TWI419856B - 具有降低透氣性密封組成物的絕緣玻璃單元 - Google Patents
具有降低透氣性密封組成物的絕緣玻璃單元 Download PDFInfo
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- TWI419856B TWI419856B TW96103415A TW96103415A TWI419856B TW I419856 B TWI419856 B TW I419856B TW 96103415 A TW96103415 A TW 96103415A TW 96103415 A TW96103415 A TW 96103415A TW I419856 B TWI419856 B TW I419856B
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- glass unit
- insulating glass
- group
- density polyethylene
- thiolated
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Description
本發明大致有關熱絕緣結構,更明確地係有關高度熱效率並以具有降低對於氣體或氣體混合物透氣性之室溫固化組成物密封的絕緣玻璃單元結構。
已詳知室溫固化(RTC)組成物作為密封劑之用途。製造絕緣玻璃單元(IGU)時,將玻璃板彼此平行放置,並密封其周圍,如此完全封閉該等玻璃板間之空隙,或該內部空間。該內部空間通常填充空氣。候該內部空間中空氣絕緣層的隔絕作用之故,與單一玻璃板相較,經由此種代表性構造之絕緣玻璃單元傳送的能量減少。可藉由增加該等基材間之間隔以增加空氣的絕緣層,進一步降低能量傳送。超過該最大間隔的限制後,該玻璃板內的空氣對流會提高能量傳送。可藉由後額外內部空間該能量傳送與封閉玻璃板形式之更多層進一步降低該能量傳送。例如,以兩個內部空間並密封其周圍將三片平行分開之玻璃板隔開。以此種方式,使該玻璃板的間隔保持低於空隙中因對流效果所造成的最大限制,但可進一步降低整體能量傳送。若需要進一步降低能量傳送,則可添加額外內部空間。
另外,以密度更高之低傳導性氣體取代密封玻璃單元窗中之空氣,可以降低密封玻璃單元的能量傳送。適用的
氣體應為無色、無毒、非腐蝕性、不可燃、曝露於紫外線下不受影響、密度比空氣高而且傳導性低於空氣。氬、氪、氙與六氟化硫係常用以取代絕緣玻璃窗中之空氣以降低能量傳送的氣體實例。目前用於製造絕緣玻璃單元的各種密封劑種類包括固化與非固化系統。常用者有液態多硫化物、聚胺基甲酸酯類與存在固化系統中之聚矽氧,不過以熱熔融密封劑為基底之聚丁烯-聚異戊二烯共聚物橡膠亦為常用非固化系統。
液態多硫化物類與聚胺基甲酸酯類通常係雙組份系統,其包括一基質與一固化劑,然後於塗覆於玻璃之前才將之混合。聚矽氧類可為一種組份以及又組份系統。在該絕緣玻璃單元可進到次一製造階段之前,雙組份系統需要三組混合比、兩部分之混合設備與該絕緣玻璃單元前的固化時間。
不過,現有的RTC聚矽氧密封劑組成物雖然有某種程度效果,但對於避免例如氬等低熱傳導氣體自IGU內部空間流失的能力有限。此種透氣性的結果係介於玻璃板間之氣體所維持之降低能量傳送會隨著時間喪失。
因此,需要一種具有透氣性比習知RTC組成物低之RTC組成物的IGU。當使用該密封劑作為IGU時,降低透氣性的RTC組成物可比透氣性較佳之RTC組成物的IGU玻璃板內絕緣氣體保留更長時間,因此使該IGU的絕緣性質時間延長。
本發明有關提高熱絕緣安定性之絕緣玻璃單元。更明確地說,本發明有關一種絕緣玻璃單元,其包含至少兩片彼此呈分隔關係之分開之玻璃片(玻璃板)或其他功能相同的材料,置於其間的低導熱性氣體,以及一氣體密封元件,此氣體密封元件包括由含有濕份可固化之矽基化樹脂的組成物固化所形成之固化密封組成物,該含有濕份可固化之矽基化樹脂的組成物包括:a)濕份可固化之矽基化樹脂,其於固化時提供顯示透氣性之固化樹脂;及b)至少一種透氣性低於固化樹脂(a)之其他聚合物,以及c)視情況需要之至少一種額外組份,其係選自觸媒、填料、UV安定劑、抗氧化劑、黏著促進劑、固化加速劑、搖變劑、去濕劑、顏料、染料、界面活性劑、溶劑與殺生物劑。
當前述固化密封組成物作為IGU氣體密封劑之組份時,其減少氣體自該IGU流失,因此延長IGU的使用期限。
本發明提出一種絕緣玻璃單元,其包括至少兩片彼此呈分隔關係之分開之玻璃片,置於其間之低導熱性氣體,以及一氣體密封元件,該氣體密封元件包括一經固化
(即,交聯或硫化)之密封組成物,此固化之密封組成物是由包含下列成分之含有濕份可固化之矽基化樹脂的組成物固化所形成:a)濕份可固化之矽基化樹脂,其於固化時提供顯示透氣性之固化樹脂;以及b)至少一種透氣性低於固化樹脂(a)之其他聚合物,以及視情況需要之c)至少一種額外組份,其係選自填料、黏著促進劑、觸媒、界面活性劑、UV安定劑、抗氧化劑、固化加速劑、搖變劑、去濕劑、顏料、染料、溶劑與殺生物劑。
