TW201518109A - 可撓性金屬層疊體及其製備方法 - Google Patents
可撓性金屬層疊體及其製備方法 Download PDFInfo
- Publication number
- TW201518109A TW201518109A TW103134116A TW103134116A TW201518109A TW 201518109 A TW201518109 A TW 201518109A TW 103134116 A TW103134116 A TW 103134116A TW 103134116 A TW103134116 A TW 103134116A TW 201518109 A TW201518109 A TW 201518109A
- Authority
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- Taiwan
- Prior art keywords
- resin layer
- porous
- flexible metal
- metal laminate
- resin
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 85
- 239000002184 metal Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title description 24
- 239000011347 resin Substances 0.000 claims abstract description 123
- 229920005989 resin Polymers 0.000 claims abstract description 123
- 229920001721 polyimide Polymers 0.000 claims abstract description 52
- 239000009719 polyimide resin Substances 0.000 claims abstract description 41
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011737 fluorine Substances 0.000 claims abstract description 40
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000010408 film Substances 0.000 claims description 43
- 239000011342 resin composition Substances 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 17
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
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- 238000009826 distribution Methods 0.000 claims description 6
- 238000001723 curing Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229920001780 ECTFE Polymers 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 3
- CHJAYYWUZLWNSQ-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;ethene Chemical group C=C.FC(F)=C(F)Cl CHJAYYWUZLWNSQ-UHFFFAOYSA-N 0.000 claims description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
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- 238000001029 thermal curing Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
