TWI711681B - 接著片 - Google Patents

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Publication number
TWI711681B
TWI711681B TW105111191A TW105111191A TWI711681B TW I711681 B TWI711681 B TW I711681B TW 105111191 A TW105111191 A TW 105111191A TW 105111191 A TW105111191 A TW 105111191A TW I711681 B TWI711681 B TW I711681B
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TW
Taiwan
Prior art keywords
adhesive sheet
adhesive
adhesive layer
expandable
resin
Prior art date
Application number
TW105111191A
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English (en)
Other versions
TW201641635A (zh
Inventor
雷鳴
戶高勝則
Original Assignee
日商寺岡製作所股份有限公司
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=57073190&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=TWI711681(B) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 日商寺岡製作所股份有限公司 filed Critical 日商寺岡製作所股份有限公司
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Abstract

本發明揭示一種接著片,其於基材1之單面或雙面具有膨脹性接著劑層2,膨脹性接著劑層2係含有包含多官能環氧樹脂之環氧樹脂、作為硬化劑之酚樹脂、作為硬化觸媒之咪唑系化合物、及感溫性發泡劑而成。該接著片平衡性良好地具有尤其是快速硬化性、耐熱性、接著性等特性,且因充分之填充性而導熱性等各特性亦優異。

Description

接著片
本發明係關於一種具有包含環氧樹脂或感溫性發泡劑之膨脹性接著劑層之接著片。本發明之接著片可用於例如以下用途:使用於如馬達發電機(motor generator)之定子與線圈般之兩個構件之間,並將其加熱,藉此使其膨脹、發泡、硬化,填充於該間隙中而將構件彼此接著。
環氧樹脂接著劑因具有優異之耐熱性及牢固之接著性,故而廣泛用於構件接著或構造接著等。
例如,於近年來快速普及之電動汽車或油電混合車之馬達中,捲繞漆包線而成之線圈藉由環氧樹脂固定於定子鐵芯(stator core)。於習知之方法中,藉由以下方式進行固定:將絕緣紙插入至導體線圈與定子鐵芯之間,並將液狀環氧樹脂接著劑注入至導體線圈與定子鐵芯之間之間隙(縫隙)中,進行加熱使接著劑硬化。其中,由於導體線圈與定子鐵芯之縫隙非常窄,接著劑難以進入,故而出現空隙,或於為了避免此狀況而擴大縫隙之情況時,由於接著劑之散熱性較低,故而馬達之散熱性降低而性能降低,或為了完全填埋縫隙而需要大量之接著劑。又,需要將過量之接著劑自定子鐵芯去除之作業。進而,液狀接著劑通常難以準確地控制塗佈量或塗佈位置。而且,環氧樹脂等加熱硬化性接著劑藉由加熱而黏 度降低,容易滴下液體,有污染被黏體或作業周邊之虞,而需要使用圍欄或障壁等治具防止液體滴落於接著部以外之區域。如此,液狀環氧樹脂接著劑於使用時之作業性方面存在較多問題。
因此,業界提出有使用具有發泡性之環氧樹脂接著劑層之接著片代替液狀環氧樹脂接著劑(專利文獻1~4)。然而,製造汽車馬達所使用之接著片所要求之特性除作業性以外涉及多方面。例如,於接著劑層之發泡硬化步驟中,較佳為接著劑保持適度之黏性,同時於短時間內均勻地發泡硬化。具體而言,謀求於180℃下以30分鐘左右,較佳為以10分鐘左右進行發泡硬化。又,發泡硬化後之接著片需要接著劑層不會脫落之柔軟性或對於基材之密接性。又,謀求不僅於室溫下,而且於高溫環境下,具體而言,即便於150℃下,較佳為於200℃下加熱500小時以上接著強度亦不會降低之耐熱性、與即便浸漬於潤滑油中接著強度亦不會降低之耐油性。又,必須以填埋導線成為束之線圈等被黏體之凹凸之方式進行填充。為了抑制馬達之因溫度上升所致之性能降低,亦需要優異之散熱性及導熱性。進而,為了可將接著片快速插入至導體線圈與定子之間之狹窄縫隙中,謀求形狀保持性或基材之韌性且需要用以確保定子與被覆導線之絕緣可靠性之絕緣性。出於產生垃圾之環境考慮,亦存在謀求不使用剝離紙之情況。
於專利文獻1中,以藉由接著片使定子之線圈確實地固定於定子鐵芯作為目的,但未研究快速硬化性或耐熱性(例如抑制高溫下之接著強度之降低)。於專利文獻2及3中,由於接著片之中間層為發泡層,其外側具有不發泡之接著劑層,故而對於凹凸被黏體之填充性或導熱性較差,又,未研究快速硬化性或耐熱性(例 如抑制高溫下之接著強度之降低)。於專利文獻4中,以接著性或作業性之提高作為主要目的,但未研究快速硬化性或耐熱性(抑制高溫下之接著強度之降低)。
[先前技術文獻] [專利文獻]
專利文獻1:日本專利特開2011-244596號公報
專利文獻2:日本專利特開2010-261030號公報
專利文獻3:日本專利特開2012-170248號公報
專利文獻4:日本專利特開2013-104044號公報
本發明之目的在於提供一種平衡性良好地具有尤其是快速硬化性、耐熱性、接著性等特性,且因充分之填充性而導熱性等各特性亦優異之接著片。
本發明係一種具有膨脹性接著劑層之接著片,該膨脹性接著劑層係含有包含多官能環氧樹脂之環氧樹脂、作為硬化劑之酚樹脂、作為硬化觸媒之咪唑系化合物、及感溫性發泡劑而成。
