TWI797268B - 層合玻璃用中間膜、及層合玻璃 - Google Patents
層合玻璃用中間膜、及層合玻璃 Download PDFInfo
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- TWI797268B TWI797268B TW108106776A TW108106776A TWI797268B TW I797268 B TWI797268 B TW I797268B TW 108106776 A TW108106776 A TW 108106776A TW 108106776 A TW108106776 A TW 108106776A TW I797268 B TWI797268 B TW I797268B
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- laminated glass
- interlayer film
- transmittance
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Abstract
本發明之層合玻璃用中間膜含有最大吸收波長峰值為370 nm以上且405 nm以下之苯并三唑系化合物,將於黑面板(black panel)溫度83℃、槽內溫度50℃及槽內濕度50%RH下照射輻照度180 w/m2
之氙光1000小時後之於400 nm的透射率設為T1000
,將照射前之於400 nm的透射率設為T0
時,T1000
-T0
所表示之透射率差未達2.0%。
Description
本發明係關於一種層合玻璃用中間膜、及具備層合玻璃用中間膜之層合玻璃。
以往使中間膜介於2片玻璃板之間並進行一體化而成之層合玻璃廣為人知。中間膜大多由在聚乙烯縮醛樹脂中摻合塑化劑而成之塑化聚乙烯縮醛所形成。層合玻璃即便受到外部撞擊而破損,玻璃碎片之飛散亦少且安全,故而廣泛地用作汽車等車輛、航空器、建築物等之窗玻璃。層合玻璃於用作窗玻璃之情形時,一般於照射陽光之環境下使用。已知陽光中含有紫外線,故以往為了防止紫外線照射至車輛內部、建築物內部,而於層合玻璃用中間膜摻合紫外線吸收劑。
作為紫外線吸收劑,於300~360 nm左右具有最大吸收波長峰值者多為人所知。例如,於專利文獻1中揭示有於聚乙烯縮醛樹脂中使用草醯替苯胺(Oxanilide)型化合物作為紫外線吸收劑,且揭示該化合物以高吸收率吸收UV-B即280~325 nm左右之紫外線。
又,已知紫外線中波長400 nm附近之紫外線會對人的眼睛或皮膚造成負擔,從而對於層合玻璃,持續要求亦以高吸收率吸收400 nm附近之紫外線。因此,例如已知有如專利文獻2所示般,於層合玻璃用中間膜中摻合具有特定結構之吲哚系紫外線吸收劑與具有特定結構之苯并三唑化合物。專利文獻2中,顯示藉由使用該等2種紫外線吸收劑,400 nm之吸收率會變高。
先前技術文獻
專利文獻
專利文獻1:日本特開2012-46748號公報
專利文獻2:國際公開2012/023616號
發明所欲解決之課題
但是,窗玻璃一般會長期被使用,故而層合玻璃用中間膜亦會長期暴露於陽光下。因此,要求與以往相比,即便長期暴露於陽光下,亦良好地維持紫外線吸收性能,特別是400 nm附近之紫外線吸收性能。
因此,本發明之課題在於提供一種長期良好地維持400 nm附近之紫外線吸收性能的層合玻璃用中間膜。
解決課題之技術手段
本發明人等經潛心研究後,結果發現藉由使用具有特定最大吸收波長峰值之苯并三唑化合物,且使層合玻璃用中間膜具有特定之透射率特性,而可解決上述課題,從而完成以下之本發明。
即,本發明提供以下之[1]~[11]。
[1]一種層合玻璃用中間膜,其含有最大吸收波長峰值為370 nm以上且405 nm以下之苯并三唑系化合物,
將於黑面板(black panel)溫度83℃、槽內溫度50℃及槽內濕度50%RH下照射輻照度180 w/m2
之氙光1000小時後之於400 nm的透射率設為T1000
,將照射前之於400 nm的透射率設為T0
時,T1000
-T0
所表示之透射率差未達2.0%。
[2]如上述[1]所述之層合玻璃用中間膜,其中,該透射率差為-0.4%以上。
[3]如該[1]或[2]所述之層合玻璃用中間膜,其進而含有熱塑性樹脂。
[4]如該[1]至[3]中任一項所述之層合玻璃用中間膜,其含有選自由聚乙烯縮醛樹脂及乙烯-乙酸乙烯酯共聚物樹脂所組成之群中的至少1種。
[5]如該[1]至[4]中任一項所述之層合玻璃用中間膜,其含有聚乙烯縮醛樹脂與塑化劑。
[6]如該[1]至[5]中任一項所述之層合玻璃用中間膜,其進而含有最大吸收波長峰值為330 nm以上且未達370 nm之紫外線吸收劑。
[7]如該[1]至[6]中任一項所述之層合玻璃用中間膜,其中,該苯并三唑系化合物係以下之式(1)所表示之化合物,
(式(1)中,R10
為氫原子或亦可具有雜原子之碳數1~30之烴基,R11
~R15
分別獨立地為氫原子、羥基、磺酸基或亦可具有雜原子之碳數1~30之烴基;R11
~R15
之至少1者為羥基)。
[8]如該[1]至[7]中任一項所述之層合玻璃用中間膜,其中,該苯并三唑系化合物之含量為0.005~0.2質量%。
[9]如該[1]至[8]中任一項所述之層合玻璃用中間膜,其該照射前之於400 nm的透射率T0
為7.0%以下。
[10]一種層合玻璃,其具備:
2片玻璃板,與
配置於該等2片玻璃板之間的該[1]至[9]中任一項所述之層合玻璃用中間膜。
[11]如該[10]所述之層合玻璃,其不含調光體。
發明之效果
本發明中,可提供一種長期良好地維持400 nm附近之紫外線吸收性能的層合玻璃用中間膜。
[層合玻璃用中間膜]
以下,詳細說明本發明之層合玻璃用中間膜。
