CN104830058A - 低介电常数及低光泽度的聚酰亚胺膜及其制备方法 - Google Patents
低介电常数及低光泽度的聚酰亚胺膜及其制备方法 Download PDFInfo
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- CN104830058A CN104830058A CN201510160254.4A CN201510160254A CN104830058A CN 104830058 A CN104830058 A CN 104830058A CN 201510160254 A CN201510160254 A CN 201510160254A CN 104830058 A CN104830058 A CN 104830058A
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- Prior art keywords
- polyimide
- polyimide film
- amido
- film
- dianhydride
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- 238000002360 preparation method Methods 0.000 title abstract description 3
- 239000004642 Polyimide Substances 0.000 claims abstract description 65
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000006229 carbon black Substances 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims description 52
- 125000001153 fluoro group Chemical group F* 0.000 claims description 35
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 229920005575 poly(amic acid) Polymers 0.000 claims description 24
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 22
- -1 perfluoroethylene-propylene Chemical group 0.000 claims description 22
- 150000004985 diamines Chemical class 0.000 claims description 20
- 150000008064 anhydrides Chemical class 0.000 claims description 15
- 238000002834 transmittance Methods 0.000 claims description 12
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 11
- 239000001294 propane Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 9
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 5
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 5
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- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims 2
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
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- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