本發明之接著片即便膨脹性接著劑層於短時間內發泡硬化亦具有較高之柔軟性,而且例如製造汽車馬達所使用之接著片所要求之各特性亦優異。即,根據本發明,提供一種平衡性良好地具有尤其是快速硬化性、耐熱性、接著性等特性,且因充分之填 充性而導熱性等各特性亦優異之接著片。
1:基材
2:膨脹性接著劑層
3:脫模劑層
4:薄膜
5:貼合用接著劑層
6:不織布
7:紙
8:功能性接著劑層
9:剝離薄膜
10:接著片
11:SPCC板
12:金屬測隙規
13:鋁L字形框
14:接著片
15:推壓治具
圖1係表示本發明之接著片之一實施形態之示意剖面圖。
圖2係表示本發明之接著片之一實施形態之示意剖面圖。
圖3係表示本發明之接著片之一實施形態之示意剖面圖。
圖4係表示本發明之接著片之一實施形態之示意剖面圖。
圖5係表示本發明之接著片之一實施形態之示意剖面圖。
圖6係表示本發明之接著片之一實施形態之示意剖面圖。
圖7係表示本發明之接著片之一實施形態之示意剖面圖。
圖8(A)及(B)係用以說明實施例之剪切接著力之試驗方法之示意圖。
圖9係用以說明實施例之形狀保持性之試驗方法之示意圖。
圖1~7係表示本發明之接著片之一實施形態之示意剖面圖。於圖1所示之實施形態中,於單層之基材1之雙面設置有膨脹性接著劑層2,膨脹性接著劑層2包含有適量耐熱性填料。又,存在視需要於其中一個膨脹性接著劑層2之表面設置有脫模劑層3之情況。
於圖2所示之實施形態中,基材1包含具有經由貼合用接著劑層5積層2片樹脂薄膜4而成之構造之積層體。貼合用接著劑層5包含有適量耐熱性填料。並且,於基材1之雙面設置有膨脹性接著劑層2,膨脹性接著劑層2包含有適量耐熱性填料。又,存在視需要於其中一個膨脹性接著劑層2之表面設置有脫模劑層3 之情況。
於圖3所示之實施形態中,基材1包含具有經由貼合用接著劑層5積層樹脂薄膜4與不織布6而成之構造之積層體。於不織布6中含浸有包含適量耐熱性填料之樹脂組成物。其他構成與圖2相同。
於圖4所示之實施形態中,基材1包含具有經由貼合用接著劑層5積層樹脂薄膜4與紙6而成之構造之積層體。其他構成與圖2相同。
於圖5所示之實施形態中,基材1包含於樹脂薄膜4之雙面具有功能性接著劑層8之積層體。功能性接著劑層8包含有適量耐熱性填料及纖維狀填料。其他構成與圖2相同。
於圖6所示之實施形態中,於單層之基材1之單面設置有膨脹性接著劑層2,膨脹性接著劑層2包含有適量耐熱性填料。又,於膨脹性接著劑層2或基材1之表面設置有脫模劑層3。
於圖7所示之實施形態中,無基材1,於膨脹性接著劑層2之雙面設置有剝離薄膜9。膨脹性接著劑層2包含有適量耐熱性填料。此種無基底型接著片係剝去剝離薄膜9而使用。
以下,對本發明之接著片之各構成進行說明。
[基材1]
如圖1~6所示,本發明之基材1係用以支撐膨脹性接著劑層2之構件。其中,亦可為如圖7所示般無基材1之無基底型接著片。
基材1較佳為具有耐熱性。耐熱性之等級因使用用途而異,例如,基材1之熔融溫度較佳為200℃以上,更佳為250℃ 以上。又,例如依據UL-746B而測定之基材1之連續使用溫度較佳為100℃以上,更佳為150℃以上。又,於基材1包含樹脂之情況時,該樹脂之玻璃轉移點較佳為80℃以上,更佳為140℃以上,尤佳為200℃以上。
基材1可為如圖1及6所示般包含一個構件之單層基材,亦可為如圖2~4所示般包含具有藉由貼合用接著劑貼合一個構件與其他構件而成之積層構造之積層體之基材,亦可為如圖5所示般包含構件之單面或雙面具有功能性接著劑層之積層體之基材。基材1可具有柔軟性,或亦可具有反彈性,其性狀根據用途而適當選擇。於要求接著片之強度(剛性)或形狀保持性之用途中,基材1較佳為如圖2~4所示般包含具有藉由貼合用接著劑貼合一個構件與其他構件而成之積層構造之積層體之基材,及如圖5所示般包含構件之單面或雙面具有功能性接著劑層之積層體之基材,該構件更佳為選自由樹脂薄膜4、不織布6及紙7所組成之群組中之一種以上之構件。進而具體而言,更佳為如圖2~4所示般包含具有藉由貼合用接著劑貼合樹脂薄膜4與不織布6、或樹脂薄膜4與紙7、或樹脂薄膜4與樹脂薄膜4而成之積層構造之積層體之基材1。該等較佳之實施形態例如於馬達槽之製造等用途中非常適宜。於此種用途中,需要將接著片快速且穩定地插入至如槽般之狹窄間隙中,故而謀求強度(剛性)較高且彎折後之形狀保持性優異之基材。
作為樹脂薄膜4之具體例,可列舉:聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯(PEN)、芳香族聚酯等聚酯系樹脂;聚碳酸酯;聚芳酯;聚胺基甲酸乙酯;聚醯胺、聚醚醯胺等聚醯胺系樹脂;聚醯亞胺、聚醚醯亞胺、聚醯胺醯 亞胺等聚醯亞胺系樹脂;聚碸、聚醚碸等聚碸系樹脂;聚醚酮、聚醚醚酮等聚醚酮系樹脂;聚苯硫醚(PPS);改質聚苯醚。亦可併用2種以上之樹脂薄膜4。其中,就耐熱性、絕緣性及成本之平衡之方面而言,較佳為聚萘二甲酸乙二酯(PEN)。
作為不織布6之具體例,可列舉包含纖維素纖維、聚酯纖維、尼龍纖維、聚芳醯胺纖維(aramid fiber)、聚苯硫醚纖維、液晶聚合物纖維、玻璃纖維、金屬纖維、碳纖維等纖維之不織布。亦可併用2種以上之不織布6。其中,較佳為聚芳醯胺纖維不織布、玻璃纖維不織布、聚苯硫醚纖維不織布、耐熱尼龍纖維不織布、耐熱聚酯纖維不織布。就耐熱性、導熱性、及膨脹性接著劑層2之滲入防止等方面而言,較佳為於不織布6中含浸包含耐熱性填料之樹脂組成物。作為樹脂之具體例,可列舉聚酯樹脂、聚醯胺樹脂、丁醛樹脂、胺基甲酸乙酯樹脂、丙烯酸系樹脂、環氧樹脂。其中,較佳為胺基甲酸乙酯樹脂。耐熱性填料之具體例與後述之各接著劑中所包含之耐熱性填料之具體例相同。
作為紙7,較佳為吸水性較低,耐熱性較高者。尤佳為包含全芳香族聚醯胺聚合物之高耐熱性紙。亦可將紙7設為包含2種以上之纖維之混抄紙之樣態。
貼合用接著劑層5及功能性接著劑層8皆為使用接著劑而形成之層。並且,貼合用接著劑層5係以貼合構成基材之構件為目的而設置之層,亦可視需要適量填充賦予導熱性、絕緣性、耐熱性等特殊功能之添加劑。功能性接著劑層8係以藉由包含接著劑以外之成分(填料等)賦予接著片某些功能(耐熱性、導熱性、強度(剛性)等)為目的而設置之層。功能性接著劑層8例如設置於選自由樹 脂薄膜4、不織布6及紙7所組成之群組中之構件之單面或雙面。
