TW201718755A - 金屬面板補強材及金屬面板的補強方法 - Google Patents
金屬面板補強材及金屬面板的補強方法 Download PDFInfo
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- TW201718755A TW201718755A TW105127236A TW105127236A TW201718755A TW 201718755 A TW201718755 A TW 201718755A TW 105127236 A TW105127236 A TW 105127236A TW 105127236 A TW105127236 A TW 105127236A TW 201718755 A TW201718755 A TW 201718755A
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- Prior art keywords
- metal panel
- reinforcing material
- meth
- acrylate
- panel reinforcing
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Abstract
本發明為一種金屬面板補強材,其係包含樹脂組成物及片狀纖維基材,該樹脂組成物係至少含有具硬化性的交聯高分子基質之可塑成分、前述可塑成分之硬化劑、前述可塑成分的硬化促進劑及交聯高分子基質,且前述金屬面板補強材在貼著在0.8mm厚之金屬面板,經過加熱而一體化從而形成補強金屬面板時,相對於前述金屬面板顯示以下的性質:在以跨距100mm測定之3點彎曲試驗中,(i)強度在1mm位移時的強度增加率為120%以上,(ii)最大強度增加率為200%以上,而且,(iii)至最大點的應變能為0.5N‧m以上。
Description
本發明係有關於金屬面板補強材及金屬面板之補強方法。更詳細言之,本發明係有關於用以提高使用在輸送機器、金屬框體等之鋼板、鋁複合板等金屬面板的剛性之金屬面板補強材及金屬面板之補強方法。
輸送機器(例如車體)、金屬框體等所使用之鋼板、鋁複合板等金屬面板,為了輕量化而有變薄的傾向。近年來係以使用約0.6至0.8mm厚度之金屬面板為主。因此,金屬面板存在著受到弱力時即容易變形/挫曲,產生歪曲而使外觀劣化的問題。而且,在薄的金屬面板時,會造成剛性及耐衝擊性降低,因此用在輸送機器的車體時會有損害乘坐者對於衝擊的安全性之情形。因此,對於認為可能受衝擊的部位要求更進一步提高金屬面板須的剛性。
先前,需要剛性之金屬面板有的部位之補強,係以在內側貼著片狀補強材而與金屬面板一體化的方法實施。補強材方面已知一種在醇酸樹脂、環氧樹脂、丙烯酸樹脂、氨酯樹脂、尿素甲醛樹脂等之中調配液狀橡膠、固體橡膠、
硬化劑、填充劑、發泡劑、各種添加劑,以壓延輥進行混練,再將混練物擠壓而形成片狀,加工成預定的厚度而成者。此種補強材係藉由貼著在金屬面板,經過加熱而硬化,以補強金屬面板。
金屬面板補強材方面,例如專利文獻1(日本特開2005-139218號公報)中曾提出一種玻璃布等固定層與由加熱發泡硬化性之樹脂組成物所構成的片狀樹脂層之積層體。其中的樹脂組成物,包含NBR橡膠、SBR橡膠、填充料、發泡劑、環氧系樹脂及其硬化劑。加熱發泡硬化後之樹脂層,可賦予金屬面板高剛性及強彎曲強度。同時,在專利文獻2(日本特開2008-105688號公報)中曾提出一種與專利文獻1類似之調配,惟含有如玻璃球之中空的無機填充材的非發泡之金屬面板補強材。
專利文獻1:日本特開2005-139218號公報
專利文獻2:日本特開2008-105688號公報
然而,專利文獻1及2的樹脂層,由於容易脆性破壞、斷裂點應變亦小,因此有破壞所需的能量較小之課題。由於該課題在汽車時係與乘坐者之安全性的降低有所關聯,因此使樹脂層有韌性之需要。並且,對金屬面