參考圖1,具有習知且習用構造之絕緣玻璃單元10包括玻璃片1與2,其係藉由具有主要氣體密封構件4、連續間隔件5與低透氣性密封組成物7(其製備方式容後說明)之氣體密封元件保持分隔狀態,玻璃片1與2之間的空間6係填充一或更多種絕緣氣體,諸如氬。如本技術所習知,將玻璃壓條8置於玻璃片1與2及窗框9之間。玻璃片1與2可由各種材料任一者製造,諸如玻璃,例如透明浮法玻璃、退火玻璃、回火玻璃、太陽能玻璃、有色玻璃,例如低能量玻璃等、丙烯酸樹脂與聚碳酸酯樹脂等。
在前述氣體密封元件中包含固化密封劑組成物7提供比習知且習用氣體密封劑有所改良之氣體阻隔特徵與濕氣滲漏特徵。因此,固化密封組成物7對於所有構造(包括前文特別描述者)之絕緣玻璃單元提供更長使用期限性能。
該絕緣玻璃單元的主要密封構件4可由本技術中習知之聚合材料組成,例如橡膠為底質材料,諸如聚異丁烯、
丁基橡膠、多硫化物、EPDM橡膠、腈橡膠等等。其他適用材料包括聚異丁烯/聚異戊二烯共聚物、聚異丁烯聚合物、溴化烯烴聚合物、聚異丁烯與對甲基苯乙烯之共聚物、聚異丁烯與溴化對-甲基苯乙烯之共聚物、丁基橡膠-異丁烯與異戊二烯之共聚物、乙烯-丙烯聚合物、多硫化物聚合物、聚胺基甲酸酯聚合物、苯乙烯丁二烯聚合物等等。
如上述,主要氣體密封構件4可由諸如聚異丁烯等具有極良好密封性質之材料製造。玻璃壓條8係有時稱為玻璃墊料,而且可以聚矽氧或丁基橡膠形式提供。連續間隔件5中可包含乾燥器以去除該等玻璃板1與2之間絕緣氣體所佔據空間的濕氣。適用的乾燥劑不會吸收填充在該絕緣玻璃單元內部之一或更多種絕緣氣體之乾燥劑。
適用於該絕緣玻璃單元之低熱傳導氣體及此等氣體混合物已為人詳知,而且包括諸如空氣、二氧化碳、六氟化硫、氮、氬、氪、氙等及其混合物之透明氣體。
可用於本發明之濕份可固化之矽基化樹脂(a)係習知材料,而且通常可藉由(i)反應異氰酸酯末端聚胺基甲酸酯(PUR)預聚合物與一種適用矽烷,例如兼具可溶解官能基(諸如烷氧基等)與活性含氫官能基(諸如硫醇、一級與二級胺,較佳係後者等)之矽烷而製得;或藉由(ii)反應羥基末端PUR預聚合物與一適用異氰酸酯末端矽烷,例如具有一係三個烷氧基之矽烷而製得。此等反應之細節以及其中所使用異氰酸酯末端與羥基末端PUR
預聚合物之製備細節可參考美國專利第4,985,491、5,919,888、6,207,794、6,303,731、6,359,101與6,515,164號;以及早期公開美國專利申請案第2004/0122253與2005/0020706號(異氰酸酯末端PUR預聚合物);美國專利第3,786,081與4,481,367號(羥基末端PUR預聚合物);美國專利第3,627,722、3,632,557、3,971,751、5,623,044,5,852,137,6,197,912與6,310,170號(由異氰酸酯末端PUR預聚合物與反應性矽烷(例如胺基烷氧基矽烷)反應製得之濕份可固化之SPUR);以及美國專利第4,345,053,4,625,012、6,833,423號與早期公開美國專利申請案2002/0198352(由羥基末端PUR預聚合物與異氰酸基矽烷反應製得之濕份可固化之SPUR)。前述美國專利文件全文內容係以提及的方式併入本文中。
本發明之濕份可固化之矽基化樹脂(a)亦可藉由(iii)直接反應異氰酸基矽烷與多元醇而製得。
該異氰酸酯末端PUR預聚合物係藉由反應一或更多種多元醇,較佳係二醇,與一或更多種聚異氰酸酯類,較佳係二異氰酸酯類而製得,其比例係使所形成之預聚合物益異氰酸酯為末端。在反應一種二醇與一種二異氰酸酯的實例中,可使用莫耳過量二異氰酸酯。
包括在可用於製備該異氰酸酯末端PUR預聚合物的多元醇內之多元醇係聚醚多元醇類、聚酯多元醇類,諸如羥基末端聚己內酯、聚醚酯多元醇類,諸如自聚醚多元醇與e-己內酯反應製得者、聚酯醚多元醇類,諸如由羥基末端聚己內酯與一或更多種環氧烷類,諸如環氧乙烷與環氧丙烷反應製得者、羥基末端聚丁二烯類等等。
特定之適用多元醇類包括聚醚二醇類,特別是聚(氧伸乙)二醇、聚(氧伸丙)二醇與聚(氧伸乙-氧伸丙)二醇、聚氧伸烷三醇、聚伸丁二醇類、聚縮醛、多羥基聚丙烯酸酯類、多羥基聚酯醯胺類與多羥基聚硫醚類、聚己內酯二醇類與三醇類等等。本發明一具體實例中,用於製造該異氰酸酯末端PUR預聚合物之多元醇類係當量介於約500與25,000之聚(氧伸乙)二醇。在本發明另一具體實例中,用於製造該異氰酸酯末端PUR預聚合物之多元醇類係當量介於約1,000至20,000之聚(氧伸丙)二醇。亦可使用具有各種結構、分子量及/或官能度之多元醇類混合物。