構成貼合用接著劑層5及功能性接著劑層8之接著劑並無特別限定。亦可較佳地使用與後述之構成膨脹性接著劑層2之接著劑相同之接著劑。尤其是就對於薄膜4等之潤濕性或接著之均勻性之方面而言,較佳為包含軟化點較低之成分或液狀成分。又,就積層基材之平滑性之方面而言,較佳為硬化收縮率較小之環氧樹脂。構成貼合用接著劑層5及功能性接著劑層8之接著劑亦可含有感溫性發泡劑,但亦存在不含感溫性發泡劑而不發泡時較佳之情況。
就耐熱性或導熱性之方面而言,構成貼合用接著劑層5及功能性接著劑層8之接著劑較佳為包含耐熱性填料。耐熱性填料之種類並無特別限定,例如可列舉:氧化鋁、氧化鎂、氧化鈣、氫氧化鋁、氫氧化鎂、氮化硼、氮化矽、氧化矽、滑石(矽酸鎂)等無機填料。亦可併用2種以上之耐熱性填料。耐熱性填料之含量相對於接著劑中之樹脂成分100質量份,較佳為10~300質量份,更佳為50~150質量份。
構成貼合用接著劑層5及功能性接著劑層8之接著劑亦可包含纖維狀填料作為耐熱性填料。尤其是構成功能性接著劑層8之接著劑較佳為包含纖維狀填料。纖維狀填料於提高接著片之強度(剛性)之方面有用。作為纖維狀填料之具體例,可列舉聚酯纖維、聚醯胺纖維、玻璃纖維。亦可併用2種以上之纖維狀填料。其中,較佳為玻璃纖維。纖維狀填料之平均纖維直徑較佳為1~20μm,平均纖維長度較佳為10~150μm。
為了提高與膨脹性接著層2之密接性,亦可對基材1 實施電暈處理或底塗處理等。
基材1之厚度只要根據使用用途適當選擇即可,一般而言為2~200μm。尤其是用於馬達之定子與線圈之接著絕緣等之情況時,較佳為9~100μm,更佳為12~50μm。
[膨脹性接著劑層2]
本發明之膨脹性接著劑層2含有包含多官能環氧樹脂之環氧樹脂、作為硬化劑之酚樹脂、作為硬化觸媒之咪唑系化合物、及感溫性發泡劑。
膨脹性接著劑層2較佳為包含環氧樹脂作為主成分。多官能環氧樹脂之種類並無限定,較佳為苯酚酚醛清漆型、甲酚酚醛清漆型等酚醛清漆型環氧樹脂及該等之混合物。若使用酚醛清漆型環氧樹脂,則硬化物之玻璃轉移點變高,故而存在即便於高溫下接著力亦穩定之傾向。
作為環氧樹脂,亦可併用多官能環氧樹脂以外之環氧樹脂。藉由混合使用多官能環氧樹脂及其以外之環氧樹脂,可容易且詳細地調整環氧樹脂之軟化點、熔融黏度、玻璃轉移點、儲存彈性模數等物性。一般而言,若混合軟化點較低或液狀之環氧樹脂,則可提高接著劑層之加熱時之流動性及硬化前後之可撓性。另一方面,若混合軟化點較高或者半固體或固體之環氧樹脂,則可降低接著劑層表面之黏著性。又,液狀之環氧樹脂亦可用於使感溫性發泡劑中所包含之粉狀或粒狀之熱膨脹性微膠囊等成分預分散之目的或使環氧樹脂成分均勻混合之目的。
作為此種能夠混合之環氧樹脂之具體例,可列舉:雙 酚A型、二聚酸改質雙酚A型、雙酚F型等雙酚型環氧樹脂;己二醇二縮水甘油醚等具有脂肪族骨架之環氧樹脂;苯氧基樹脂(由雙酚類與表氯醇合成之多羥基聚醚);結晶環氧樹脂。結晶環氧樹脂於常溫下為無黏著性之固體,與此相對,於熔點以上熔融黏度大幅降低,就該方面而言,於熔點以上時作為反應性稀釋劑而發揮作用。因此,若使結晶環氧樹脂包含於接著層中,則可進一步提高接著層之加熱時之流動性,有利地作用於接著層之熱膨脹。又,就於室溫下為非黏著性之固體之方面而言,有助於降低接著層表面之黏著性或使接著層表面變為非黏著性。於藉由熔融塗佈法形成接著層之情況時,藉由加熱至結晶環氧樹脂之熔點以上,亦可降低環氧樹脂之熔融黏度,提高熔融塗佈之速度。
環氧樹脂之數量平均分子量以基於凝膠滲透層析法(GPC,gel permeation chromatography)之標準聚苯乙烯換算,一般而言為100~60000。環氧樹脂之環氧當量一般而言為50~30000g/eq。
作為膨脹性接著劑層2所使用之環氧樹脂之硬化劑,使用酚樹脂。於本發明中,使用酚樹脂作為硬化劑,並組合使用後述之作為硬化觸媒之咪唑系化合物於縮短硬化時間且提高耐熱性之方面較為重要。又,藉由使用酚樹脂作為硬化劑,而使耐熱性、電氣特性等之設計變得容易。酚樹脂之添加量於理論上而言,以酚樹脂之羥基當量數相對於環氧樹脂之環氧當量數為1比1左右之方式決定。酚樹脂之羥基當量數相對於環氧樹脂之環氧當量數之比率通常為0.5~2.0,較佳為0.8~1.2。
作為膨脹性接著劑層2所使用之環氧樹脂之硬化觸 媒,使用咪唑系化合物。於本發明中,使用咪唑系化合物作為硬化觸媒,並組合使用作為硬化劑之酚樹脂於縮短硬化時間且提高耐熱性之方面較為重要。例如,於習知技術中,存在不使用酚樹脂作為硬化劑,而大量使用咪唑系化合物作為硬化劑之情況,該情況難以獲得如本發明般之優異之長期耐熱等耐久性。於本發明中,使用咪唑系化合物作為硬化觸媒,即僅使用作為觸媒之量(少量),且使用酚樹脂作為硬化劑,即,使用作為硬化劑之量(大量),藉此獲得本發明之效果。又,咪唑系化合物與其他硬化觸媒相比,能夠單獨用作觸媒,且亦具有粒徑非常細之等級,故而具有使用方便之優點。
作為咪唑系化合物之具體例,可列舉:2-苯基-4,5-二羥甲基咪唑、2-苯基-4-甲基咪唑、2-乙基-4-甲基咪唑、2,4-二乙基咪唑、2-苯基-4-甲基-5-羥基咪唑等咪唑衍生物。亦可併用2種以上之咪唑系化合物。其中,較佳為2-苯基-4,5-二羥甲基咪唑。咪唑系化合物之含量相對於膨脹性接著劑層中之樹脂成分100質量份,較佳為0.1~1.0質量份,更佳為0.3~0.8質量份。
作為膨脹性接著劑層2所使用之感溫性發泡劑,例如可列舉:碳酸銨、碳酸氫銨、亞硝酸銨、硼氫化銨、疊氮類等無機系發泡劑;三氯單氟甲烷等氟化烷烴、偶氮二異丁腈等偶氮系化合物、對甲苯磺醯肼等肼系化合物、對甲苯磺醯胺基脲等胺基脲系化合物、5-
Figure 105111191-A0101-12-0011-15
啉基-1,2,3,4-噻三唑等三唑系化合物、N,N-二亞硝基對苯二甲醯胺等N-亞硝基化合物等有機系發泡劑;使包含烴系化合物等之熱膨脹劑微膠囊化而成之熱膨脹性微膠囊。亦可併用2種以上之感溫性發泡劑。其中,就不阻礙環氧樹脂之硬化,減少對環氧樹脂之物性造成之不良影響之方面而言,較佳為熱膨脹性微膠囊。
