CN103183961A - 含互穿型网络聚合物的聚酰胺酸树脂的溶液及聚酰亚胺金属积层板 - Google Patents
含互穿型网络聚合物的聚酰胺酸树脂的溶液及聚酰亚胺金属积层板 Download PDFInfo
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- CN103183961A CN103183961A CN2011104612130A CN201110461213A CN103183961A CN 103183961 A CN103183961 A CN 103183961A CN 2011104612130 A CN2011104612130 A CN 2011104612130A CN 201110461213 A CN201110461213 A CN 201110461213A CN 103183961 A CN103183961 A CN 103183961A
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- Prior art keywords
- bismaleimides
- polyamic acid
- amino
- benzene
- solution
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 74
- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 229920005989 resin Polymers 0.000 title claims abstract description 48
- 239000011347 resin Substances 0.000 title claims abstract description 48
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 47
- 239000004642 Polyimide Substances 0.000 title claims abstract description 39
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 98
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims description 75
- -1 bismaleimide amine Chemical class 0.000 claims description 55
- 229910052757 nitrogen Inorganic materials 0.000 claims description 54
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 43
- 150000004985 diamines Chemical class 0.000 claims description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 150000008064 anhydrides Chemical class 0.000 claims description 24
- 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 claims description 22
- 239000011889 copper foil Substances 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 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 12
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 9
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 7
- 239000001294 propane Substances 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 5
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 claims description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000006884 silylation reaction Methods 0.000 claims description 3