板補強材亦期望可因初期狀態之黏著性而顯現暫時黏著力,將被接著物予以暫時固定,使接著操作之作業性良好,且可藉由加熱處理之簡單操作產生硬化而展現剛性。
本發明係鑑於上述課題而完成者,其目的在提供一種金屬面板補強材,其係可藉由初期狀態之黏著性而顯現充分的暫時黏著力,同時確實保持輕量性及剛性,使斷裂應變提高且可藉由加熱硬化賦予金屬面板靭性之金屬面板補強材。本案發明人等,為解決上述課題經過深入研究,結果發現,一種包含樹脂組成物及片狀纖維基材,且具有特定性質之金屬面板補強材,其中樹脂組成物係至少含有具硬化性的交聯高分子基質之可塑成分、可塑成分之硬化劑、可塑成分的硬化促進劑及交聯高分子基質者可解決上述課題,遂完成本發明。
如此,根據本發明,可提供一種金屬面板補強材,其係包含樹脂組成物及片狀纖維基材,該樹脂組成物係至少含有具硬化性的交聯高分子基質之可塑成分、前述可塑成分之硬化劑、前述可塑成分的硬化促進劑及交聯高分子基質,且前述金屬面板補強材在貼著在0.8mm厚之金屬面板,經過加熱而一體化從而形成補強金屬面板時,相對於前述金屬面板顯示以下的性質:在以跨距(span)100mm測定之3點彎曲試驗中,(i)強度在1mm位移時的強度增加率為120%以上,
(ii)最大強度增加率為200%以上,而且,(iii)至最大點的應變能為0.5N‧m以上。
又,根據本發明,可提供一種將上述金屬面板補強材貼著在金屬被接著體予以暫時固定,並在150至250℃加熱硬化的金屬面板之補強方法。
據據本發明,可提供一種可藉由初期狀態的黏著性而顯現充分之暫時黏著力,同時確實保持輕量性及剛性,使斷裂應變提高且可藉由加熱硬化賦予金屬面板靭性之金屬面板補強材。
而且,在據據以下之任意1種或其組合之情況下,可提供一種具更高之暫時黏著力,並確實保持輕量性及剛性,使斷裂應變提高且可藉由加熱硬化賦予金屬面板靭性之金屬面板補強材。
(1)金屬面板補強材係顯示0.01至0.5N/mm2之黏著力。
(2)片狀纖維基材係選自由無機纖維或有機纖維所構成的不織布及織布中之2種以上不同之片狀纖維基材的積層體。
(3)片狀纖維基材係無機纖維之織布或單向單向布帛,且位在金屬面板補強材的單側表層。
(4)交聯高分子基質係含有1個聚合性官能基之單官能性單體與含有2個以上聚合性官能基之多官能性單體之共聚物。
(5)可塑成分係在25℃時顯示在500至30000mPa‧s範圍之黏度的液狀環氧系樹脂,且液狀環氧系樹脂至少含有1種具有苯骨架之成分。
(6)硬化劑至少含有二氰基二醯胺。
(7)硬化促進劑為胺系或咪唑系之硬化促進劑。
(8)金屬面板係選自厚度為3mm以下之鋼板及鋁合板。
而且,根據使用上述金屬面板補強材的金屬面板之補強方法,可對金屬面板簡便地達成確實保持輕量性及剛性、及提高斷裂應變且賦予靭性。
以下,再對本發明之金屬面板補強材及金屬面板之補強方法詳細說明。惟本發明並不限定於以下之說明,在其構想的範圍內亦可作各種變化。
金屬面板補強材(以下,亦可簡稱為補強材)係包含樹脂組成物及片狀纖維基材,該樹脂組成物係至少含有具硬化性的交聯高分子基質之可塑成分、可塑成分之硬化劑、可塑成分的硬化促進劑及交聯高分子基質。而且,該補強材在貼著在0.8mm厚度之金屬面板,經過加熱而一體化從而形成補強金屬面板時,相對於補強前之金屬面板顯示以下的性質:在以跨距10mm測定之3點彎曲試驗中,
(i)強度在1mm位移時的強度增加率為120%以上,(ii)最大強度增加率為200%以上,而且,(iii)至最大點的應變能為0.5N‧m以上。上述加熱係在180℃進行20分鐘。
在強度增加率未達120%時,會有補強後之金屬面板的剛性變差之情形。強度增加率可為120%、140%、200%、250%、300%、350%、400%、500%、600%、700%、800%、900%、1000%。該強度增加率並無特別之限定,惟為了在實際使用時可獲得充分的補強性,以140%以上為佳,200%以上更佳。