熱膨脹性微膠囊係將具有阻氣性之熱塑性樹脂作為外殼,於外殼之內部包含熱膨脹劑之微膠囊。若將熱膨脹性微膠囊加熱,則外殼之熱塑性樹脂軟化,熱膨脹劑之體積增大,藉此膠囊膨脹。例如,可將低沸點之烴系化合物之氣化用於膠囊之膨脹。
熱膨脹性微膠囊之膨脹(發泡)溫度較佳為環氧樹脂之軟化點以上且環氧樹脂之硬化反應之活化性溫度以下。若該發泡溫度為環氧樹脂之軟化點以上,則可於變軟之環氧樹脂之中使熱膨脹劑充分膨脹,而可使發泡後之膨脹性接著劑層2之厚度均勻。又,若該發泡溫度為環氧樹脂之硬化反應之活化性溫度以下,則可防止環氧樹脂於發泡前硬化。進而,藉由將環氧樹脂之軟化點設為硬化反應之活化性溫度以下,於接著片之製造步驟中包含熔融或溶液塗佈之情況時,可防止於該等塗佈步驟及伴隨其之乾燥步驟中環氧樹脂凝膠化。
環氧樹脂之軟化點可使用JIS K 2207中所規定之環球式軟化點試驗法而測定。所謂熱膨脹性微膠囊之發泡溫度,係指產生熱膨脹性微膠囊之體積變化之溫度,例如可自70℃以上且200℃以下、較佳為100℃以上且180℃以下之範圍選擇。
感溫性發泡劑之含量及體積膨脹率可根據硬化後之膨脹性接著劑層2所要求之強度及接著力、接著片所要求之膨脹率等而適當決定。感溫性發泡劑之含量相對於膨脹性接著劑層2中之樹脂成分100質量份,較佳為0.5~20質量份,更佳為2~15質量份。發泡後之接著片之厚度之增加倍數例如可設為1.1倍以上且10倍以下。
就與基材1之密接性、彎折接著片時之柔軟性、接著 劑塗佈時之勻平性、防止加熱發泡硬化時之液體滴落等方面而言,較佳為於膨脹性接著劑層2中添加其他樹脂(耐熱性樹脂等)。作為其他樹脂之具體例,可列舉聚酯樹脂、丁醛樹脂、胺基甲酸乙酯樹脂、羧基末端丁二烯腈橡膠(CTBN)、環氧改質丁二烯。其中,就柔軟性或接著性之方面而言,最佳為胺基甲酸乙酯樹脂。
胺基甲酸乙酯樹脂一般而言係含有包含多元醇單體單位之軟鏈段、與包含多官能異氰酸酯化合物或低分子二醇單體單位之硬鏈段之樹脂。胺基甲酸乙酯樹脂中所使用之多元醇係具有2個以上羥基之化合物。就提高橡膠彈性伸長恢復率等特性之方面而言,多元醇之羥基數較佳為2~3,更佳為2。作為多元醇,例如可使用聚酯多元醇、聚醚多元醇、聚己內酯多元醇、聚碳酸酯多元醇、蓖麻油系多元醇。亦可併用2種以上之多元醇。
作為用作用以使多元醇交聯之交聯劑之多官能異氰酸酯化合物,例如可使用多官能脂肪族系異氰酸酯化合物、多官能脂環族系異氰酸酯化合物、多官能芳香族系異氰酸酯化合物。又,亦可使用該等化合物之三羥甲基丙烷加成體、與水反應而獲得之縮二脲體、具有異氰脲酸酯環之三聚物。亦可併用2種以上之多官能異氰酸酯化合物。
作為多官能脂肪族系異氰酸酯化合物之具體例,可列舉:三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、五亞甲基二異氰酸酯、1,2-伸丙基二異氰酸酯、1,3-伸丁基二異氰酸酯、十二亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯。
作為多官能脂環族系異氰酸酯化合物之具體例,可列 舉:1,3-環戊烯二異氰酸酯、1,3-環己烷二異氰酸酯、1,4-環己烷二異氰酸酯、異佛爾酮二異氰酸酯、氫化二苯基甲烷二異氰酸酯、氫化苯二甲基二異氰酸酯、氫化甲苯二異氰酸酯、氫化四甲基苯二甲基二異氰酸酯。
作為多官能芳香族系二異氰酸酯化合物之具體例,可列舉:伸苯基二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、2,2'-二苯基甲烷二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、4,4'-甲苯胺二異氰酸酯、4,4'-二苯醚二異氰酸酯、4,4'-二苯基二異氰酸酯、1,5-萘二異氰酸酯、苯二甲基二異氰酸酯。
胺基甲酸乙酯樹脂係使含有以上說明之多元醇與多官能異氰酸酯化合物之組成物硬化而獲得。尤其是就橡膠彈性伸長恢復率等特性之方面而言,較佳為低結晶性之線性聚酯系聚胺基甲酸酯樹脂,更佳為己二醇共聚酯系聚胺基甲酸酯樹脂、聚四亞甲基二醇系聚胺基甲酸酯樹脂。
胺基甲酸乙酯樹脂之含量於膨脹性接著劑層2中之樹脂成分100質量份中,較佳為60質量份以下。
就耐熱性或導熱性之方面而言,膨脹性接著劑層2較佳為包含耐熱性填料。耐熱性填料之種類並無特別限定,例如可列舉:氧化鋁、氧化鎂、氧化鈣、氫氧化鋁、氫氧化鎂、氮化硼、氮化矽、氧化矽、滑石(矽酸鎂)等無機填料。亦可併用2種以上之耐熱性填料。耐熱性填料之含量相對於接著劑中之樹脂成分100質量份,較佳為20~300質量份,更佳為50~100質量份。
膨脹性接著劑層2亦可視需要包含酚系抗氧化劑、硫系抗氧化劑等抗氧化劑、環氧改質烷氧基矽烷等矽烷偶合劑、熏矽 (fumed silica)等觸變劑、及用以識別之顏料或染料等添加劑。
膨脹性接著劑層2可為連續層,亦可為包含數種條紋、圓點等圖案之不連續者。進而,亦可於膨脹性接著劑層2之表面形成有壓紋等凹凸。藉由將膨脹性接著劑層2製成不連續者,或於接著劑層之表面形成壓紋等凹凸,可降低膨脹性接著劑層2之表面之黏著性或實質上將接著劑層設為非黏著性,或者調整接著力,或者僅於需要部分形成接著劑層。又,此種膨脹性接著劑層2之表面之不均勻性於發泡時會減輕或消除,故而亦難以產生該不均勻性對接著力之不良影響。
[脫模劑層3]
於一般之雙面接著片,通常以防止接著劑層黏連之目的而設置有剝離紙。然而,近年來出於環境考慮,亦存在謀求不使用剝離紙之接著片之情況。又,一般而言,期待接著劑層具有可暫時固定於被黏體之程度之黏著性之情況較多,亦存在於加熱前接著劑層為非黏著性(不黏著)而較為有利之情況。例如,若熱膨脹性接著劑層2為非黏著性,則進而提高接著片之操作性及作業性。具體而言,於將定子鐵芯與線圈接著之情況時,具有非黏著性之接著劑層之接著片可更加平滑地插入至定子鐵芯之間隙,且可於插入接著片而變得更狹窄之間隙更加平滑地插入線圈。就此方面而言,於本發明之接著片中,較佳為於至少一個膨脹性接著劑層2之表面塗佈脫模劑。進而,於基材1之雙面具有膨脹性接著劑層2之情況時,較佳為於至少一個膨脹性接著劑層2之表面塗佈脫模劑。