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 claims description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- 229910001120 nichrome Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229960003418 phenoxybenzamine Drugs 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- 229940044174 4-phenylenediamine Drugs 0.000 claims 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims 2
- 238000007334 copolymerization reaction Methods 0.000 claims 2
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 claims 1
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims 1
- 229940095102 methyl benzoate Drugs 0.000 claims 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 abstract description 12
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 238000003756 stirring Methods 0.000 description 35
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- 238000006243 chemical reaction Methods 0.000 description 28
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 18
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- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 17
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Abstract
本发明提供一种含互穿型网络聚合物的聚酰胺酸树脂的溶液,包括一聚酰胺酸树脂溶于一溶剂中,其中该聚酰胺酸树脂包含一互穿型网络聚合物,该互穿型网络聚合物是由一具超分岐结构的聚双马来酰亚胺及一缠绕该聚双马来酰亚胺的聚酰胺酸形成,其中该具超分岐结构的聚双马来酰亚胺包含双马来酰亚胺高分子、双马来酰亚胺寡聚物、巴比土酸-双马来酰亚胺共聚物、或前述的组合。本发明还提供一聚酰亚胺金属积层板。
Description
技术领域
本发明是涉及聚酰胺酸树脂(polyamic acid resin)组合物,且特别是涉及一种能够提供良好的耐热性、尺寸稳定性及对金属基板接着性的聚酰胺酸树脂组合物,以及运用此种聚酰胺酸树脂组合物所制成的聚酰亚胺金属积层板。
背景技术
聚酰亚胺已广泛地应用于各种工业中,特别是在电子工业中,由于聚酰亚胺具有良好的耐热性及电气绝缘特性,可与金属基材形成层积结构。此层积结构可作为例如软性电路板,提供各类电子元件形成于其上。
传统软性印刷电路板,尤其是聚酰亚胺双层软性印刷电路板,是在金属基板上涂布一层聚酰胺酸树脂,并经过热烘烤程序,以形成聚酰亚胺薄膜。由于聚酰胺酸树脂在转换形成聚酰亚胺薄膜的过程中,是进行加热脱水的缩合聚合反应,并同时去除溶剂。因此,聚酰亚胺双层软性印刷电路板会因为聚酰亚胺薄膜与金属基材的热膨胀系数的差异所形成的热应力效应,造成基板卷曲、结构韧性差,以及接着强度不佳等的问题。
为能改善并解决上述的问题,过去已有许多的技术与手段被提出。例如,世界专利WO 2010/137832揭示了一种软性金属积层板的制作方法,其为在金属基材上多次涂布聚酰亚胺前驱物树脂(polyimide precursor resin)的涂层,再经过80~180℃的烘干程序及以80~400℃的红外线(infrared ray)系统烘烤后,以形成聚酰亚胺薄膜。如此,可使聚酰亚胺薄膜的线热膨胀系数减降至20ppm/℃或以下。因此,聚酰亚胺薄膜在热处理过程的尺寸变化率变小,且软性金属基板在蚀刻前后已无明显的卷曲现象。然而,其制程过于复杂且冗长,对于需制程简化及成本降低的考虑时并非有利。又如日本专利JP 300639/89所提出制作软性印刷电路板的制程,是在聚酰胺酸树脂内添加10%~50%的四级胺(tertiaryamino)化合物,使有机薄膜的线膨胀系数可以更接近金属基材,而降低软性金属基板产生卷曲(curling)、扭曲变形(warping)和起皱(wrinkling)的程度。