TW202330861A - 接著劑組成物 - Google Patents
接著劑組成物 Download PDFInfo
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- TW202330861A TW202330861A TW111126150A TW111126150A TW202330861A TW 202330861 A TW202330861 A TW 202330861A TW 111126150 A TW111126150 A TW 111126150A TW 111126150 A TW111126150 A TW 111126150A TW 202330861 A TW202330861 A TW 202330861A
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- Prior art keywords
- adhesive composition
- acid
- group
- styrene
- based polymer
- Prior art date
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 53
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- 229920000642 polymer Polymers 0.000 claims abstract description 52
- 229920001971 elastomer Polymers 0.000 claims abstract description 42
- 239000000806 elastomer Substances 0.000 claims abstract description 41
- 239000012948 isocyanate Substances 0.000 claims abstract description 28
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011859 microparticle Substances 0.000 claims description 33
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- 239000011737 fluorine Substances 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
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- 229920001228 polyisocyanate Polymers 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
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- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
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- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
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- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明之目的係提供一種接著劑組成物,其係具有優異的低介電性質及樹脂與金屬之間的接著性。
本案發明者等專心研討之結果發現,以特定比例含有(A)酸改性苯乙烯系彈性物、(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物、(C)氟系聚合物微粒子及(D)烯烴系聚合物微粒子的接著劑組成物,係具有優異的低介電性質及樹脂與金屬之間的接著性,因而可解決前述課題。
Description
本發明係有關於優異的低介電性質(低介電係數、低介電損耗因數)及接著性,且適用於電子零件,特別是軟性印刷電路板(Flexible Printed Circuit,以下稱為FPC)的相關構件的製造之接著劑組成物。
近年來,隨著智慧型手機或移動型電腦等無線通信技術的發展,要求高速地處理大量情報,發展傳輸信號的高頻率化。隨著高頻率化,屬於無線通信裝置的構成要素之一的FPC及其相關構件也被要求在高頻帶的低介電性質(低介電係數、低介電損耗因數)(例如國際公開第2016/017473號(專利文獻1))。
此外,就上述相關構件而言,例如在製造FPC時為了保護配線部分,使用稱為「覆蓋膜(coverlay film)」的附有接著劑層的積層體,在該接著劑層中,也要求對配線部分及基材膜具有堅固的接著性。
[先前技術文獻]
[專利文獻]
[專利文獻1]國際公開第2016/017473號
本發明有鑑於如此之情事,而以提供一種具有優異的低介電性質及樹脂與金屬之間的接著性之接著劑組成物為目的。
本發明者等為了解決上述課題而專心研討之結果,發現根據以特定的比例含有(A)酸改性苯乙烯系彈性物、(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物、(C)氟系聚合物微粒子及(D)烯烴系聚合物微粒子的接著劑組成物,而可解決前述課題。具體而言,本發明係包含下列發明。
[1]
一種接著劑組成物,係含有(A)酸改性苯乙烯系彈性物、(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物、(C)氟系聚合物微粒子及(D)烯烴系聚合物微粒子,其中,
(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物中的異氰酸酯基相對於(A)酸改性苯乙烯系彈性物中的全酸性基之莫耳比(異氰酸酯基/全酸性基)為0.3至3.0,
相對於(A)酸改性苯乙烯系彈性物100重量份,(C)氟系聚合物微粒子的含量為15至100重量份,
相對於(A)酸改性苯乙烯系彈性物100重量份,(D)烯烴系聚合物微粒子的含量為7至55重量份。
[2]
如[1]所述之接著劑組成物,其中,上述(A)酸改性苯乙烯系彈性物係將選自由苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物及苯乙烯-乙烯丙烯嵌段共聚物所構成的群組中之至少1種苯乙烯系彈性物,藉由選自由不飽和羧酸及不飽和羧酸酐所構成之群組中之至少1種改性而成者。
[3]
如[1]或[2]所述之接著劑組成物,其中,上述(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物,係選自由脂肪族聚異氰酸酯、脂環族聚異氰酸酯及其衍生物所構成之群組中的至少1種化合物。
[4]
如[1]至[3]中任一項所述之接著劑組成物,其中,上述(C)氟系聚合物微粒子係由選自由聚四氟乙烯、氟化乙烯-丙烯共聚物、全氟烷氧基聚合物、四氟乙烯-三氟氯乙烯共聚物、乙烯-三氟氯乙烯共聚物及聚三氟氯乙烯所構成之群組中的至少1種氟系聚合物構成的微粒子。
[5]
如[1]至[4]中任一項所述之接著劑組成物,其中,上述(D)烯烴系聚合物微粒子係由選自由聚乙烯、聚丙烯及乙烯-丙烯共聚物所構成之群組中的至少1種烯烴系聚合物構成的微粒子。
[6]
如[1]至[5]中任一項所述之接著劑組成物,係更含有(E)有機溶劑。
[7]
一種接著膜,係使用[1]至[6]中任一項所述之接著劑組成物而形成者。
