TW201825436A - 著色之層合玻璃用中間膜及著色之層合玻璃 - Google Patents
著色之層合玻璃用中間膜及著色之層合玻璃 Download PDFInfo
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- TW201825436A TW201825436A TW106126232A TW106126232A TW201825436A TW 201825436 A TW201825436 A TW 201825436A TW 106126232 A TW106126232 A TW 106126232A TW 106126232 A TW106126232 A TW 106126232A TW 201825436 A TW201825436 A TW 201825436A
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Abstract
本發明之目的在於提供一種著色之層合玻璃用中間膜及使用該著色之層合玻璃用中間膜之著色之層合玻璃,該著色之層合玻璃用中間膜於使用依據JIS R3202(1996)之2片透明玻璃製作層合玻璃時,可見光線穿透率Tv為5%以下,並且因部位不同所導致之可見光線穿透率之偏差較小,美觀優異。
本發明係一種著色之層合玻璃用中間膜,其係於至少一表面具有凹部,且於使用依據JIS R3202(1996)之2片透明玻璃製作層合玻璃時,可見光線穿透率Tv為5%以下者,並且係由含有熱塑性樹脂與著色劑之第1樹脂層及含有熱塑性樹脂且不含著色劑之第2樹脂層的至少2層之積層體構成,上述第1樹脂層之彈性模數E1與上述第2樹脂層之彈性模數E2之比E1/E2為1.25以上,且上述第1樹脂層之厚度t1與上述第2樹脂層之厚度t2之比t1/t2為2.0以下。
Description
本發明係關於一種著色之層合玻璃用中間膜及使用該著色之層合玻璃用中間膜之著色之層合玻璃,該著色之層合玻璃用中間膜於使用依據JIS R3202(1996)之2片透明玻璃製作層合玻璃時,可見光線穿透率Tv為5%以下,並且可見光線穿透率之偏差較小,美觀優異。
層合玻璃由於即便受到外部衝擊而破損,玻璃碎片飛濺之情況亦較少而安全,故而被廣泛用作汽車等車輛之擋風玻璃、側窗玻璃、後窗玻璃、天窗玻璃或飛機、建築物等之窗玻璃等。作為層合玻璃,可列舉使例如含有液狀塑化劑與聚乙烯醇縮醛樹脂之層合玻璃用中間膜介存於至少一對玻璃間並使之一體化而成的層合玻璃等。
近年來,玻璃所要求之性能亦逐漸多樣化,就設計性、隱私保護性、遮光性等觀點而言,逐漸要求被著色之層合玻璃。尤其是因為可見光線穿透率Tv為5%以下之經高著色之層合玻璃可發揮特別高之隱私保護性,故而適合用作車輛之天窗玻璃或建築物等之窗玻璃等。進而,認為若具備車載相機之無後視鏡之汽車逐漸普及,則汽車之側窗玻璃亦會採用 經高著色之層合玻璃。
經著色之層合玻璃通常係使用摻合有顏料等著色劑之層合玻璃用中間膜而製作(例如,專利文獻1)。然而,為了利用該方法達成可見光線穿透率Tv5%以下,必須於層合玻璃用中間膜中摻合大量著色劑。於此種摻合有大量著色劑之層合玻璃用中間膜中,存在因部位不同而可見光線穿透率大幅偏差,從而於美觀之方面產生不良情況之問題。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2010-248026號公報
本發明之目的在於鑒於上述現狀,提供一種著色之層合玻璃用中間膜及使用該著色之層合玻璃用中間膜之著色之層合玻璃,該著色之層合玻璃用中間膜於使用依據JIS R3202(1996)之2片透明玻璃製作層合玻璃時,可見光線穿透率Tv為5%以下,並且因部位不同所導致之可見光線穿透率之偏差較小,美觀優異。
本發明係一種著色之層合玻璃用中間膜,其係於至少一表面具有凹部,且於使用依據JIS R3202(1996)之2片透明玻璃製作層合玻璃時,可見光線穿透率Tv為5%以下者,並且係由含有熱塑性樹脂與著色劑之第1樹脂層及含有熱塑性樹脂且不含著色劑之第2樹脂層的至少2層之 積層體構成,上述第1樹脂層之彈性模數E1與上述第2樹脂層之彈性模數E2之比E1/E2為1.25以上,且上述第1樹脂層之厚度t1與上述第2樹脂層之厚度t2之比t1/t2為2.0以下。
以下,對本發明進行詳細說明。