美国专利US2004/0180227则揭露一种由6-胺基-2-(对苯二胺)-苯并咪唑(6-amino-2-(p-aminophenyl)-benzimidazole)与至少一种双胺(diamines)及两种四羧酸二酐(tetracarboxylic acid dianhydrides)所形成的聚酰亚胺共聚合物,其具有良好的成膜性、接着强度和尺寸稳定性,并具有低的吸水率及低的卷曲率。此外,美国专利US1994/5372891也提出一种双层软性印刷电路板的制程,其为在铜箔金属基材上,以双层挤出成型模具(double-layered extrusion die)同时挤出聚酰亚胺(上层薄膜)和经双马来酰亚胺改质的聚酰亚胺(下层薄膜)的双层聚酰亚胺薄膜,增加其与金属基材的接着强度,并改善尺寸稳定性和表面的平坦性。其中,所添加做为改质剂的双马来酰亚胺主要为单体成份,会与双胺(diamines)起作用反应,造成聚酰亚胺结构中的双胺与酸酐组成比率的变化,以至较难掌控,其合成的条件较为严苛。
另外,Chunhong Zhang等人在Composites Science and Technology 67(2007)380-389的期刊论文中,揭示运用溶凝胶(sol-gel)技术合成由异构聚酰亚胺(isomeric polyimide)及二氧化硅所组成的复合材料,主要是先使用3-[(4-苯基乙炔基)邻苯二甲酰亚胺基]丙基三乙氧基硅烷([3-[(4-phenylethynyl)phthalimide]propyl triethoxysilane],PEIPTES)改质二氧化硅的纳米前驱物(nano-SiO2 precursor);然后再将异构聚酰亚胺与改质的二氧化硅的纳米前驱物进行交联固化反应(cross-curing reaction),以制备出异构聚酰亚胺/二氧化硅复合材料,其可呈现出优异的热性质及纳米压痕性质。Jiann-Wen Huang等人在Short Communication Polymer Journal(2007)39,654~658的期刊论文中提出一种可从纳米级二氧化硅胶体中制备聚酰亚胺/二氧化硅纳米复合材料的方法,即是在聚酰胺酸溶液内直接混合市售的纳米级二氧化硅胶体溶液(commercialnanoscale colloidal silica sol),并经过热交联固化反应,以使聚酰胺酸及纳米级二氧化硅形成聚酰亚胺/二氧化硅纳米复合材料的膜层。由此方法形成的膜层可呈现出好的光学穿透率,以及展现出良好的机械强度、高玻璃转化温度、热稳定性佳和低的热膨胀系数等的性能。Soo-Min HWANG等人为解决聚酰亚胺薄膜与金属铜箔间的接着问题,于Trans.Nonferrous Met.Soc.China 19(2009)970-974的期刊中发表一篇使用铜的无电电镀及电镀的预处理作业程序,其可改善铜箔表面的结构组态,提增其与聚酰亚胺的间的接着强度。
由上述可得知,如欲得到性能良好的聚酰亚胺双层软性基板,改良聚酰胺酸树脂的性质是最快速且有效的方法。上述所举例的形成聚酰亚胺膜的方法可大致整理如图1所示。首先,提供如方块102所示的双胺类单体、酸酐类单体及溶剂。进行步骤S102,将双胺类单体及酸酐类单体加入于溶剂中,并于室温下搅拌,使双胺类单体及酸酐类单体聚合形成如方块104所示的聚酰胺酸树脂溶液。接着,进行步骤S104,其为以改质剂或添加无机添加物至此聚酰胺酸溶液中,并视需要进行改质反应,以得到如方块106所示的改质的聚酰胺酸树脂或混掺无机物的聚酰胺酸树脂。
由图1可知,已知方法大多为在聚酰胺酸树脂形成后,才对其作进一步的改质。如此,仍难以大幅改良聚酰胺酸树脂的性质。因此,目前所需的是一种可以简单制程及可大幅改良聚酰胺酸树脂性质的方法。
发明内容
本发明的目的在于提供一种含互穿型网络聚合物的聚酰胺酸树脂的溶液,以可以使制程简单及可大幅改良聚酰胺酸树脂的性质。
本发明的另一目的在于提供一聚酰亚胺金属积层板。
本发明提供一种含互穿型网络聚合物的聚酰胺酸树脂的溶液,包括:
一聚酰胺酸树脂溶于一溶剂中,其中该聚酰胺酸树脂包含一互穿型网络聚合物,该互穿型网络聚合物是由一具超分岐结构的聚双马来酰亚胺及一缠绕该聚双马来酰亚胺的聚酰胺酸形成,其中该具超分岐结构的聚双马来酰亚胺包含双马来酰亚胺高分子、双马来酰亚胺寡聚物、巴比土酸-双马来酰亚胺共聚物、或前述的组合。
本发明也提供一种聚酰亚胺金属积层板,包括:一金属基材,及一由上述的含互穿型网络聚合物的聚酰胺酸树脂的溶液形成的聚酰亚胺膜覆于此金属基材上。
本发明的优点在于:依照本发明实施例提供的含互穿型网络聚合物的聚酰亚胺膜本身就具有极佳的耐热性及尺寸稳定性,且可保持其为有机材料的优点,例如良好的电性绝缘性及较轻的重量。此外,以此含互穿型网络聚合物的聚酰亚胺薄膜与金属基材所形成的聚酰亚胺金属积层板,除了具有含互穿型网络聚合物的聚酰亚胺膜本身的上述优点外,此含互穿型网络聚合物的聚酰亚胺薄膜与金属基材之间也可具有高接着强度。因此,依照本发明实施例所提供的聚酰亚胺金属积层板可足以应用于各种的电子元件中,并提供更优良的性能。
为让本发明的上述和其它目的、特征、和优点能更明显易懂,下文特举出较佳实施例,并配合所附图式,作详细说明如下:
附图说明
图1显示依照已知的聚酰亚胺膜的改质方法的流程图;
图2显示依照本发明一实施例的含互穿型网络聚合物的聚酰胺酸树脂溶液的制造方法的流程图;
图3显示依照本发明另一实施例的含互穿型网络聚合物的聚酰胺酸树脂溶液的制造方法的流程图;
图4显示依照本发明一实施例的聚酰亚胺膜金属积层板的示意图;
图5显示以胶体渗透层析仪分析二苯甲烷双马来酰亚胺的单体的NMP溶液及实施例1的含5wt%的聚二苯甲烷双马来酰亚胺的NMP溶液;
其中,主要元件符号说明:
112~金属基材 114~聚酰亚胺膜。
具体实施方式
本发明提供一种含互穿型网络聚合物(interpenetrating polymer)的聚酰胺酸树脂组合物和以此聚酰胺酸树脂组合物所形成的聚酰亚胺金属积层板。在本发明实施例中,主要是先将双胺类单体及酸酐类单体,依比例加入于含具超分歧结构的聚双马来酰亚胺(polybismaleimide)的溶液中搅拌溶解,接着再持续搅拌以使双胺与酸酐进行形成聚酰胺酸的聚合反应。此聚双马来酰亚胺可包含双马来酰亚胺高分子、双马来酰亚胺寡聚物、巴比土酸-双马来酰亚胺共聚物、或前述的组合。由于具超分歧结构的聚双马来酰亚胺高分子或其寡合物内有许多纳米级的孔洞和孔隙(pore/cage),双胺类单体及酸酐类单体可进入这些纳米级的孔洞和孔隙(pore/cage)中,并可原位(in situ)反应形成聚酰胺酸。因此,所形成的聚酰胺酸可与聚双马来酰亚胺高分子或其寡合物组构形成互穿网络式结构的聚合物。此种互穿网络结构的聚合物可增加材料成膜的结构强度与韧性,并具有极佳的耐热稳定度和尺寸稳定性。
参见图2,其显示依照本发明一实施例的形成含互穿型网络聚合物的聚酰胺酸树脂组合物的流程图。首先,提供方块202所示的一双马来酰亚胺单体及一溶剂。进行步骤S202,将双马来酰亚胺单体加入至溶剂中,并搅拌使其充分溶解,得到方块204所示的双马来酰亚胺单体溶液。双马来酰亚胺单体可具有如下的结构式(I)或(II):
其中在上述式(I)中,R1可为:
-R-CH2-R-、-R-NH-R-、-C(O)-、-C(O)-CH2-,-CH2OCH2-、-C(O)-、-R-C(O)-R-、-O-、-O-O-、-S-、-S-S-、-S(O)-、-R-S(O)-R-、-(O)S(O)-、-R-(O)S(O)-R-、-C6H4-、-R-(C6H4)-R-、-R(C6H4)(O)-、-(C6H4)-(C6H4)-、-R-(C6H4)-(C6H4)-R-或-R-(C6H4)-(C6H4)-O-,其中R为C1-8的烷撑基、(C6H4)为苯撑基,及(C6H4)-(C6H4)为联苯撑基;
其中在上述式(II)中,R2可为:
-R-、-O-、-O-O-、-S-、-S-S-、-C(O)-、-S(O)-或-(O)S(O)-,其中X1、X2、X3、X4、X5、X6、X7、X8可各自择自卤素、氢原子、C1-8的烷基、C1-8的环烷基或C1-8的硅烷基。
例如,双马来酰亚胺的单体可择自二苯甲烷双马来酰亚胺(N,N’-bismaleimide-4,4’-diphenylmethane)、1,1’-(亚甲基双-4,1-亚苯基)双马来酰亚胺[1,1’-(methylenedi-4,1-phenylene)bismaleimide]、N,N’-(1,1’-二苯基-4,4’-二亚甲基)双马来酰亚胺[N,N’-(1,1’-biphenyl-4,4’-diyl)bismaleimide]、N,N’-(4-甲基-1,3-亚苯基)双马来酰亚胺[N,N’-(4-methyl-1,3-phenylene)bismaleimide]、1,1,-(3,3’-二甲基-1,1’-二苯基-4,4’-二亚甲基)双马来酰亚胺[1,1’-(3,3’dimethyl-1,1’-biphenyl-4,4’-diyl)bismaleimide]、N,N’-乙烯基二马来酰亚胺(N,N’-ethylenedimaleimide)、N,N’-(1,2-亚苯基)双马来酰亚胺[N,N’-(1,2-phenylene)dimaleimide]、N,N’-(1,3-亚苯基)二马来酰亚胺[N,N’-(1,3-phenylene)dimaleimide]、N,N’-双马来酰亚胺硫(N,N’-thiodimaleimid)、N,N’-双马来酰亚胺二硫(N,N’-dithiodimaleimid)、N,N’-双马来酰亚胺酮(N,N’-ketonedimaleimid)、N,N’-亚甲基双马来酰亚胺(N,N’-methylene-bis-maleinimid)、双马来酰亚胺甲-醚(bis-maleinimidomethyl-ether)、1,2-双马来酰亚胺基-1,2-乙二醇[1,2-bis-(maleimido)-1,2-ethandiol]、N,N’-4,4’-二苯醚-双马来酰亚胺(N,N’-4,4’-diphenylether-bis-maleimid)及4,4’-双马来酰亚胺-二苯砜(4,4’-bis(maleimido)-diphenylsulfone)所组成的族群。