本發明的接著劑組成物具有優異的低介電性質及樹脂與金屬之間的接著性。因此,本發明的接著劑組成物適合用於例如附有接著劑層的積層體(覆蓋膜、黏合片(bonding sheet))、附有樹脂的銅箔、撓性敷銅積層板(flexible copper clad laminate)、及軟性扁平排線(flexible flat cable)等的用途。
以下,詳細地記載本發明。此外,本發明不限於以下的實施形態,能夠在其主旨的範圍內進行各種改變並實施。
<本發明的接著劑組成物>
本發明的接著劑組成物含有(A)酸改性苯乙烯系彈性物、(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物、(C)氟系聚合物微粒子及(D)烯烴系聚合物微粒子。以下,具體地說明上述(A)至(D)。
[(A)酸改性苯乙烯系彈性物]
在本發明中,構成接著劑組成物之主成分係使用經選自由不飽和羧酸及不飽和羧酸酐所構成之群組中的至少1種改性的苯乙烯系彈性物(酸改性苯乙烯系彈性物)。將苯乙烯系彈性物改性的方法可舉例如:使苯乙烯系彈性物與選自由不飽和羧酸及不飽和羧酸酐所構成之群組中的至少1種進行接枝反應的方法等。
苯乙烯系彈性物的具體例可舉例如:苯乙烯-丁二烯嵌段共聚物、苯乙烯-乙烯丙烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-異戊二烯-苯乙烯嵌段共聚物(SIS)、苯乙烯-乙烯丁烯-苯乙
烯嵌段共聚物(SEBS)、苯乙烯-乙烯丙烯-苯乙烯嵌段共聚物(SEPS)等。在此等苯乙烯系彈性物中,從接著性及低介電性質的觀點而言,較佳為苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-乙烯丙烯-苯乙烯嵌段共聚物(SEPS)。
不飽和羧酸可舉例如:丙烯酸、甲基丙烯酸、順丁烯二酸、伊康酸、反丁烯二酸等。不飽和羧酸酐可舉例如:順丁烯二酸酐、伊康酸酐、反丁烯二酸酐等。在此等不飽和羧酸及不飽和羧酸酐中,較佳為順丁烯二酸、反丁烯二酸、順丁烯二酸酐,更佳為順丁烯二酸酐。藉由選自由不飽和羧酸及不飽和羧酸酐所構成之群組中的至少1種所致之改性量通常為酸改性苯乙烯系彈性物全體的0.1至10重量%左右。此外,酸改性苯乙烯系彈性物較佳為該酸改性彈性物中的總酸性基的至少一部分為酸酐。
酸改性苯乙烯系彈性物的酸價例如為0.1mgCH3ONa/g以上,較佳為0.5mgCH3ONa/g以上,更佳為1.0mgCH3ONa/g以上,又,例如為20mgCH3ONa/g以下,較佳為18mgCH3ONa/g以下,更佳為15mgCH3ONa/g以下。
酸改性苯乙烯系彈性物的分子量係例如重量平均分子量為1萬以上,較佳為3萬以上,更佳為5萬以上,又,例如為50萬以下,較佳為30萬以下,更佳為20萬以下。此外,本發明中的重量平均分子量為藉由凝膠滲透層析術(GPC)測得的聚苯乙烯換算的分子量。
酸改性苯乙烯基彈性物的市售品可舉例如:旭化成公司製的Tuftec M系列或Kraton Polymer Japan公司製的Kraton FG系列等。
在本發明中,上述酸改性苯乙烯系彈性物可以單獨使用,亦可以併用2種以上。
[(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物]
在本發明中,就1分子中具有2個以上異氰酸酯基的異氰酸酯化合物(以下,有稱為聚異氰酸酯化合物之情形)可舉例如:芳香族聚異氰酸酯、脂肪族聚異氰酸酯、芳香族脂肪族聚異氰酸酯、脂環族聚異氰酸酯及此等的衍生物等。芳香族聚異氰酸酯可舉例如:1,3-二異氰酸伸苯基酯、4,4’-二異氰酸二苯基酯、1,4二異氰酸-伸苯基酯、4,4’-二苯甲烷二異氰酸酯、2,4-二異氰酸苯亞甲基酯、2,6-二異氰酸苯亞甲基酯、4,4’-甲苯胺二異氰酸酯、二甲氧苯胺二異氰酸酯、4,4’-二苯醚二異氰酸酯等芳香族二異氰酸酯;2,4,6-三異氰酸酯甲苯、1,3,5-三異氰酸酯苯等芳香族三異氰酸酯等。