該聚醚多元醇類可具有至高達約8但較佳係自約2至4,且更佳係2之官能度(即,二醇類)。特別適用者係於存在雙金屬氰化物(DMC)觸媒、鹼金屬氫氧化物觸媒或鹼土金屬烷氧化物觸媒之下製備之聚醚多元醇類;詳見系統美國專利第3,829,505、3,941,849、4,242,490、4,335,188、4,687,851、4,985,491、5,096,993、5,100,997、5,106,874、5,116,931、5,136,010、5,185,420
與5,266,681號,該等案件全文係以提及的方式併入本文中。於存在此等觸媒下製得之聚醚多元醇類容易具有高分子量與低飽和度,一般認為其性質係本發明反光物件性能改變的原因。該聚醚多元醇類較佳係數量平均分子量自約1,000至約25,000,更佳係自約2,000至約20,000,更佳係自約4,000至約18,000。該聚醚多元醇類較佳係端基不飽和水準不大於每克多元醇約0.04。更佳情況係,該聚醚多元醇的端基不飽和度不大於每克多元醇約0.02毫當量。適於製造該異氰酸酯末端PUR預聚合物之市售二醇類包括ARCOL R-1819(數量平均分子量為8,000)、E-2204(數量平均分子量為4,000)以及ARCOL E-2211(數量平均分子量為11,000)。
可使用許多聚異氰酸酯類其中任一者(較佳係二異氰酸酯類及其混合物)以提供該異氰酸酯末端PUR預聚合物。在一具體實例中,該聚異氰酸酯可為二苯基甲烷二異氰酸酯(”MDI“)、聚亞甲基聚異氰酸酯(”PMDI“)、對伸苯基二異氰酸酯、伸萘基二異氰酸酯、經液態碳二醯亞胺改良MDI及其衍生物、異佛爾酮二異氰酸酯、二環己基甲烷-4,4’-二異氰酸酯、甲苯二異氰酸酯(”TDI“),特別是2,6-TDI異構物以及各種其他本技術中已充分確認之脂族與芳族聚異氰酸酯類與其組合物。
用於與上述異氰酸酯末端PUR預聚合物反應之矽基化反應物必須包含可與異氰酸根反應之官能基與至少一個容易水解然後交聯之基團,例如烷氧基。特別適用之矽基
化反應物係胺基矽烷類,尤其是具有以下通式者:
其中,R1
係氫、至高達8個碳原子之烷基或環己基,或至高達8個碳原子之芳基,R2
係至高達12個碳原子之烯基,視情況需要包含一或更多種雜原子,各個R3
係相同或不同之至高達8個碳原子的烷基或芳基,各個R4
係相同或不同之至高達6個碳原子的烷基或芳基,而x係0、1或2。在一具體實例中,R1
係氫或甲基、乙基、丙基、異丙基、正丁基、第三丁基、環己基或苯基,R2
具有1至4個碳原子,每個R4
係相同或不同之甲基、乙基、丙基或異丙基,且x係0。
本文使用之特定胺基矽烷類包括例如胺基丙基三甲氧基矽烷、胺基丙基三乙氧基矽烷、胺基丁基三乙氧基矽烷、N-(2-胺基乙基-3-胺基丙基)三乙氧基矽烷、胺基十一基三甲氧基矽烷及胺基丙基甲基二乙氧基矽烷。其他適用之胺基矽烷類包括但不局限於苯基胺基丙基三甲氧基矽烷、甲基胺基丙基三甲氧基矽烷、正丁基胺基丙基三甲氧基矽烷、第三丁基胺基丙基三甲氧基矽烷、環己基胺基丙基三甲氧基矽烷、順丁烯二酸二丁酯胺基丙基三甲氧基矽烷、經順丁烯二酸二丁酯取代之4-胺基-3,3-二甲基丁基三甲氧基矽烷、N-甲基-3-胺基-2-甲基丙基三甲氧基矽烷、N-乙基-3-胺基-2-甲基丙基三甲氧基矽烷、N-乙基-3-胺基-
2-甲基丙基二乙氧基矽烷、N-乙基-3-胺基-2-甲基羥丙基三乙氧基矽烷、N-乙基-3-胺基-2-甲基丙基甲基二甲氧基矽烷、N-丁基-3-胺基-2-甲基丙基三甲氧基矽烷、3-(N-甲基-3-胺基-1-甲基-1-乙氧基)丙基三甲氧基矽烷、N-乙基-4-胺基-3,3-二甲基丁基二甲氧基甲基矽烷及N-乙基-4-胺基-3,3二甲基丁基三甲氧基矽烷。
該異氰酸酯末端PUR預聚合物之製備當中通常會使用觸媒。因為縮合觸媒亦會催化本發明固化組成物之SPUR樹脂組份的固化作用之故(水解然後交聯),較佳係使用縮合觸媒。適用的縮合觸媒包括二羧酸類之二烷基錫,諸如二月桂酸二丁錫與醋酸二丁錫,三級胺類、該羧酸類之亞錫鹽,諸如辛酸亞錫與醋酸亞錫等等。本發明一具體實例中,該PUR預聚合物的製造方法中係使用二月桂酸二丁錫。其他適用觸媒包括鋯錯合物(KAT XC6212,K-KAT XC-A209,可得自King Industries,Inc)、鋁螯合劑(TYZER®
型,其可得自DuPont公司,與KR型,其可得自Kenrich Petrochemical,Inc.,),以及其他有機金屬,諸如Zn、Co、Ni與Fe等等。
如前文所示,可藉由反應羥基末端PUR預聚合物與一種異氰酸基矽烷而製備該濕份可固化之SPUR樹脂可。該羥基末端PUR預聚合物可使用與前文所述製備異氰酸酯末端PUR預聚合物之實質相同材料(即,多元醇類、
聚異氰酸酯類與視情況需要之觸媒(較佳係縮合觸媒)之實質相同方式製得,其主要差別係該多元醇與該聚異氰酸酯的比例使得形成之預聚合物中形成羥基末端。如此,例如在二醇與二異氰酸酯之實例中,茲使用莫耳過量之前者,因而形成羥基末端PUR預聚合物。