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- 239000000126 substance Substances 0.000 description 22
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- 230000000052 comparative effect Effects 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000006344 nonafluoro n-butyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 5
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- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
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- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 230000008054 signal transmission Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本發明係關於一可撓性金屬層疊體及其製備方法,該可撓性金屬層疊體包括一多孔聚亞醯胺樹脂層,其包括30wt%至95wt%之一聚亞醯胺樹脂及5wt%至70wt%之複數含氟樹脂顆粒,其中,在該多孔聚亞醯胺樹脂層中,分佈具有0.05μm至20μm的複數微孔。
Description
本發明係關於一可撓性金屬層疊體及其製備方法,尤指具有低介電常數、低吸溼性,且亦高彈性之一可撓性金屬層疊體,及製造該可撓性金屬層疊體的方法。
近來,電子裝置具有微型化及高速、並結合各式功能的趨勢,於其內的信號傳輸速度或於其外的信號傳輸速度係不停地增進。故,需要使用比現有絕緣體具有更低介電常數及更低介電損失係數的絕緣體之印刷電路板。
於近期,反映上述趨勢,已出現應用液晶聚合物(LCP)於可撓性印刷電路板之嘗試,LCP比現有聚亞醯胺具有更低介電常數及較不受溼氣吸收所影響。然而,儘管應用LCP,其介電常數(Dk=2.9)並未與聚亞醯胺(Dk=3.2)有顯著不同,因而出於該LCP的改善程度微乎其微。再者,由於該LCP之耐熱性相當低,可能會導致於在焊接過程中發生問題,又該LCP係具熱塑性,就與運用雷射之穿孔製程之使用習知聚亞醯胺之PCB製程的相容程度而言,係出現問題。
因此,作為其解決方法,曾有嘗試降低用於習
知可撓性電路板之絕緣體之聚亞醯胺的介電常數。例如,美國專利第4816516號述及將一聚亞醯胺與含氟聚合物混合,以製備一成型產物。然而上述專利並未提及產物可用作需要低介電常數的電子裝置,而是提及一成型產物,並實際使用一具有大熱膨脹係數及低玻璃轉化溫度的聚亞醯胺。此外,聚亞醯胺樹脂應製備為薄膜型,而使之可用於印刷電路板,但上述美國專利並未述及銅箔層疊體製備成薄膜型。
又,美國專利第7026032號揭露藉由在聚亞醯胺中分散含氟聚合物微粉,以降低製備產物的介電常數的方法。該美國專利述及之含氟聚合物微粉係大多分散於絕緣體的相較於內核之外表面。然而,如該美國專利所述,由於該含氟聚合物於該絕緣體的最外層中所佔份量高,藉由於外表面的含氟聚合物,可降低溼氣的滲入或吸收,因此,減少了整體的溼氣吸收性,不過,可能會產生習知由聚亞醯胺組成之可撓性銅箔層疊體中未見的問題。例如,在上述美國專利所述的聚亞醯胺對覆蓋層或預浸材及ACF的黏著度可能較低,其聚亞醯胺樹脂的熱膨脹係數(CTE)過高而無法用於可撓性銅箔層疊體中,以及在該聚亞醯胺的表面上具有過量的氟樹脂,因而氟樹脂可能會在PCB製程間,於收板過程(receiving process)所使用的溫度約380℃下熔化,並具有使銅箔電路從絕緣體剝離的風險。
因此,為了製造具有低介電常數的印刷電路板,亟需開發具有低介電常數,亦具低熱膨脹係數、高彈性及
低吸溼性的材料。
上述先前技術引用文件為:美國專利第4816516號、及美國專利第7026032號。
本發明之目的係提供具有低介電常數、低吸溼性、亦具有高彈性之一可撓性金屬層疊體。
本發明之另一目的係提供具有低介電常數、低溼氣吸附性、亦具有高彈性之一可撓性金屬層疊體之製備方法。
本發明係提供一可撓性金屬層疊體,其包括一多孔聚亞醯胺樹脂層,其包括30wt%至95wt%之一聚亞醯胺樹脂及5wt%至70wt%之複數含氟樹脂顆粒,其中,在該多孔聚亞醯胺樹脂層中,分佈具有0.05μm至20μm的複數微孔。