脂肪族聚異氰酸酯可舉例如:二異氰酸三亞甲基酯、二異氰酸四亞甲基酯、二異氰酸六亞甲基酯、二異氰酸五亞甲基酯、1,2-丙烯二異氰酸酯、2,3-丁烯二異氰酸酯、1,3-丁烯二異氰酸酯、二異氰酸十二亞甲基酯、2,4,4-二異氰酸三甲基六亞甲基酯等脂肪族二異氰酸酯;離胺酸三異氰酸酯等脂肪族三異氰酸酯等。芳香脂肪族聚異氰酸酯可舉例如:ω,ω’-二異氰酸酯-1,3-二甲基苯、ω,ω’-二異氰酸酯-1,4-二甲基苯、ω,ω’-二異氰酸酯-1,4-二乙基苯、1,4-四甲基二甲苯二異氰酸酯、1,3-四甲基二甲苯二異氰酸酯等芳香脂肪族三異氰酸酯;4,4’,4”-三苯甲烷三異氰酸酯等芳香脂肪族三異氰酸酯等。脂環族聚異氰酸酯可舉例如:3-異氰酸酯甲基-3,5,5-三甲基環己基異氰酸酯[別稱:異佛爾酮二異氰酸酯]、1,3-環戊烷二異氰酸酯、1,3-環己烷二異氰酸酯、1,4-環己烷二異氰酸酯、甲基-2,4-環己烷二異氰酸甲酯、甲基-2,6-環己烷
二異氰酸酯、4,4’-亞甲基雙(環己基異氰酸酯)、1,3-雙(異氰酸酯甲基)環己烷、1,4-雙(異氰酸酯甲基)環己烷等脂環族二異氰酸酯等。
聚異氰酸酯化合物的衍生物可舉例如:上述聚異氰酸酯化合物的多聚物(如2聚物、3聚物(如三聚異氰酸酯衍生物)等)、脲基甲酸酯衍生物、雙縮脲衍生物、脲二酮(Uretdione)衍生物、以使末端成為異氰酸酯的方式使二異氰酸酯化合物與低分子量的多元醇或多元胺反應而成的胺基甲酸乙脂預聚合物等。
再者,亦可以使用聚異氰酸酯化合物的異氰酸酯基的至少一部分藉由封端劑而經封端的封端異氰酸酯。具體例可舉例如:異氰酸酯化合物的異氰酸酯基經ε-己內醯胺、MEK(甲基乙基酮)肟、環己酮肟、吡唑、苯等封端而成者。
此等1分子中具有2個以上異氰酸酯基的異氰酸酯化合物中,較佳為脂肪族聚異氰酸酯、脂環族聚異氰酸酯及其衍生物,更佳為脂肪族二異氰酸酯、脂環族二異氰酸酯及其3聚物。特佳為1,3-雙(異氰酸酯甲基)環己烷及六亞甲基二異氰酸酯的3聚物。
1分子中具有2個以上異氰酸酯基的異氰酸酯化合物的市售品可舉例如:Baxenden公司製的TrixeneBI7982、TrixeneBI7951、TrixeneBI7961、TrixeneBI7991;三井化學公司製的TAKENATE B-820NP;Evonik公司製的VESTAGONB1530、VESTAGONBF1540等。在本發明中,上述異氰酸酯化合物可以單獨使用,亦可以併用2種以上。
在本發明的接著劑組成物中,(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物中的異氰酸酯基相對於(A)酸改性苯乙烯系彈性
物中的全酸性基之莫耳比(異氰酸酯基/全酸性基)通常為0.3至3.0,較佳為0.5至2.5,更佳為0.7至2.0。此外,酸改性苯乙烯系彈性物中的全酸性基(mol)可以藉由將酸改性苯乙烯系彈性物的酸價(mgCH3ONa/g)除以CH3ONa(甲氧基鈉)的分子量後,再除以103,算出酸改性苯乙烯系彈性物每1g的全酸性基量(mol/g),並乘以接著劑組成物中的酸改性苯乙烯系彈性物的量(g)而求得。
[(C)氟系聚合物微粒子]
本發明中的氟系聚合物微粒子係主要以氟系聚合物構成的微粒子。氟系聚合物係適用例如:聚四氟乙烯(PTFE)、氟化乙烯-丙烯共聚物(FEP)、全氟烷氧基聚合物(PFA)、四氟乙烯-三氟氯乙烯共聚物(TFE/CTFE)、乙烯-三氟氯乙烯共聚物(ECTFE)、聚三氟氯乙烯(PCTFE)。在此等氟系聚合物中,較佳為聚四氟乙烯(PTFE)。
氟系聚合物微粒子的市售品可舉例如:MicroPowders公司製的Fluo400XF、大金工業公司製的LUBRON L-5F、Shamrock公司製的SST-1MG等。
氟系聚合物微粒子可以由此等氟系聚合物單獨構成,亦可以併用2種以上構成。再者,在本發明中,上述氟系聚合物微粒子可以單獨使用,亦可併用2種以上不同構成者。
從分散性等觀點而言,氟系聚合物微粒子的平均粒徑較佳為10μm以下,更佳為7μm以下,再更佳為5μm以下。該平均粒徑通常為0.1μm以上。