本發明之層合玻璃用中間膜含有最大吸收波長峰值為370 nm以上且405 nm以下之苯并三唑系化合物。本發明中,藉由含有此種苯并三唑系化合物,可使層合玻璃用中間膜於400 nm附近之紫外線吸收性能變得良好,並且可將下述透射率差調整至規定範圍。
(苯并三唑系化合物)
上述苯并三唑系化合物之最大吸收波長峰值為370 nm以上且405 nm以下,但若最大吸收波長峰值低於370 nm、高於405 nm,則難以使於400 nm附近之紫外線吸收性能變得良好,或者會使層合玻璃中間膜著色。最大吸收波長峰值較佳為373 nm以上,更佳為375 nm以上。又,較佳為400 nm以下,更佳為395 nm以下。
於本發明中,各種苯并三唑系化合物及紫外線吸收劑之最大吸收波長可藉由以下之方法進行測定。對氯仿100質量份混合要測定之化合物0.0002~0.002質量份,獲得氯仿溶液。將所獲得之氯仿溶液放入至光程長度1.0 cm之分光光度計用石英槽中。使用自記分光光度計(日立製作所公司製造之「U4100」)測定300~2500 nm透射率,求出極大吸收波長。該極大吸收波長係透射率顯示極小值之波長,有時存在多個,但於該情形時,最大吸收波長係指該極小值為最小之波長。
式(1)中,R10
為氫原子或亦可具有雜原子之碳數1~30的烴基,R11
~R15
分別獨立地為氫原子、羥基(-OH)、磺酸基(-SO3
H)或亦可具有雜原子之碳數1~30的烴基。R11
~R15
之至少1個為羥基。
此處,作為R10
中亦可具有雜原子之碳數1~30的烴基,可列舉:烷基、芳基、雜芳基、芳基烷基、雜芳基烷基、烯基及炔基。
又,作為R11
~R15
中亦可具有雜原子之碳數1~30之烴基,可列舉:烷基、芳基烷基、雜芳基烷基、環烷基、環雜烷基、烯基、芳基。
再者,作為雜原子,可列舉:氮原子、氧原子、硫原子、鹵素原子。作為烷基,可舉碳數1~25之烷基,可具有直鏈結構,亦可具有分支結構。又,環烷基為碳數1~25,可為由環狀烷基單獨構成者,亦可為組合環狀烷基與支鏈及直鏈之至少任一烷基而成者。環雜烷基係環烷基中之構成環之碳原子的至少1個被取代成雜原子者。又,烷基或環烷基之一部分氫原子亦可被鹵基等取代。烯基及炔基可具有直鏈結構,亦可具有分支結構。
作為芳基,可列舉:具有單環式或二環式、三環式等多環式芳香環之碳數6~30的芳基。雜芳基為單環式或二環式、三環式等多環式,構成環之原子的總數為5~30個。又,雜芳基可舉上述芳基之環之基本骨架中的至少1個碳原子被取代為雜原子者等。芳基及雜芳基的芳香環上之氫原子亦可被烷基、鹵基等取代。於二環式等多環式之情形時,所有的環可為芳香族,或一部分的環為芳香族。
芳基烷基係具有經由烷基鍵結之芳基-烷基之結構之基,亦稱為芳烷基。芳基烷基中之烷基及芳基均如上述。又,雜芳基烷基係具有經由烷基鍵結之雜芳基-烷基之結構之基。雜芳基烷基中之烷基及雜芳基均如上述。
式(2)中,較佳為R10
為烷基,且R12
及R14
分別獨立地選自芳基烷基(即,芳烷基)或烷基。其中,R10
更佳為碳數2~20之烷基,更佳為R12
及R14
分別獨立地為苯基烷基、烷基。R12
及R14
之烷基的碳數較佳為5~15。又,作為苯基烷基,較佳為碳數7~12。
作為R10
、R12
、及R14
之烷基,例如可列舉:甲基、乙基、異丙基、正丙基、異丁基、正丁基、戊基、己基、2-乙基己基、正辛基、1,1,3,3-四甲基丁基等。又,作為苯基烷基,可列舉:苄基、苯基乙基、苯基丙基、苯基丁基。再者,苯基丙基中亦包括1-甲基-1-苯基乙基等丙基部分具有分支結構者,又,苯基之鍵結位置亦可為任意位置。苯基乙基、苯基丁基等亦相同。
又,式(2)中,較佳為R12
為芳烷基,R14
為烷基。
作為此種苯并三唑化合物,具體而言,可列舉:6-丁基-2-[2-羥基-3-(1-甲基-1-苯基乙基)-5-(1,1,3,3-四甲基丁基)-苯基]-吡咯并(pyrrolo)[3,4-f][苯并三唑-5,7(2H,6H)-二酮]等。又,作為市售品,可列舉:TINUVIN CarboProtect(商品名,BASF公司製造)等。
層合玻璃用中間膜中之上述苯并三唑系化合物之含量以層合玻璃用中間膜總量基準計,較佳為0.005~0.2質量%。藉由將含量設為上述下限值以上,而使400 nm附近之紫外線吸收性能變得良好,且易於將下述透射率差調整至特定範圍。就使400 nm附近之紫外線吸收性能變得優異,且同時易於將透射率差調整至期望的範圍之觀點而言,上述含量更佳為0.01質量%以上,進而較佳為0.02質量%以上,進而更佳為0.04質量%以上。
又,三唑系化合物藉由將含量設為上述上限值以下,而發揮與含量匹配之性能,且亦防止層合玻璃用中間膜著色。就該等觀點而言,三唑系化合物之含量更佳為0.15質量%以下,進而較佳為0.1質量%以下,進而更佳為0.06質量%以下,特佳為0.042質量%以下。
(透射率特性)
關於本發明之層合玻璃用中間膜,將於以下之條件下照射氙光1000小時後之於400 nm的透射率設為T1000
,且將照射前之於400 nm的透射率設為T0
時,T1000
-T0
所表示之透射率差未達2.0%。
條件:於黑面板溫度83℃、槽內溫度50℃及槽內濕度50%RH下以輻照度180 w/m2
照射氙光。
再者,於透射率T0
、T1000
之測定中,以於將層合玻璃用中間膜夾持於2片透明玻璃板之間,且將該等透明玻璃板接著而製成層合玻璃之狀態下所測得之層合玻璃整體的透射率作為層合玻璃用中間膜之透射率。又,對層合玻璃照射氙光。作為透明玻璃板,使用依據JIS R 3202:2011之厚度2.5 mm之透明玻璃(可見光透射率90.4%)。此種透明玻璃由於透射率高,故而藉由確認上述層合玻璃之透射率及透射率差,可實質上確認層合玻璃中間膜之透射率及透射率差。再者,試驗方法之詳細內容如下述實施例所記載。