本發明亦提供一可撓性金屬層疊體之製備方法,其包括下列步驟:在約280℃至320℃之溫度範圍同時變化升溫速率,熱固化一樹脂組成物,以形成一多孔聚亞醯胺樹脂層;其中該樹脂組成物包括30wt%至95wt%的聚醯胺酸樹脂,及5wt%至70wt%的含氟樹脂顆粒,及設置一金屬薄膜於該多孔聚亞醯胺樹脂層之至少一面上。
於後,將詳細解釋根據本發明之具體實施例之
可撓性金屬層疊體及製備其之方法。
根據本發明之一實施例,提供了一可撓性金屬層疊體,其包括一多孔聚亞醯胺樹脂層,其包括30wt%至95wt%之一聚亞醯胺樹脂及5wt%至70wt%之複數含氟樹脂顆粒,其中,在該多孔聚亞醯胺樹脂層中,分佈具有0.05μm至20μm的複數微孔。
前述,為了降低聚合物樹脂的介電常數,例如用於可撓性金屬層疊體的聚亞醯胺等,習知方法為添加含氟聚合物樹脂。然而,具代表性的含氟樹脂,例如聚四氟乙烯(PTFE)、四氟乙烯-六氟丙烯共聚物(FEP)、及全氟烷氧基(PFA),其熱膨脹係數分別為135ppm、150ppm、及230ppm,其相較於一般聚亞醯胺之10ppm至30ppm熱膨脹係數,有極大的差異,又,為了充分降低聚亞醯胺的介電常數,需加入約10wt%至60wt%的氟樹脂,因而勢必增加熱膨脹係數。
相反地,實施例之該可撓性金屬層疊體包括一具有預定大小的複數孔分佈於其中之一多孔聚亞醯胺樹脂層,故,當顯著降低介電常數的同時,保有高彈性,以及容易控制熱膨脹係數於一最佳化之範圍,以作可撓性金屬層疊體之用。
在該多孔聚亞醯胺樹脂層的製備過程中,可混合一聚亞醯胺樹脂或其前趨物(例如聚醯胺酸等等)以及一
含氟樹脂,並於高溫加熱處理,由於在聚亞醯胺樹脂或其前趨物以及一含氟樹脂之間的熱膨脹係數的差異,最後可製備出一多孔聚亞醯胺樹脂層或多孔聚合物樹脂膜,其具有預定大小的複數孔分佈於其中。
具體來說,在該多孔聚亞醯胺樹脂層的製備過程中,包含一聚亞醯胺樹脂或其前趨物(例如聚醯胺酸等)以及一含氟樹脂顆粒之樹脂組成物係塗佈於一基板上,提升組合物溫度至約280℃至320℃的溫度範圍,同時變化該升溫速率,因此在該多孔聚亞醯胺樹脂層中,形成具有0.05μm至20μm或0.1μm至5μm直徑的複數微孔。
更具體來說,將包含聚亞醯胺樹脂或其前趨物以及一含氟樹脂顆粒之樹脂組成物塗佈於一基板上,在相等或小於300℃的溫度範圍以3℃/min至10℃/min的速率、並在大於300℃的溫度範圍以0.2℃/min至2℃/min的速率提升組成物之溫度,因此在該多孔聚亞醯胺樹脂層中,形成具有0.05μm至20μm或0.1μm至5μm直徑的複數微孔。
當具有0.05μm至20μm直徑之該複數微孔分佈於該多孔聚亞醯胺樹脂層時,該多孔聚亞醯胺樹脂層密度可為1.2g/cm2至1.9g/cm2、或1.3g/cm2至1.5g/cm2。
該些微孔可為該多孔聚亞醯胺樹脂層的0.1vol%至5vol%或0.2vol%至1vol%。
包含在該多孔聚亞醯胺樹脂層中的該些含氟樹脂之平均顆粒直徑(D50)可為0.05μm至9.5μm或1.0μm至5.0μm。當該含氟樹脂顆粒具上述之平均直徑,由於熱膨脹程度差異,及含氟樹脂顆粒固化收縮之程度差異,該聚亞醯胺樹脂層可形成為一複數微孔均勻散佈於其中的多孔樹脂層。
具體來說,該含氟樹脂顆粒之該平均直徑(D50)可以藉雷射粒徑分析儀測量D50值。由於該含氟樹脂顆粒之粒徑分佈呈常態分佈,D50可設為該含氟樹脂顆粒的平均直徑,其中D50為基於在粒徑分佈之最大值(常態分佈曲線圖的下方區域的大小)之50%累積大小的值。
該多孔聚亞醯胺樹脂層可包括30wt%至95wt%的聚亞醯胺樹脂以及5wt%至70wt%的含氟樹脂顆粒,其分佈於包含該聚亞醯胺樹脂之基層中,其中,包含該聚亞醯胺樹脂之該基層可為一具有0.05μm至20μm直徑複數微孔分佈於其中的多孔聚亞醯胺樹脂層。
該些含氟樹脂顆粒可包括一含氟聚合物,其包括至少一選自由下方所組成之群組:聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)、四氟乙烯-六氟丙烯共聚物(FEP)、乙烯-四氟乙烯共聚物樹脂(ETFE)、四氟乙烯-氯三氟乙烯共聚物(TFE/CTFE)、及乙烯三氟氯乙烯樹脂(ECTFE)。
包含於該多孔聚亞醯胺樹脂層的該聚亞醯胺之性質並未有特別限制,又,可使用習知用於可撓性金屬
層疊體中的聚亞醯胺樹脂而無特別限制。
例如,該聚亞醯胺樹脂之重量平均分子量可為1000至500,000或10,000至300,000。若該聚亞醯胺之重量平均分子量太低,則可能無法有充分確保用作可撓性金屬層疊體等所需要的機械性質。再者,若該聚亞醯胺之重量平均分子量太高,則實施例之聚亞醯胺樹脂膜之彈性或機械性質可能會劣化。
