層中,相對於上述樹脂成分100重量份,上述萜酚樹脂之含量為10重量份以上且150重量份以下。
- 如請求項1至3中任一項之樹脂膜,其具備含有熱塑性樹脂與塑化劑之第2層,且 上述第2層係配置於上述第1層之第1表面側。
- 如請求項6之樹脂膜,其具備含有熱塑性樹脂與塑化劑之第3層,且 上述第3層係配置於上述第1層之與上述第1表面相反之第2表面側。
- 如請求項1至3中任一項之樹脂膜,其係貼合於玻璃板而使用之樹脂膜。
- 一種含有玻璃板之積層體,其具備: 第1玻璃板、與 如請求項1至8中任一項之樹脂膜,且 於上述第1玻璃板貼合有上述樹脂膜。
- 如請求項9之含有玻璃板之積層體,其具備: 作為第1層合玻璃構件之上述第1玻璃板、 上述樹脂膜、及 第2層合玻璃構件,且 於上述第1玻璃板貼合有上述樹脂膜, 於上述第2層合玻璃構件貼合有上述樹脂膜, 於上述第1玻璃板與上述第2層合玻璃構件之間配置有上述樹脂膜。
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