於習知技術中,脫模劑通常塗佈於基材之表面而非塗 佈於接著劑層。另一方面,於本發明中,可以新穎之構思實現將脫模劑直接塗佈於膨脹性接著劑層2之表面,且不影響接著性等特性。為了減少對於膨脹性接著劑層2之不良影響,本發明中所使用之脫模劑必須滿足以下之必要條件(a)及(b)之任一者。
(a)構成脫模劑之成分為低分子量,於低溫(使用前之接著片之保管時溫度)下發揮脫模功能,但於高溫(使用時之接著片之發泡硬化溫度)下其成分分解、蒸發或昇華,幾乎喪失脫模功能。
(b)脫模劑之塗佈量較少,於使用時之接著片之膨脹性接著劑層2之軟化、熔融、流動及發泡所致之混合至硬化之過程中,脫模劑進入接著劑層中而幾乎喪失脫模功能。
作為脫模劑之具體例,可列舉石蠟或長鏈烷基系化合物等有機系熱熔融聚合物;矽酮、碳酸鈣、氧化矽微粒子等無機系微粒子。其中,就接著片之保存穩定性或接著性之方面而言,較佳為長鏈烷基系化合物。有機或無機系油會污染接著片之生產線或使用線,並且大幅降低膨脹性接著劑層2之接著性,故而不佳。
作為長鏈烷基系化合物,可使用市售之長鏈烷基系脫模劑。例如,有作為有機溶劑可溶型長鏈烷基系脫模劑之「PEELOIL(註冊商標)1010」(Lion.Specialty.Chemicals公司製造)、作為水分散型長鏈烷基系脫模劑之「NC003」(中京油脂公司製造)。尤其是就防止有機溶劑向接著劑層滲入或接著劑成分滲出之方面而言,較佳為水分散型長鏈烷基系化合物。
水分散型長鏈烷基系化合物只要以成為適度濃度之方式用水稀釋,並以乾燥後之脫模劑層3之厚度成為0.02~0.2μm之方式塗佈即可。若該厚度為0.02μm以上,則有脫模性穩定之傾 向,若為0.2μm以下,則有膨脹性接著劑層2之發泡硬化時之接著性難以降低之傾向。將水分散型長鏈烷基系化合物於如環氧樹脂接著劑層般之極性相對較低之層之表面塗佈成薄膜時,較佳為使用適合之潤濕性改善劑。作為潤濕性改善劑之具體例,可列舉乙炔二醇。
[接著片]
本發明之接著片係具有以上說明之膨脹性接著劑層2之接著片,更具體而言,係於基材1之單面或雙面具有膨脹性接著劑層2之接著片,或無基材1之無基底型接著片。接著片亦可具有基材1及膨脹性接著劑層2以外之層或構件,例如脫模劑層3或脫模薄膜9。
本發明之接著片於發泡硬化前之厚度例如為10~1000μm。於將本發明之接著片插入至例如定子鐵芯與線圈間之狹窄間隙之情況時,發泡硬化前之厚度較佳為250μm以下,更佳為20~200μm。
本發明之接著片之初期接著性優異,並且耐熱性亦優異。具體而言,膨脹性接著劑層2發泡硬化後之接著片之依據JIS Z 1541測得之剪切接著力於室溫(23℃)時較佳為200N/cm2以上,更佳為300N/cm2以上,200℃加熱時較佳為50N/cm2以上,更佳為100N/cm2以上。
本發明之接著片之電氣絕緣性優異。具體而言,膨脹性接著劑層2發泡硬化後之接著片之依據JIS C 2107測得之絕緣破壞電壓較佳為3kV以上,更佳為5kV以上,導熱率較佳為0.1W/mK 以上,更佳為0.15W/mK以上。
本發明之接著片之彎曲強度與彎折後之形狀保持性優異。具體而言,膨脹性接著劑層2發泡硬化前之接著片之依據JIS P 8125測得之彎曲力矩較佳為40~600gf.cm,更佳為50~150gf.cm。並且,膨脹性接著劑層發泡硬化前之接著片之利用以下方法所測定之形狀保持率較佳為70%以上,更佳為90%以上。
(形狀保持率)
將膨脹性接著劑層發泡硬化前之接著片放置於鋁L字形框中,將推壓治具以45度之角度自接著片上向角隅(corner)推壓,以成為L字形之方式實施彎曲加工,取出試驗片,5秒後測定試驗片之角度,藉由下式進行計算。
形狀保持率(%)=90度÷(彎折加工5秒後之角度)×100(%)
本發明之接著片之製造方法並無特別限定。雙面接著片可藉由於基材1之一表面上形成第1膨脹性接著劑層2,繼而於基材1之另一表面上形成第2膨脹性接著劑層2而製造。無基底型接著片可藉由於剝離薄膜9之表面上形成膨脹性接著劑層2,繼而於膨脹性接著劑層2上貼合另一剝離薄膜9而製造。但,亦能夠利用該等以外之方法,例如亦能夠同時塗佈膨脹性接著劑,或不使用單面之剝離薄膜9而製作。
膨脹性接著劑層2可利用例如溶液塗佈法、熔融塗佈法、熔融擠出法、軋壓法等習知之方法而形成。熔融塗佈法可於無溶劑下進行,無需溶劑之去除步驟、處理設備等,故而於生產性及經濟性之方面而言較佳。於使用熔融塗佈法之情況時,較佳為環氧樹脂包含結晶環氧樹脂。於該情況時,藉由加熱至結晶環氧樹脂之 熔點以上,可降低環氧樹脂之熔融黏度,可提高熔融塗佈之速度。
<實施例>
以下,藉由實施例進而說明本發明,但本發明並不限定於該等。
<基材製作用接著劑之製備>
以表1所示之量(質量份)混合以下之各成分,而獲得基材製作用接著劑(組成1~5)。
「EP1」:環氧樹脂(液狀、黏度13,500mPa.s(25℃)、環氧當量189g/eq、BPA型、標準液狀品)
「EP2」:環氧樹脂(半固形、環氧當量173g/eq、多官能苯酚酚醛清漆型、耐熱性型)
「EP3」:環氧樹脂(軟化點70℃、環氧當量210g/eq、特殊酚醛清漆型、耐熱性型)
「EP4」:環氧樹脂(軟化點92℃、環氧當量200g/eq、特殊多官能型、高耐熱性型)
「EP5」:環氧樹脂(軟化點86℃、環氧當量230g/eq、萘環型、耐熱性.韌性型)
「EP6」:環氧樹脂(軟化點92℃、環氧當量395g/eq、異氰酸酯改質型、高Tg.高韌性.強接著型)
「PU」:線性聚酯聚胺基甲酸酯樹脂(軟化點87℃、分子量222300、羥基含量0.1%、接著性.柔軟性型)
「H」:熱膨脹性微膠囊(平均粒徑9μm、膨脹開始溫度120~130 ℃、最大膨脹溫度145~155℃)
「T1」:酚樹脂(軟化點87℃、羥基當量178g/eq、酚醛清漆型、高耐熱性型)
「T2」:異氰酸酯系硬化劑(Nippon Polyurethane Industry公司製造,Coronate(註冊商標)L)