具體來說,該聚亞醯胺樹脂可包括下方化學式1之重覆單元。
Y1為一四價有機芳香族官能團,X為一二價有機芳香族官能團,以及n為一1至300的整數。
Y1可為選自由下方化學式21至27之所組成之群組之一四價有機芳香族官能團。
在化學式22中,Y1為一單鍵、-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-C(CF3)2-、-CONH-、-COO-、-(CH2)n1-、-O(CH2)n2O-、或-OCO(CH2)n3OCO-,以及n1、n2、及n3分別為1至10的整數。
在化學式23中,Y2及Y3可為相同或不同,以及分別為一單鍵、-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-C(CF3)2-、-CONH-、-COO-、-(CH2)n1-、-O(CH2)n2O-、或-OCO(CH2)n3OCO-,以及n1、n2、及n3分別為1至10的整數。
在化學式24中,Y4、Y5、及Y6可為相同或不同,以及分別為一單鍵、-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-C(CF3)2-、-CONH-、-COO-、-(CH2)n1-、-O(CH2)n2O-、或-OCO(CH2)n3OCO-,以及n1、n2、及n3分別為1至10的整數。
在化學式21至27中,註記「*」係為一鍵結點。
此外,在化學式1中的Y1較佳為選自由下方化學式28至39所組成之群組的一四價官能團,使該多孔聚
亞醯胺樹脂層可具有低介電常數、低吸溼性、並又具有高彈性,及最佳化的熱膨脹係數。Y1在化學式1的重覆單元中,可為相同或不同。
在化學式28至20中,註記「*」係為一鍵結點。
此外,在化學式1中,該X可為選自由下方化學式21至24之群組所組成的組合之一二價官能團。
在化學式31中,R1可為氫、-CH3、-CH2CH3、-CH2CH2CH2CH3、-CF3、-CF2CF3、-CF2CF2CF3、或-CF2CF2CF2CF3。
在化學式32中,L1係一單鍵、-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-C(CF3)2-、-CONH-、-COO-、-(CH2)n1、-O(CH2)n2O-、-OCH2-C(CH3)2-CH2O-、-OCO(CH2)n3OCO-,n1、n2、及n3分別為1至10的整數,以及R1及R2可為相同或不同,且係分別為氫、-CH3、-CH2CH3、-CH2CH2CH2CH3、-CF3、-CF2CF3、-CF2CF2CF3、或-CF2CF2CF2CF3。
在化學式33中,L2及L3可為相同或不同,且分別為一單鍵、-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-C(CF3)2-、-CONH-、-COO-、-(CH2)n1、-O(CH2)n2O-、-OCH2-C(CH3)2-CH2O-、-OCO(CH2)n3OCO-,n1、n2、及n3分別為1至10的整數,以及R1、R2及R3可為相同或不同,且係分別為氫、-CH3、-CH2CH3、-CH2CH2CH2CH3、-CF3、-CF2CF3、-CF2CF2CF3、或
-CF2CF2CF2CF3。
在化學式34中,L4、L5及L6可為相同或不同,且分別為一單鍵、-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-C(CF3)2-、-CONH-、-COO-、-(CH2)n1、-O(CH2)n2O-、-OCH2-C(CH3)2-CH2O--OCO(CH2)n3OCO-,n1、n2、及n3分別為1至10的整數,以及R1、R2、R3、及R4可為相同或不同,且係分別為氫、-CH3、-CH2CH3、-CH2CH2CH2CH3、-CF3、-CF2CF3、-CF2CF2CF3、或-CF2CF2CF2CF3。
尤其,若化學式1中的X為下方化學式35的二價官能團,該多孔聚亞醯胺樹脂層可具有低介電常數、低吸溼性、並又可保有高彈性,及最佳化的熱膨脹係數。在化學式1的每一重覆單元中,該X可為相同或不同。
在化學式35中,R1、及R2可為相同或不同,且係分別為-CH3、-CH2CH3、-CH2CH2CH2CH3、-CF3、-CF2CF3、-CF2CF2CF3、或-CF2CF2CF2CF3。