層合玻璃用中間膜若透射率差為2.0%以上,則由於長期用於窗玻璃等,故而會因陽光等之照射而劣化,因此長期使用後之於400 nm的透射率變高,變得難以長期良好地維持400 nm附近之紫外線吸收性能。
就使400 nm附近之紫外線吸收性能長期優異之觀點而言,上述透射率差較佳為1.85%以下,進而較佳為0.55%以下,更佳為0.1%以下。
又,透射率差較佳為0%或接近0%,較佳為-0.4%以上,更佳為-0.3%以上,進而較佳為-0.1%以上,特佳為-0.04%以上。
關於在400 nm的透射率T0
,就提高400 nm附近之紫外線吸收性能之觀點而言,較低者為佳,例如為7.0%以下,較佳為3%以下,更佳為1.5%以下,進而較佳為1%以下,特佳為0.75%以下。
又,在400 nm的透射率T0
例如為0.01%以上,較佳為0.1%以上,更佳為0.2%以上,進而較佳為0.4%以上。藉由將透射率T0
設為該等下限值以上,變得易於確保於可見光區域之透明性,防止層合玻璃用中間膜被著色。
又,層合玻璃用中間膜之可見光透射率較佳為70%以上。藉由將可見光透射率設為70%以上,即便用於汽車之前窗玻璃等各種窗玻璃,亦可防止視野被遮擋住。又,可見光透射率較佳為75%以上。再者,可見光透射率之上限並無特別限定,但例如為95%以下。
再者,可見光透射率係與透射率T0
、T1000
之測定同樣地,以於將層合玻璃用中間膜夾持於2片透明玻璃板之間,且將該等透明玻璃板接著而製成層合玻璃之狀態下所測得之層合玻璃之可見光透射率作為層合玻璃用中間膜之可見光透射率。再者,可見光透射率係依據JISR 3106(1998)進行測定。
(第2紫外線吸收劑)
本發明之層合玻璃用中間膜除最大吸收波長峰值為370 nm以上且405 nm以下之苯并三唑系化合物(以下,亦稱為「第1紫外線吸收劑」)以外,較佳還含有第2紫外線吸收劑。第2紫外線吸收劑係最大吸收波長峰值為330 nm以上且未達370 nm之紫外線吸收劑。
層合玻璃用中間膜除第1紫外線吸收劑以外,亦含有第2紫外線吸收劑,藉此使得紫外線吸收性能於寬廣之波長區域變得良好。又,變得易於將上述吸收率差調整至期望之範圍內。
第2紫外線吸收劑之最大吸收波長峰值較佳為340 nm以上且360 nm以下。
作為第2紫外線吸收劑之較佳具體例,可列舉:三口井系化合物、苯并三唑系化合物、二苯甲酮系化合物、鋅粒子等。更佳為苯并三唑系化合物。
用於第2紫外線吸收劑之苯并三唑系化合物具有與用於第1紫外線吸收劑之苯并三唑系化合物不同的結構,例如為以下之式(3)所示之化合物。
式(3)中,R21
表示氫原子、碳數為1~8之烷基或碳數4~20之烷氧基羰基烷基,R22
表示氫原子、或碳數為1~8之烷基。X為氯原子或氫原子。
式(3)中,R21
、R22
之烷基可為具有直鏈結構者,亦可為具有分支結構者。烷氧基羰基烷基可為具有直鏈結構者,亦可為具有分支結構者。作為R21
、R22
,例如可列舉:氫原子、甲基、乙基、正丙基、異丙基、正丁基、三級丁基、戊基、己基、辛基。R21
除該等以外,還可列舉:甲氧基羰基丙基、辛氧基羰基丙基等。其中,R21
較佳為氫原子或烷基,特佳為氫原子、甲基、三級丁基、戊基、辛基。R21
與R22
可相同,亦可不同。
又,作為式(3)所示之化合物的具體例,可列舉:2-(3-三級丁基-5-甲基-2-羥基苯基)-5-氯苯并三唑、2-(3,5-二-三級丁基-2-羥基苯基)-5-氯苯并三唑、3-[3-三級丁基-5-(5-氯-2H-苯并三唑-2-基)-4-羥基苯基]丙酸辛酯、3-(5-氯-2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羥基苯基丙酸甲酯、2-(3,5-二-第三戊基-2-羥基苯基)苯并三唑等。
進而,用於第2紫外線吸收劑之苯并三唑系化合物可使用市售品,例如可列舉:TINUVIN 326、TINUVIN 327(商品名,Ciba Specialty Chemicals Inc.製造)等。
又,作為三口井系化合物,可舉具有三口井骨架且用作紫外線吸收劑之公知化合物。作為三口井系化合物之具體例,可列舉:TINUVIN460、TINUVIN477(商品名,Ciba Specialty Chemicals Inc.製造)所代表之羥基苯基三口井系化合物等。
關於層合玻璃用中間膜中之第2紫外線吸收劑的含量,以層合玻璃用中間膜總量基準計,較佳為0.1~2質量%。藉由設為上述下限值以上,而於寬廣之波長區域易使紫外線吸收性能變得良好。進而,變得易於防止第1紫外線吸收劑之劣化,而易於減小吸收率差。就該等觀點而言,第2紫外線吸收劑之含量更佳為0.2質量%以上,進而較佳為0.5質量%以上。
又,第2紫外線吸收劑藉由設為上述上限值以下,而發揮與摻合量匹配之性能,進而,防止層合玻璃用中間膜著色。就該等觀點而言,上述含量較佳為1.5質量%以下,進而較佳為1.0質量%以下。
(第3紫外線吸收劑)
本發明之層合玻璃用中間膜除上述第1及第2紫外線吸收劑以外,亦可含有第3紫外線吸收劑。第3紫外線吸收劑之最大吸收波長峰值為370 nm以上且405 nm以下,但為苯并三唑系化合物以外之化合物。
作為第3紫外線吸收劑之較佳具體例,可列舉:吲哚系化合物、香豆素系化合物等。第3紫外線吸收劑之最大吸收波長峰值更佳為373 nm以上,進而較佳為375 nm以上。又,更佳為400 nm以下,進而較佳為395 nm以下。
本發明中,藉由使用第3紫外線吸收劑,變得易於提高400 nm附近之紫外線吸收性能。又,若第3紫外線吸收劑長期暴露於陽光下,則會產生劣化,紫外線吸收性能易降低,但藉由與上述第1紫外線吸收劑併用,而可抑制劣化,防止上述透射率差變大。
R23
及R24
之烷基分別可為具有直鏈結構者,亦可為具有分支結構者。作為上述式(4)中之R23
,例如可列舉:甲基、乙基、異丙基、正丙基等。其中,R23
較佳為甲基、乙基、異丙基,就耐光性之觀點而言,更佳為甲基或乙基。
式(4)中之R24