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- IBKFNGCWUPNUHY-UHFFFAOYSA-N 2-(4-aminophenyl)-1,3-benzoxazol-6-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2O1 IBKFNGCWUPNUHY-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- KZSXRDLXTFEHJM-UHFFFAOYSA-N 5-(trifluoromethyl)benzene-1,3-diamine Chemical compound NC1=CC(N)=CC(C(F)(F)F)=C1 KZSXRDLXTFEHJM-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
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- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
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- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
本发明公开了一种聚酰亚胺膜及其制备方法,该聚酰亚胺膜具有低介电常数及低光泽度,其包括构成该膜主结构的聚酰亚胺、0.5wt%至5wt%的碳黑、及15wt%至40wt%的含氟高分子。该聚酰亚胺膜可为单层膜或多层膜。
Description
技术领域
本发明有关于一种聚酰亚胺膜,尤其是一种低介电常数的聚酰亚胺膜。
背景技术
随着技术发展及产品需求,印刷电路板的尺寸趋向轻、薄、短、小,而因应无线网络及通信产品的频率高频化,传输速率快的高频基板逐渐成为发展重点。作为高频通信基板所使用的材料,能够快速传送数据为基本要求,且在传送过程中不能造成数据损失或被干扰。
已知电子信号在金属导线间传递所造成的延迟,为半导体元件速度受限的主要原因。为了降低信号传递的时间延迟,可以低介电常数的材料作为导线间绝缘层,以降低导线间的电容值、提升元件运作速度及降低噪声干扰。绝缘层阻绝电流通过,而具备较低介电常数(Dielectric Constant,Dk)的绝缘材料可避免于线路上形成不必要的杂散电容(stray capacitance)。另外,该材料若造成损耗会浪费电能,故要求材料的损耗因子(DissipationFactor,Df)越小越好。
聚酰亚胺(PI)具备良好耐热性、耐化性、机械强度与高电阻抗等特性,已大量应用于电子产业,例如作为印刷电路板材料。然而,已知聚酰亚胺膜具有高介电常数及高损耗因子,作为高频材料仍有缺点与限制。又,为了防止电路设计被抄袭,必须以低透光性的覆盖膜遮盖设计,而为了达到质感与美观,低光泽度的覆盖膜有其需求。因此,发展可同时达到上述所欲特性的聚酰亚胺膜仍有其必要性。
发明内容
本发明提供一种聚酰亚胺膜,包括:构成该膜主结构的聚酰亚胺,由二胺单体及二酐单体经缩合反应而形成;碳黑,占该膜总重量的0.5wt%至5wt%;以及含氟高分子,占该膜总重量的15wt%至40wt%;其中,该碳黑及该含氟高分子分布于该聚酰亚胺膜中,该聚酰亚胺膜的介电常数(Dk)低于3.05,且光泽度值为10以下。
于实施例中,本发明亦提供一种多层聚酰亚胺膜,包括:第一聚酰亚胺层,包括构成该膜主结构的聚酰亚胺;占该第一聚酰亚胺层总重量的0.5wt%至5wt%的碳黑;占该第一聚酰亚胺层总重量的15wt%至40wt%的含氟高分子;且该碳黑及该含氟高分子分布于该第一聚酰亚胺层中;第二聚酰亚胺层,至少包括构成该膜主结构的聚酰亚胺;其中,该第一聚酰亚胺层的厚度为h1,该第二聚酰亚胺层的厚度为h2,且h2/h1的值为1/5以下。
于实施例中,本发明亦提供一种制备多层聚酰亚胺膜的方法,包括:制备第一聚酰胺酸溶液,其包括二胺单体、二酐单体、碳黑及含氟高分子;将该第一聚酰胺酸溶液涂布于一基板上,并烘烤以形成第一聚酰亚胺层;制备第二聚酰胺酸溶液,其包括二胺单体及二酐单体;将该第二聚酰胺酸溶液涂布于该第一聚酰亚胺层上,并烘烤以于该第一聚酰亚胺层上形成第二聚酰亚胺层;其中,该第一聚酰亚胺层的厚度为h1,该第二聚酰亚胺层的厚度为h2,且h2/h1的值为1/5以下。