此外,該多孔聚亞醯胺樹脂層可包括30wt%至95wt%或40wt%至90wt%之含有化學式1重覆單元的聚亞醯胺樹脂,以及其餘為含氟樹脂顆粒。若該含氟樹脂顆粒的量太少,則最終所製備的該多孔聚亞醯胺樹脂層的介電常數或吸溼性可能不夠低。再者,若該含氟樹脂顆粒的量太多,則該可撓性金屬層疊物的機械性質可能會劣化,因而其可能易致破裂或損壞,並且包含於該可撓性金屬層疊物中的該多孔聚亞醯胺樹脂層之熱膨脹係數會明顯地升高。
該多孔聚亞醯胺樹脂層之厚度可為0.1μm至100μm或1μm至50μm。
該多孔聚亞醯胺樹脂層之介電常數(Dk)在5GHz的乾燥態下,可具為2.7以下、2.2至2.7或2.3至2.6。對照習知聚亞醯胺的介電常數在5GHz的乾燥態下,一般為3.0以上,相較下,該多孔聚亞醯胺樹脂層可具有較低的介電常數。
該多孔聚亞醯胺樹脂層之熱膨脹係數在100℃至200℃時可為1ppm至28ppm。
由於銅箔為常用在可撓性金屬層疊體之金屬箔,其熱膨脹係數為約18ppm,實施例之該聚亞醯胺樹脂膜的熱膨脹係數必須在上述範圍內,以期最小化由金屬箔熱膨脹係數的差異所導致的彎曲,並最小化與其它構成印刷電路板的材料間的收縮差異。
實施例之該可撓性金屬層疊體可包括該聚亞
醯胺樹脂膜及一金屬薄膜,以及該金屬薄膜可包括至少一金屬係選自由下列所組成之群組:銅、鐵、鎳、鈦、鋁、銀、金、及其合金。
該金屬薄膜可設置於該聚亞醯胺膜之至少一面上。
具體來說,該可撓性金屬層疊體可包括一金屬薄膜或兩彼此相對的金屬薄膜,以及在於後的例子中,該聚亞醯胺可位於該兩彼此相對的金屬薄膜之間。
該金屬薄膜的表面之十點平均粗糙度(Rz)為0.5μm至2.5μm。若該金屬薄膜的表面之該十點平均粗糙度太低,則對該聚合物樹脂的黏著度下降,又,若該金屬薄膜的表面之該十點平均粗糙度太高,則表面粗糙度會上升,因而在高頻時的穿透率損失可能會增加。
該金屬薄膜之厚度可為0.1μm至50μm。
上述之可撓性金屬層疊體可更包括一聚亞醯胺樹脂層,其形成於該聚亞醯胺樹脂膜的至少一側。
具體來說,該可撓性金屬層疊體可更包括第二或第三聚亞醯胺樹脂膜或連結於該聚亞醯胺樹脂膜之兩面的聚亞醯胺樹脂層。該第二及第三聚亞醯胺樹脂膜之組成可分別為相同或不同於上述聚亞醯胺樹脂。
另外,該第二及第三聚亞醯胺樹脂膜之厚度可分別為相同或不同於上述聚亞醯胺樹脂膜,並該厚度可為0.1μm至100μm或1μm至50μm之間。
根據本發明之另一實施例,本發明提供一可撓
性金屬層疊體之製備方法,其包括下列步驟:在約280℃至320℃之溫度範圍同時變化升溫速率,熱固化一樹脂組成物,以形成一多孔聚亞醯胺樹脂層;其中該樹脂組成物包括30wt%至95wt%的聚醯胺酸樹脂,及5wt%至70wt%的含氟樹脂顆粒,及設置一金屬薄膜於該多孔聚亞醯胺樹脂層之至少一面上。
在該多孔聚亞醯胺樹脂層的製備過程中,藉由在約280℃至320℃的溫度範圍變化包含一聚亞醯胺樹脂或其前趨物(例如聚醯胺酸等)以及一含氟樹脂顆粒之樹脂組成物之升溫速率,可在該多孔聚亞醯胺樹脂層中形成具有0.1μm至5μm直徑的複數微孔。
具體來說,包含有一聚亞醯胺樹脂或其前趨物(例如聚醯胺酸等)以及一含氟樹脂顆粒之該樹脂組成物係塗佈於一基板上,並且於相等或小於300℃的溫度範圍以3℃/min至10℃/min的速率提升該樹脂組成物溫度,並在大於300℃的溫度範圍以0.2℃/min至2℃/min的速率提升該樹脂組成物溫度,以在該多孔聚亞醯胺樹脂層中,形成具有0.05μm至20μm或0.1μm至5μm直徑的複數微孔。即,形成該多孔聚亞醯胺樹脂層之步驟可包括:於相等或小於300℃的溫度範圍以3℃/min至10℃/min的速率提升該樹脂組成物溫度,並在大於300℃的溫度範圍以0.2℃/min至2℃/min的速率提升該樹脂組成物溫度。
該樹脂組成物的熱處理或提升之溫度可完成於340℃至370℃或350℃至360℃。
在包括30wt%至95wt%的聚醯胺酸樹脂及5wt%至70wt%的含氟樹脂顆粒之該樹脂組成物的升溫過程中,若在低於280℃至320℃或低於300℃之升溫速率太高,則含於該可撓性金屬層疊體之複數層可能會剝離,以及該多孔聚亞醯胺樹脂層的熱膨脹係數可能會顯著增加。
在包括30wt%至95wt%的聚醯胺酸樹脂及5wt%至70wt%的含氟樹脂顆粒之該樹脂組成物的升溫過程中,若在低於280℃至320℃或低於300℃之升溫速率太低,則在該聚亞醯胺樹脂層中,可能不易形成孔洞,因而可能難以確保足夠的孔隙性,且恐難足以使所形成的聚亞醯胺樹脂層的密度或熱膨脹係數下降。
再者,在包括30wt%至95wt%的聚醯胺酸樹脂及5wt%至70wt%的含氟樹脂顆粒之該樹脂組成物的升溫過程中,若在低於280℃至320℃或低於300℃之升溫速率太高,則在該聚亞醯胺樹脂層中,可能產生起泡,或對該聚亞醯胺樹脂層可能難以與該可撓性金屬層疊體的其它薄膜或層(例如一金屬薄膜等)進行穩固地連接或黏著。