較佳為碳數為1~10之烷基,更佳為碳數為1~8之烷基。作為碳數為1~10之烷基,例如可列舉:甲基、乙基、異丙基、正丙基、異丁基、正丁基、戊基、己基、2-乙基己基、正辛基等。又,作為碳數為7~10之芳烷基,例如可列舉:苄基、苯基乙基、苯基丙基、苯基丁基等。
作為香豆素系化合物,可使用作為紫外線吸收劑使用之公知者,例如可列舉:Eusorb UV-1990(商品名.U-tec Chemical公司製造)等。
關於第3紫外線吸收劑之含量,以層合玻璃用中間膜總量基準計,較佳為0.001~0.2質量%。藉由設為上述下限值以上,而利用第3紫外線吸收劑可使400 nm附近之紫外線吸收性良好。就使400 nm附近之紫外線吸收性良好之觀點而言,第3紫外線吸收劑之含量更佳為0.005質量%以上,進而較佳為0.007質量%以上。
又,藉由設為上述上限值以下,易於發揮與含量匹配之性能。又,易於產生層合玻璃用中間膜著色,或者上述透射率差變大之不良情形。就該等觀點而言,第3紫外線吸收劑之含量較佳為0.1質量%以下,更佳為0.05質量%以下,進而較佳為0.03質量%以下。
(熱塑性樹脂)
層合玻璃用中間膜較佳含有熱塑性樹脂。層合玻璃用中間膜藉由含有熱塑性樹脂,變得易於達成作為接著層之功能,而與玻璃板等之接著性變得良好。
作為熱塑性樹脂,並無特別限定,例如可列舉:聚乙烯縮醛樹脂、乙烯-乙酸乙烯酯共聚物樹脂、離子聚合物樹脂、聚胺酯樹脂及熱塑性彈性體等。藉由使用該等樹脂,變得易於確保與玻璃板之接著性。於層合玻璃用中間膜中,熱塑性樹脂可單獨使用1種,亦可併用2種以上。該等中,較佳為選自聚乙烯縮醛樹脂及乙烯-乙酸乙烯酯共聚物樹脂之至少1種,特別是在與塑化劑併用之情形時,就對玻璃發揮優異之接著性之方面而言,更佳為聚乙烯縮醛樹脂。
(聚乙烯縮醛樹脂)
聚乙烯縮醛樹脂若為利用醛對聚乙烯醇進行縮醛化所獲得之聚乙烯縮醛樹脂,則無特別限定,但較佳為聚乙烯醇縮丁醛樹脂。
上述聚乙烯縮醛樹脂之縮醛化度的較佳下限為40莫耳%,較佳上限為85莫耳%,更佳下限為60莫耳%,更佳上限為75莫耳%。
上述聚乙烯縮醛樹脂之羥基量的較佳下限為15莫耳%,較佳上限為35莫耳%。藉由將羥基量設為15莫耳%以上,與玻璃板等之接著性易變得良好,而變得易於使層合玻璃之耐貫通性等良好。又,藉由將羥基量設為35莫耳%以下,而防止層合玻璃變得過硬。上述羥基量之更佳下限為25莫耳%,更佳上限為33莫耳%。
於使用聚乙烯醇縮丁醛樹脂作為聚乙烯縮醛樹脂之情形時,就相同之觀點而言,羥基量之較佳下限為15莫耳%,較佳上限為35莫耳%,更佳下限為25莫耳%,更佳上限為33莫耳%。
再者,上述縮醛化度及上述羥基量例如可藉由依據JIS K6728「聚乙烯醇縮丁醛試驗方法」之方法進行測定。
聚乙烯縮醛樹脂可藉由利用醛對聚乙烯醇進行縮醛化來製備。聚乙烯醇通常藉由使聚乙酸乙烯酯皂化而獲得,一般使用皂化度80~99.8莫耳%之聚乙烯醇。
聚乙烯縮醛樹脂之聚合度的較佳下限為500,較佳上限為4000。藉由將聚合度設為500以上,層合玻璃之耐貫通性變得良好。又,藉由將聚合度設為4000以下,而層合玻璃之成形變得容易。聚合度之更佳下限為1000,更佳上限為3600。
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。上述碳數為1~10之醛並無特別限定,例如可列舉: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、甲醛、乙醛、苯甲醛等。其中,較佳為正丁醛、正己醛、正戊醛,更佳為正丁醛。該等醛可單獨使用,亦可併用2種以上。
(乙烯-乙酸乙烯酯共聚物樹脂)
作為乙烯-乙酸乙烯酯共聚物樹脂,可為非交聯型之乙烯-乙酸乙烯酯共聚物樹脂,又,亦可為高溫交聯型之乙烯-乙酸乙烯酯共聚物樹脂。又,作為乙烯-乙酸乙烯酯共聚物樹脂,亦可使用如乙烯-乙酸乙烯酯共聚物皂化物、乙烯-乙酸乙烯酯之水解物等之乙烯-乙酸乙烯酯改質體樹脂。
乙烯-乙酸乙烯酯共聚物樹脂其依據JIS K 6730「乙烯-乙酸乙烯酯樹脂試驗方法」所測定之乙酸乙烯酯含量較佳為10~50質量%,更佳為20~40質量%。藉由將乙酸乙烯酯含量設為該等下限值以上,對於玻璃之接著性變高,又,層合玻璃之耐貫通性易於變良好。又,藉由將乙酸乙烯酯含量設為該等上限值以下,層合玻璃用中間膜之斷裂強度變高,層合玻璃之耐撞擊性變得良好。
(離子聚合物樹脂)
作為離子聚合物樹脂,並無特別限定,可使用各種離子聚合物樹脂。具體而言,可列舉:乙烯系離子聚合物、苯乙烯系離子聚合物、全氟碳系離子聚合物、遙爪離子聚合物、聚胺酯離子聚合物等。該等中,就層合玻璃之機械強度、耐久性、透明性等變得良好之方面、對於玻璃之接著性優異之方面而言,較佳為乙烯系離子聚合物。
作為乙烯系離子聚合物,乙烯-不飽和羧酸共聚物之離子聚合物由於透明性與強韌性優異,故適合使用。乙烯-不飽和羧酸共聚物係至少具有來自乙烯之結構單元及來自不飽和羧酸之結構單元的共聚物,亦可具有來自其他單體之結構單元。
作為不飽和羧酸,可列舉:丙烯酸、甲基丙烯酸、馬來酸等。較佳為丙烯酸、甲基丙烯酸,特佳為甲基丙烯酸。又,作為其他單體,可列舉:丙烯酸酯、甲基丙烯酸酯、1-丁烯等。
作為乙烯-不飽和羧酸共聚物,若將該共聚物所具有之全部結構單元設為100莫耳%,則較佳具有75~99莫耳%之來自乙烯的結構單元,較佳具有1~25莫耳%之來自不飽和羧酸的結構單元。
乙烯-不飽和羧酸共聚物之離子聚合物係藉由利用金屬離子使乙烯-不飽和羧酸共聚物所具有之羧基的至少一部分中和或交聯而獲得之離子聚合物樹脂,但該羧基之中和度通常為1~90%,較佳為5~85%。
作為離子聚合物樹脂中之離子源,可列舉:鋰、鈉、鉀、銣、銫等鹼金屬;鎂、鈣、鋅等多價金屬。較佳為鈉、鋅。