附图说明
图1绘示依据本发明的多层聚酰亚胺膜的一实施例。
【附图标记说明】
1:第一聚酰亚胺层
11:聚酰亚胺
12:碳黑
13:含氟高分子
2:第二聚酰亚胺层
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,并参照附图,对本发明进一步详细说明。
本发明所提供的聚酰亚胺膜,包括聚酰亚胺、碳黑及含氟高分子,且具有所欲的低介电常数(Dk)、低光泽度值、低损耗因子(Df)及高遮蔽度。
该聚酰亚胺膜包含碳黑,分布于该聚酰亚胺膜中。以该膜总重量为基础,该碳黑的比例为0.5wt%至5wt%,例如:0.5、0.7、0.9、1、1.5、2、2.5、3、3.5、4、4.5、5wt%,或前述任两点之间的值。于实施例中,该碳黑的比例可为0.5至4.5wt%,较佳为0.5至3wt%,更佳为1至3wt%。
该聚酰亚胺膜中另包括含氟高分子(fluorine-containing polymer)。该含氟高分子可以分子型式独立存在于该聚酰亚胺膜中,或,以该含氟高分子的部分或全部官能基与聚酰亚胺分子产生化学反应(如:共价结合)的型式存在于该聚酰亚胺膜中。
该含氟高分子可为,举例但非限定,氟烃类(fluorocarbons)。具体而言,该含氟高分子的实例包括氟化聚烯(fluorinated polyalkene)、具有氟取代基的聚烷、具有氟取代基的聚烷氧、氯氟烃(chlorofluorocarbons)等。
于部分实施例中,该含氟高分子为聚四氟乙烯(polytetrafluoroethylene(PTFE))、聚全氟乙丙烯(polyfluorinated ethylene propylene(FEP))、全氟亚乙烯基(polyfluorinated vinylidene(PVDF))的聚合物、全氟烷氧基(perfluoroalkoxy(PFA))的聚合物、三氟氯乙烯(chlorotrifluoroethylene(CTFE))的聚合物、乙烯-三氟氯乙烯(ethylene chlorotrifuloroethylene(ECTFE))的聚合物等,可单独使用或组合使用。
于实施例中,以该膜总重量为基础,该含氟高分子比例为15wt%至40wt%,例如:16、17、20、22、25、28、30、32、35、37、38、39、40wt%,或前述任两点之间的值。于部分实施例中,该含氟高分子的比例可为20至40wt%。于部分实施例中,该含氟高分子的比例可为15至30wt%,较佳为15至25wt%。
所采用的含氟高分子为粉体状,该含氟高分子的平均粒径为约1至10μm,例如,1μm、2μm、2.5μm、3μm、4μm、5μm、6μm、7μm、7.5μm、8μm、9μm、10μm或前述任两点之间的值。于一些实施例中,可采用平均粒径为1至5μm的含氟高分子。于另一些实施例中,可采用平均粒径为6至10μm的含氟高分子。于较佳实施例中,该含氟高分子的平均粒径为约2至8μm。
本发明的聚酰亚胺膜可为单层膜或多层膜,例如双层膜、三层膜等。于多层膜的实施例中,至少一层膜如前述,包括碳黑及含氟高分子,而其余层的聚酰亚胺膜则可包括相同或不同的添加物。另外,于多层膜的实施例中,各层聚酰亚胺所采用的二胺及二酐单体可互为相同或不同。
于一实施例中,该多层聚酰亚胺膜,如图1所示,包括第一聚酰亚胺层1及第二聚酰亚胺层2,该第二聚酰亚胺层2设置于该第一聚酰亚胺层1的一表面上,且与该第一聚酰亚胺层1的表面为直接接触。第一聚酰亚胺层1包括:构成该层主结构的聚酰亚胺11、碳黑12、含氟高分子13,且该碳黑12及该含氟高分子13呈颗粒状并分布于该第一聚酰亚胺层的主结构中。第二聚酰亚胺层2则至少包括构成该层主结构的聚酰亚胺。于实施例中,以该第一聚酰亚胺层1的总重量为基础,该碳黑12为0.5wt%至3wt%,该含氟高分子13为15wt%至40wt%。
于该多层聚酰亚胺膜中,该第一聚酰亚胺层1的厚度为h1,该第二聚酰亚胺层2的厚度为h2,而h2/h1的值为1/5以下,例如,举例但非限制,1/5、1/6、1/7、1/8、1/10、1/12、1/15、或前述任两点之间的值。
于一实施例中,如图1所示的双层聚酰亚胺膜可依以下方法制备。首先,将选定作为第一聚酰亚胺层成分的二胺单体及二酐单体置于溶剂中作用,以获得第一聚酰胺酸溶液。将碳黑及含氟高分子加入该第一聚酰胺酸溶液中,混合均匀后,于一玻璃平板或不锈钢平板上涂布成层。接着以约90℃至约350℃的温度烘烤,而形成第一聚酰亚胺层。