本發明人等對於在至少一表面具有凹部,且於使用依據JIS R3202(1996)之2片透明玻璃製作層合玻璃時,可見光線穿透率Tv為5%以下之著色之層合玻璃用中間膜中,會產生因部位不同所導致之可見光線穿透率之偏差之原因進行了研究。其結果為,發現形成於層合玻璃用中間膜之表面之凹部存在原因。於層合玻璃之製造中,通常係使於至少2片玻璃板之間積層有層合玻璃用中間膜之積層體通過夾輥後抽出(抽出脫氣法),或將該積層體放入至橡膠中進行減壓抽吸(真空脫氣法),一面使殘留於玻璃板與中間膜之間之空氣脫氣,一面進行壓接。繼而,將上述積層體於例如高壓釜內進行加熱加壓而進行壓接,藉此製造層合玻璃。於層合玻璃之製造步驟中,將玻璃與層合玻璃用中間膜積層時之脫氣性較為重要。為了確保層合玻璃製造時之脫氣性,於層合玻璃用中間膜之至少一表面形成微細之凹凸。尤其是將該凹凸中之凹部製成具有底部連續之槽形狀(以下,亦稱為「刻線狀」)且鄰接之該刻線狀之凹部平行且規則地形成之結構,藉此可發揮極其優異之脫氣性。形成於層合玻璃用中間膜之表面之凹部通常於層合玻璃製造步驟中之壓接時被壓扁,因此在所獲得之層合玻璃中幾乎不會成為問題。
然而,本發明人等發現,於積層有包含含有著色劑之層之2層以上之樹脂層之層合玻璃用中間膜的情形時,於經過層合玻璃製造步驟而獲得之 層合玻璃中,於含有著色劑之層殘留有凹部之影響,從而因部位不同而導致可見光線穿透率產生偏差。
即,認為於使用壓紋輥等於積層有包含含有著色劑之層之2層以上之樹脂層的層合玻璃用中間膜之表面形成凹部之情形時,不僅是僅於中間膜之表面形成凹部,亦會因加工時之壓力而導致凹部被轉印至樹脂層之層間之界面,從而使得界面變得不平滑。認為尤其是若於表面形成刻線狀之凹部,該刻線狀之凹部亦會被明顯地轉印至層間之界面。於層合玻璃製造步驟中之壓接時,中間膜之表面之凹部雖然會被壓扁,但被轉印至樹脂層之層間之界面之凹凸會殘留。認為此種殘留於樹脂層之界面之凹凸雖然於透明之部分幾乎無法用肉眼識別出,但會成為可見光線之偏差而被識別出。
對此,本發明人等將著色之層合玻璃用中間膜設為由含有熱塑性樹脂與著色劑之第1樹脂層及含有熱塑性樹脂且不含著色劑之第2樹脂層的至少2層之積層體構成者。並且發現,藉由增大該第1樹脂層之彈性模數,可抑制凹部向界面之轉印,其結果為可防止可見光線穿透率之偏差,從而完成了本發明。
本發明之著色之層合玻璃用中間膜係由含有熱塑性樹脂與著色劑之第1樹脂層及含有熱塑性樹脂且不含著色劑之第2樹脂層的至少2層之積層體構成。上述第1樹脂層具有調整本發明之著色之層合玻璃用中間膜之可見光線穿透率之作用。
本發明之著色之層合玻璃用中間膜較佳為上述第1樹脂層被夾於2片上述第2樹脂層之間的3層以上之積層體。藉由設為此種3層以上之積層 體,即便於在兩面具有凹部之情形時,亦可防止可見光線穿透率之偏差。
本發明之著色之層合玻璃用中間膜於至少一表面具有凹部。於本發明之著色之層合玻璃用中間膜中,上述凹部較佳為具有底部連續之槽形狀(刻線狀),且規則地並列。
又,於本發明之著色之層合玻璃用中間膜中,上述凹部較佳為具有底部連續之槽形狀,且平行地並列。進而,於本發明之著色之層合玻璃用中間膜中,上述凹部較佳為具有底部連續之槽形狀,且上述凹部平行且規則地並列。
一般而言,對在2片玻璃板之間積層有層合玻璃用中間膜的積層體進行預壓接及正式壓接時之空氣之抽取容易性與上述凹部之底部之連通性及平滑性具有密切之關係。
將層合玻璃用中間膜之至少一面之凹部之形狀設為底部連續之槽形狀之凹部規則地並列之形狀,藉此,底部之連通性更優異,預壓接及正式壓接時脫氣性顯著提高。
又,將層合玻璃用中間膜之至少一面之凹部之形狀設為底部連續之槽形狀之凹部平行地並列之形狀,藉此,底部之連通性更優異,預壓接及正式壓接時脫氣性顯著提高。
進而,將層合玻璃用中間膜之至少一面之凹部之形狀設為底部連續之槽形狀之凹部平行且規則地並列之形狀,藉此,底部之連通性進一步優異,預壓接及正式壓接時脫氣性進一步顯著提高。
再者,所謂「規則地並列」,意指於對具有凹部之中間膜之表面進行觀察時,底部連續之槽形狀之凹部於一定方向上週期性地並列。又,所謂「平 行地並列」,意指如下:既可為鄰接之上述凹部以等間隔平行地並列,亦可為鄰接之上述凹部雖平行地並列,但所有鄰接之上述凹部之間隔並非為等間隔。
於圖1及圖2中示出表示於表面底部連續之槽形狀之凹部以等間隔且鄰接之凹部平行地並列之層合玻璃用中間膜之一例之模式圖。於圖3中表示使用三維粗糙度測定器(KEYENCE公司製造,「KS-1100」,前端頭型號「LT-9510VM」)對底部連續之槽形狀之凹部於表面規則地並列的層合玻璃用中間膜之表面進行測定所得之三維粗糙度之圖像資料。
具有上述凹部之表面之粗糙度(Rz)之較佳之下限為5μm,較佳之上限為90μm。藉由將具有上述凹部之表面之粗糙度(Rz)設為該範圍內,可發揮優異之脫氣性。
再者,於本說明書中,具有上述凹部之表面之粗糙度(Rz)係藉由依據JIS B-0601(1994)之方法進行測定。