在最大強度增加率未達200%時,會有補強後之金屬面板的剛性變差之情形。強度增加率可為200%、250%、300%、350%、400%、500%、600%、700%、800%、900%、1000%。該強度增加率並無特別之限定,惟為了在實際使用時可獲得充分的補強性,以250%以上為佳,300%以上更佳。
在至最大點的應變能未達0.5N‧m時,會有補強後之金屬面板的衝擊吸收性變差之情形。應變能可為0.5N‧m、0.7N‧m、1.0N‧m、1.2N‧m、1.5N‧m、1.7N‧m、2.0N‧m、2.2N‧m、2.5N‧m、2.7N‧m、3.0N‧m。該應變能並無特別之限定,惟為了在實際使用時可獲得充分的衝擊吸收性,以1.0N‧m以上為佳,1.5N‧m以上更佳。
補強材以可顯示0.01至0.5N/mm2之黏著力為佳。在黏
著力未達0.01N/mm2時,會有對金屬面板的黏著力不足之情形。在較0.5N/mm2為高時,會有黏著力過強而減低作業性之情形。黏著力可為0.01N/mm2、0.05N/mm2、0.1N/mm2、0.15N/mm2、0.2N/mm2、0.25N/mm2、0.3N/mm2、0.35N/mm2、0.4N/mm2、0.45N/mm2、0.5N/mm2。黏著力。以0.05至0.3N/mm2更佳。
補強材之厚度,只要是在操作時可維持補強材的形狀之厚度即可,並無特別之限定。例如0.1至5mm。
可塑成分,只要是可賦予交聯高分子基質可塑性,且本身具有硬化性者即可,並無特別之限定。可例舉如一般使用在環氧樹脂接著劑的公知之環氧樹脂。
環氧樹脂方面可舉例如:雙酚F型、雙酚A型等雙酚型環氧樹脂、酚醛清漆型環氧樹脂、聯苯型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、環己烷型環氧樹脂、氫化雙酚A型環氧樹脂、氧化環己烯型環氧樹脂、縮水甘油胺型環氧樹脂等。其中,雙酚F型、雙酚A型等雙酚型環氧樹脂、酚醛清漆型環氧樹脂在接著強度、耐久性、耐衝擊性、耐熱性等性能與成本之平衡上良好,因此屬較佳。環氧系樹脂,以在溫度25℃時具有在500至30000mPa‧s範圍之黏度的液狀物為佳。黏度可為500mPa‧s、1000mPa‧s、3000mPa‧s、5000mPa‧s、10000mPa‧s、15000mPa‧s、20000mPa‧s、25000mPa‧s、30000mPa‧s。又,環氧系樹
脂之黏度係依照JIS K 7117-1(1999),使用布氏(Brookfield)型旋轉黏度計在試驗溫度25℃測定之值。
硬化劑,只要與上述可塑成分具有反應性即可,並無特別之限定。硬化劑可舉例如:胺型之硬化劑、酸酐、酚醛清漆樹脂、酚、硫醇、路易斯酸錯合物、鎓鹽、咪唑等。胺型之硬化劑可舉例如:二胺基二苯基甲烷、二胺基二苯基碸等芳族胺、脂族胺、咪唑衍生物、二氰基二醯胺、四甲基胍、硫脲加成胺等、及該等的異構物、改質化合物等。胺型以外之硬化劑方面可舉例如:4,4-二胺基二苯基碸、2-n-十七烷基咪唑等咪唑衍生物、間苯二甲酸二醯肼、N,N-二烷基脲衍生物、N,N-二烷基硫脲衍生物、四氫鄰苯二甲酸酐等酸酐、異佛酮二胺、間苯二胺、N-胺基乙基哌、三聚氰胺、胍胺、三氟化硼錯化合物、參二甲基胺基甲基酚、聚硫醇等。其中,以胺型之硬化劑較佳,特佳為二氰基二醯胺。硬化劑可以單獨或組合2種以上使用。
硬化劑之含量,並無特別之限定,最適量可依硬化劑的種類而不同。例如,可使用已往公知之各種硬化劑的各種最適量。該最適量,可採用如「綜合 環氧樹脂 基礎編」(環氧樹脂技術協會,2003年發行)第3章中所載之量。
例如,相對於可塑成分100質量份,其含量可為0.01質量份、0.05質量份、0.1質量份、0.5質量份、1.5質量份、
10質量份、15質量份、20質量份、25質量份、30質量份。