適用於羥基末端SPUR樹脂的矽基化反應物係包含異氰酸酯末端與容易溶解官能基(例如,1至3個烷氧基)者。適用的矽基化反應物係如以下通式之異氰酸酯類:
其中R5
係至高達12個碳原子之烯基,視情況需要包含一或更多種雜原子,每個R6
係相同或不同之至高達8個碳原子之烷基或芳基,每個R7
係相同或不同之至高達6個碳原子之烷基,且y係0、1或2。在一具體實例中,R5
具有1至4個碳原子,每個R7
係相同或不同之甲基、乙基、丙基或異丁基,且y係0。
本文可用以與前述羥基末端PUR預聚合物反應以提供濕份可固化之SPUR樹脂之特定之異氰酸基矽烷類包括異氰酸基丙基三甲氧基矽烷、異氰酸基異丙基三甲氧基矽烷、異氰酸基-正丁基三甲氧基矽烷、異氰酸基-第三丁基三甲氧基矽烷、異氰酸基丙基三乙氧基矽烷、異氰酸基異丙基三乙氧基矽烷、異氰基-正丁基三乙氧基矽烷、異氰酸基-第三丁基三乙氧基矽烷等等。
本發明之濕份可固化之SPUR樹脂可由一種多元醇(較佳係二醇類)與異氰酸基矽烷直接反應製得,不需要先形成聚胺基甲酸酯預聚合物。
該材料-即,適用於製造濕份可固化之SPUR樹脂的多元醇類與矽烷類(例如兼具可溶解與異氰酸基官能基者)係如上述。因此,適用之多元醇類包括分子量介於約4,000至20,000間之羥基末端多元醇類。不過,亦可使用各種結構、分子量及/或官能基之多元醇類的混合物。適用於與前述多元醇類反應以提供濕份可固化之SPUR樹脂之異氰酸基矽烷係如上述。
該胺基甲酸酯預聚合物合成與隨後之矽基化反應,以及多元醇與異氰酸基矽烷之直接反應係在無水條件下進行,而且較佳係在惰性氣氛(諸如氮之包圍)中進行,以避免烷氧基矽烷基團過早水解。此二反應步驟的代表溫度範圍係0℃至150℃,更佳係介於60℃與90℃間。典弄來說,合成該矽基化聚胺基甲酸酯的總反應時間介於4至8小時。
使用標準滴定技術(ASTM 2572-87)或紅外線分析監測該合成作用。當以任一種技術都偵測不到殘留NCO時,則視該胺基甲酸酯預聚合物之矽基化作用已完成。
本文之固化密封組成物包括至少一種其他聚合物
(b),其顯示出對於氣體或氣體混合物的透氣性低於該固化樹脂(a)。適用之聚合物包括聚乙烯類,諸如低密度聚乙烯(LDPE)、極低密度聚乙烯(VLDPE)、線性低密度聚乙烯(LLDPE)與高密度聚乙烯(HDPE);聚丙烯(PP)、聚異丁烯(PIB)、聚乙酸乙烯酯(PVAc)、聚乙烯醇(PVoH)、聚苯乙烯、聚碳酸酯、聚酯,諸如聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)、聚萘二甲酸乙二酯(PEN)、經二醇改良聚對苯二甲酸乙二酯(PETG);聚氯乙烯(PVC)、聚偏二氯乙烯、聚偏二氟乙烯、熱塑性聚胺基甲酸酯(TPU)、丙烯腈丁二烯苯乙烯(ABS)、聚甲基丙烯酸甲酯(PMMA)、聚氟乙烯(PVF)、聚醯胺類(耐綸)、聚甲基戊烯、聚醯亞胺(PI)、聚醚醯亞胺(PE1)、聚醚醚酮(PEEK)、聚碸、聚醚碸、乙烯氯三氟乙烯、聚四氟乙烯(PTFE)、乙酸纖維素、乙酸丁酸纖維素、增塑聚氯乙烯、離子聚合物(Surtyn)、聚苯硫醚(PPS)、苯乙烯-順式丁烯二酸酐、經改良聚苯醚(PPO)等及其混合物。
聚合物(b)亦可能具有彈性性質,例如包括但不局限於乙烯-丙烯橡膠(EPDM)、聚丁二烯、聚氯丁二烯、聚異戊二烯、聚胺基甲酸酯(TPU)、苯乙烯-丁二烯-苯乙烯(SBS)、苯乙烯-乙烯-丁二烯-苯乙烯(SEEBS)、聚甲基苯基矽氧烷(PMPS)等等。
此等聚合物可單獨摻合物或以合併摻合物,或呈共聚
物形式,例如聚碳酸酯-ABS摻合物、聚碳酸酯-聚酯摻合物、接枝聚合物,諸如矽烷接枝聚乙烯類,以及矽烷接枝聚胺基甲酸酯類。
本發明一具體實例中,聚合物(b)係選自低密度聚乙烯(LDPE)、極低密度聚乙烯(VLDPE)、線性低密度聚乙烯(LLDPE)、高密度聚乙烯(HDPE)及其混合物。本發明另一具體實例中,聚合物(b)係選自低密度聚乙烯(LDPE)、極低密度聚乙烯(VLDPE)、線性低密度聚乙烯(LLDPE)及其混合物。本發明又一具體實例中,聚合物(b)係線性低密度聚乙烯(LLDPE)。
視情況需要,本文之固化密封組成物亦可包含一或更多種填料,諸如嵌段與膠態碳酸鈣類,其已經以化合物硬脂酸酯或硬脂酸處理;強化二氧化矽類,諸如煙製二氧化矽、沉澱二氧化矽、矽膠、疏水化二氧化矽與矽膠;粉碎與經碾磨石英、氧化鋁、氫氧化鋁、氫氧化鈦、矽藻土、氧化鐵、碳黑、雲母、滑石等及其混合物。
本發明其中一方面,該固化組成物的填料組份係碳酸鈣、二氧化矽或其混合物。所添加之填料種類與數量係視該固化聚矽氧組成物所需之物理性質而定。因此,該填料可為單一種類或兩種或更多種種類之混合物。