作為離子聚合物樹脂之製造方法,並無特別限定,可藉由以往公知之製造方法進行製造。例如於使用乙烯-不飽和羧酸共聚物之離子聚合物作為離子聚合物樹脂之情形時,例如於高溫、高壓下使乙烯與不飽和羧酸進行自由基共聚而製造乙烯-不飽和羧酸共聚物。然後,使該乙烯-不飽和羧酸共聚物與含有上述離子源之金屬化合物反應,藉此可製造乙烯-不飽和羧酸共聚物之離子聚合物。
(聚胺酯樹脂)
作為聚胺酯樹脂,可列舉:使異氰酸酯化合物與二醇化合物進行反應所獲得之聚胺酯;藉由使異氰酸酯化合物與二醇化合物、進而與聚胺等擴鏈劑反應所獲得之聚胺酯等。又,聚胺酯樹脂可為含有硫原子者。於該情形時,可將上述二醇之一部分或全部設為選自聚硫醇及含硫多元醇中者。聚胺酯樹脂可使與有機玻璃之接著性良好。因此,於玻璃板為有機玻璃之情形時可適合使用。
(熱塑性彈性體)
作為熱塑性彈性體,可列舉:苯乙烯系熱塑性彈性體、脂肪族聚烯烴。作為苯乙烯系熱塑性彈性體,並無特別限定,可使用公知者。苯乙烯系熱塑性彈性體,一般而言,具有成為硬鏈段之苯乙烯單體聚合物嵌段、及成為軟鏈段之共軛二烯化合物聚合物嵌段或其氫化嵌段。作為苯乙烯系熱塑性彈性體之具體例,可列舉:苯乙烯-異戊二烯二嵌段共聚物、苯乙烯-丁二烯二嵌段共聚物、苯乙烯-異戊二烯-苯乙烯三嵌段共聚物、苯乙烯-丁二烯/異戊二烯-苯乙烯三嵌段共聚物、苯乙烯-丁二烯-苯乙烯三嵌段共聚物以及其氫化物。
上述脂肪族聚烯烴可為飽和脂肪族聚烯烴,亦可為不飽和脂肪族聚烯烴。上述脂肪族聚烯烴可為以鏈狀烯烴作為單體之聚烯烴,亦可為以環狀烯烴作為單體之聚烯烴。就有效提高中間膜之保存穩定性及隔音性之觀點而言,上述脂肪族聚烯烴較佳為飽和脂肪族聚烯烴。
作為上述脂肪族聚烯烴之材料,可列舉:乙烯、丙烯、1-丁烯、反式-2-丁烯、順式-2-丁烯、1-戊烯、反式-2-戊烯、順式-2-戊烯、1-己烯、反式-2-己烯、順式-2-己烯、反式-3-己烯、順式-3-己烯、1-庚烯、反式-2-庚烯、順式-2-庚烯、反式-3-庚烯、順式-3-庚烯、1-辛烯、反式-2-辛烯、順式-2-辛烯、反式-3-辛烯、順式-3-辛烯、反式-4-辛烯、順式-4-辛烯、1-壬烯、反式-2-壬烯、順式-2-壬烯、反式-3-壬烯、順式-3-壬烯、反式-4-壬烯、順式-4-壬烯、1-癸烯、反式-2-癸烯、順式-2-癸烯、反式-3-癸烯、順式-3-癸烯、反式-4-癸烯、順式-4-癸烯、反式-5-癸烯、順式-5-癸烯、4-甲基-1-戊烯及乙烯基環己烷等。
(塑化劑)
層合玻璃用中間膜於含有熱塑性樹脂之情形時,亦可進而含有塑化劑。層合玻璃用中間膜藉由含有塑化劑而變得柔軟,其結果為,使層合玻璃變得柔軟。進而亦能夠發揮對於玻璃板之高接著性。於使用聚乙烯縮醛樹脂作為層合玻璃用中間膜之熱塑性樹脂之情形時,塑化劑若含於該層,則特別有效。
作為塑化劑,例如可列舉: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磷酸塑化劑等。其中,較佳為有機酯塑化劑。
有機酯塑化劑例如可列舉: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)、癸二酸二丁酯、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)、1,2-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-乙基庚酸酯)、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)、己二酸二己酯、己二酸二辛酯、己二酸己基環己酯、己二酸二異壬酯、己二酸庚酯壬酯、癸二酸二丁酯、油改質癸二酸醇酸酯、磷酸酯與己二酸酯之混合物、混合型己二酸酯等。作為混合型己二酸酯,可舉由選自碳數4~9之烷基醇及碳數4~9之環狀醇中的2種以上之醇所製作的己二酸酯。
上述塑化劑中,尤其適合使用三乙二醇二(2-乙基己酸酯)(3GO)。
於層合玻璃用中間膜中,塑化劑之含量並無特別限定,相對於熱塑性樹脂100質量份,較佳下限為30質量份,較佳上限為70質量份。若將塑化劑之含量設為30質量份以上,則層合玻璃適度變柔軟,而處理性等變得良好。又,若將塑化劑之含量設為70質量份以下,則防止塑化劑自層合玻璃用中間膜分離。塑化劑含量之更佳下限為35質量份,更佳上限為63質量份。
又,層合玻璃用中間膜於含有熱塑性樹脂之情形時,係熱塑性樹脂、或熱塑性樹脂及塑化劑成為主要成分者,熱塑性樹脂及塑化劑之總量以層合玻璃用中間膜總量基準計,通常為70質量%以上,較佳為80質量%以上,進而較佳為90質量%以上。
(其他添加劑)
層合玻璃中間膜亦可進而含有紅外線吸收劑。藉由含有紅外線吸收劑,可發揮高隔熱性。紅外線吸收劑若具有遮蔽紅外線之性能,則無特別限定,例如較佳為摻錫氧化銦粒子。
又,層合玻璃用中間膜進而視需要,亦可含有抗氧化劑、光穩定劑、接著力調整劑、顏料、染料、螢光增白劑、結晶成核劑等添加劑。
抗氧化劑並無特別限定,例如可列舉:2,2-雙[[[3-(3,5-二-三級丁基-4-羥基苯基)丙醯基]氧基]甲基]丙烷-1,3-二醇、1,3-雙[3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯]、4,4'-硫代雙(6-三級丁基-3-甲基苯酚)、4,4'-二甲基-6,6'-二(三級丁基)[2,2'-亞甲基雙(苯酚)]、2,6-二-三級丁基-對甲酚、4,4'-亞丁基雙-(6-三級丁基-3-甲基苯酚)等。
又,作為結晶成核劑,並無特別限定,例如可列舉:二亞苄基山梨糖醇、二亞苄基木糖醇、二亞苄基半乳糖醇、二亞苄基甘露醇、杯芳烴。結晶成核劑當使用乙烯-乙酸乙烯酯共聚物樹脂作為熱塑性樹脂之情形時,適合使用。
作為接著力調整劑,例如使用各種鎂鹽或鉀鹽等。