硬化促進劑,係用以促進補強材硬化的縮合催化劑。硬化促進劑方面可舉例如:胺系、咪唑系及其衍生物。具體上可舉例如:1,1'-(4-甲基-1,3-伸苯基)雙(3,3-二甲基脲)、苯基-二甲基脲、亞甲基-二苯基-雙二甲基脲、3-苯基-1,1-二甲基脲、3-(3,4-二氯苯基)-N,N-二甲基脲(DCMU)、3-(3-氯-4-甲基苯基)-1,1-二甲基脲等脲衍生物,三級胺、2-十一烷基咪唑(C11Z)、2-十七烷基咪唑(C17Z)、2-苯基咪唑(2PZ)、1,2-二甲基咪唑(1,2DMZ)等咪唑衍生物,苯基二甲基脲(PDMU)等脲化合物,三氟化單乙基胺、三氯化胺錯合物等胺錯合物等。
其中,在使用二氰基二醯胺作為硬化劑時,適用胺系、及具有交聯胺及促進催化劑方面機能之咪唑系及其衍生物。胺系方面可舉例如3-(3,4-二氯苯基)-N,N-二甲基脲(DCMU),咪唑系方面可舉例如2-十七烷基咪唑(C17Z)。
硬化促進劑特佳為DCMU。
硬化促進劑之含量,相對於可塑成分100質量份,以0.1至15質量份為佳。含量可為0.1質量份、0.5質量份、1質量份、5質量份、10質量份、15質量份。更佳的含量為1至10質量份。
相對於可塑成分100質量份,交聯高分子基質之含量可為0.1質量份、0.5質量份、1質量份、5質量份、10質量份、15質量份。
交聯高分子基質,以由(甲基)丙烯酸系樹脂所構成為佳。(甲基)丙烯酸系樹脂方面,只要是構成高分子基質,且可在基質內包含可塑成分、硬化劑以及硬化促進劑之樹脂即可,並無特別之限定。(甲基)丙烯酸系樹脂係以含有苯骨架為佳。(甲基)丙烯酸系樹脂方面可舉例如源自於單官能(甲基)丙烯酸系單體及多官能(甲基)丙烯酸系單體的共聚物之樹脂。
單官能(甲基)丙烯酸系單體,意指1分子中含有1個(甲基)丙烯醯基的單體。例如,由分子中至少具有1個羥基之芳族或脂族醇及其環氧烷加成物與(甲基)丙烯酸反應而得之(甲基)丙烯酸酯、(甲基)丙烯醯胺或(甲基)丙烯醯胺衍生物。(甲基)丙烯酸酯方面具體上可舉例如:(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯、1,10-癸二醇(甲基)丙烯酸酯、1,9-壬二醇(甲基)丙烯酸酯等脂肪族(甲基)丙烯酸酯系單體,(甲基)丙烯酸苯甲酯、(甲基)丙烯酸苯氧基乙酯、苯基二乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙
酯、(甲基)丙烯酸甲基苯氧基乙酯、環氧化鄰苯基酚(甲基)丙烯酸酯等含有苯骨架之(甲基)丙烯酸系單體,或(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸4-羥基丁酯縮水甘油醚等具有環氧基之(甲基)丙烯酸系單體等。
(甲基)丙烯醯胺或(甲基)丙烯醯胺衍生物方面,具體上,可舉例如:第三丁基丙烯醯胺磺酸(TBAS)、第三丁基丙烯醯胺磺酸鹽、N,N-二甲基胺基乙基丙烯醯胺(DMAEAA)鹽酸鹽、N,N-二甲基胺基丙基丙烯醯胺(DMAPAA)鹽酸鹽、(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺及丙烯醯基嗎啉等。
多官能(甲基)丙烯酸系單體,意指1分子中含有2個以上之(甲基)丙烯醯基之(甲基)丙烯酸酯。例如:環己烷二甲醇二(甲基)丙烯酸酯、環己烷二甲醇(甲基)丙烯酸酯、二羥甲酯三環癸烷二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯等。
除此之外,作為多官能(甲基)丙烯酸系單體,亦可適用氨酯系(甲基)丙烯酸酯、聚酯系(甲基)丙烯酸酯、聚醚系(甲基)丙烯酸酯、環氧系(甲基)丙烯酸酯、二烯聚合物系(甲基)丙烯酸酯等。
氨酯系(甲基)丙烯酸酯,係指如分子內具有