相對於(A)酸改性苯乙烯系彈性物100重量份,本發明的接著劑組成物中所含的氟系聚合物微粒子的量通常為15至100重量份,較佳為20至80重量份。
[(D)烯烴系聚合物微粒子]
本發明中的烯烴系聚合物微粒子係主要以烯烴系聚合物構成的微粒子。烯烴系聚合物可舉例如:選自由烯烴所構成之群組中的至少1種聚合物等。烯烴可舉例如:乙烯、丙烯、1-丁烯、4-甲基-1-戊烯等。選自由烯烴所構成之群組中的至少1種聚合物的具體例可舉例如:聚乙烯、聚丙烯、聚-1-丁烯、聚-4-甲基-1-戊烯、乙烯-丙烯共聚物等。再者,構成烯烴系聚合物微粒子的烯烴系聚合物可以為選自由烯烴所構成之群組中的至少1種與二烯化合物的共聚物。二烯化合物可舉例如:丁二烯、異戊二烯、1,3-戊二烯、2,3-二甲基-1,3-丁二烯、二環戊二烯等。選自由烯烴所構成之群組中的至少1種與二烯化合物的共聚物的具體例可列舉:乙烯-丁二烯共聚物、乙烯-丙烯-丁二烯共聚物、乙烯-丙烯-二環戊二烯共聚物等。
在此等烯烴系聚合物中,較佳為聚乙烯、聚丙烯、乙烯-丙烯共聚物。
烯烴系聚合物微粒子可以單獨由此等烯烴系聚合物構成,亦可以併用2種以上構成。此外,亦可含有烯烴聚合物以外的其他熱塑性樹脂。
烯烴系聚合物微粒子的市售品可舉例如:聚乙烯微粒為MicroPowers公司製的MPP-635XF、住友精化公司製的FLOW BEADS LE-1080、FLOW BEADS HE-3040、Shamrock公司製的S-394N1;聚丙
烯微粒子為MicroPowers公司製的Micropro500、Shamrock公司製的S-363等。在本發明中,上述烯烴系聚合物微粒子可以單獨使用,亦可以併用2種以上。
從分散性等觀點而言,烯烴系聚合物微粒子的平均粒徑較佳為0.1μm至50μm,更佳為0.3μm至25μm,再更佳為0.5μm至15μm。
烯烴聚合物微粒子的熔點較佳為70至160℃,更佳為90至155℃,再更佳為100至150℃。藉由設在前述範圍內可以表現出優異的接著性。
相對於(A)酸改性苯乙烯系彈性物100重量份,本發明的接著劑組成物中所含的烯烴類聚合物微粒子的量通常為7至55重量份,較佳為10至50重量份。
[其他成分]
本發明的接著劑組成物除了上述(A)至(D)成分之外,亦可以含有(A)酸改性苯乙烯系彈性物以外的其他熱塑性樹脂、硬化促進劑、增黏劑、阻燃劑、偶合劑、抗氧化劑、(C)氟系聚合物微粒子及(D)烯烴系聚合物微粒子以外的其他填料、以及(E)有機溶劑等。
上述其他的熱塑性樹脂可舉例如:不含有酸酐基的苯乙烯系彈性物、苯氧基樹脂、聚醯胺樹脂、聚酯樹脂、聚碳酸酯樹脂、聚伸苯醚樹脂、聚胺甲酸乙酯樹脂、聚縮醛樹脂、聚乙烯系樹脂(Polyethylene resin)、聚丙烯系樹脂及聚乙烯系樹脂(Polyvinyl resin)。此等熱塑性樹脂可以單獨使用,亦可以併用2種以上。
硬化促進劑可舉例如:三乙胺、二甲吡啶、甲吡啶、DBU(1,8-二氮雜二環[5.4.0]-7-十一烯)等胺類;甲醇鋰、甲醇鈉、乙醇鈉、丁醇鉀、氟化鉀、氟化鈉等鹼金屬化合物或鹼土金屬化合物;鈦、鈷、錫、鋅、鋁等金屬、半金屬化合物等。此等硬化促進劑可以單獨使用,亦可以併用2種以上。
增黏劑可舉例如:苯并呋喃-茚樹脂(coumarone-indene resin)、萜烯樹脂、萜烯-苯酚樹脂、松香樹脂、對第三丁基苯酚-乙炔樹脂、苯酚-甲醛樹脂、二甲苯-甲醛樹脂、石油系烴樹脂、氫化烴樹脂、松節油系樹脂等。此等增黏劑可以單獨使用,亦可以併用2種以上。