再以选定作为第二聚酰亚胺层成分的二胺单体及二酐单体置于溶剂中以获得第二聚酰胺酸溶液,其所使用的单体可与第一聚酰胺酸溶液为相同或不同。将该第二聚酰胺酸溶液于该第一聚酰亚胺层上涂布成层,以约90℃至约350℃的温度烘烤,而形成第二聚酰亚胺层。据此,即可获得具有双层结构的多层聚酰亚胺膜。
本发明的聚酰亚胺膜可利用热转化或化学转化的方式形成。若采用化学转化的方式,则于涂布步骤前,可将脱水剂及催化剂添加至该聚酰胺酸溶液中。前述所使用的溶剂、脱水剂及催化剂均可为本技术领域已知。该溶剂可为非质子性极性溶剂,例如二甲基乙酰胺(DMAC)、N,N′-二甲基甲酰胺(DMF)、N-甲基吡咯啶酮(NMP)、二甲亚砜(DMSO)、四甲基砜、N,N′-二甲基-N,N′-丙烯基脲(DMPU)等。该脱水剂可为脂肪族酸酐(如醋酸酐及丙酸酐)、芳香族酸酐(如苯酸酐及邻苯二甲酸酐)等。该催化剂可为杂环三级胺(例如甲吡啶(picoline)、吡啶等)、脂肪族三级胺(例如三乙基胺(TEA)等)、芳香族三级胺(例如二甲苯胺等)等。聚酰胺酸:脱水剂:催化剂的摩尔比为1∶2∶1,即对每摩尔的聚酰胺酸,使用约2摩尔的脱水剂及约1摩尔的催化剂。
于本发明中,由二胺单体及二酐单体经缩合反应而形成聚酰亚胺,且该二胺单体与该二酐单体以约为等摩尔的比例进行反应。
于实施例中,该二胺单体可为2,2’-双(三氟甲基)联苯胺(2,2′-Bis(trifluoromethyl)benzidine(TFMB))、4,4′-二胺基二苯醚(4,4′-oxydianiline(4,4′-ODA))、对苯二胺(phenylenediamine(p-PDA))、1,3-双(4′-胺基苯氧基)苯(1,3-bis(4-aminophenoxy)benzene(TPER))、1,4-双(4-胺基苯氧基)苯(1,4-bis(4-aminophenoxy)benzene(TPEQ))、4,4’-二胺基-2,2’-二甲基-1,1’-联苯(2,2′-dimethyl[1,1′-biphenyl]-4,4′-diamine(m-TB-HG))、1,3-双(3-胺基苯氧基)苯(1,3’-Bis(3-aminophenoxy)benzene(APBN))、3,5-二胺基三氟甲苯(3,5-Diaminobenzotrifluoride(DABTF))、2,2′-双[4-(4-胺基苯氧基苯基)]丙烷(2,2′-bis[4-(4-aminophenoxy)phenyl]propane(BAPP))、6-胺基-2-(4-胺基苯基)-苯并恶唑(6-amino-2-(4-aminophenyl)benzoxazole(6PBOA))、5-胺基-2-(4-胺基苯基)-苯并恶唑(5-amino-2-(4-aminophenyl)benzoxazole(5PBOA))等,可单独使用或组合使用。
于实施例中,该二酐单体可为3,3′,4,4′-联苯四羧酸二酸酐(3,3′,4,4′-biphenyltetracarboxylic dianhydride(BPDA))、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酸酐(2,2-bis[4-(3,4dicarboxyphenoxy)phenyl]propanedianhydride(BPADA))、均苯四甲酸二酸酐(pyromellitic dianhydride(PMDA))、4,4′-(六氟异丙烯)二酞酸酐(2,2′-Bis-(3,4-Dicarboxyphenyl)hexafluoropropane dianhydride(6FDA))、二苯醚四甲酸二酸酐(4,4-Oxydiphthalic anhydride(ODPA))、苯酮四羧酸二酸酐(Benzophenonetetracarboxylic dianhydride(BTDA))、3,3′,4,4′-二环己基四甲酸二酐(3,3′,4,4′-dicyclohexyltetracarboxylic acid dianhydride(HBPDA)等,可单独使用或组合使用。
于一些实施例中,单层聚酰亚胺膜的二胺单体为2,2’-双(三氟甲基)联苯胺(TFMB),而二酐单体为3,3′,4,4′-联苯四羧酸二酸酐(BPDA)、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酸酐(BPADA)或其组合。