再者,於本說明書中,所謂具有上述凹部之表面之粗糙度(Rz),意指由JIS B-0601(1994)「表面粗糙度-定義及表示」所規定之藉由依據JIS B-0601(1994)之方法而獲得之中間膜之十點平均粗糙度(Rz)。上述凹部之粗糙度(Rz)例如可藉由如下進行測定:使用小坂研究所公司製造之「Surfcorder SE300」作為測定機,並以臨界值=2.5mm、基準長度=2.5mm、評價長度=12.5mm、觸針之前端半徑=2μm、前端角度=60°、測定速度=0.5mm/s之條件為測定時之觸針計條件進行測定。此時,將測定時之環境設為23℃及30 RH%下。關於使觸針移動之方向,於凹部為刻線狀之情形時,設為相對於槽方向垂直之方向,於凹部為刻線狀以外之情形時, 設為任意之方向。
上述刻線狀之凹部之粗糙度(Rz)之較佳之下限為10μm,較佳之上限為90μm。藉由將上述刻線狀之凹部之粗糙度(Rz)設為該範圍內,可發揮優異之脫氣性。上述刻線狀之凹部之粗糙度(Rz)之更佳之下限為20μm,更佳之上限為80μm。
再者,於本說明書中,刻線狀之凹部之粗糙度(Rz)係藉由上述依據JIS B-0601(1994)之方法進行測定。
鄰接之上述刻線狀之凹部之間隔之較佳之下限為10μm,較佳之上限為500μm。藉由將上述刻線狀之凹部之間隔設為該範圍內,可發揮優異之脫氣性。上述刻線狀之凹部之間隔之更佳之下限為50μm,更佳之上限為300μm。
再者,於本說明書中,刻線狀之凹部之間隔可藉由如下而獲得:使用光學顯微鏡(例如,SONIC公司製造之「BS-8000III」等)對層合玻璃用中間膜之第1表面及第2表面(觀察範圍20mm×20mm)進行觀察,測得鄰接之凹部之間隔,並且算出鄰接之凹部之最底部間之最短距離之平均值。
於凹部為刻線狀以外之情形時,具有上述凹部之表面之凹部之間隔Sm較佳為600μm以下,更佳為450μm以下,進而較佳為400μm以下,尤佳為350μm以下。藉此,可降低將層合玻璃用中間膜捲取成輥狀之情形時之層合玻璃用中間膜彼此之自黏力,從而容易捲出。
再者,於本說明書中,凹部為刻線狀以外之情形時之凹部之間隔Sm例如意指由JIS B-0601(1994)「表面粗糙度-定義及表示」所規定之藉由依據JIS B-0601(1994)之方法而獲得之中間膜之表面之凹部之平均間隔 (Sm)。上述凹部之間隔Sm可藉由如下進行測定:使用小坂研究所公司製造之「Surfcorder SE300」作為測定機,並以臨界值=2.5mm、基準長度=2.5mm、評價長度=12.5mm、觸針之前端半徑=2μm、前端角度=60°、測定速度=0.5mm/s之條件為測定時之觸針計條件進行測定。此時,將測定時之環境設為23℃及30 RH%下。使觸針移動之方向設為任意之方向。
再者,上述第1樹脂層可配置於本發明之著色之層合玻璃用中間膜之整個面,亦可僅配置於一部分。例如,汽車之擋風玻璃中之遮陽層可藉由將上述第1樹脂層僅配置於層合玻璃用中間膜之一部分而獲得。
藉由將本發明之著色之層合玻璃用中間膜製成上述積層體,亦可獲得抑制來自所獲得之著色之層合玻璃用中間膜之著色劑之轉印的效果。
層合玻璃用中間膜通常係以捲取成輥狀之狀態保管,並自該輥狀體抽出後供於製造層合玻璃。於以可見光線穿透率Tv成為5%以下之方式摻合有大量著色劑之層合玻璃用中間膜中,著色劑之一部分容易滲出至層合玻璃用中間膜之表面。於此種著色之層合玻璃用中間膜中,存在於以輥狀體保管之過程中或自輥狀體抽出後之作業中,所滲出之著色劑轉印至其他層合玻璃用中間膜或作業者之手上等情況。藉由積層不含著色劑之第2樹脂層,可防止來自含有著色劑之第1樹脂層之著色劑之轉印。
上述第1樹脂層含有熱塑性樹脂與著色劑。
作為上述熱塑性樹脂,例如可列舉:聚偏二氟乙烯、聚四氟乙烯、偏二氟乙烯-六氟丙烯共聚物、聚三氟乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚酯、聚醚、聚醯胺、聚碳酸酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚 氯乙烯、聚乙烯、聚丙烯、聚苯乙烯、聚乙烯醇縮醛、乙烯-乙酸乙烯酯共聚物等。其中,上述樹脂層較佳為含有聚乙烯醇縮醛或乙烯-乙酸乙烯酯共聚物,更佳為含有聚乙烯醇縮醛。
上述聚乙烯醇縮醛例如可藉由利用醛使聚乙烯醇縮醛化而製造。上述聚乙烯醇例如可藉由使聚乙酸乙烯酯皂化而製造。上述聚乙烯醇之皂化度通常為70~99.8莫耳%之範圍內。
上述聚乙烯醇之平均聚合度較佳為200以上,更佳為500以上,進而較佳為1700以上,尤佳為超過1700,且較佳為5000以下,更佳為4000以下,進而較佳為3000以下,尤佳為未達3000。若上述平均聚合度為上述下限以上,則層合玻璃之耐貫通性進一步提高。若上述平均聚合度為上述上限以下,則中間膜容易成形。
再者,上述聚乙烯醇之平均聚合度係藉由依據JIS K6726「聚乙烯醇試驗方法」之方法而求出。