「T3」:2-苯基-4,5-二羥甲基咪唑(四國化成工業公司製造,商品名2PHZ-PW、熔點220℃、活性區域141~153℃、開始區域153~168℃)
「J1」:氧化鎂(平均粒徑3μm)
「J2」:矽酸鎂(平均粒徑5μm)
「J3」:玻璃纖維(平均纖維直徑6μm、平均纖維長度50μm)
「MEK」:甲基乙基酮
Figure 105111191-A0305-02-0022-1
<基材之製作>
作為基材用構件,準備以下之各構件F1~F6、P。
「F1」:聚萘二甲酸乙二酯(PEN)薄膜(杜邦帝人薄膜公司製造,Teonex(註冊商標)Q51、厚度38μm)
「F2」:聚萘二甲酸乙二酯(PEN)薄膜(杜邦帝人薄膜公司製造,Teonex(註冊商標)Q51、厚度12μm)
「F3」:聚苯硫醚(PPS)薄膜(東麗公司製造,TORELINA(註冊商標)#50-2030、厚度50μm)
「F4」:聚對苯二甲酸乙二酯(PET)薄膜(東麗公司製造,Lumirror(註冊商標)S-10、厚度50μm)
「F5」:聚對苯二甲酸乙二酯(PET)薄膜(東麗公司製造,Lumirror(註冊商標)S-10、厚度38μm)
「F6」:含浸有接著劑(組成5)之芳族聚醯胺與聚酯之混抄不織布(該不織布F6係將作為胺基甲酸乙酯樹脂組成物之接著劑(組成5)以乾燥後之塗佈質量成為約40g/m2之方式含浸於芳族聚醯胺與聚酯之混抄不織布(帝人公司製造,Conex(註冊商標)、厚度40μm(20g/m2))中,其後進行乾燥而獲得者)
「P」:芳香族聚醯胺紙(杜邦公司製造,Nomex(註冊商標)、厚度60μm)
使用以上之各構件F1~F6、P及基材製作用接著劑(組成1~5),而製作以下之基材K1a~K10。
「K1a」:利用接著劑(組成1)貼合2片PEN薄膜F1而成之積層基材。(該積層基材K1a係將接著劑(組成1)以乾燥後之厚 度成為30μm之方式塗佈於PEN薄膜F1之單面,其後進行乾燥,利用加熱至100℃之熱輥按壓並貼合另一PEN薄膜F1而獲得者)
「K1b」:利用接著劑(組成2)貼合2片PEN薄膜F1而成之積層基材。(該積層基材K1b係除使用接著劑(組成2)以外以與積層基材K1a相同之方式而獲得者)
「K2」:利用接著劑(組成1)貼合PEN薄膜F1與PET薄膜F5而成之積層基材。(該積層基材K2係除使用PEN薄膜F1及PET薄膜F5以外以與積層基材K1a相同之方式而獲得者)
「K3」:利用接著劑(組成1)貼合2片PET薄膜F5而成之積層基材。(該積層基材K3係除使用2片PET薄膜F5以外以與積層基材K1a相同之方式而獲得者)
「K4」:利用接著劑(組成1)貼合PEN薄膜F1與芳香族聚醯胺紙P而成之積層基材。(該積層基材K4係除使用PEN薄膜F1及芳香族聚醯胺紙P以外以與積層基材K1a相同之方式而獲得者)
「K5a」:利用接著劑(組成2)貼合PEN薄膜F1與含浸有接著劑(組成5)之不織布F6而成之積層基材。(該積層基材K5a係將接著劑(組成2)以乾燥後之厚度成為25μm之方式塗佈於PEN薄膜F1之單面,其後進行乾燥,利用加熱至100℃之熱輥按壓並貼合含浸有接著劑(組成5)之不織布F6而獲得者)
「K5b」:利用接著劑(組成3)貼合PEN薄膜F1與含浸有接著劑(組成5)之不織布F6而成之積層基材。(該積層基材K5b係除使用接著劑(組成3)以外以與積層基材K5a相同之方式而獲得者)
「K6」:於1片PEN薄膜F1之雙面具有包含接著劑(組成4)之層之基材。(該基材K6係將接著劑(組成4)以乾燥後之厚度成為15μm之方式對PEN薄膜F1之雙面分別進行塗佈,其後進行乾燥而獲得者)
「K7」:利用接著劑(組成4)貼合2片PEN薄膜F2而成之積層基材。(該基材K7係將接著劑(組成4)以乾燥後之厚度成為30μm之方式塗佈於PEN薄膜F2之單面,其後進行乾燥,利用加熱至100℃之熱輥按壓並貼合另一PEN薄膜而獲得者)
「K8」:直接使用1片PEN薄膜F1之基材。
「K9」:直接使用1片PPS薄膜F3之基材。
「K10」:直接使用1片PET薄膜F4之基材。
<膨脹性接著劑層用接著劑之製備>
以表2所示之量(質量份)混合以下之各成分,而獲得膨脹性接著劑(組成2~3及6~8)。再者,組成2~3之接著劑與作為基材製作用接著劑而先製備之組成2~3相同。
「EP1」:環氧樹脂(液狀、黏度13,500mPa.s(25℃)、環氧當量189g/eq、BPA型、標準液狀品)
「EP2」:環氧樹脂(半固形、環氧當量173g/eq、多官能苯酚酚醛清漆型、耐熱性型)
「EP3」:環氧樹脂(軟化點70℃、環氧當量210g/eq、特殊酚醛清漆型、耐熱性型)
「EP4」:環氧樹脂(軟化點92℃、環氧當量200g/eq、特殊多官 能型、高耐熱性型)
「EP5」:環氧樹脂(軟化點86℃、環氧當量230g/eq、萘環型、耐熱性.韌性型)
「EP6」;環氧樹脂(軟化點92℃、環氧當量395g/eq、異氰酸酯改質型、高Tg.高韌性.強接著型)
「EP7」:環氧樹脂(軟化點92℃、環氧當量218g/eq、鄰甲酚酚醛清漆型、接著性型)
「EP8」:環氧樹脂(軟化點70℃、環氧當量288g/eq、酚醛清漆型、高韌性型)
「PU」:線性聚酯聚胺基甲酸酯樹脂(軟化點87℃、分子量222300、羥基含量0.1%、接著性.柔軟性型)
「H」:熱膨脹性微膠囊(平均粒徑9μm、膨脹開始溫度120~130℃、最大膨脹溫度145~155℃)
「T1」:酚樹脂(軟化點87℃、羥基當量178g/eq、酚醛清漆型、高耐熱性型)
「T2」:異氰酸酯系硬化劑(Nippon Polyurethane Industry公司製造,Coronate(註冊商標)L)
「T3」:2-苯基-4,5-二羥甲基咪唑(四國化成工業公司製造,商品名2PHZ-PW、熔點220℃、活性區域141~153℃、開始區域153~168℃)
「J1」:氧化鎂(平均粒徑3μm)
「J2」:矽酸鎂(平均粒徑5μm)
「J3」:玻璃纖維(平均纖維直徑6μm、平均纖維長度50μm)
「MEK」:甲基乙基酮
Figure 105111191-A0305-02-0027-4