氨酯鍵結之(甲基)丙烯酸酯。氨酯系(甲基)丙烯酸酯,可以藉由使由聚丁二烯二醇、聚醚多元醇、聚酯多元醇、聚碳酸酯二醇等與聚異氰酸酯反應而得之聚氨酯,以(甲基)丙烯酸加以酯化而製得。聚丁二烯經(甲基)丙烯酸改質所得之聚丁二烯改質氨酯系(甲基)丙烯酸酯,亦包含在氨酯系(甲基)丙烯酸酯之內。經氫化之聚丁二烯經(甲基)丙烯酸酯改質所得之氫化聚丁二烯改質氨酯系(甲基)丙烯酸酯,亦包含在氨酯系(甲基)丙烯酸酯內。氨酯系(甲基)丙烯酸酯方面,可舉例如:1,2-聚丁二烯改質氨酯系(甲基)丙烯酸酯、聚酯氨酯系(甲基)丙烯酸酯、二丁二醇氨酯系(甲基)丙烯酸酯、聚碳酸酯氨酯系(甲基)丙烯酸酯、聚醚氨酯系(甲基)丙烯酸酯等。
聚酯系(甲基)丙烯酸酯,例如可藉由以(甲基)丙烯酸使由多元羧酸與多元醇縮合所得之於兩末端具有羥基的聚酯之羥基酯化,或者以(甲基)丙烯酸使在多元羧酸加成環氧烷所得之末端的羥基酯化而製得。
聚醚系(甲基)丙烯酸酯,例如可藉由以(甲基)丙烯酸使聚醚多元醇的羥基酯化而製得。
環氧系(甲基)丙烯酸酯,例如可藉由使較為低分子量的雙酚型環氧樹脂或酚醛清漆型環氧樹脂之環氧乙烷環與(甲基)丙烯酸反應,予以酯化而製得。又,亦可使用由該環氧系(甲基)丙烯酸酯部分經二元羧酸酐改質過的羧基改質型之環氧(甲基)丙烯酸酯。
二烯聚合物系(甲基)丙烯酸酯方面,可舉例如:液狀
苯乙烯-丁二烯共聚物經(甲基)丙烯酸酯改質所獲得的SBR二(甲基)丙烯酸酯、聚異戊二烯經(甲基)丙烯酸酯改質所獲得的聚異戊二烯二(甲基)丙烯酸酯等。
單官能(甲基)丙烯酸系單體及多官能(甲基)丙烯酸系單體中至少一者以具有環氧基為佳。藉由在丙烯醯基膠體骨架中具有環氧基,可在環氧樹脂硬化時使可塑劑與丙烯醯基膠體骨架化學鍵結,而獲得更強之接著強度。
以上述單官能(甲基)丙烯酸系單體與多官能(甲基)丙烯酸系單體聚合之方法並無特別之限定,可舉例如:本體聚合、溶液聚合、懸浮聚合、乳液聚合等。上述進行共聚的方法中之聚合反應並無特別之限定,可例舉如自由基聚合反應、活性自由基聚合反應、活性陰離子聚合反應等。上述聚合反應,可藉由供予例如熱、紫外線、電子束等能量而起始。又,在上述聚合反應中,在聚合時亦可使用反應起始劑。
單官能(甲基)丙烯酸系單體與多官能(甲基)丙烯酸系單體之質量比,可為1:1、5:1、10:1、20:1、30:1、50:1。
片狀纖維基材方面可使用公知者,具體上可舉例如:由玻璃纖維、碳纖維等無機纖維,或聚酯纖維、聚醯胺纖維、聚芳醯胺纖維(aramid fiber)、維尼綸纖維及聚烯烴纖維等有機纖維經織造或開纖而獲得之織布/不織布/單向單
向布帛等。金屬面板補強材係以將選自上述公知的片狀纖維基材之2種以上不同的片狀纖維基材積層而構成為佳,更且至少一種為無機纖維的織布或單向布帛,且位在金屬面板補強材之單側表層為宜。
位在金屬面板補強材的單側表層之無機纖維的織布或單向布帛係以由下述材料所形成者為佳:可賦予硬化後的樹脂層(以下,稱為硬化體層)靭性、可成片狀、且質輕可與硬化體層密著一體化的材料,該類材料方面,可使用如具有剛直性的碳纖維之織布、玻璃纖維之織布(玻璃布)、單向強化布帛。
玻璃布係由玻璃纖維形成布者,更具體地,可例舉如由複數之玻璃絲集束成玻璃纖維束再經織造的公知之玻璃布。玻璃布中織造之組織,通常一般為平紋,但並不限定於此,亦可例如為方平織、經畝織等變形平織,或斜紋織、緞織等。而以平織較佳。又,玻璃纖維束投梭之密度,例如以使樹脂被覆處理前的玻璃布之質量(基重)成為150至300g/m2、較佳為180至260g/m2的方式織造。又,玻璃布的質量可依照JIS R3420 7.2的測定方法而算出。而且,如此所織造之玻璃布,通常厚度為100至300μm,通氣度為2至20cm3/cm2/sec。再者,通氣度可依照JIS R3420 7.14的測定方法而算出。
玻璃布方面,更具體地,只要使用例如玻璃布纖維束的支數為5至250tex(Tex支數)、玻璃絲口徑為3至13μm、束數為100至800股、玻璃纖維束捻紗數為