上述聚乙烯醇縮醛所含有之縮醛基之碳數並無特別限定。製造上述聚乙烯醇縮醛時所使用之醛並無特別限定。上述聚乙烯醇縮醛中之縮醛基之碳數之較佳之下限為3,較佳之上限為6。若上述聚乙烯醇縮醛中之縮醛基之碳數為3以上,則中間膜之玻璃轉移溫度充分地降低,又,可防止塑化劑之滲出。藉由將醛之碳數設為6以下,可使聚乙烯醇縮醛之合成容易,從而可確保生產性。作為上述碳數為3~6之醛,可為直鏈狀之醛,亦可為支鏈狀之醛,例如可列舉正丁醛、正戊醛等。
上述醛並無特別限定。作為上述醛,通常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: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、甲醛、乙醛及苯甲醛等。其中,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。
上述聚乙烯醇縮醛之羥基含有率(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。若上述羥基含有率為上述下限以上,則中間膜之接著力進一步提高。又,若上述羥基含有率為上述上限以下,則中間膜之柔軟性提高,中間膜之操作變得容易。
上述聚乙烯醇縮醛之羥基含有率係以百分率表示羥基所鍵結之乙烯基量除以主鏈之總乙烯基量所求出之莫耳分率之值。上述羥基所鍵結之乙烯基量例如可藉由依據JIS K6726「聚乙烯醇試驗方法」或依據ASTM D1396-92進行測定而求出。
上述聚乙烯醇縮醛之乙醯化度(乙醯基量)較佳為0.1莫耳%以上,更佳為0.3莫耳%以上,進而較佳為0.5莫耳%以上,且較佳為30莫耳%以下,更佳為25莫耳%以下,進而較佳為20莫耳%以下。若上述乙醯化度為上述下限以上,則聚乙烯醇縮醛與塑化劑之相溶性提高。若上述乙醯化度為上述上限以下,則中間膜及層合玻璃之耐濕性提高。
上述乙醯化度係以百分率表示主鏈之總乙烯基量減去縮醛基所鍵結之乙烯基量及羥基所鍵結之乙烯基量所得的值除以主鏈之總乙烯基量所求出的莫耳分率之值。上述縮醛基所鍵結之乙烯基量例如可依據JIS K6728「聚乙烯醇縮丁醛試驗方法」或依據ASTM D1396-92進行測定。
上述聚乙烯醇縮醛之縮醛化度(於聚乙烯醇縮丁醛樹脂之情形時為丁醛化度)較佳為50莫耳%以上,更佳為53莫耳%以上,進而較佳為60莫耳%以上,尤佳為63莫耳%以上,且較佳為85莫耳%以下,更佳為75莫耳%以下,進而較佳為70莫耳%以下。若上述縮醛化度為上述下限以上,則聚乙烯醇縮醛與塑化劑之相溶性提高。若上述縮醛化度為上述上限以下,則製造聚乙烯醇縮醛所需之反應時間縮短。
上述縮醛化度係以百分率表示縮醛基所鍵結之乙烯基量除以主鏈之總乙烯基量所求出的莫耳分率之值。
上述縮醛化度可藉由依據JIS K6728「聚乙烯醇縮丁醛試驗方法」之方法或依據ASTM D1396-92之方法,測定乙醯化度與羥基含有率,並根據所獲得之測定結果算出莫耳分率,繼而,藉由自100莫耳%中減去乙醯化度與羥基含有率而算出。
再者,上述羥基之含有率(羥基量)、縮醛化度(丁醛化度)及乙醯化度較佳為根據藉由依據JIS K6728「聚乙烯醇縮丁醛試驗方法」之方法所測得之結果而算出。於聚乙烯醇縮醛為聚乙烯醇縮丁醛樹脂之情形時,上述羥基之含有率(羥基量)、縮醛化度(丁醛化度)及乙醯化度較佳為根據藉由依據JIS K6728「聚乙烯醇縮丁醛試驗方法」之方法所測得之結果而算出。
作為上述著色劑,並無特別限定,可使用習知以來摻合於層合玻璃用中間膜中之顏料、染料。其中,就容易將著色之層合玻璃用中間膜之可見光線穿透率Tv設為5%以下之方面而言,較佳為顏料。
作為上述顏料,並無特別限定,例如可列舉酞青、酞青之衍 生物、蒽醌、蒽醌之衍生物、苝、苝之衍生物、氧化鈦、氧化鈦之衍生物、偶氮化合物、碳黑等。其中,就與上述熱塑性樹脂之親和性較高而不易滲出之方面而言,較佳為酞青、酞青之衍生物、蒽醌、蒽醌之衍生物、苝、苝之衍生物、碳黑,尤佳為碳黑。
關於上述第1樹脂層中之上述著色劑之含量,只要於使用依據JIS R3202(1996)之2片透明玻璃製作層合玻璃時,可使可見光線穿透率Tv為5%以下,則並無特別限定。例如,於上述著色劑為碳黑之情形時,相對於上述第1樹脂層100質量%之碳黑之含量之較佳之下限為0.01質量%,較佳之上限為0.30質量%。若上述碳黑之含量為該範圍內,則可防止滲出,並且將著色之層合玻璃之可見光線穿透率Tv調整為5%以下。上述著色劑之含量之更佳之下限為0.02質量%,更佳之上限為0.20質量%,進而較佳之下限為0.03質量%,進而較佳之上限為0.10質量%,尤佳之上限為0.08質量%,最佳之上限為0.05質量%。
上述第1樹脂層較佳為含有塑化劑。