<脫模劑X之製備>
藉由混合水分散型長鏈烷基系化合物(中京油脂公司製造,商品名NC003)10質量份、乙炔二醇(AIR PRODUCTS公司製造)0.4質量份、蒸餾水389.6質量份而獲得脫模劑X。
<實施例1~10、參考例1~3及比較例1~2>
將膨脹性接著劑(組成2~3及6~7)以乾燥後之厚度成為約35μm(於實施例8中為約25μm、於實施例9及10中為約30μm)之方式塗佈於基材K1a~K10之單面,其後於90℃下乾燥5分鐘,藉此去除溶劑,而形成膨脹性接著劑層。利用加熱至100℃之熱輥將單面經矽酮脫模處理之厚度38μm之聚酯薄膜按壓於該膨脹性接著劑 層之表面,而獲得第1製成品。將相同種類之膨脹性接著劑組成物以乾燥後之厚度成為約35μm(於實施例8中為約25μm、於實施例9及10中為約30μm)之方式塗佈於該第1製成品之基材之另一面,其後於90℃下乾燥5分鐘,藉此去除溶劑,而形成膨脹性接著劑層。利用加熱至100℃之熱輥將單面經矽酮脫模處理之厚度38μm之聚酯薄膜按壓於該膨脹性接著劑層之表面,而獲得第2製成品。繼而,剝離其中一聚酯薄膜,於該剝離面塗佈約10g/m2之脫模劑X,其後於90℃下乾燥3分鐘,而於膨脹性接著劑層上形成脫模劑層。繼而,一面剝離另一聚酯薄膜一面進行捲取,而獲得實施例1~10、參考例1~3及比較例1~2之接著片。
<實施例11>
將膨脹性接著劑(組成8)以乾燥後之厚度成為25μm之方式塗佈於38μm之單面經矽酮重剝離.脫模處理之聚酯薄膜,其後於90℃下乾燥5分鐘,藉此去除溶劑,而形成膨脹性接著劑層。於該膨脹性接著劑層之表面貼合38μm之單面經矽酮輕剝離.脫模處理之聚酯薄膜並進行捲取,藉此獲得實施例11之接著片。該接著片於使用時剝離雙面之經脫模處理之聚酯薄膜,作為僅包含膨脹性接著劑層之無基底型接著片而使用。
根據以下方法對以上之實施例1~11、參考例1~3及比較例1~2之接著片進行評價。將結果示於表3~5。
[接著片之厚度]
發泡前之接著片之厚度係依據JIS Z 0237「黏著帶.黏著片試驗 方法」,藉由利用厚度規之試驗方法而測定。發泡後之接著片之厚度係將發泡前之接著片切割為50×50mm之尺寸,縱向吊於熱風乾燥機中,於170℃、10分鐘之條件下使其發泡硬化,於室溫下冷卻2小時,其後以與上述相同之方法測定。
[拉伸強度]
依據JIS C 2107「電氣絕緣用黏著帶試驗方法」,測定發泡後之接著片之拉伸強度(N/10mm)。再者,接著片之發泡方法係與上述接著片之厚度項目中所記載之方法相同(以下相同)。
[伸長率]
依據JIS C 2107「電氣絕緣用黏著帶試驗方法」,測定發泡後之接著片之伸長率(%)。
[絕緣破壞電壓]
依據JIS C 2107「電氣絕緣用黏著帶試驗方法」,測定發泡後之接著片之絕緣破壞電壓(kV)。
[剪切接著力(室溫(23℃)、200℃加熱)]
依據JIS Z 1541「超強力雙面黏著帶」中所記載之拉伸剪切接著力試驗方法,測定如以下所示之發泡後之接著片之剪切接著力。作為被黏體,使用SPCC板(日新製鋼公司製造,商品名SPCC-SB NCB、厚度1.0mm、12×100mm)。試樣貼附面積設為10×10mm,發泡硬化條件設為170℃、10分鐘,拉伸速度設為200mm/min。 首先,如圖8(A)所示,將發泡前之接著片10載置於SPCC板11上,進而透過2個金屬測隙規12將其載置於另一SPCC板11上,繼而如圖8(B)所示,使接著片10發泡硬化,對該發泡後之接著片10進行拉伸剪切接著力測定(室溫(23℃)、200℃加熱)。
[導熱率]
使用京都電子工業公司製造之迅速導熱率計,於薄膜測定模式下測定發泡後之接著片之導熱率。具體而言,於鋁板(厚度10mm、250×350mm)上載置導熱率已知之3種參考之塊體(block),於其上載置測定用試驗片(45×100mm),進而於其上載置配備有加熱線與熱電偶之導熱率測定用感測器探針(商品名PD-11、40×97mm、820g),開始測定。作為參考之塊體,使用發泡聚乙烯(導熱率0.0347W/mK)、矽酮橡膠(導熱率0.236W/mK)、石英玻璃(導熱率1.416)。
[強度(剛性)]
作為發泡前之接著片之強度(剛性),測定彎曲發泡接著片時之阻力。具體而言,依據JIS P 8125「紙及板紙-剛性試驗方法-(TABER剛性試驗方法)」進行試驗,藉由下式算出彎曲力矩。
彎曲力矩(gf.cm)=(刻度之讀數)×38.0(mm)÷(所測定之試驗片之寬度:mm)
[樹脂密接性]
於下述形狀保持性試驗中,觀察進行彎折加工評價後之試驗片,以目視觀察發泡接著劑層是否部分地自耐熱基材脫落。
[形狀保持性]
如圖9所示,於鋁L字形框(板厚3mm)13中放置發泡前之試驗片(接著片14),一面將如披薩刀(pizza cutter)般之形狀之推壓治具15以45度之角度自試驗片14上向角隅推壓並旋轉,一面如圖9(i)所示以使試驗片14成為L字形之方式實施彎折加工。彎折加工後取出試驗片,利用分度器測定如圖9(ii)所示之5秒後之試驗片14之形狀。藉由下式進行計算,利用以下之基準評價形狀保持性。
形狀保持率(%)=90度÷(彎折加工5秒後之角度)×100(%)
「◎」:形狀保持率為80%以上且100%以下
「○」:形狀保持率為65%以上且未滿80%
「×」:形狀保持率未滿65%
[發泡後厚度之均勻性]
於上述發泡後之接著片之厚度測定之試驗片中測定10點,根據以下判定基準評價相對於平均厚度之最大或最小之厚度。
「◎」:相對於平均厚度之最大或最小之厚度為5%以內。
[黏連性]
以25×80mm之大小切割出2片發泡硬化前之試樣,直至距膨脹接著劑層面之長度方向之單側端部15mm之位置薄薄地擦拭碳酸鈣之粉體,而形成無黏著部(接著面積為25×65mm)。其後,將於該面貼合有試樣之脫模劑層之試驗片夾於2片不鏽鋼板間,施加1kg之負重,於40℃下放置336小時後取出,於室溫下放冷2小時 後進行剝離以分開試驗片,按照以下之基準評價黏連之程度。
「◎」:接著面之雙面均有光澤,完全未融合。
Figure 105111191-A0305-02-0032-5