于另一些实施例中,制备多层聚酰亚胺膜,其中,第一层的二胺单体为2,2’-双(三氟甲基)联苯胺(TFMB),而二酐单体为3,3′,4,4′-联苯四羧酸二酸酐(BPDA)、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酸酐(BPADA)、或其组合。第二层的二胺单体及二酐单体可与第一层相同,或,该二胺单体为4,4′-二胺基二苯醚(4,4′-ODA),而该二酐单体为均苯四甲酸二酸酐(PMDA)。
本发明的聚酰亚胺膜具有下列至少一项的膜特性:介电常数(Dk)低于3.05、损失因子(Df)低于0.0115、光泽度值为10以下、光穿透率低于30%。
于实施例中,该介电常数(Dk)低于约3.05,例如3.04、3.0、2.8、2.5、2.0、1.5、1.2等,或前述任两点之间的值。该损失因子(Df)则低于约0.0115,例如0.011、0.010、0.008、0.005、0.002、0.001等,或前述任两点之间的值。该光泽度值为10以下,例如:9.9、9.5、9、8、7、6、5、3、1、0.1等,或前述任两点之间的值。该光穿透率低于30%,例如:29%、25%、20%、15%、10%、5%、1%、0.5%、0.1%等,或前述任两点之间的值。
于一实施例中,该单层聚酰亚胺膜同时具有低于3.05的介电常数(Dk)、低于0.0115的损失因子(Df)、10以下的光泽度值及低于30%的光穿透率。
于一较佳实施例中,该单层聚酰亚胺膜具有下列至少一项的膜特性:介电常数(Dk)为2.99以下、损失因子(Df)为0.011以下、光泽度值为9.6以下、光穿透率低于30%。
于另一实施例中,该双层聚酰亚胺膜同时具有低于3.05的介电常数(Dk)、低于0.0115的损失因子(Df)、10以下的光泽度值及低于30%的光穿透率。
以下以实施例详述本发明。
实施例
<实施例1>
将69.11克的TFMB与412.5克的DMAc置入三颈烧瓶内。于30℃下搅拌至完全溶解后再加入56.83克的BPDA与11.23克的BPADA(TFMB、BPDA与BPADA单体总重量百分率为25wt%)。接着,续持搅拌并于25℃持续反应20个小时,即可获得第一聚酰胺酸溶液,其于25℃的旋转粘度为140,000cps。于所得第一聚酰胺酸溶液中加入24.2克的PTFE粉末(占单体总重量的15wt%)及4.24克的碳黑(型号SB4A,购自ORION公司)(占单体总重量的3wt%),搅拌均匀后再加入醋酸酐及甲基吡啶作为催化剂(添加比例为聚酰胺酸溶液∶醋酸酐∶甲基吡啶的摩尔比为约1∶2∶1),脱泡完涂布于玻璃板上,并放入80℃的烘箱内加热约30分钟,以移除大多数的溶剂。接着,将上述涂布有聚酰胺酸溶液的玻璃板放入170℃~260℃的烘箱内,加热约4小时,以令聚酰胺酸溶液烤干成膜。所得聚酰亚胺膜厚度为12μm。
<实施例2>
重复实施例1的步骤制备单层聚酰亚胺膜,但PTFE含量改为45.72克(占单体总重量的25wt%)。
<实施例3>
重复实施例1的步骤制备单层聚酰亚胺膜,但PTFE含量改为91.45克(占单体总重量的40wt%)。
<实施例4>
重复实施例2的步骤制备单层聚酰亚胺膜,但碳黑含量改为0.69克(占单体总重量的0.5wt%)。
<实施例5>
重复实施例2的步骤制备单层聚酰亚胺膜,但碳黑含量改为7.22克(占单体总重量的5wt%)。
<实施例6>
重复实施例1的步骤制备单层聚酰亚胺膜,但碳黑含量改为7.22克(占单体总重量的5wt%)。
<实施例7>
重复实施例1的步骤制备单层聚酰亚胺膜,但碳黑含量改为0.69克(占单体总重量的0.5wt%)。
<实施例8>
重复实施例3的步骤制备单层聚酰亚胺膜,但碳黑含量改为0.69克(占单体总重量的0.5wt%)。
<实施例9>制备双层聚酰亚胺膜
第一层聚酰亚胺膜重复实施例6的步骤而形成。将所得第一聚酰亚胺层固定于玻璃板上。接着,重复实施例1的步骤以制备第二层聚酰亚胺膜,将脱泡完的第二聚酰胺酸溶液涂布于该第一聚酰亚胺层上再进行烘烤,但各成份重量改为:37.15克的ODA、12.14克的PDA、88.21克的PMDA,单体占反应溶液总重量的百分比约25wt%,且不添加PTFE粉末及碳黑。所得双层聚酰亚胺膜的总厚度为14.4μm,其中,第一层厚度为12μm,第二层厚度为2.4μm。
<比较例1>
重复实施例4的步骤制备单层聚酰亚胺膜,但不添加PTFE。
<比较例2>
重复实施例3的步骤制备单层聚酰亚胺膜,但不添加碳黑。
<比较例3>
重复实施例4的步骤制备单层聚酰亚胺膜,但PTFE含量改为10wt%。