上述阻燃劑可舉例如:有機阻燃劑、無機阻燃劑等。有機阻燃劑可舉例如:磷酸三聚氰胺、聚磷酸三聚氰胺、磷酸胍、聚磷酸胍、磷酸銨、聚磷酸銨、醯胺磷酸銨、醯胺聚磷酸銨、磷酸胺甲酸酯、聚磷酸胺甲酸酯、三(二乙基次磷酸)鋁、三(甲基乙基次磷酸)鋁、三(二苯基次磷酸)鋁、雙(二乙基次磷酸)鋅、雙(甲基乙基次磷酸)鋅、雙(二苯基次磷酸)鋅、雙(二乙基次磷酸)氧鈦、四(二乙基次磷酸)鈦、雙(甲基乙基次磷酸)氧鈦、四(甲基乙基次磷酸)鈦、雙(二苯基次磷酸)氧鈦、四(二苯基次磷酸)鈦等磷系阻燃劑;三聚氰胺、蜜白胺、三聚氰胺氰尿酸酯(Melamine cyanurate)等三系化合物;三聚氰酸化合物、異三聚氰酸化合物、三唑系化合物、四唑系化合物、重氮化合物、尿素等氮系阻燃劑;矽氧化合物、矽烷化合物等矽系阻燃劑。再者,無機阻燃劑可舉例如:氫氧化鋁、氫氧化鎂、氫氧化鋯、氫氧化鋇、氫氧化鈣等金屬氫氧化物;氧化錫、氧化鋁、氧化鎂、氧化鋯、氧化鋅、氧化鉬、氧化鎳等金屬氧化物;碳酸鋅、碳酸鎂、碳酸
鋇、硼酸鋅、水合玻璃等。此等阻燃劑可以單獨使用,亦可以併用2種以上。
上述偶合劑可舉例如:乙烯基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-丙烯醯氧丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、雙(三乙氧基矽烷基丙基)四硫化物、3-異氰酸酯丙基三乙氧基矽烷、咪唑矽烷等矽烷系偶合劑;鈦酸酯系偶合劑;鋁酸酯系偶合劑;鋯系偶合劑等。此等可以單獨使用,亦可以併用2種以上。
上述抗氧化劑可舉例如:2,6-二-第三丁基-4-甲苯酚、正十八烷基-3-(3’,5’-二-第三丁基-4’-羥苯基)丙酸酯、四[亞甲基-3-(3,5-二-第三丁基-4-羥苯基)丙酸酯]甲烷、新戊四醇四[3-(3,5-二-第三丁基-4-羥苯基)丙酸酯]、三乙二醇雙[3-(3-第三丁基-4-羥基-5-甲基苯基)丙酸酯]等苯酚系抗氧化劑;3,3’-硫代二丙酸二月桂酯、3,3’-硫代二丙酸肉豆蔻基酯等硫系抗氧化劑;三(壬基苯基)亞磷酸酯、三(2,4-二-第三丁基苯基)亞磷酸酯等磷系抗氧化劑等。此等可以單獨使用,亦可以併用2種以上。
上述其他填料可舉例如:除了聚丙烯酸酯粉末、環氧樹脂粉末、聚醯胺粉末、聚胺甲酸乙酯粉末、聚矽氧烷粉末等以外,使用了聚矽氧、丙烯酸、苯乙烯丁二烯橡膠、丁二烯橡膠等的多層結構的核殼層等的高分子填料;氧化矽、雲母、滑石、高嶺土、黏土、水滑石、矽灰石、硬矽鈣石、氮化矽、氮化硼、氮化鋁、磷酸氫鈣、磷酸鈣、玻璃薄片、水合玻璃、鈦酸鈣、海泡石、硫酸鎂、氫氧化鋁、氫氧化鎂、氫氧化鋯、氫氧化
鋇、氫氧化鈣、氧化鈦、氧化錫、氧化鋁、氧化鎂、氧化鋯、氧化鋅、氧化鉬、氧化銻、氧化鎳、碳酸鋅、碳酸鎂、碳酸鈣、碳酸鋇、硼酸鋅、硼酸鋁等無機填料等。此等填料可以單獨使用,亦可以併用2種以上。再者,形狀可使用例如:球形、粉狀、纖維狀、針狀、鱗片狀等。
上述(E)有機溶劑可舉例如:丙酮、甲基乙基酮、甲基異丁基酮、環己酮、環戊酮、環己烷、甲基環己烷、甲苯、二甲苯、乙酸乙酯、乙酸丙酯、乙酸異丙酯、乙酸丁酯、乙酸異丁酯、四氫呋喃、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、二甲亞碸、乙二醇單甲基醚乙酸酯、丙二醇二甲基醚乙酸酯、二烷、環戊基甲醚、二氯甲烷、氯仿、1,2-二氯乙烷、γ-丁內酯、賽路蘇、丁賽路蘇、卡必醇、丁基卡必醇等。此等有機溶劑可以單獨使用,亦可以併用2種以上。
再者,本發明的接著劑組成物除了上述其他成分以外,亦可以含有例如耐光穩定劑、耐候穩定劑、熱穩定劑等穩定劑;調平劑、消泡劑等的陰離子系、陽離子系、非離子系的界面活性劑;染料、顏料、塑化劑等。
本發明的接著劑組成物可以藉由混合(A)酸改性苯乙烯系彈性物、(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物、(C)氟系聚合物微粒子、(D)烯烴系聚合物微粒子,及因應所需的其他成分而製造。混合方法沒有特別限定,只要接著劑組成物可成為均勻狀即可。由於接著劑組成物較佳為使用微粒子呈分散之溶液的狀態(以下稱為液狀的接著劑組成物),因此通常亦使用上述(E)有機溶劑。藉由成為液狀的接著劑組成物,
在製造FPC相關構件時,能夠更順利地進行在基材膜上的塗佈及接著劑層的形成,而能夠更容易地得到具有期望厚度的接著劑層。