其他適用之填料係奈米黏土,其具有,其具有某一尺寸係奈米範圍的獨特形態。該奈米黏土可與離子鍵合於構成該等黏土粒子表面之夾間物質形成化學錯合物。此夾間物質與黏土粒子的結合形成可與許多不同種類容許黏土填
料分散於其中之主體樹脂相容的材料。
當描述本發明之奈米黏土填料時,除非另有指示,否則下列術語具有下列意思。
此處使用之「剝離」一辭描述一種方法,其中奈米黏土片的小塊在一種聚合物基質中彼此分離。於剝離期間,在每個小塊最外面區域的小片裂開,露出更多待分開之小片。
此處使用之「通道」一辭描述介於黏土小片平行層之間的空間。該通道間隔係視佔據該空間的分子或聚合物性質而改變。介於個別奈米黏土小片之間的層間空間亦視佔據該空間的分子種類而變化。
此處使用之「夾間物質」一辭包括可以進入該黏土通道並且黏於其表面之任何無機或有機化合物。
此處使用之「間夾物」一辭表示一種黏土-化學錯合物,其中該黏土通道間隙已因表面改良處理而增大。在適當溫度與剪切條件下,間夾物可在樹脂基質中剝離。
此處所使用之「經改良黏土」一辭表示一種已經以可以與存在該黏土層間表面之陽離子進行離子交換反應之任何無機或有機化合物處理之黏土材料。
此處所使用之「有機黏土」一辭表示一種已經以可與存在該黏土層間表面之陽離子進行離子交換反應有機分子(其他名稱為「剝離劑」、「表面改良劑」或「夾間物質」)處理之黏土或其他層狀材料。
此處所使用之「有機奈米黏土」一辭描述一種已經以
有機或半有機夾間物質(例如二有機聚矽氧烷)處理之奈米黏土,其中該夾間物質可離子鍵合於構成該黏土粒子之層間表面。
適於作為本發明組成物之有機奈米黏土填料組份的奈米黏土包括天然或合成頁矽酸鹽,特別是碟狀黏土,諸如蒙脫石、鈉蒙脫石、鈣蒙脫石、鎂蒙脫石、綠脫石、鋁膨潤石、鉻膨潤石、合成鋰膨潤石、鋰膨潤石、皂石、鋅膨潤石、瑪伽石(magadite)、斜水矽鈉石、梭波石(sobockite)、史溫朵石(svindordite)、矽鎂石、滑石、雲母、高嶺石、蛭石、多水高嶺石、鋁酸鹽氧化物(aluminate oxides)或水滑石類等及其混合物。在另一具體實例中,適用之奈米黏土包括雲母礦,諸如伊利石與混合層狀伊利石/層列形礦,諸如累托石、塔洛蘇石(tarosovite)、三八伊來石以及伊利石類與一或更多種上述黏土礦之混合物。任何會充分吸收有機分子使頁矽酸鹽小片之間的層間間隙增加至少約5埃或至少10埃(當該頁矽酸鹽係大約乾燥時)的可潤脹層狀材料均可用以製造該填料組份,以提供本發明之固化密封組成物。
該奈米黏土可為天然或合成材料。其特徵會影響粒子大小,而且對本發明而言,該粒子的橫向尺寸介於約0.01μm與約5μm之間,較佳係介於約0.05μm與約2μm,更佳係介於約0.1μm與約1μm。該粒子的厚度或垂直尺寸通常介於約0.5nm與約10nm間,較佳係介於約1nm與約5nm間。
本發明一具體實例中,適於處理奈米黏土與層狀材料以提供本文之填料組份的有機與無機化合物包括陽離子界面活性劑,諸如銨,氯化銨,烷基銨(一級、二級、三級與四級),脂族、芳族、或芳基脂族胺類、膦類或硫化物類之鏻或鋶衍生物。
本文可使用之奈米黏土的其他有機處理劑包括胺化合物及/或四級銨化合物R5
R6
R7
R8
N+
X-
,各者至高達60個碳原子之獨立為烷氧基矽烷基團、烷基或烯基,且X-
係陰離子,諸如Cl-
、F-
、SO4 -
等。
該固化密封組成物亦可包括一或更多種烷氧基矽烷類作為黏著促進劑。適用之黏著促進劑包括N-2-胺基乙基-3-胺基丙基三乙氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、胺基丙基三甲氧基矽烷、雙-γ-三甲氧基矽基丙基)胺、N-苯基-γ-胺基丙基三甲氧基矽烷、三胺基官能基三甲氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、甲基丙烯醯氧基丙基三甲氧基矽烷、甲基胺基丙基三甲氧基矽烷、γ-環氧丙氧基丙基乙基二甲氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基乙基三甲氧基矽烷、β-(3,4-環氧基環己基)丙基三甲氧基矽烷、β-(3,4-環氧基環己基)乙基甲基二甲氧基矽烷、異氰酸基丙基三乙氧基矽烷、異氰酸基丙基甲基二甲氧基矽烷、β-氰基乙基三甲氧基矽烷、γ-丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、4-胺基-3,3,-二甲基丁基三甲氧基矽烷
及N-乙基-3-三甲氧基矽基-2-甲基丙胺等等。在一具體實例中,該黏著促進劑可為n-2-胺基乙基-3-胺基丙基三甲氧基矽烷與1,3,5-參(三甲氧基矽基丙基)異三聚氰酸酯之組合物。
用以製備上述胺基甲酸酯預聚合物以及相關矽基化聚胺基甲酸酯類(SPUR)之代表觸媒包括習知適用於促進聚矽氧密封組成物中之交聯作用者。該觸媒可包括金屬與非金屬觸媒。適用於本發明之金屬縮合觸媒的金屬部分實例包括錫、鈦、鋯、鉛、鐵、鈷、銻、錳、鉍與鋅化合物。