由於在該多孔聚亞醯胺樹脂層中,散佈有直徑為0.05μm至20μm的複數微孔,該多孔聚亞醯胺樹脂層之密度可為1.2g/cm2至1.9g/cm2或1.3g/cm2至1.5g/cm2。
該複數微孔在該多孔聚亞醯胺樹脂層可為0.1vol%至5vol%或0.2vol%至1vol%。
包含於該多孔聚亞醯胺樹脂層之中的該含氟樹脂顆粒之平均顆粒直徑(D50)為0.05μm至9.5μm或1.0μm至5.0μm。
該聚醯胺酸樹脂及該含氟樹脂顆粒的細節包含上述關於一實施例之該可撓性金屬層疊體的內容。此外,由該聚醯胺酸樹脂所製備的該聚亞醯胺樹脂的細節,包含上述關於一實施例之該可撓性金屬層疊體的內容。
該包括30wt%至95wt%的聚醯胺酸樹脂及5wt%至70wt%的含氟樹脂顆粒之該樹脂組成物可更包括一分散劑,而該分散劑的具體實施例可包括至少一選自由聚酯聚合物(polyester polymer)、聚醚改性聚二甲基矽氧烷(polyether-modified polydimethylsiloxane)、及聚酯/聚胺聚合物(polyester/polyamine polymer)所組成的群組。
如前所述,為了在聚醯胺酸或聚亞醯胺中分散含氟樹脂,已知方法為使用含氟分散劑或含氟介面活性劑。然而,根據該方法,雖然可降低所製備聚合物樹脂層的介電常數至特定程度,但由於使用含氟分散劑或含氟介面活性劑,所製備之聚合物樹脂層的熱膨脹係數會顯著增加。相反地,若用作製備多孔聚亞醯胺樹脂層的樹脂組成物包含一分散劑,則該多孔聚亞醯胺樹脂層在具有低介電常數
的同時,其熱膨脹係數並不會過高,又,包含於該聚亞醯胺樹脂中的含氟樹脂在製備可撓性金屬層疊體或印刷電路板的過程中可防止熔化。
基於100重量份的該含氟樹脂顆粒,該樹脂組成物可包括0.1至25重量份或0.5至10重量份的分散劑。
形成多孔樹脂層的步驟可更包括:在熱固化前,於基板上塗佈該樹脂組成物至0.1μm至200μm厚。
此外,設置一金屬薄膜於該多孔聚亞醯胺樹脂層之至少一側上的步驟,包括於溫度為250℃至450℃並施加壓力為500Kgf至3000Kgf的條件下,於該多孔聚亞醯胺樹脂層之至少一側上設置一金屬薄膜,其包括至少一金屬係選自由下列所組成之群組:銅、鐵、鎳、鈦、鋁、銀、金、及其兩種以上之合金。
根據本發明,提供具有低介電常數、低吸溼性、亦具有高彈性及最佳化熱膨脹係數之一可撓性金屬層疊體,以及該可撓性金屬層疊體之製備方法。
因此,本發明提供一聚亞醯胺樹脂膜,其具有低介電常數,亦具習知聚亞醯胺絕緣體的性質,例如高耐熱性、抗化學性、及尺寸穩定性等,以作為由資料傳輸速度增加的裝置,如筆記型電腦、電腦、手機等增加的資料損失、或作為厚化的印刷電路板及印刷電路板中之電線寬
度窄的解決方法。
再者,提供了使用該低介電常數聚亞醯胺之一低介電常數銅箔層疊體。因此,在可製作較薄的印刷電路板且具匹配阻抗的條件下,所製作之行動電子裝置因而較薄,以及寬化印刷電路板之線寬,因而可顯著減少PCB製造業之瑕疵率,故對降低製造成本具極大的貢獻。
圖1係示例一聚亞醯胺樹脂之掃描式電子顯微鏡(SEM)截切面圖。
於後,將參考下方實施例以詳細說明本發明。然而,該些實施例僅作示例本發明,並且本發明之範圍並不限此於。
[製備例:製備聚醯胺酸溶液]
製備例1:製備包含含氟樹脂之聚醯胺酸溶液(P1)
在1L的聚乙烯(PE)的瓶中充入氮氣,引入765克二甲基乙醯胺(DMAc)、219克的聚四氟乙烯(PTFE)微粉(粒徑:約1.0μm至5.0μm)、及765克的具有直徑2mm之珠(beads)於其中,並且將所得物在一球磨裝置攪拌。
將16克其中分散有聚四氟乙烯(PTFE)微粉之溶液、107克二甲基乙醯胺(dimethylacetamide)、13克苯四
酸二酐(pyromellitic dianhydride)、及20克2,2'-雙(三氟甲基)-4,4-'二氨基聯苯(2,2’-bis(trifluoromethyl)-4,4’-diaminobiphenyl),置入到500mL的圓底燒瓶中,並在攪拌的同時,並於其中通入氮氣,使所得物在50℃下10小時的條件下進行反應,以獲得具有約25,000cps黏度的聚醯胺酸溶液(P1)。
製備例2:製備包含含氟樹脂之聚醯胺酸溶液(P2)
在1L的聚乙烯(PE)的瓶中充入氮氣,引入765克二甲基乙醯胺(DMAc)、219克的聚四氟乙烯(PTFE)微粉(粒徑:約1.0μm至5.0μm)、及765克的具有直徑2mm之珠(beads)於其中,並且將所得物在一球磨裝置攪拌。