<比较例4>
重复实施例4的步骤制备单层聚酰亚胺膜,但PTFE含量改为45wt%。
<比较例5>
重复实施例1的步骤制备单层聚酰亚胺膜,但碳黑含量改为7wt%。
<比较例6>制备双层聚酰亚胺膜
重复实施例9的步骤制备双层聚酰亚胺膜,但所得双层聚酰亚胺膜的总厚度改为15μm,其中,第一层厚度为12μm,第二层厚度为3μm。
将上述实施例与比较例的薄膜进行下列测试,测试结果如表1及表2所示。
介电常数(Dk)及损耗因子(Df):将待测样品于去离子水中浸泡约10分钟,接着置于烘箱中以温度约110℃烘烤约30分钟进行干燥。以精密阻抗分析仪(型号Agilent 4294A)测量该待测样品的Dk/Df值。
光泽度值(GU):60度角光泽度测量以手持式光泽度计(型号:MicroTri Gloss-BYK Gardner)测得。
光穿透率(TT)(%):以雾度计(型号:Nippon Denshoku NDH 2000 HazeMeter)测得。
表1、单层聚酰亚胺膜的测试结果。
表2、双层聚酰亚胺膜的测试结果。
本发明的聚酰亚胺膜,通过添加适量的PTFE(15-40wt%)以达到降低介电常数、损失因子及60度光泽度值,同时并通过添加适量的碳黑(0.5-5wt%),以达到足够低的光穿透率。
如表1所示,相较于实施例4,比较例1、3虽然添加相同比例的碳黑(0.5wt%),但PTFE添加量过低时,聚酰亚胺膜的Dk、Df、光穿透率、光泽度的数值均过高,无法达到所欲的薄膜性质。
相较于实施例3及8,比较例2显示添加相同比例的适量PTFE,但未添加碳黑时,仍无法获得所欲的低光穿透率(低于30%)的聚酰亚胺膜。
比较例4及5则分别显示,当PTFE及碳黑其中任一者添加量过高时,会无法成膜。详细而言,比较例4及5的聚酰亚胺膜质地过脆,自玻璃板剥离时碎裂,而无法获得完整的聚酰亚胺膜。
另外,在制备多层聚酰亚胺膜时,实施例9的具有特定双层厚度比例的薄膜具有所欲性质;相对地,比较例6则显示,当h1/h2的厚度比例过高时,所得薄膜的介电常数(Dk)及损失因子(Df)皆显著上升,不利于后续应用。
综上所述,本发明所提供的聚酰亚胺膜,以较佳的单体组合形成聚酰亚胺,并采用特定比例的碳黑及含氟高分子,于多层结构中还必须具备特定的各层厚度比例,才能获得具有所欲低介电常数(Dk)、低光泽度值、低损耗因子(Df)及高遮蔽度的聚酰亚胺膜。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (16)
1.一种聚酰亚胺膜,其特征在于,包括:
构成该膜主结构的聚酰亚胺,由二胺单体及二酐单体经缩合反应而形成;
碳黑,占该膜总重量的0.5wt%至5wt%;以及
含氟高分子,占该膜总重量的15wt%至40wt%;
其中,该碳黑及该含氟高分子分布于该聚酰亚胺膜中,该聚酰亚胺膜的介电常数(Dk)低于3.05,且光泽度值为10以下。
2.如权利要求1所述的聚酰亚胺膜,其中,该含氟高分子选自由聚四氟乙烯(PTFE)、聚全氟乙丙烯(FEP)、全氟亚乙烯基(PVDF)聚合物、全氟烷氧基(PFA)聚合物、三氟氯乙烯(CTFE)聚合物及乙烯-三氟氯乙烯(ECTFE)聚合物所组成群组中的一种或多种。
3.如权利要求1所述的聚酰亚胺膜,其中,该含氟高分子的平均粒径为约1至10μm。
4.如权利要求1所述的聚酰亚胺膜,其中,该二胺单体选自由2,2’-双(三氟甲基)联苯胺(TFMB)、4,4′-二胺基二苯醚(4,4′-ODA)、对苯二胺(p-PDA)、1,3-双(4′-胺基苯氧基)苯(TPER)、1,4-双(4-胺基苯氧基)苯(TPEQ)、4,4’-二胺基-2,2’-二甲基-1,1’-联苯(m-TB-HG)、1,3-双(3-胺基苯氧基)苯(APBN)、3,5-二胺基三氟甲苯(DABTF)、2,2’-双(三氟甲基)联苯胺(TFMB)、2,2′-双[4-(4-胺基苯氧基苯基)]丙烷(BAPP)、6-胺基-2-(4-胺基苯基)-苯并恶唑(6PBOA)及5-胺基-2-(4-胺基苯基)-苯并恶唑(5PBOA)所组成群组中的一种或多种。
5.如权利要求1所述的聚酰亚胺膜,其中,该二酐单体选自由3,3′,4,4′-联苯四羧酸二酸酐(BPDA)、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酸酐(BPADA)、均苯四甲酸二酸酐(PMDA)、3,3′,4,4′-联苯四羧酸二酸酐(BPDA)、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酸酐(BPADA)、4,4′-(六氟异丙烯)二酞酸酐(6FDA)、二苯醚四甲酸二酸酐(ODPA)、苯酮四羧酸二酸酐(BTDA)、3,3′,4,4′-二环己基四甲酸二酐(HBPDA)所组成群组中的一种或多种。