作為上述塑化劑,只要為層合玻璃用中間膜所通常使用之塑化劑,則並無特別限定,例如可列舉一元有機酸酯、多元有機酸酯等有機塑化劑或有機磷酸化合物、有機亞磷酸化合物等磷酸塑化劑等。
作為上述有機塑化劑,例如可列舉:三乙二醇二(2-乙基己酸酯)、三乙二醇二(2-乙基丁酸酯)、三乙二醇二正庚酸酯、四乙二醇二(2-乙基己酸酯)、四乙二醇二(2-乙基丁酸酯)、四乙二醇二正庚酸酯、二乙二醇二(2-乙基己酸酯)、二乙二醇二(2-乙基丁酸酯)、二乙二醇二正庚酸酯等。其中,上述樹脂層較佳為含有三乙二醇二(2-乙基己酸酯)、三 乙二醇二(2-乙基丁酸酯)或三乙二醇二正庚酸酯,更佳為含有三乙二醇二(2-乙基己酸酯)。
上述第1樹脂層中之上述塑化劑之含量並無特別限定,相對於上述熱塑性樹脂100質量份之較佳之下限為25質量份,較佳之上限為80質量份。若上述塑化劑之含量為該範圍內,則可發揮較高之耐貫通性。上述塑化劑之含量之更佳之下限為30質量份,更佳之上限為70質量份。
上述第1樹脂層於作為最外層與玻璃直接接觸之情形時,較佳為含有接著力調整劑。
作為上述接著力調整劑,例如可較佳地使用鹼金屬鹽或鹼土金屬鹽。作為上述接著力調整劑,例如可列舉鉀、鈉、鎂等之鹽。其中,就於製造層合玻璃時可容易地調整玻璃與中間膜之接著力之方面而言,較佳為鎂鹽。
作為構成上述鹽之酸,例如可列舉辛酸、己酸、2-乙基丁酸、丁酸、乙酸、甲酸等羧酸之有機酸或鹽酸、硝酸等無機酸。
上述第1樹脂層亦可視需要含有抗氧化劑、光穩定劑、作為接著力調整劑之改質聚矽氧油、難燃劑、抗靜電劑、耐濕劑、熱線反射劑、螢光劑、熱線吸收劑等添加劑。
上述第2樹脂層含有熱塑性樹脂。作為上述第2樹脂層所含有之熱塑性樹脂,可列舉與上述第1樹脂層所含有者相同之熱塑性樹脂。
又,上述第2樹脂層亦可含有上述塑化劑、接著力調整劑或視需要之抗氧化劑、光穩定劑、作為接著力調整劑之改質聚矽氧油、難燃劑、抗靜電劑、耐濕劑、熱線反射劑、螢光劑、熱線吸收劑等添加劑。
上述第2樹脂層不含著色劑。但是,只要為不會產生滲出或 轉印之範圍之少量,則亦可含有著色劑。又,即便於上述第1樹脂層中所含之著色劑之一部分移行至剛開始不含著色劑之上述第2樹脂層般的情形時,只要為不會產生滲出或轉印之範圍之少量,則上述第2樹脂層亦可含有著色劑。具體而言,例如,只要相對於上述熱塑性樹脂100質量份而為0.001質量份以下之著色劑,則既不會產生滲出或轉印,亦不會阻礙本發明之優異之效果。
於上述第2樹脂層含有著色劑之情形時,可使用與上述第1樹脂層所含有者相同之著色劑。
於本發明之著色之層合玻璃用中間膜中,上述第1樹脂層之彈性模數E1與上述第2樹脂層之彈性模數E2之比E1/E2為1.25以上。藉由積層彈性模數如上所述般高之第2樹脂層,可防止賦予壓紋時之凹部向界面之轉印,從而可防止可見光線穿透率之偏差。上述比E1/E2較佳為1.30以上,更佳為1.35以上。
再者,上述各樹脂層之彈性模數係利用以下之方法進行測定。
利用混合輥將用以形成第1樹脂層之組成物充分地混練(混合)後,於150℃加壓成型,獲得厚度800μm之成形體(第1樹脂層)。利用DUMBBELL公司製造之SUPER DUMBBELL CUTTER:SDK-600對所獲得之成形體進行沖裁,獲得試片。將所獲得之試片以23℃及濕度30%RH保管12小時。其後,於23℃之恆溫室中,使用A&D公司製造之Tensilon以200mm/min進行試片之拉伸試驗。算出所獲得之應力-應變曲線之應變為0~10%之斜率,並將其設為楊氏模數。將所獲得之楊氏模數設為第1樹脂層之彈性模數。第2樹脂層、其他樹脂層亦可利用相同之方法進行測 定。
再者,亦可將藉由於23℃之環境下將第1樹脂層及第2樹脂層自中間膜剝離而獲得之第1樹脂層以厚度成為800μm之方式於150℃加壓成型(於未加壓之狀態下在150℃加壓成型10分鐘,於加壓之狀態下在150℃加壓成型10分鐘)後,利用DUMBBELL公司製造之SUPER DUMBBELL CUTTER:SDK-600進行沖裁而獲得試片。
將上述比E1/E2設為1.25以上之方法並無限定,可列舉選擇各個樹脂層所使用之上述熱塑性樹脂之方法等。例如,熱塑性樹脂之交聯度越高,重量平均分子量越高,樹脂層之彈性模數越高。又,樹脂層之彈性模數亦可藉由上述塑化劑之摻合量進行調整,塑化劑之摻合量越多,樹脂層之彈性模數越低。又,樹脂層之彈性模數亦可藉由上述著色劑之摻合量進行調節,著色劑之摻合量越多,樹脂層之彈性模數越高。具體而言,藉由將上述第1樹脂層中之著色劑之含量設為0.07質量%以上,可容易地增大E1相對於E2之值。藉由將上述第1樹脂層中之著色劑之含量設為0.09質量%以上,可進一步容易地增大E1相對於E2之值。藉由將上述第1樹脂層中之著色劑之含量設為0.12質量%以上,可進而容易地增大E1相對於E2之值。