Figure 105111191-A0305-02-0033-6
Figure 105111191-A0305-02-0034-7
<評價>
根據表3所示之結果可明確,實施例1~10之接著片之全部物性均優異。具體而言,於初期接著強度及電氣絕緣性優異。又,具有適度之片材強度與彎折後之形狀保持性,作業性優異。而且,藉由於接著劑層之表面塗佈脫模劑,能夠實現未必需要使用剝離紙之構成。又,實施例11之接著片於初期接著強度亦優異。
另一方面,比較例1及2之接著片使用不含酚樹脂T1之接著劑(組成3)作為用以形成膨脹性接著劑層之接著劑,故而剪切接著力較差。
參考例1~3及比較例1之接著片之強度(剛性)及形狀保持性較差。可認為其原因在於,使用了作為較薄之單層薄膜之基 材K8~K10(再者,於實施例10中亦使用了作為較薄之單層薄膜之基材K8,但於實施例10中因膨脹性接著劑層使用了含有玻璃纖維之接著劑(組成7),故而強度(剛性)及形狀保持性未出現問題)。其中,參考例1~3之接著片由於使用了不含酚樹脂T1之接著劑(組成2或6)作為用以形成膨脹性接著劑層之接著劑,故而剪切接著力優於比較例1及2。因此,可以說於參考例1~3中亦表現出了本發明之效果。
(產業上之可利用性)
本發明之接著片即便於短時間內發泡硬化,其柔軟性、電氣絕緣性、耐熱性及接著性亦優異。因此,例如於為了被接著構件間之接著及絕緣,使膨脹性接著劑層發泡硬化而填埋被接著構件間之間隙之用途較為有用。尤其是可較佳地用於馬達槽之接著絕緣。具體而言,使用於如馬達發電機之定子與線圈般之2個構件間,並將其加熱,藉此可使其發泡、膨脹,填充於該間隙中而將構件彼此接著。
1‧‧‧基材
2‧‧‧膨脹性接著劑層
3‧‧‧脫模劑層
4‧‧‧薄膜
5‧‧‧貼合用接著劑層

Claims (25)

  1. 一種接著片,其具有膨脹性接著劑層,該膨脹性接著劑層含有包含多官能環氧樹脂之環氧樹脂、作為硬化劑之酚樹脂、作為硬化觸媒之咪唑系化合物、及感溫性發泡劑而成;其於至少一個膨脹性接著劑層之表面塗佈有脫模劑。
  2. 如請求項1之接著片,其中,感溫性發泡劑包含熱膨脹性微膠囊,該熱膨脹性微膠囊之發泡溫度為環氧樹脂之軟化點以上且環氧樹脂之硬化反應之活性化溫度以下。
  3. 如請求項1之接著片,其中,膨脹性接著劑層中之作為硬化劑之酚樹脂之羥基當量數相對於環氧樹脂之環氧當量數之比率為0.5~2.0。
  4. 如請求項1之接著片,其中,咪唑系化合物之含量相對於膨脹性接著劑層中之樹脂成分100質量份為0.1~1.0質量份。
  5. 如請求項1之接著片,其中,感溫性發泡劑之含量相對於膨脹性接著劑層中之樹脂成分100質量份為0.5~20質量份。
  6. 如請求項1之接著片,其中,膨脹性接著劑層進而包含胺基甲酸乙酯樹脂。
  7. 如請求項1之接著片,其於基材之單面或雙面具有膨脹性接著劑層。
  8. 如請求項7之接著片,其中,基材包含積層體,該積層體具有藉由貼合用接著劑貼合樹脂薄膜與不織布、或樹脂薄膜與紙、或樹脂薄膜與樹脂薄膜之積層構造。
  9. 如請求項8之接著片,其中,膨脹性接著劑層或貼合用接著劑包含耐熱性填料。
  10. 如請求項8之接著片,其中,膨脹性接著劑層或貼合用接著劑包含纖維狀填料。
  11. 如請求項7之接著片,其中,基材包含於選自由樹脂薄膜、不織布及紙所構成群組中之構件的單面或雙面具有功能性接著劑層之積層體。
  12. 如請求項11之接著片,其中,膨脹性接著劑層或功能性接著劑層包含耐熱性填料。
  13. 如請求項11之接著片,其中,膨脹性接著劑層或功能性接著劑層包含纖維狀填料。
  14. 如請求項10或13之接著片,其中,纖維狀填料為玻璃纖維,該玻璃纖維之平均纖維直徑為1~20μm,平均纖維長度為10~200μm。
  15. 如請求項8之接著片,其中,不織布為選自由聚芳醯胺纖維(aramid fiber)不織布、玻璃纖維不織布、聚苯硫醚纖維不織布、耐熱尼龍纖維不織布及耐熱聚酯纖維不織布所構成群組中之一種以上之不織布。
  16. 如請求項8之接著片,其中,紙為包含全芳香族聚醯胺聚合物之高耐熱性紙。
  17. 如請求項1之接著片,其於基材之雙面具有膨脹性接著劑層,於至少一個該膨脹性接著劑層之表面塗佈有脫模劑。
  18. 如請求項1之接著片,其中,脫模劑為長鏈烷基系化合物。
  19. 如請求項1之接著片,其中,膨脹性接著劑層發泡硬化後之接著片依據JIS Z 1541測得之剪切接著力,於室溫(23℃)時為200N/cm2以上,於200℃加熱時為50N/cm2以上。
  20. 如請求項1之接著片,其中,膨脹性接著劑層發泡硬化後之接著片依據JIS C 2107測得之絕緣破壞電壓為10kV以上,導熱率為0.1W/mK以上。
  21. 如請求項1之接著片,其中,膨脹性接著劑層發泡硬化前之接著片依據JIS P 8125測得之彎曲力矩為40~600gf.cm。
  22. 如請求項1之接著片,其中,膨脹性接著劑層發泡硬化前之接著片利用以下方法所測定之形狀保持率為70%以上,(形狀保持率)將膨脹性接著劑層發泡硬化前之接著片放置於鋁L字形框中,將推壓治具以45度之角度自接著片上向角隅推壓,以成為L字形之方式實施彎曲加工,取出試驗片,測定5秒後之試驗片之彎折部分之角度,藉由下式進行計算,形狀保持率(%)=90度÷(彎折加工5秒後之角度)×100(%)。
  23. 如請求項1之接著片,其中,膨脹性接著劑層發泡硬化前之接著片之厚度為250μm以下。
  24. 如請求項1之接著片,其用於為了被接著構件間之接著及絕緣,使膨脹性接著劑層發泡硬化而填埋該被接著構件間之間隙之用途。
  25. 如請求項24之接著片,其用於馬達槽之接著絕緣。
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JP7556489B1 (ja) 2023-04-18 2024-09-26 大日本印刷株式会社 接着シート、接着シートの製造方法、および物品の製造方法

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