將73克其中分散有聚四氟乙烯(PTFE)微粉之溶液、115克二甲基乙醯胺(dimethylacetamide)、11.609克苯四酸二酐(pyromellitic dianhydride)、及17.391克2,2'-雙(三氟甲基)-4,4-'二氨基聯苯(2,2’-bis(trifluoromethyl)-4,4’-diaminobiphenyl),置入到500mL的圓底燒瓶中,並在攪拌的同時,並於其中通入氮氣,使所得物在50℃下10小時的條件下進行反應,以獲得具有約100,000cps黏度的聚醯胺酸溶液(P2)。
製備例3:製備包含含氟樹脂之聚醯胺酸溶液(P3)
將107克其中分散有聚四氟乙烯(PTFE)微粉之溶液、13克苯四酸二酐(pyromellitic dianhydride)、及20克
2,2'-雙(三氟甲基)-4,4-'二氨基聯苯(2,2’-bis(trifluoromethyl)-4,4’-diaminobiphenyl),置入到500mL的圓底燒瓶,並在攪拌的同時,並於其中通入氮氣,使所得物在50℃下10小時的條件下進行反應,以獲得具有約25,000cps黏度的聚醯胺酸溶液(P3)。
[實施例1和2及比較例1和2:製備用以作為一可撓性金屬層疊體及一可撓性金屬層疊體之聚亞醯胺樹脂膜]
實施例1和2
(1)製備聚亞醯胺樹脂膜
將製備例1和2所分別製備的聚醯胺酸塗佈於銅箔(厚度:12μm)的毛面,使最終厚度呈25μm,而後於80℃乾燥10分鐘。在等於或小於300℃的溫度範圍,從室溫以5℃/min的速率提升乾燥產物的溫度,並在大於300℃並小於350℃的溫度範圍以1℃/min的速率進行固化。在完成固化後,蝕刻該銅箔以製備具有25μm厚的聚亞醯胺樹脂膜。
(2)製備可撓性金屬層疊體
藉由在380℃施加1700Kgf的壓力於分別於上述實施例1及2所得之聚亞醯胺樹脂膜及厚度為12μm的銅箔,以將兩者壓合,製備得一金屬層疊體。
比較例1
(1)製備聚亞醯胺樹脂膜
以相同於實施例1的方法製備具有厚度為25
μm的聚亞醯胺樹脂膜,除了使用製備例3所得之該聚醯胺酸溶液代替製備例1所得之該聚醯胺酸溶液。
(2)製備可撓性金屬層疊體
藉由在380℃施加1700Kgf的壓力於上述所得之聚亞醯胺樹脂膜及厚度為12μm的銅箔,以將兩者壓合,製備得一金屬層疊體。
比較例2
(1)製備聚亞醯胺樹脂膜
將製備例2所製備的聚醯胺酸塗佈於銅箔(厚度:12μm)的毛面,使最終厚度呈25μm,而後於80℃乾燥10分鐘。在氮氣烘箱中從室溫提升乾燥產物的溫度,並以350℃的溫度進行固化30分鐘。在完成固化後,蝕刻該銅箔以製備具有25um厚的聚亞醯胺樹脂膜。
(2)製備可撓性金屬層疊體
藉由在380℃施加1700Kgf的壓力於上述所得之聚亞醯胺樹脂膜及厚度為12μm的銅箔,以將兩者壓合,製備得一金屬層疊體。
[實驗例]
1.實驗例1:觀測該可撓性金屬層疊體的截面
透過電子掃描式顯微鏡(SEM)確認在實施例1中所得之該銅箔層疊體的截面。如圖1所示,其證實在實施例1中所得之該聚亞醯胺樹脂層中分佈有0.05μm至20μm的複數微孔。
2.實驗例2:測量該可撓性金屬層疊體的物理
性質
對於實施例及比較例中所得之該銅箔層疊體,介電常數、熱膨脹係數(CTE)、吸收性係測量如下,並且其結果為在下方表1中所示。
(1)介電常數的量測方法
在實施例及比較例中所得之該聚亞醯胺樹脂膜係於150℃經30分乾燥,並且藉由分裂介電共振(SPDR)法,在25℃及50%RH的條件下,使用一共振器Agilent E5071B ENA測量該該聚亞醯胺樹脂膜的介電常數。
(2)線性熱膨脹係數的量測方法(CTE)
在實施例及比較例中所得之該聚亞醯胺樹脂膜的熱膨脹係數係根據IPC TM-650 2.4.24.3標準,在100℃至200℃的測量條件下使用儀器TMA/SDTA 840(Mettler Company)進行測量。
(3)吸收性的量測方法
根據IPC TM-650 2.6.2C標準,在實施例及比較例中所得之該聚亞醯胺樹脂膜係於23℃蒸餾水中浸漬24小時,並且測量浸漬前與後的重量以計算吸收性。
如表1所示,證實在實施例1及2中所得之該多孔聚亞醯胺樹脂層中分佈有0.5μm至2μm的複數微孔,並且該聚亞醯胺樹脂層之密度為1.30cm2至1.40g/cm2。亦在實施例1及2中所得之該聚亞醯胺樹脂層具有小於2.6之低介電常數,以及小於1.5%的吸收性,亦具有12至22ppm的線性膨脹係數。
相反地,其證實比較例1及2的聚亞醯胺樹脂層中並未形成微孔,其中,比較例1呈現較高的介電常數(2.9)、低線性膨脹係數、及高吸收性,而比較例2相對於具有相同PTFE成份的實施例2,具有較高的密度及較高的介電常數。