本發明一具體實例中,適於促進聚矽氧密封組成物中交聯作用的錫化合物包括:諸如二月桂酸二丁基錫、二醋酸二丁基錫、二甲氧化二丁基錫、辛酸錫、三色若酸異丁錫(isobutyltintriceroate)、氧化二丁錫、可溶性氧化二丁錫、雙二異辛基苯二甲酸二丁錫、雙-三丙氧基矽基二辛錫、雙-乙醯丙酮二丁錫、矽基化二氧化二丁錫、三辛二酸羧基甲氧基苯錫、三色若酸異丁錫(isobutyl tintriceroate)、二丁酸二甲錫、二新癸酸二甲錫、酒石酸三乙錫、二苯甲酸二丁錫、油酸錫、環烷酸錫(tin naphthenate)、三-2-乙基己基己酸丁錫與丁酸錫等錫化合物。在另一具體實例中,適於促進聚矽氧密封組成物中交聯作用之化合物係經螯合鈦化合物,例如雙(乙基乙醯醋酸)1,3-丙烷二氧鈦;雙(乙基乙醯醋酸)二異丙氧基鈦÷以及鈦酸四烷酯類,例如鈦酸四正丁酯與鈦酸四異丙
酯。在本發明又一具體實例中,雙β-二酮酸二有機錫係用以促進聚矽氧密封組成物中之交聯作用。
在本發明其中一方面,該觸媒係金屬觸媒。本發明另一方面,該金屬觸媒係選自錫化合物,而在本發明又一方面,該金屬觸媒係二月桂酸二丁錫。
本發明之組成物亦可包括一或更多種非離子界面活性劑,諸如聚乙二醇、聚丙二醇、乙氧化篦麻油、油酸乙氧基化物、烷基酚乙氧基化物、環氧乙烷(EO)與環氧丙烷(PO)之共聚物以及聚矽氧類與聚醚類之共聚物(聚矽氧聚醚共聚物)、聚矽氧與環氧乙烷及環氧丙烷之共聚物的共聚物及其混合物。
在不影響該固化組成物所需之性質的前提下,本發明之固化組成物可包括習知且習用數量之習用於RTC含聚矽氧組成物的額外成份,諸如著色劑、顏料、增塑劑、固化加速劑、搖變劑、去濕劑、染料、溶劑、抗氧化劑、UV安定劑、殺生物劑等。
該濕份可固化之矽基化樹脂(a)、其他聚合物(b)與視情況需要之組份,諸如本文揭示之填料、黏著促進劑、交聯劑與離子界面活性劑的數量可大幅變化,而且較佳係選自下表所示範圍內之數量。
可藉由本技術詳知之製程,例如熔融摻合作用、擠出摻合作用、溶液摻合作用、乾式混合作用、在Banbury混合機中之摻合作用等,於存在濕氣下製得本文之固化密封組成物,以提供實質上均勻之混合物。
雖然已詳細舉例並說明本發明較佳具體實例,但例如組份、材料與參數之各種修改對熟悉本技術之人士而言極為顯而易見,因此希望附錄申請專利範圍中涵括屬於本發明範圍內之所有此等修改與變化。
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10‧‧‧絕緣玻璃單元
圖1係具有包括本發明固化密封劑組成物之氣體密封元件的雙層玻璃絕緣玻璃單元(IGU)橫剖面圖。
1‧‧‧玻璃片
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4‧‧‧氣體密封構件
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8‧‧‧玻璃壓條
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10‧‧‧絕緣玻璃單元
Claims (21)
- 一種絕緣玻璃單元,其包含至少兩片彼此呈分隔關係之分開之玻璃片或其他功能相同的材料,置於其間的低導熱性氣體或氣體混合物,以及一氣體密封元件,此氣體密封元件包括由含有濕份可固化之矽基化樹脂的組成物固化所形成之固化密封組成物,該含有濕份可固化之矽基化樹脂的組成物包括:a)濕份可固化之矽基化樹脂,係藉由羥基末端聚胺基甲酸酯預聚合物與異氰酸基矽烷反應而製得,其中該羥基末端預聚合物係藉由莫耳過量聚醚多元醇與二異氰酸酯反應而製得,其中該聚醚多元醇係選自具有數量平均分子量自4,000至18,000克/莫耳及端基不飽和水準以每克多元醇計不大於0.04毫當量之聚(氧伸乙)二醇類、聚(氧伸丙)二醇類、聚(氧伸乙-氧伸丙)二醇類、聚(氧伸烷)三醇類、及聚(伸丁)二醇類,且其中該異氰酸基矽烷係如式OCN-R5 -Si(R6 )y (OR7 )3-y 其中R5 為至多12個碳原子的伸烷基,R6 為至多8個碳原子的烷基或芳基,R7 為至多6個碳原子之相同或相異的烷基,且y為0、1或2,此濕份可固化之矽基化樹脂於固化時提供顯示透氣性之固化樹脂;及b)至少一種透氣性低於固化樹脂(a)之其他聚合 物,以及c)至少一種經陽離子界面活性剝離劑改質之奈米黏土,其中奈米黏土粒子具有橫向尺寸介於0.01μm與5μm之間及垂直尺寸介於0.5nm與約10nm之間。
- 如申請專利範圍第1項之絕緣玻璃單元,其中該濕份可固化之矽基化樹脂(a)係選自(i)由異氰酸酯末端聚胺基甲酸酯預聚合物與含活性氫之有機官能基矽烷反應而獲得之矽基化樹脂;(ii)由羥基末端之聚胺基甲酸酯預聚合物與異氰酸基矽烷反應獲得之矽基化樹脂;以及(iii)由多元醇與異氰酸基矽烷反應獲得之矽基化聚合物其中至少一者。