於本發明之著色之層合玻璃用中間膜中,上述第1樹脂層之厚度t1與上述第2樹脂層之厚度t2之比t1/t2為2.0以下。藉由使第2樹脂層之厚度相對較厚,可防止賦予壓紋時之凹部向界面之轉印,從而可防止可見光線穿透率之偏差。上述比t1/t2較佳為1.5以下,更佳為1.2以下。
具體而言,較佳為將上述第1樹脂層之平均厚度設為100~ 500μm,將第2樹脂層之平均厚度設為100μm以上。
若上述第1樹脂層之平均厚度為100~500μm之範圍內,則可藉由上述著色劑之摻合,將使用依據JIS R3202(1996)之2片透明玻璃製作層合玻璃時之可見光線穿透率Tv容易地調整為5%以下。上述第1樹脂層之平均厚度之更佳之下限為150μm,更佳之上限為450μm,進而較佳之下限為200μm,尤佳之下限為300μm,進而較佳之上限為400μm。
若上述第2樹脂層之平均厚度為100μm以上,則可抑制上述第1樹脂層之平均厚度之變動。上述第2樹脂層之平均厚度更佳為200μm以上,進而較佳為250μm以上。上述第2樹脂層之平均厚度之上限並無特別限定,實質性之上限為1000μm左右。
再者,關於著色之層合玻璃用中間膜之各樹脂層之厚度,利用鋒利之雷射刀以各樹脂層之剖面露出之方式將上述中間膜沿厚度方向垂直切斷後,利用數位顯微鏡對上述中間膜所露出之剖面進行觀察,並利用比例尺(微計測器)及簡易測量功能測定上述中間膜之各樹脂層之厚度。作為數位顯微鏡,例如可使用OLYMPUS公司製造之「DSX500」等。再者,於簡易測量功能中,較佳為選擇平行寬度距離或2點間距離。又,觀察時之倍率較佳為277倍,視野範圍較佳為980μm×980μm。利用上述數位顯微鏡對層合玻璃用中間膜之任意20個部位進行觀察,測定同一視野之各樹脂層之5個部位之厚度。自合計20×5個部位即100個部位之測定結果中求出平均值,並求出第1樹脂層之平均厚度、第2樹脂層之平均厚度。
本發明之著色之層合玻璃用中間膜之可見光線穿透率Tv為5%以下。藉此,可發揮優異之設計性、隱私保護性、遮光性等,從而可較 佳地用作車輛之側窗玻璃、後窗玻璃、天窗玻璃或建築物等之窗玻璃等。本發明之著色之層合玻璃用中間膜之可見光線穿透率Tv較佳為2%以下。
再者,上述可見光線穿透率係依據以下之順序進行測定。使用依據JIS R3202(1996)之2片透明玻璃製作層合玻璃,針對所獲得之層合玻璃之任意20個部位,使用分光光度計(日立高新技術公司製造之「U-4100」)並依據JIS R 3106(1998)測定所獲得之層合玻璃之波長380~780nm之可見光線穿透率。求出所測得之可見光線穿透率之20點之平均值與標準偏差,算出可見光線穿透率之平均值除以標準偏差所得之值(可見光線穿透率之平均值/標準偏差)作為CV值。
再者,就於製作層合玻璃時之可見光線穿透率之測定中可抑制測定之偏差之方面而言,所使用之依據JIS R3202(1996)之2片透明玻璃較佳為1片之厚度為2.4~2.5mm且1片之可見光線穿透率為90.0~91.0%之透明玻璃。其中,更佳為使用1片之厚度為2.5mm、1片之可見光線穿透率為90.5%之透明玻璃。
本發明之著色之層合玻璃用中間膜於至少一表面具有凹部。藉此,可確保層合玻璃之製造時之脫氣性。其中,較佳為上述凹部具有底部連續之槽形狀(刻線狀),且鄰接之該刻線狀之凹部平行且規則地形成。
於本發明之著色之層合玻璃用中間膜中,使上述比E1/E2為1.25以上且比t1/t2為2.0以下,藉此,即便於具有刻線狀之凹部之情形時,亦可防止可見光線穿透率之偏差。
製造本發明之著色之層合玻璃用中間膜之方法並無特別限 定,可列舉利用共擠壓法對上述第1樹脂層與第2樹脂層進行擠壓之方法。
再者,於利用共擠壓法製造本發明之著色之層合玻璃用中間膜之情形時,較佳為採用複合分配法。關於複合分配法,例如欲參照日本專利第5220607號公報。用於複合分配法之層合玻璃用中間膜製造裝置具有1個最表層形成用之第1擠出機。於第1擠出機連接有設置於層配置用導件之1個第1供給孔,於該層配置用導件內,最表層形成用流路之一端連接於該第1供給孔。該最表層形成用流路於中間被分支成第1、第2分支流路,第1、第2分支流路之端部分別連接於第1、第2最表層形成用出口。
藉由採用複合分配法,例如於製造上述第1樹脂層僅配置於一部分之著色之層合玻璃用中間膜之情形時,可自由地設定上述第1樹脂層之厚度及寬度,且可製造不存在色條或褪色之著色之層合玻璃用中間膜。
又,本發明之著色之層合玻璃用中間膜積層於一對玻璃板之間之著色之層合玻璃亦為本發明之一態樣。
上述玻璃板可使用通常使用之透明板玻璃。例如,可列舉浮式平板玻璃、拋光板玻璃、模板玻璃、鋼絲網玻璃、夾線玻璃、經著色之板玻璃、吸熱板玻璃、熱反射板玻璃、綠玻璃等無機玻璃。又,亦可使用於玻璃之表面具有紫外線遮蔽塗層之紫外線遮蔽玻璃。進而,亦可使用聚對苯二甲酸乙二酯、聚碳酸酯、聚丙烯酸酯等有機塑膠板。