0.1至5.0次/25mm、玻璃纖維束投梭密度為30至80股/25mm者即可。又,為增加環氧樹脂的纖維浸透性亦可再以矽烷耦合劑處理。此種矽烷耦合劑方面,具體上可使用例如:乙烯基三氯矽烷、乙烯基三乙氧基矽烷、乙烯基參(β-甲氧基乙氧基)矽烷、γ-甲基丙烯氧基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-苯胺基丙基三甲氧基矽烷、N-β-胺基乙基-γ-胺基丙基三甲氧基矽烷、N-乙烯基苯甲基-胺基乙基-γ-胺基丙基三甲氧基矽烷(鹽酸鹽)、γ-縮水甘油氧基丙基三甲氧基矽烷、β-(3,4-乙氧基環己基)乙基三甲氧基矽烷、γ-氫硫基丙基三甲氧基矽烷、γ-氯丙基三甲氧基矽烷等。此種矽烷耦合劑,可單獨使用或者併用。其中,以使用γ-縮水甘油氧基丙基三甲氧基矽烷較佳。此種矽烷耦合劑對玻璃布之吸附量,相對於玻璃布為0.01至2重量%,較佳為0.05至0.5重量%。
而且,亦可使用下述的開纖處理玻璃布:在織造玻璃纖維束而獲得玻璃布(包含經過上漿劑附著處理過的玻璃布及經過矽烷耦合劑附著處理過的玻璃布)之後,施行在高壓水流或溶液中之超音波處理等開纖處理,使玻璃纖維束的經紗及緯紗開幅,藉此成為一定程度細纖的開纖處理玻璃布。
位在金屬面板補強材的單側表層之無機纖維織布或單向布帛以外的片狀纖維基材,主要由用來增加有助於硬化後的樹脂層之剛性的厚度者、形成片狀、且質輕可與硬化體層密著一體化的材料所形成者為佳,此種材
料方面,例如不織布、積層布、切股氈等,其構成材料方面,可列舉1種或2種以上選自聚酯纖維、聚醯胺纖維、聚芳醯胺纖維、維尼綸纖維、碳纖維、玻璃纖維及聚烯烴纖維等者。又,為提高環氧樹脂的纖維浸透性纖維,以經過矽烷耦合劑處理為佳。
玻璃不織布係纖維不經過編織而交纏成片狀者,更具體地,係藉由乾式抄紙法、濕式抄紙法、紡絲黏合法等任意地聚積而化學性、機械性地交纏之玻璃不織布,可使用公知之玻璃不織布。
其厚度以0.1至5mm為佳,0.4至2mm更佳。又,為了形成前述厚度,玻璃不織布的單位面積重量係以10至500g/m2為佳,30至200g/m2更佳。
凝膠片中,視須要亦可含有:矽烷耦合劑、安定劑、填充劑、滑動劑、著色劑、紫外線吸收劑、抗氧化劑、抗老化劑、耐候安定劑等該技術領域中公知之添加劑。
補強材可藉由經過下述步驟而製造:將包含含有高分子基質形成用之單官能(甲基)丙烯酸系單體及多官能(甲基)丙烯酸系單體之單體混合物、含有聚合起始劑、可塑成分及硬化劑的聚合性組成物成形為所欲之形狀之步驟(成形步驟);以及,使聚合性組成物中之單體混合物藉由聚合
起始劑聚合之步驟(聚合步驟)。聚合起始劑方面,可使用對應熱、紫外線、電子束等能量的公知之聚合起始劑。
對補強材之成形,並無特別之限定,可採用公知之方法。例如將聚合性組成物倒入所欲之形狀的模框之方法。其他方法方面,可例舉將聚合性組成物倒入由2片樹脂膜所構成之保護膜之間,並保持一定厚度的方法。
依照例如以下操作,可以使補強材含有片狀纖維基材。可列舉在成形步驟中將聚合性組成物倒入模框時,在倒入之前、中及後將片狀纖維基材配置在模具內的方法。又,亦可列舉在補強材上裝載片狀纖維基材,再於其上裝載其他補強材,使片狀纖維基材被一對補強材包夾的方法。
藉由使成形的聚合性組成物其中的單體混合物聚合,可形成補強材。聚合可列舉如自由基聚合反應、活性自由基聚合反應、活性陰離子聚合反應等。上述聚合反應可藉由供應如熱、紫外線、電子束等能量而起始。
補強方法包含:在金屬面板上貼著上述補強材使金屬面板與補強材暫時固定之步驟(暫時固定步驟);以及,藉由在補強材的黏著前或黏著後加熱補強材,使補強材硬化
而固定金屬面板與補強材之步驟(固定步驟)。暫時固定步驟係利用補強材之黏著力,而固定步驟則利用接著力。補強材之加熱通常在150至250℃之範圍內操作。在加熱溫度未達150℃時,會有硬化不完全之情形。在高於250℃時,會有交聯密度提高而易脆之情形。加熱溫度以180至200℃為佳。
又,金屬面板,只要是藉由薄層化而獲得期望的補強者即可,並無特別之限定。可列舉例如使用在輸送機器、金屬框體等中之鋼板、鋁複合板等。該補強方法,對於厚度為3mm以下之金屬面板為有用。