- 如申請專利範圍第1項之絕緣玻璃單元,其中該濕份可固化之矽基化樹脂(a)係佔總組成物約1至約99重量百分比。
- 如申請專利範圍第1項之絕緣玻璃單元,其中該濕份可固化之矽基化樹脂(a)係佔總組成物約10至約50重量百分比。
- 如申請專利範圍第1項之絕緣玻璃單元,其中該濕份可固化之矽基化樹脂(a)係佔總組成物約20至約30重量百分比。
- 如申請專利範圍第1項之絕緣玻璃單元,其中該聚合物(b)係選自低密度聚乙烯、極低密度聚乙烯、線性低密度聚乙烯、高密度聚乙烯、聚丙烯、聚異丁烯、聚乙 酸乙烯酯、聚乙烯醇、聚苯乙烯、聚碳酸酯、聚酯(諸如聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、經二醇改良之聚對苯二甲酸乙二酯)、聚氯乙烯、聚偏二氯乙烯、聚偏二氟乙烯、熱塑性聚胺基甲酸酯、丙烯腈丁二烯苯乙烯、聚甲基丙烯酸甲酯、聚氟乙烯、聚醯胺類、聚甲基戊烯、聚醯亞胺、聚醚醯亞胺、聚醚醚酮、聚碸、聚醚碸、乙烯氯三氟乙烯、聚四氟乙烯、乙酸纖維素、乙酸丁酸纖維素、增塑聚氯乙烯、離子聚合物、聚苯硫醚、苯乙烯-順式丁烯二酸酐、經改良聚苯醚、乙烯-丙烯橡膠、聚丁二烯、聚氯丁二烯、聚異戊二烯、聚胺基甲酸酯、苯乙烯-丁二烯-苯乙烯、苯乙烯-乙烯-丁二烯-苯乙烯、聚甲基苯基矽氧烷及其混合物。
- 如申請專利範圍第6項之絕緣玻璃單元,其中該聚合物(b)係選自低密度聚乙烯、極低密度聚乙烯、線性低密度聚乙烯、高密度聚乙烯及其混合物。
- 如申請專利範圍第7項之絕緣玻璃單元,其中該聚合物(b)係選自低密度聚乙烯、極低密度聚乙烯、線性低密度聚乙烯及其混合物。
- 如申請專利範圍第1項之絕緣玻璃單元,其中該聚合物(b)係佔總組成物約1至約99重量百分比。
- 如申請專利範圍第1項之絕緣玻璃單元,其中該聚合物(b)係佔總組成物約5至約50重量百分比。
- 如申請專利範圍第1項之絕緣玻璃單元,其中該聚合物(b)係佔總組成物約10至約20重量百分比。
- 如申請專利範圍第1項之絕緣玻璃單元,還包含至少一種其他填料,其中該其他填料係選自碳酸鈣、沉澱碳酸鈣、膠態碳酸鈣、以化合物硬脂酸酯或硬脂酸處理之碳酸鈣、煙製二氧化矽、沉澱二氧化矽、矽膠、疏水化二氧化矽、親水性矽膠、粉碎石英、經碾磨石英、氧化鋁、氫氧化鋁、氫氧化鈦、黏土、高嶺土、皂土、蒙脫石、矽藻土、氧化鐵、碳黑與石墨、雲母、滑石及其混合物。
- 如申請專利範圍第1項之絕緣玻璃單元,其中該奈米黏土係選自蒙脫石、鈉蒙脫石、鈣蒙脫石、鎂蒙脫石、綠脫石、鋁膨潤石、鉻膨潤石、合成鋰膨潤石、鋰膨潤石、皂石、鋅膨潤石、瑪伽石(magadite)、斜水矽鈉石、梭波石(sobockite)、史溫朵石(svindordite)、矽鎂石、蛭石、多水高嶺石、鋁酸鹽氧化物(aluminate oxides)、水滑石、伊利石、累托石、塔洛蘇石(tarosovite)、三八伊來石、高嶺石及其混合物。
- 如申請專利範圍第1項之絕緣玻璃單元,其中該奈米黏土係以至少一種三級胺化合物R3 R4 R5 N及/或四級銨化合物R5 R6 R7 R8 N+ X- 改良,其中,R3 、R4 、R5 、R6 、R7 與R8 各者獨立為至高達60個碳原子之烷基、烯基或烷氧基矽烷基團,且X- 係陰離子。
- 如申請專利範圍第1項之絕緣玻璃單元,其中該奈米黏土係以銨,一級烷銨,二級烷銨,三級烷銨,四級烷銨,脂族、芳族、或芳基脂族之胺類、膦類或硫化物類的鏻衍生物,或脂族、芳族、或芳基脂族之胺類、膦類或 硫化物類的鋶衍生物加以改良。
- 如申請專利範圍第1項之絕緣玻璃單元,還包含黏著促進劑,其中該黏著促進劑係選自n-2-胺基乙基-3-胺基丙基三甲氧基矽烷、1,3,5-參(三甲氧基矽基丙基)異三聚氰酸酯、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、胺基丙基三甲氧基矽烷、雙-γ-三甲氧基矽基丙基)胺、N-苯基-γ-胺基丙基三甲氧基矽烷、三胺基官能基三甲氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、甲基丙烯醯氧基丙基三甲氧基矽烷、甲基胺基丙基三甲氧基矽烷、γ-環氧丙氧基丙基乙基二甲氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基乙基三甲氧基矽烷、β-(3,4-環氧基環己基)丙基三甲氧基矽烷、β-(3,4-環氧基環己基)乙基甲基二甲氧基矽烷、異氰酸基丙基三乙氧基矽烷、異氰酸基丙基甲基二甲氧基矽烷、β-氰基乙基三甲氧基矽烷、γ-丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、4-胺基-3,3,-二甲基丁基三甲氧基矽烷、n-乙基-3-三甲氧基矽基-2-甲基丙胺及其混合物。