層合玻璃用中間膜之厚度較佳為0.1~3 mm。藉由將層合玻璃用中間膜之厚度設為0.1 mm以上,可發揮充分之紫外線吸收性能。又,層合玻璃之耐貫通性亦良好。又,藉由將層合玻璃用中間膜之厚度設為3 mm以下,防止層合玻璃用中間膜之透明性降低。層合玻璃用中間膜之厚度之更佳下限為0.25 mm,更佳上限為2 mm。
層合玻璃中間膜例如只要混練熱塑性樹脂、苯并三唑化合物等構成中間膜之材料,並將所獲得之組成物進行擠壓成形、加壓成形等來進行成形即可。此時,於使用塑化劑之情形時,亦可使苯并三唑化合物等紫外線吸收劑溶解於塑化劑而獲得該等混合物,將該混合物與聚乙烯縮醛樹脂等熱塑性樹脂進行混練而製作組成物。
[層合玻璃]
本發明之層合玻璃,具備2片玻璃板與配置於2片玻璃板之間的上述層合玻璃用中間膜。
於層合玻璃中,2片玻璃板之間的層可由1層樹脂層構成,亦可為2層以上之樹脂層積層而成的積層結構。於由1層樹脂層構成之情形時,該1層樹脂層為上述層合玻璃用中間膜。
於由2層以上之樹脂層構成之積層結構的情形時,至少1層樹脂層為上述層合玻璃用中間膜即可,亦可含有除上述層合玻璃用中間膜以外之樹脂層。
作為除上述層合玻璃用中間膜以外之樹脂層,除不含最大吸收波長峰值為370 nm以上且405 nm以下之苯并三唑系化合物以外,可具有與上述層合玻璃用中間膜相同之構成。即,此種樹脂層較佳使用熱塑性樹脂作為樹脂,作為熱塑性樹脂之具體例,可舉上述各種熱塑性樹脂,詳細內容如上述。又,除熱塑性樹脂以外亦可含有塑化劑,又,亦可含有其他添加劑。進而,亦可含有第2紫外線吸收劑等。塑化劑及其他添加劑之詳細內容如上述,故而省略其說明。
(玻璃板)
作為層合玻璃所使用之玻璃板,可為無機玻璃、有機玻璃之任一者,但較佳為無機玻璃。作為無機玻璃,並無特別限定,但可列舉:透明玻璃、浮法平板玻璃、研磨平板玻璃、壓花玻璃、嵌網板玻璃(meshed plate glass)、嵌線板玻璃(wired plate glass)、綠玻璃(green glass)等。
又,作為有機玻璃,一般而言使用稱為樹脂玻璃者,並無特別限定,但可舉由聚碳酸酯、丙烯酸樹脂、丙烯酸共聚物樹脂、聚酯等樹脂所構成之有機玻璃。
2片玻璃板相互可由同類材質構成,亦可由不同材質構成。例如,一者可為無機玻璃,而另一者為有機玻璃,但較佳為2片玻璃板兩者皆為無機玻璃,或皆為有機玻璃。
又,各玻璃板之厚度並無特別限定,但例如為0.1~15 mm左右,較佳為0.5~5 mm。各玻璃板之厚度相互可相同,亦可不同,但較佳為相同。
層合玻璃只要以如下方式進行製造即可:於2片玻璃板之間配置上述層合玻璃用中間膜及視需要所使用之樹脂層,對該等進行壓接等,藉此進行一體化。
本發明之層合玻璃典型而言不含調光體。層合玻璃只要於2片玻璃板之間不含調光體即可。所謂調光體,係指藉由賦予光能、電能、熱能等各種能量,而於特定波長下之透射率等光學特性產生變化之片狀或層狀構件,較佳為藉由賦予電能而使光學特性產生變化者。例如,調光體含有液晶層及電致變色層之任一者。
(液晶層)
液晶層係含有液晶之層,例如可舉藉由間隔件等形成用以將液晶填充至內部之空間,於該空間內填充液晶並進行密封而成者。作為液晶,可為任何方式者,可為TN型,亦可為STN型。又,液晶層可藉由聚合物分散型液晶(PDLC)而構成。作為聚合物分散型液晶,可舉稱為網狀液晶者,其係於液晶層中藉由聚合物而形成有網狀結構。又,可為將液晶微膠囊化並使之分散於黏合劑樹脂中而成之微膠囊型液晶(PDMLC)。作為PDMLC所使用之黏合劑樹脂,可列舉:聚乙烯醇縮丁醛樹脂等聚乙烯縮醛樹脂。
調光體例如具有一對透明電極,且藉由在透明電極間配置液晶層而構成液晶單元。又,根據液晶之種類,亦可於電極與液晶層之間設置配向膜等。但於PDLC、PDMLC等中不需要配向膜。關於液晶層,若對透明電極間施加電壓,則液晶於一方向上配向,而於調光體之厚度方向上透過光。因此,當調光體具有液晶層之情形時,調光體及具有該調光體之層合玻璃於經施加電壓時,光透射率變高而變得透明。另一方面,若不施加電壓,則調光體及具有該調光體之層合玻璃之光透射率變低,例如變得不透明。
(電致變色層)
電致變色層係由電致變色材料構成之層。作為電致變色材料,若為具有電致變色性之化合物,則無限定,可為無機化合物、有機化合物、混合原子價錯合物之任一者。
作為無機化合物,例如可列舉:MO2
O3
、Ir2
O3
、NiO、V2
O5
、WO3
、TiO2
等。作為有機化合物,例如可列舉:聚吡咯化合物、聚噻吩化合物、聚對伸苯基伸乙烯基(polyparaphenylene vinylene)化合物、聚苯胺化合物、聚乙炔化合物、聚乙烯二氧噻吩(polyethylene dioxythiophene)化合物、金屬酞青化合物、紫羅鹼(viologen)化合物、紫羅鹼鹽化合物、二茂鐵化合物、對苯二甲酸二甲酯化合物、對苯二甲酸二乙酯化合物等。其中,較佳為聚乙炔化合物。又,作為混合原子價錯合物,例如可列舉:普魯士藍型錯合物(KFe[Fe(CN)6
]等)。
電致變色層可藉由公知之方法來成膜,亦可藉由濺鍍來成膜,亦可藉由塗佈電致變色材料經稀釋而成之溶液來成膜。
調光體於具有電致變色層之情形時,亦可具有一對透明電極,並於該透明電極間配置電致變色層。電致變色層藉由對透明電極間施加電壓,例如特定波長區域之透射率產生變化,由此調光體自透明變得不透明,或者照射可見光時之色調產生變化。因此,例如能夠實現於不施加電壓時成為無色透明,另一方面於施加了電壓時具有藍色、黃色、綠色、紅色等色調。
於透明電極與電致變色層之間亦可設置電解質層等來與電致變色層併用之各種層。電解質層視需要亦可含有具有熱致變色性之物質等,該熱致變色性係因熱而使得特定區域之透射率產生變化之性質。調光體藉由含有具有熱致變色性之物質,而可利用加熱、冷卻來改變特定波長區域之透射率。
調光體一般而言,係具有由樹脂膜等所構成之一對基材,且於該一對基材之間配置有一對透明電極及電致變色層或液晶層者。又,調光體亦可為省略一樹脂膜,於玻璃板上直接設置有一透明電極者。