以下,再以實施例更具體地說明本發明,惟本發明並不受其等任何限定。首先,先敘述實施例中進行測定的各種物性之測定方法。
先將補強材裁切成3×3cm,面向以雙面膠帶(Sliontec公司製造之No.5486)固定之SUS板,將位於用以測定的補強材表層且具有織布基材之面之相反面朝上,並對另一面使用雙面膠帶(Sliontec公司製造之No.5486),將凝膠片貼著在SUS板。探針黏附力試驗係使用質地分析儀-TX-AT(英弘精機公司製造)測定。探針係使用直徑10mm之SUS製造之探針。以1000g之載重,施加負載在探針之黏著面10秒後,測定在10mm/sec之速度下剝離探針時的最大載重(N)。黏著力係最大載重(N)除以黏著面面積之值(N/mm2)。
同時以肉眼觀察探針黏附力試驗後之補強材,並以以下之基準評估復原性。
○…在補強材未留下探針負載之痕跡,而維持為原來的形狀。
×…在補強材留下探針負載之痕跡而凹下,無法維持為原來的形狀。
剝離各實施例及各比較例之金屬面板補強材的剝離板,將各個金屬面板補強材在20℃環境下分別貼著於作為金屬面板之25mm寬×150mm長×0.8mm厚之油面冷軋延鋼板(SPCC-SD)(Nippon Testpanel公司製造),並以180℃加熱20分鐘,藉此使可塑成分硬化,製作成試驗片。
然後,以鋼板向上之狀態,以跨距100mm支撐各試驗片,在其長方向中央,由垂直方向上方將試驗用棒以壓縮速度5mm/分鐘降下,測定由接觸鋼板後至試驗片產生1mm位移時之彎曲強度(N)及彎曲強度的最大點(N)。另外,只使用厚度0.8mm之油面冷軋延鋼板(SPCC-SD)同樣進行3點彎曲強度試驗,測定由接觸鋼板後至1mm位移時之彎曲強度(N)及彎曲強度的最大點(N)。1mm位移時之強度增加率[%]及最大點強度增加率[%]可以下述式計算。
1mm位移時之強度增加率[%]=(以補強材補強之試驗片產生1mm位移時之彎曲強度/只有鋼板時產生1mm位移時之
彎曲強度)×100
最大點強度增加率[%]=(以補強材補強之試驗片的彎曲強度之最大點/只有鋼板的彎曲強度之最大點)×100
同時,根據3點彎曲強度試驗所得的應力-應變曲線,由應變0[mm]至彎曲強度之最大點的應變[mm]為止以積分範圍積分計算所得之面積值作為應變能[N‧m]。
將各實施例及各比較例之金屬面板補強材,裁切成寬度25mm、長度150mm,再以電子天平測定其重量,換算為每1m2之重量,計算基重[g/m2]。
將多官能性單體及官能性單體混合,再於其中溶解光聚起始劑而獲得單體混合物,然後在單體混合物中添加環氧樹脂、硬化劑及硬化促進劑,製得金屬面板補強材製造用之樹脂組成物。多官能性單體、官能性單體、光聚起始劑、環氧樹脂、硬化劑及硬化促進劑之種類及量,如表1所示。
其次,於剝離膜(38μm之PET)上依照順序覆蓋平織玻璃布及玻璃紙,並從上方倒入樹脂組成物,再覆蓋剝離膜(38μm之PET),在以輥塗布機壓緊之情況下使樹脂組成物含浸於平織玻璃布及玻璃紙。然後,使用小型UV聚合機(JATEC公司製造之J-cure 1500,金屬鹵化物燈型號
MJ-1500L)以輸送帶速度0.4m/min、成品間距離150mm之條件,以使累積照光量成為約7500mJ/cm2的方式進行UV照射,製得0.7mm厚度之補強材。
將環氧樹脂、丙烯腈/丁二烯橡膠、苯乙烯/丁二烯橡膠、聚丁烯橡膠、作為填充劑之滑石、碳酸鈣及碳黑依照表2之調配混合,再於揉合機在120℃混練1小時之後,將揉合機溫度降低至70℃,然後加入硬化劑、硬化促進劑及發泡劑並再混練1小時。丙烯腈/丁二烯橡膠、苯乙烯/丁二烯橡膠、聚丁烯橡膠、滑石、碳酸鈣、碳黑、硬化劑、硬化促進劑及發泡劑之種類及量,如表2所示。然後取出混拌物,以擠壓機擠壓成形為片狀。在薄片之一面黏貼緞織玻璃布預浸物,再以擠壓機擠壓成形為厚度0.7mm,製得0.7mm厚度之補強材。
又,表1及表2中之簡稱等之說明如以下所示。
‧jER828:雙酚A型環氧樹脂,商品名「jER828」,環氧當量180g/eqiv.,三菱化學公司製造