6.如权利要求1所述的聚酰亚胺膜,其损失因子(Df)低于0.0115。
7.如权利要求1所述的聚酰亚胺膜,其光穿透率低于30%。
8.一种多层聚酰亚胺膜的结构,其特征在于,包括:
第一聚酰亚胺层,其为如权利要求1至8任一项所述的聚酰亚胺膜;及
第二聚酰亚胺层,至少包括构成该膜主结构的聚酰亚胺;
其中,该第一聚酰亚胺层的厚度为h1,该第二聚酰亚胺层的厚度为h2,且h2/h1的值为1/5以下。
9.如权利要求8所述的多层聚酰亚胺膜的结构,其中,该第一及第二聚酰亚胺层的聚酰亚胺由二胺单体及二酐单体经缩合反应而形成,且该两层的聚酰亚胺为相同或不同。
10.如权利要求9所述的多层聚酰亚胺膜的结构,其中,该第一聚酰亚胺层的二胺单体为2,2’-双(三氟甲基)联苯胺(TFMB),且第二聚酰亚胺层的二胺单体选自由2,2’-双(三氟甲基)联苯胺(TFMB)、4,4′-二胺基二苯醚(4,4′-ODA)、对苯二胺(p-PDA)、1,3-双(4′-胺基苯氧基)苯(TPER)、1,4-双(4-胺基苯氧基)苯(TPEQ)、4,4’-二胺基-2,2’-二甲基-1,1’-联苯(m-TB-HG)、1,3-双(3-胺基苯氧基)苯(APBN)、3,5-二胺基三氟甲苯(DABTF)、2,2’-双(三氟甲基)联苯胺(TFMB)、2,2′-双[4-(4-胺基苯氧基苯基)]丙烷(BAPP)、6-胺基-2-(4-胺基苯基)-苯并恶唑(6PBOA)及5-胺基-2-(4-胺基苯基)-苯并恶唑(5PBOA)所组成群组中的一种或多种。
11.如权利要求9所述的多层聚酰亚胺膜的结构,其中,该第一聚酰亚胺层的二酐单体为3,3′,4,4′-联苯四羧酸二酸酐(BPDA)、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酸酐(BPADA)或其组合,且第二聚酰亚胺层的二酐单体选自由3,3′,4,4′-联苯四羧酸二酸酐(BPDA)、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酸酐(BPADA)、均苯四甲酸二酸酐(PMDA)、3,3′,4,4′-联苯四羧酸二酸酐(BPDA)、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酸酐(BPADA)、4,4′-(六氟异丙烯)二酞酸酐(6FDA)、二苯醚四甲酸二酸酐(ODPA)、苯酮四羧酸二酸酐(BTDA)、3,3′,4,4′-二环己基四甲酸二酐(HBPDA)所组成群组中的一种或多种。
12.如权利要求8所述的多层聚酰亚胺膜的结构,其具有选自下列至少一种膜特性:低于3.05的介电常数(Dk)、10以下的光泽度值、低于0.0115的损失因子(Df)及低于30%的光穿透率。
13.一种制备多层聚酰亚胺膜的方法,其特征在于,包括:
制备第一聚酰胺酸溶液,其包括二胺单体、二酐单体、碳黑及含氟高分子;
将该第一聚酰胺酸溶液涂布于一基板上,并烘烤以形成第一聚酰亚胺层;
制备第二聚酰胺酸溶液,其包括二胺单体及二酐单体;及
将该第二聚酰胺酸溶液涂布于该第一聚酰亚胺层上,并烘烤以于该第一聚酰亚胺层上形成第二聚酰亚胺层;
其中,该第一聚酰亚胺层的厚度为h1,该第二聚酰亚胺层的厚度为h2,且h2/h1的值为1/5以下。
14.如权利要求13所述的方法,其中,该碳黑占该第一聚酰亚胺膜总重量的0.5wt%至5wt%。
15.如权利要求13所述的方法,其中,该含氟高分子占该第一聚酰亚胺膜总重量的15wt%至40wt%。
16.如权利要求13所述的方法,进一步包括于涂布前,将脱水剂及催化剂添加至该第一聚酰胺酸溶液及该第二聚酰胺酸溶液中。
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US20150307709A1 (en) | 2015-10-29 |
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CN104830058B (zh) | 2018-06-26 |
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