調光體於如上述般施加電壓等來賦予能量,或未賦予能量時,透射率變高而變得透明。如此於透射率變高時之可見光線透射率成為70%以上,有時成為80%以上,有時亦成為90%以上。可見光線透射率可依據JIS R3106(1998)並使用分光光度計進行測定。
本發明之層合玻璃可用於各種領域,但較佳用於汽車、電車等車輛、船舶、飛機等各種交通工具,或者大廈、公寓、獨棟建築、會館、體育館等各種建築物等之窗玻璃。又,窗玻璃較佳配置於陽光入射之位置。本發明之層合玻璃由於層合玻璃用中間膜具有上述規定之透射率特性,故而即便長期用作陽光入射之窗玻璃,亦可長期良好地維持400 nm附近之紫外線吸收性能。
實施例
藉由實施例而進一步詳細地說明本發明,但本發明不受該等之例的任何限定。
[透射率特性之測定]
(層合玻璃之製作)
將各實施例、比較例中所得之層合玻璃用中間膜於23℃、28%RH之恆溫恆濕條件下保持4小時後,夾持於2片透明玻璃(縱50 mm×橫65 mm×厚度2.5 mm,可見光透射率90.4%,依據JIS R 3202:2011)之間而製成積層體。使用230℃之加熱輥暫時壓接所獲得之積層體。使用高壓釜於135℃、壓力1.2 MPa之條件下將經暫時壓接之層合玻璃壓接20分鐘,製作層合玻璃。
(透射率T0
之測定)
依據JIS R 3106(1998)並使用分光光度計(日立製作所股份有限公司製造之「U-4000」)測定上述中所得之層合玻璃於400 nm的光線透射率(%),設為層合玻璃用中間膜於400 nm的透射率T0
。
(透射率T1000
之測定)
於氙照射機(須賀試驗機股份有限公司製造之「SX75」)中,於黑面板溫度83℃、槽內溫度50℃及槽內濕度50%RH之條件下,對上述中所得之層合玻璃照射輻照度180 w/m2
(輻照度測定波長為300~400 nm)之氙光1000小時。此時,內部濾波器係使用石英,且外部濾波器係使用石英:#275(截止275 nm)。然後,利用與透射率T0
之測定相同之方法測定層合玻璃用中間膜於400 nm的透射率T1000
。根據所獲得之透射率T0
、T1000
算出透射率差(T1000
-T0
)。
(層合玻璃中間膜之判定)
根據上述中所獲得之透射率差(T1000
-T0
)並以下述評價基準來進行評價。
A:透射率差為0.55%以下且為-0.4%以上
B:透射率差大於0.55%且未達2.0%
C:透射率差為0.55%以下但未達-0.4%
D:透射率差為2.0%以上
(可見光透射率)
依據JIS R 3106(1998)測定上述中所得之層合玻璃之可見光透射率,將所獲得之值作為層合玻璃用中間膜之可見光透射率。
(YI值)
對於上述中所得之層合玻璃,以與測定透射率T0
時相同之方式測定初始之層合玻璃之YI值。
關於層合玻璃之YI值,使用分光光度計(日立高新技術公司製造之「U-4100」)並依據JIS K7103,藉由透過法測定標準光C之X、Y、Z,藉此求出YI值。YI值係藉由絕對值來表示。
[實施例1~5、比較例1~8]
以層合玻璃用中間膜中之各成分之含量成為表1所示之摻合的方式混合各成分,藉由雙軸各向異性擠壓機對所獲得之混合物進行擠壓成形,製作膜厚760 μm之層合玻璃用中間膜。再者,於實施例1、3~5、比較例1~8中,混合各化合物時,進而將作為接著力調整劑之有機酸鎂水溶液以層合玻璃用中間膜中之Mg濃度成為65 ppm之方式進行添加。再者,鹼金屬、鹼土類金屬、K、Mg等之含量可藉由ICP發光分析裝置(島津製作所製造之「ICPE-9000」)進行測定。
※表1、2所示之各成分係如下所述。
(1)熱塑性樹脂
聚乙烯醇縮丁醛樹脂(PVB):縮醛化度69莫耳%、羥基量30莫耳%、乙醯化度1莫耳%、聚合度1700
乙烯-乙酸乙烯酯共聚物樹脂(EVA):乙酸乙烯酯含量28質量%
(2)第1紫外線吸收劑(UVA1)
苯并三唑系化合物、TINUVIN CarboProtect(商品名,BASF公司製造)、化合物名「6-丁基-2-[2-羥基-3-(1-甲基-1-苯基乙基)-5-(1,1,3,3-四甲基丁基)-苯基]-吡咯并[3,4-f][苯并三唑-5,7(2H,6H)-二酮]」、最大吸收波長峰值375 nm(表中簡稱為CarboProtect)
(3)第2紫外線吸收劑(UVA2)
苯并三唑系化合物,商品名:Tinuvin326,Ciba Specialty Chemicals Inc.製造,最大吸收波長峰值353 nm(表中簡稱為T326)
(4)第3紫外線吸收劑(UVA3)
香豆素系化合物:Eusorb UV-1990(商品名,U-tec Chemical公司製造),最大吸收波長峰值384 nm
吲哚系化合物:藉由以下之製造方法所製造之吲哚系化合物
於甲醇120 ml中添加1-甲基-2-苯基-1H-吲哚-2-甲醛(carboaldehyde)23.5 g(0.10 mol)及氰基乙酸甲酯11.9 g(0.12 mol)。其次,添加哌啶2.5 g(0.03 mol),於回流下反應6小時,冷卻至室溫後,獲得所析出之結晶。利用少量之醇將所獲得之結晶洗淨後,進行乾燥,獲得上述式(4)中R23
為甲基(CH3
)且R24
為甲基(CH3
)之吲哚系化合物A之淡黃色結晶30.9 g。再者,所獲得之吲哚化合物之熔點為193.7℃,最大吸收波長峰值為391 nm。
使用乙醇代替甲醇,使用氰基乙酸乙酯(0.12 mol)代替氰基乙酸甲酯,使用1-乙基-2-苯基-1H-吲哚-3-甲醛(0.10 mol)代替1-甲基-2-苯基-1H-吲哚-3-甲醛。除此以外,藉由與上述吲哚化合物A之製備方法相同之方法獲得上述通式(4)中R23
為乙基(C2
H5
)且R24
為乙基(C2
H5
)之吲哚化合物B之淡黃色結晶30.8 g。
使用乙醇代替甲醇,使用氰基乙酸乙酯(0.12 mol)代替氰基乙酸甲酯。除此以外,藉由與上述吲哚化合物A之製備方法相同之方法獲得上述通式(4)中R23