作為上述玻璃板,亦可使用2種以上之玻璃板。例如可列舉於透明浮式平板玻璃與如綠玻璃般經著色的玻璃板之間積層有本發明之著色之層合玻璃用中間膜的著色之層合玻璃。又,作為上述玻璃板,亦可使用厚度不同之2種以上之玻璃板。
根據本發明,可提供一種著色之層合玻璃用中間膜及使用該著色之層合玻璃用中間膜之著色之層合玻璃,該著色之層合玻璃用中間膜於使用依據JIS R3202(1996)之2片透明玻璃製作層合玻璃時,可見光線穿透率Tv為5%以下,並且因部位不同所導致之可見光線穿透率之偏差較小,美觀優異。
圖1係表示於表面底部連續之槽形狀之凹部以等間隔且鄰接之凹部平行地並列之層合玻璃用中間膜之一例之模式圖。
圖2係表示於表面底部連續之槽形狀之凹部以等間隔且鄰接之凹部平行地並列之層合玻璃用中間膜之一例之模式圖。
圖3係利用三維粗糙度測定器對在表面底部連續之槽形狀之凹部規則地並列之層合玻璃用中間膜之表面進行測定所得之三維粗糙度之圖像資料。
以下,列舉實施例對本發明之態樣進而詳細地進行說明,但本發明並不僅限定於該等實施例。
(實施例1)
(1)第1樹脂層用樹脂組成物之製備
利用正丁醛使平均聚合度為1700之聚乙烯醇縮醛化,藉此獲得乙醯基 量1莫耳%、丁醛基量69莫耳%、羥基量30莫耳%之聚乙烯醇縮丁醛(以下,亦稱為「PVB」)。相對於所獲得之PVB100質量份,添加作為塑化劑之三乙二醇二(2-乙基己酸酯)(3GO)40質量份、作為著色劑之碳黑,並利用混合輥充分地進行混練,獲得第1樹脂層用樹脂組成物。著色劑之添加量設為於第1樹脂層100質量%中成為0.095質量%之量,且於所獲得之著色之層合玻璃用中間膜整體100質量%中成為0.038質量%之量。
(2)第2樹脂層用樹脂組成物之製備
相對於PVB100質量份,添加作為塑化劑之三乙二醇二(2-乙基己酸酯)(3GO)40質量份,並利用混合輥充分地進行混練,獲得第2樹脂層用樹脂組成物。
(3)著色之層合玻璃用中間膜之製作
使用共擠出機將所獲得之第1樹脂層用樹脂組成物與第2樹脂層用樹脂組成物於擠出溫度200℃之條件下擠出,藉此獲得第1樹脂層/第2樹脂層的2層結構之積層體。
(4)凹部之形成
使用形成有大量微細之凹部與大量微細之凸部之一對壓紋輥作為微細凹凸轉印裝置,並使所獲得之積層體通過該壓紋輥,獲得形成有大量微細之凹部與大量微細之凸部之積層體。
進而,使用一對壓紋輥作為凹凸形狀轉印裝置,使所獲得之形成有大量微細之凹部與大量微細之凸部之積層體通過該壓紋輥,對積層體之兩面賦予底部連續之槽形狀(刻線狀)之凹部以等間隔平行地形成之表面粗糙度(Rz)31μm之凹部,獲得著色之層合玻璃用中間膜。上述一對壓紋輥 係由使用三角形斜線型研磨機對表面實施了研磨加工之金屬輥與具有45~75之JIS硬度之橡膠輥構成。
再者,上述表面粗糙度Rz係藉由依據JIS B-0601(1994)之方法進行測定。作為形成槽形狀(刻線狀)之凹部時之轉印條件,將積層體之溫度設為95℃,將輥溫度設為130℃,將加壓壓力設為500kPa。
針對所獲得之著色之層合玻璃用中間膜,利用上述方法測定各樹脂層之彈性模數及厚度。
其結果為,第1樹脂層之彈性模數E1為9.6N/mm2,厚度t1為305μm。又,第2樹脂層之彈性模數E2為7.0N/mm2,厚度t2為455μm。
(5)著色之層合玻璃之製造
將所獲得之著色之層合玻璃用中間膜積層於長5cm×寬5cm之一對透明玻璃(厚度1.0mm)之間,獲得積層體。利用真空層壓機一面將所獲得之積層體於90℃下保持30分鐘,一面進行真空加壓而進行壓接。壓接後,使用高壓釜於140℃、14MPa之條件下進行20分鐘壓接,獲得著色之層合玻璃。
(實施例2、3)
以著色劑之量及各樹脂層之厚度成為表1記載之值之方式製造第2樹脂層/第1樹脂層/第2樹脂層的3層結構之著色之層合玻璃用中間膜,獲得著色之層合玻璃。於著色之層合玻璃用中間膜及層合玻璃之製造中進行與實施例1相同之操作。
(比較例1)
於第1樹脂層用樹脂組成物之製備中,將著色劑之添加量變更為於所 獲得之第1樹脂層100質量%中成為0.052質量%之量且於所獲得之著色之層合玻璃用中間膜整體100質量%中成為0.037質量%之量。使用該第1樹脂層用樹脂組成物,以與實施例2相同之方式製造各樹脂層之厚度成為表1記載之值的3層結構之著色之層合玻璃用中間膜,獲得著色之層合玻璃。
(比較例2)
於第1樹脂層用樹脂組成物之製備中,將著色劑之添加量變更為於所獲得之第1樹脂層100質量%中成為0.043質量%之量且於所獲得之著色之層合玻璃用中間膜整體100質量%中成為0.037質量%之量。使用該第1樹脂層用樹脂組成物,以與實施例2相同之方式製造各樹脂層之厚度成為表1記載之值的3層結構之著色之層合玻璃用中間膜。