‧jER630:N,N-二環氧丙基-4-環氧丙氧基苯胺,商品名「jER630」,環氧當量105g/eqiv.,三菱化學公司製造
‧DICY:二氰基二醯胺,商品名「DICY7」,三菱化學公司製造
‧DCMU:3-(3,4-二氯苯基)-N,N-二甲基脲,商品名「DCMU
99」,保土谷化學公司製造
‧Nipo 11042:丙烯腈/丁二烯橡膠,商品名「Nipo 11042」,丙烯腈含量33.5重量%,慕尼黏度77.5(ML 1+4,100℃),日本ZEON公司製造
‧SBR:苯乙烯/丁二烯橡膠,商品名「Asaprene T411」,苯乙烯含量30%,旭化成公司製造
‧HV-300:聚丁烯橡膠,商品名「日石Polybutene HV-300」,數量平均分子量1400,JXE日礦日石能公司製造
‧碳酸鈣:商品名「白豔華TDD」,白石工業公司製造
‧碳黑:商品名「CB#3050B」,三菱化學公司製造
‧OBSH:4,4'-氧雙(苯磺醯肼),商品名「Cellmic SX」,三協化成公司製造
‧SP-1509:環氧丙烯酸酯,商品名「Ripoxy SP-1509」,昭和電工公司製造
‧UV 7605B:氨酯丙烯酸酯,商品名「紫光UV 7605B」,鉛筆硬度:4H,官能基數:6,日本合成化學公司製造
‧DMAAm:N,N-二甲基丙烯醯胺,Tg=約120℃,KJ Chemicals公司製造
‧P2HA:苯氧基二乙二醇丙烯酸酯,商品名「LIGHT ACRYLATE P2HA」,Tg=約-20℃,共榮社化學公司製造
‧IBXA:丙烯酸異莰酯,Tg=約97℃,大阪有機化學公司製造
由表1及2可知,實施例1至4,可藉由初期狀態之黏著性而顯現充分的暫時黏著力,同時確實保持輕量性及剛性,使斷裂應變提高且可藉由加熱硬化賦予金屬面板靭性。
Claims (10)
- 一種金屬面板補強材,其係包含樹脂組成物及片狀纖維基材,該樹脂組成物係至少含有具硬化性的交聯高分子基質之可塑成分、前述可塑成分之硬化劑、前述可塑成分的硬化促進劑及交聯高分子基質,其中前述金屬面板補強材在貼著在0.8mm厚之金屬面板,經過加熱而一體化從而形成補強金屬面板時,相對於前述金屬面板顯示下述性質:在以跨距100mm測定之3點彎曲試驗中,(i)強度在1mm位移時的強度增加率為120%以上,(ii)最大強度增加率為200%以上,而且,(iii)至最大點的應變能為0.5N‧m以上。
- 如申請專利範圍第1項所述之金屬面板補強材,其中,前述金屬面板補強材係顯示0.01至0.5N/mm2之黏著力。
- 如申請專利範圍第1項所述之金屬面板補強材,其中,前述片狀纖維基材係選自由無機纖維或有機纖維所構成的不織布及織布中之2種以上不同之片狀纖維基材的積層體。
- 如申請專利範圍第1項所述之金屬面板補強材,其中,前述片狀纖維基材為無機纖維之織布或單向布帛,且位在金屬面板補強材的單側表層。
- 如申請專利範圍第1項所述之金屬面板補強材,其中,前述交聯高分子基質係含有1個聚合性官能基之單官 能性單體與含有2個以上聚合性官能基之多官能性單體之共聚物。
- 如申請專利範圍第1項所述之金屬面板補強材,其中,前述可塑成分在溫度25℃時顯示在500至30000mPa‧s範圍之黏度的液狀環氧系樹脂,且前述液狀環氧系樹脂至少含有1種具有苯骨架之成分。
- 如申請專利範圍第1項所述之金屬面板補強材,其中,前述硬化劑至少含有二氰基二醯胺。
- 如申請專利範圍第1項所述之金屬面板補強材,其中,前述硬化促進劑為胺系或咪唑系之硬化促進劑。
- 如申請專利範圍第1項所述之金屬面板補強材,其中,前述金屬面板係選自厚度為3mm以下之鋼板及鋁合板。
- 一種金屬面板之補強方法,其係將申請專利範圍第1項所述之金屬面板補強材貼著在金屬被接著體予以暫時固定,並在150至250℃加熱硬化。
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