為乙基(C2
H5
)且R24
為甲基(CH3
)之吲哚化合物C之淡黃色結晶28.9 g。再者,所獲得之吲哚化合物C之熔點為145℃。
使用1-丁基-2-苯基-1H-吲哚-3-甲醛(0.10 mol)代替1-甲基-2-苯基-1H-吲哚-3-甲醛。除此以外,藉由與上述吲哚化合物A之製備方法相同之方法獲得上述通式(4)中R23
為甲基(CH3
)且R24
為丁基(C4
H9
)之吲哚化合物D之淡黃色結晶33.7g。
(5)塑化劑
三乙二醇二(2-乙基己酸酯)(3GO)
(6)其他添加劑
抗氧化劑1:2,6-二三級丁基對甲苯酚(BHT)
抗氧化劑2:IRGANOX1010(商品名),BASF公司製造
結晶成核劑:二亞苄基山梨糖醇
實施例1~5中,藉由摻合最大吸收波長峰值為370 nm以上且405 nm以下之苯并三唑系化合物,且將透射率差設為特定範圍內,可長期使400 nm附近之紫外線吸收性能良好。相對於此,於各比較例中,雖使用1種或2種紫外線吸收劑,但均非最大吸收波長峰值為370 nm以上且405 nm以下之苯并三唑系化合物,因此無法長期使400 nm附近之紫外線吸收性能良好。
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Claims (10)
- 一種層合玻璃用中間膜,其含有最大吸收波長峰值為370nm以上且405nm以下之苯并三唑系化合物及最大吸收波長峰值為330nm以上且未達370nm之第2紫外線吸收劑,將於黑面板(black panel)溫度83℃、槽內溫度50℃及槽內濕度50%RH下照射輻照度180w/m2之氙光1000小時後之於400nm的透射率設為T1000,將照射前之於400nm的透射率設為T0時,T1000-T0所表示之透射率差未達2.0%。
- 如請求項1所述之層合玻璃用中間膜,其中,該透射率差為-0.4%以上。
- 如請求項1或2所述之層合玻璃用中間膜,其進而含有熱塑性樹脂。
- 如請求項1或2所述之層合玻璃用中間膜,其含有選自由聚乙烯縮醛樹脂及乙烯-乙酸乙烯酯共聚物樹脂所組成之群中的至少1種。
- 如請求項1或2所述之層合玻璃用中間膜,其含有聚乙烯縮醛樹脂與塑化劑。
- 如請求項1或2所述之層合玻璃用中間膜,其中,該苯并三唑系化合物之含量為0.005~0.2質量%。
- 如請求項1或2所述之層合玻璃用中間膜,其該照射前之於400nm的透射率T0為7.0%以下。
- 一種層合玻璃,其具備:2片玻璃板,與配置於該等2片玻璃板之間的請求項1至8中任一項所述之層合玻璃用中間膜。
- 如請求項9所述之層合玻璃,其不含調光體。
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| JP5913102B2 (ja) | 2010-08-20 | 2016-04-27 | 積水化学工業株式会社 | 合わせガラス用中間膜及び合わせガラス |
| EP2422614A1 (de) | 2010-08-26 | 2012-02-29 | Kuraray Europe GmbH | Weichmacherhaltige Folien auf Basis von Polyvinylacetal mit selektiver Durchlässigkeit für UV-Strahlung |
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| CN106574027B (zh) * | 2014-08-12 | 2020-05-22 | 横滨橡胶株式会社 | 紫外线硬化性树脂组合物及利用其的叠层体 |
| EP3260891B1 (en) | 2015-02-02 | 2023-11-29 | Mitsui Chemicals, Inc. | Polymerizable composition for optical material, optical material, and application for same |
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| CN111201457A (zh) * | 2017-09-29 | 2020-05-26 | 积水化学工业株式会社 | 玻璃结构体 |
| KR102790175B1 (ko) * | 2018-02-27 | 2025-04-03 | 세키스이가가쿠 고교가부시키가이샤 | 접합 유리용 중간막, 및 접합 유리 |
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| CN116082989A (zh) | 2023-05-09 |
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| US20200391487A1 (en) | 2020-12-17 |
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| CN111757860A (zh) | 2020-10-09 |
| JP7286537B2 (ja) | 2023-06-05 |
| KR20200128003A (ko) | 2020-11-11 |
| MX2020008841A (es) | 2020-10-05 |
| EP3760600A1 (en) | 2021-01-06 |
| JP2023113729A (ja) | 2023-08-16 |
| US11440296B2 (en) | 2022-09-13 |
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