作為液狀的接著劑組成物時,從包含接著劑層的形成之加工性等觀點而言,固形份濃度例如為3至80重量%,較佳為10至50重量%。
[接著劑組成物的特性]
使本發明的接著劑組成物硬化而成的硬化物係低介電性質優異。硬化後的接著劑組成物的介電係數通常未達2.30,較佳為未達2.25。再者,介電損耗因數(亦稱介質損耗因數)通常未達0.002,較佳為未達0.001。
使本發明的接著劑組成物硬化而成的硬化物係剝離接著強度優異。硬化後的接著劑組成物的剝離接著強度係90°剝離強度通常為1.3N/mm,較佳為1.5N/mm。
此外,此等本發明的接著劑組成物的特性係以後述實施例的項目所記載的方法測定。
<用途>
本發明的接著劑組成物由於低介電性質、樹脂與金屬之間的接著性優異,因而可適合作為用以製造FPC相關構件的接著劑(例如接著膜)。本發明中的FPC的相關構件可舉例如:覆蓋膜、黏合片、附有樹脂的銅箔、撓性敷銅積層板、軟性扁平排線等。
[實施例]
以下列舉實施例等更詳細地說明本發明,但本發明不限於此。此外,在下列實施例等中,接著劑層為B階段狀係指接著劑組成物的一部
分開始硬化的半硬化狀態,藉由加熱等進一步進行接著劑組成物的硬化的狀態。
(實施例1至10)
將各成分以表1所示的比例(重量份)添加至附有攪拌裝置的1000ml燒瓶中,藉由在室溫下攪拌6小時使其分散而調製出接著劑組成物。使用得到的接著劑組成物,用下述方法進行各物性的測定及評估。所得結果示於表1。莫耳比係藉由(異氰酸酯基/全酸性基)而算出。
(比較例1至7)
將各成分以表2所示的比例(重量份)添加至附有攪拌裝置的1000ml燒瓶中,藉由在室溫下攪拌6小時使其分散而調製出接著劑組成物。使用得到的接著劑組成物,用下述方法進行各物性的測定及評估。所得結果示於表2。莫耳比係藉由(異氰酸酯基或環氧基/全酸性基)而算出。
(1)介電係數、介電損耗因數
準備經離型處理的玻璃板,以使乾燥後的厚度成為100μm之方式,在其一面塗佈表1及表2記載的接著劑組成物。接著,將該附有塗膜的玻璃板靜置於烘箱內,並在100℃下乾燥10分鐘,而形成B階段狀的接著劑組成物(厚度100μm),然後將該接著劑層靜置於烘箱內,並在160℃下加熱硬化處理60分鐘,而製作出試驗片。對於該試驗片,使用AET公司製的介電係數測定裝置,藉由空腔共振器法求得在測定溫度25℃、測定頻率10GHz下的介電係數(Dk)及介電損耗因數(Df)。評估基準如下述。
(介電係數)
A‧‧‧介電常數未達2.25
B‧‧‧介電常數為2.25以上且未達2.30
C‧‧‧介電常數為2.30以上
(介電損耗因數)
A‧‧‧介電損耗因數未達0.001
B‧‧‧介電損耗因數為0.001以上且未達0.002
C‧‧‧介電損耗因數為0.002以上
(2)剝離接著強度
準備厚度25μm的聚醯亞胺膜[DU PONT-TORAY公司製造的「Kapton 100EN」],並將表1及表2記載的接著劑組成物塗佈於其一表面上。接著,將該附有塗膜的薄膜靜置於烘箱中,在100℃下乾燥5分鐘,形成B階段狀的接著劑層(厚度約15μm),並得到覆蓋膜。然後,以使厚度18μm的電解銅箔與覆蓋膜之接著劑層的表面進行面接觸的方式重疊(聚醯亞胺膜/接著劑層/銅箔),在溫度160℃及壓力4.5MPa的條件下加熱壓接60分鐘,得到撓性敷銅積層板。將該撓性敷銅積層板裁切成寬10mm×長100mm,使用島津製作所製的Autograph AGS-500,在90°方向(與積層板之面方向正交的方向)用下述測定條件測定剝離接著強度。測定條件為將測試速度設為50mm/min。評估基準如下。
A‧‧‧剝離接著強度為1.5N/mm以上
B‧‧‧剝離接著強度為1.3N/mm以上且未達1.5N/mm
C‧‧‧剝離接著強度未達1.3N/mm
此外,表1及表2中的各成分如下。
[(A):酸改性苯乙烯彈性物]
(A-1):Tuftec M1913(旭化成化學公司製,順丁烯二酸酐改性苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物,酸價:10mgCH3ONa/g,重量平均分子量:15萬)