(實施例4~8、比較例3~6)
將塑化劑之量、著色劑之濃度及各樹脂層之厚度以成為表2所記載之值之方式進行變更,除此以外,以與實施例1相同之方式獲得著色之層合玻璃用中間膜及著色之層合玻璃。
(評價)
針對實施例及比較例中所獲得之層合玻璃用中間膜,利用以下之方法進行評價。將結果示於表1及表2。
(可見光線穿透率之測定)
針對所獲得之層合玻璃之任意之20個部位,使用分光光度計(日立高新技術公司製造之「U-4100」),並依據JIS R 3106(1998)測定波長380~780nm之可見光線穿透率。
求出所測得之可見光線穿透率之20點之平均值與標準偏差。算出所獲 得之標準偏差除以可見光線穿透率之平均值後乘以100倍所得之值(標準偏差/可見光線穿透率之平均值×100)作為CV值。
再者,對實施例及比較例中所使用之透明玻璃之可見光線穿透率進行了測定,結果為90.5%。
[產業上之可利用性]
根據本發明,可提供一種著色之層合玻璃用中間膜及使用該著色之層合玻璃用中間膜之著色之層合玻璃,該著色之層合玻璃用中間膜於使用依據JIS R3202(1996)之2片透明玻璃製作層合玻璃時,可見光線穿透率Tv為5%以下,並且因部位不同所導致之可見光線穿透率之偏差較小,美觀優異。
Claims (3)
- 一種著色之層合玻璃用中間膜,其係於至少一表面具有凹部,且於使用依據JIS R3202(1996)之2片透明玻璃製作層合玻璃時,可見光線穿透率Tv為5%以下者,其特徵在於:其係由含有熱塑性樹脂與著色劑之第1樹脂層及含有熱塑性樹脂且不含著色劑之第2樹脂層的至少2層之積層體構成,上述第1樹脂層之彈性模數E 1與上述第2樹脂層之彈性模數E 2之比E 1/E 2為1.25以上,且上述第1樹脂層之厚度t 1與上述第2樹脂層之厚度t 2之比t 1/t 2為2.0以下。
- 如申請專利範圍第1項之著色之層合玻璃用中間膜,其係由第1樹脂層被夾於2片第2樹脂層之間之3層以上之積層體構成。
- 一種著色之層合玻璃,其於一對玻璃板之間積層有申請專利範圍第1或2項之著色之層合玻璃用中間膜。
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KR20220061278A (ko) | 2022-05-12 |
JP6943767B2 (ja) | 2021-10-06 |
EP3495333A1 (en) | 2019-06-12 |
US10926515B2 (en) | 2021-02-23 |
KR102623134B1 (ko) | 2024-01-09 |
KR102554523B1 (ko) | 2023-07-11 |
CN109562990A (zh) | 2019-04-02 |
US20190291389A1 (en) | 2019-09-26 |
US11117351B2 (en) | 2021-09-14 |
MX2019001177A (es) | 2019-07-22 |
KR20220101003A (ko) | 2022-07-18 |
JPWO2018025932A1 (ja) | 2019-06-06 |
WO2018025937A1 (ja) | 2018-02-08 |
US20210362478A1 (en) | 2021-11-25 |
WO2018025932A1 (ja) | 2018-02-08 |
CN109219585A (zh) | 2019-01-15 |
TWI749041B (zh) | 2021-12-11 |
JPWO2018025937A1 (ja) | 2019-06-06 |
EP3495332A4 (en) | 2020-04-08 |
MX2019001178A (es) | 2019-07-22 |
TW201819182A (zh) | 2018-06-01 |
EP3495333A4 (en) | 2020-03-11 |
JP6949715B2 (ja) | 2021-10-13 |
US20190299569A1 (en) | 2019-10-03 |
KR20190038476A (ko) | 2019-04-08 |
KR20190035606A (ko) | 2019-04-03 |
US11724480B2 (en) | 2023-08-15 |
EP3495332A1 (en) | 2019-06-12 |
TWI742126B (zh) | 2021-10-11 |
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