- 如申請專利範圍第1項之絕緣玻璃單元,還包含觸媒,其中該觸媒係錫觸媒。
- 如申請專利範圍第17項之絕緣玻璃單元,其中該錫觸媒係選自二月桂酸二丁基錫、二醋酸二丁基錫、二甲氧化二丁基錫、辛酸錫、三色若酸異丁錫(isobutyltintriceroate)、氧化二丁錫、溶解之氧化二丁 錫、雙-二異辛基苯二甲酸二丁錫、雙-三丙氧基矽基二辛錫、雙-乙醯丙酮二丁錫、矽基化二氧化二丁錫、三辛二酸羧基甲氧基苯錫、三色若酸異丁錫(isobutyl tintriceroate)、二丁酸二甲錫、二新癸酸二甲錫、酒石酸三乙錫、二苯甲酸二丁錫、油酸錫、環烷酸錫(tin naphthenate)、三-2-乙基己基己酸丁錫、丁酸錫、雙β-二酮酸二有機錫及其混合物。
- 如申請專利範圍第1項之絕緣玻璃單元,還包含界面活性劑,其中該界面活性劑係非離子界面活性劑,其係選自聚乙二醇、聚丙二醇、乙氧化篦麻油、油酸乙氧基化物、烷基酚乙氧基化物、環氧乙烷與環氧丙烷之共聚物與聚矽氧類與聚醚類之共聚物、聚矽氧與環氧乙烷及環氧丙烷之共聚物的共聚物及其混合物。
- 如申請專利範圍第19項之絕緣玻璃單元,其中該非離子界面活性劑係選自環氧乙烷與環氧丙烷之共聚物、聚矽氧類與聚醚類之共聚物、聚矽氧與環氧乙烷及環氧丙烷之共聚物的共聚物及其混合物。
- 如申請專利範圍第1項之絕緣玻璃單元,其中該絕緣氣體係選自空氣、二氧化碳、六氟化硫、氮、氬、氪、氙及其混合物。
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US11/345,463 US7541076B2 (en) | 2006-02-01 | 2006-02-01 | Insulated glass unit with sealant composition having reduced permeability to gas |
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- 2007-01-30 EP EP07762647.1A patent/EP1984307B1/en not_active Not-in-force
- 2007-01-30 CN CN2007800102944A patent/CN101405235B/zh not_active Expired - Fee Related
- 2007-01-30 WO PCT/US2007/002385 patent/WO2007089698A2/en active Application Filing
- 2007-01-30 JP JP2008553286A patent/JP5542338B2/ja not_active Expired - Fee Related
- 2007-01-30 CA CA 2640210 patent/CA2640210C/en not_active Expired - Fee Related
- 2007-01-30 AU AU2007209944A patent/AU2007209944B2/en not_active Ceased
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Also Published As
Publication number | Publication date |
---|---|
CA2640210A1 (en) | 2007-08-09 |
CN101405235A (zh) | 2009-04-08 |
WO2007089698A3 (en) | 2007-09-20 |
CA2640210C (en) | 2014-06-03 |
JP2009525255A (ja) | 2009-07-09 |
EP1984307A2 (en) | 2008-10-29 |
AU2007209944A1 (en) | 2007-08-09 |
US7541076B2 (en) | 2009-06-02 |
CN101405235B (zh) | 2013-10-02 |
TW200744969A (en) | 2007-12-16 |
AU2007209944B2 (en) | 2012-12-06 |
EP1984307B1 (en) | 2018-10-10 |
WO2007089698A2 (en) | 2007-08-09 |
JP5542338B2 (ja) | 2014-07-09 |
US20070178257A1 (en) | 2007-08-02 |
HK1130242A1 (en) | 2009-12-24 |
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