(A-2):Tuftec M1911(旭化成化學公司製,順丁烯二酸酐改性苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物,酸價:2mgCH3ONa/g,重量平均分子量:15萬)
[(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物]
(B-1):Trixene BI7982(Baxenden公司製,二異氰酸六亞甲基酯的3聚物的封端化物,固形份濃度:70重量%,異氰酸酯當量(每個異氰酸酯基的分子量):410g/eq)
(B-2):TAKENATE B-820NP(三井化學製,1,3-雙(異氰酸酯甲基)環己烷的封端化物,固形份濃度:60重量%,異氰酸酯當量:656g/eq)
[(C)氟系聚合物微粒子]
(C-1):Fluo400XF(MicroPowers公司製,PTFE微粒子,平均粒徑:3μm)
(C-2):LUBRON L-5F(大金工業公司製,PTFE微粒,平均粒徑:5μm)
[(D)烯烴系聚合物微粒子]
(D-1):MPP-635XF(MicroPowers製,聚乙烯微粒子,平均粒徑:5μm,熔點:124℃)
(D-2):Micropro500(MicroPowers製,聚丙烯微粒子,平均粒徑:6μm,熔點:142℃)
[(E)溶劑]
(E-1):甲苯
[(F)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物以外的交聯劑]
(F-1):HP-7200HH(DIC公司製,雙環戊二烯型環氧樹脂,環氧當量:280g/eq)
[(G)硬化促進劑]
(G-1):2-十一基咪唑
Claims (7)
- 一種接著劑組成物,係含有(A)酸改性苯乙烯系彈性物、(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物、(C)氟系聚合物微粒子及(D)烯烴系聚合物微粒子,其中,(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物中的異氰酸酯基相對於(A)酸改性苯乙烯系彈性物中的全酸性基之莫耳比(異氰酸酯基/全酸性基)為0.3至3.0,相對於(A)酸改性苯乙烯系彈性物100重量份,(C)氟系聚合物微粒子的含量為15至100重量份,相對於(A)酸改性苯乙烯系彈性物100重量份,(D)烯烴系聚合物微粒子的含量為7至55重量份。
- 如請求項1所述之接著劑組成物,其中,上述(A)酸改性苯乙烯系彈性物係將選自由苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物及苯乙烯-乙烯丙烯嵌段共聚物所構成的群組中的至少1種苯乙烯系彈性物,藉由選自由不飽和羧酸及不飽和羧酸酐所構成之群組中之至少1種改性而成者。
- 如請求項1或2所述之接著劑組成物,其中,上述(B)1分子中具有2個以上異氰酸酯基的異氰酸酯化合物係選自由脂肪族聚異氰酸酯、脂環族聚異氰酸酯及此等之衍生物所構成之群組中的至少1種化合物。
- 如請求項1至3中任一項所述之接著劑組成物,其中,上述(C)氟系聚合物微粒子係由選自由聚四氟乙烯、氟化乙烯-丙烯共聚物、全氟烷氧基聚合物、四氟乙烯-三氟氯乙烯共聚物、乙烯-三氟氯乙烯共聚物及聚三氟氯乙烯所構成之群組中的至少1種氟系聚合物所構成的微粒子。
- 如請求項1至4中任一項所述之接著劑組成物,其中,上述(D)烯烴系聚合物微粒子係由選自由聚乙烯、聚丙烯及乙烯-丙烯共聚物所構成之群組中的至少1種烯烴系聚合物所構成的微粒子。
- 如請求項1至5中任一項所述之接著劑組成物,係更含有(E)有機溶劑。
- 一種接著膜,係使用請求項1至6中任一項所述之接著劑組成物而成者。
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