Claims (18)
- 一可撓性金屬層疊體,包括:一多孔聚亞醯胺樹脂層,其包括30wt%至95wt%之一聚亞醯胺樹脂及5wt%至70wt%之複數含氟樹脂顆粒,其中,在該多孔聚亞醯胺樹脂層中,分佈具有0.05μm至20μm的複數微孔。
- 如申請專利範圍第1項所述之可撓性金屬層疊體,其中,該多孔聚亞醯胺樹脂層之密度為1.2g/cm2至1.9g/cm2。
- 如申請專利範圍第1項所述之可撓性金屬層疊體,其中,該多孔聚亞醯胺樹脂層包含0.1vol%至5vol%之該些微孔。
- 如申請專利範圍第1項所述之可撓性金屬層疊體,其中,該些含氟樹脂顆粒之平均顆粒直徑(D50)為0.05μm至9.5μm。
- 如申請專利範圍第1項所述之可撓性金屬層疊體,其中,該聚亞醯胺樹脂之重量平均分子量為1000至500,000。
- 如申請專利範圍第1項所述之可撓性金屬層疊體,其中,該多孔聚亞醯胺樹脂層之厚度為0.1μm至200μm。
- 如申請專利範圍第1項所述之可撓性金屬層疊體,其中,該些含氟樹脂顆粒包括至少一化合物係選自由下方所組成之群組:聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)、四氟乙烯-六氟丙烯共聚物(FEP)、乙烯-四氟乙烯共聚物樹脂(ETFE)、四氟乙烯-氯三氟乙烯共聚物(TFE/CTFE)、及乙烯三氟氯乙烯樹脂(ECTFE)。
- 如申請專利範圍第1項所述之可撓性金屬層疊體,其中,該多孔聚亞醯胺樹脂層之介電常數於5GHz為2.7以下。
- 如申請專利範圍第1項所述之可撓性金屬層疊體,其中,該可撓性金屬層疊體包含一或多個該多孔聚亞醯胺樹脂層。
- 如申請專利範圍第1項所述之可撓性金屬層疊體,更包含至少一具有0.1μm至200μm厚度之熱塑性聚亞醯胺樹脂層。
- 如申請專利範圍第1項所述之可撓性金屬層疊體,其中,該可撓性金屬層疊體包括一金屬薄膜,其包括至少一金屬係選自由下列所組成之群組:銅、鐵、鎳、鈦、鋁、銀、金、及其兩種以上之合金。
- 如申請專利範圍第11項所述之可撓性金屬層疊體,其中,該金屬薄膜之厚度為0.1μm至50μm。
- 如申請專利範圍第11項所述之可撓性金屬層疊體,其中,該金屬薄膜係設置於該多孔聚亞醯胺樹脂層之至少一側上。
- 一種可撓性金屬層疊體之製備方法,其包括下列步驟:在約280℃至320℃之溫度範圍同時變化升溫速率,熱固化一樹脂組成物,以形成一多孔聚亞醯胺樹脂層;其中該樹脂組成物包括30wt%至95wt%的一聚醯胺酸樹脂,及5wt%至70wt%的複數含氟樹脂顆粒;以及 設置一金屬薄膜於該多孔聚亞醯胺樹脂層之至少一面上。
- 如申請專利範圍第14項所述之方法,其中,形成該多孔聚亞醯胺樹脂層之步驟包括:於相等或小於300℃的溫度範圍以3℃/min至10℃/min的速率提升該樹脂組成物之溫度,並在大於300℃的溫度範圍以0.2℃/min至2℃/min的速率提升該溫度。
- 如申請專利範圍第15項所述之方法,其中,提升之溫度係完成於340℃至370℃。
- 如申請專利範圍第14項所述之方法,其中,形成該多孔聚亞醯胺樹脂層之步驟更包括:在熱固化前,於一基板上塗佈該樹脂組成物至0.1μm至200μm厚度。
- 如申請專利範圍第14項所述之方法,其中,設置該金屬薄膜於該多孔聚亞醯胺樹脂層之至少一面上之步驟包括:於250℃至450℃溫度並施加500Kgf至3000Kgf壓力的條件下,沉積該金屬薄膜於該多孔聚亞醯胺樹脂層之至少一面上,該金屬薄膜包括至少一金屬係選自由下列所組成之群組:銅、鐵、鎳、鈦、鋁、銀、金、及其合金。
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JP6701834B2 (ja) * | 2015-03-26 | 2020-05-27 | 富士ゼロックス株式会社 | 樹脂粒子分散ポリイミド前駆体溶液の製造方法、樹脂粒子分散ポリイミド前駆体溶液、樹脂粒子含有ポリイミドフィルム、多孔質ポリイミドフィルムの製造方法、及び多孔質ポリイミドフィルム |
JP2017031256A (ja) * | 2015-07-29 | 2017-02-09 | 日東電工株式会社 | フッ素樹脂多孔質体、それを用いた金属層付多孔質体及び配線基板 |
CN106555214B (zh) * | 2015-09-25 | 2019-05-17 | 比亚迪股份有限公司 | 金属表面微孔化处理方法以及金属树脂复合体的制备方法 |
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