溶剂可为任意可溶解双马来酰亚胺的溶剂,例如可包含N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、吡咯烷酮(pyrrolidone)、N-月桂基吡咯烷酮(N-dodecylpyrrolidone)及γ-丁酸内酯(γ-butyrolactone)等有机溶剂。
接着,进行步骤S204,将双马来酰亚胺溶液204加热搅拌,以使双马来酰亚胺单体溶液204中的双马来酰亚胺单体聚合形成具有超分岐结构的聚双马来酰亚胺,而得到如方块206所示的含聚双马来酰亚胺的溶液。例如,可在40℃~150℃的温度下,搅拌6~96小时。此聚双马来酰亚胺具有超分歧结构,具有许多纳米级的孔洞和孔隙(pore/cage)于其超分歧结构内。在本实施例中,具有超分岐结构的聚双马来酰亚胺可为双马来酰亚胺高分子或双马来酰亚胺寡聚物。例如,当此具有超分岐结构的聚双马来酰亚胺为高分子时,可具有50,000~1,500,000的重量平均分子量。当具有超分岐结构的聚双马来酰亚胺为寡聚物时,可具有5,000~50,000的重量平均分子量。在一实施例中,此具有超分岐结构的聚双马来酰亚胺的平均尺寸可为约10~50nm。
接着,进行步骤S206,将方块208所示的双胺类单体加入至含聚双马来酰亚胺的溶液206中,使其完全溶解,得到如方块210所示的含聚双马来酰亚胺及双胺类单体的溶液。双胺类单体可包含对苯二胺(p-phenylene diamine)、间苯二胺(m-phenylenediamine)、三氟甲基-2,4-苯二胺(trifluoromethyl-2,4-diaminobenzene)、三氟甲基-3,5-苯二胺(trifluoromethyl-3,5-diaminobenzene)、2,5-二甲基-1,4-苯二胺(2,5-dimethyl-1,4-phenylenediamine,DPX)、2,2-双-(4-胺基苯基)-丙烷(2,2-bis-(4-aminophenyl)propane)、4,4’-二氨基-联苯(4,4’-diaminobiphenyl)、4,4’-二氨基二苯甲酮(4,4’-diaminobenzophenone)、4,4’-二氨基二苯甲烷(4,4’-diaminodiphenylmethane)、4,4-二氨基二苯硫醚(4,4’-diaminodiphenyl sulfide)、4,4’-二氨基二苯砜(4,4’-diaminodiphenylsulfone)、3,3’-二氨基二苯砜(4,4’-diaminodiphenyl sulfone)、4,4’-双(4-氨基苯氧基)二苯砜bis-(4-(4-aminophenoxy)phenyl sulfone,BAPS)、4,4’-双(3-氨基苯氧基)联苯(4,4’-bis-(aminophenoxy)biphenyl,BAPB)、4,4`-二氨基二苯醚(4,4’-diaminodiphenyl ether)、3,4`-二氨基二苯醚(3,4’-diaminodiphenyl ether)、2,2-双-(3-胺基苯基)-丙烷(2,2-bis-(3-aminophenyl)propane)、N,N-双-(4-胺基苯基)-正丁基胺(N,N-bis-(4-aminophenyl)-n-butylamine)、N,N-双-(4-胺基苯基)-甲基胺(N,N-bis-(4-aminophenyl)methylamine)、1,5-二氨基萘(1,5-diaminonaphthalene)、4,4’-二氨基-3,3’-二甲基联苯(3,3’-dimethyl-4,4’-diaminobiphenyl)、m-胺基苯甲酰-p-胺基苯胺(m-amino benzoyl-p-aminoaniline)、4-氨基苯基-3-胺基苯甲酸甲酯(4-aminophenyl-3-aminobenzoate)、N,N-双-(4-胺基苯基)-苯胺(N,N-bis-(4-aminophenyl)aniline),2,4-二氨基甲苯(2,4-diaminotoluene)、2,5-二氨基甲苯(2,5-diaminotoluene)、2,6-二氨基甲苯(2,5-diaminotoluene)、2,4-二氨基-5-氯甲苯(2,4-diamine-5-chlorotoluene)、2,4-二氨基-6-氯甲苯(2,4-diamine-6-chlorotoluene)、2,4-双-(β-氨基叔丁基)甲苯(2,4-bis-(beta-amino-t-butyl)toluene)、双-(对-β-氨基叔丁基苯基)醚(bis-(p-beta-amino-t-butyl phenyl)ether)、对-双-2(2-甲基-4-氨基戊基)苯(p-bis-2-(2-methyl-4-aminopentyl)benzene)、间苯二甲胺(m-xylylene diamine)、对苯二甲胺(p-xylylene diamine)或前述的组合。
或者,双胺类单体可包含如下的芳香族双胺,例如1,2-双-(4-氨基苯氧基)苯(1,2-bis-(4-aminophenoxy)benzene)、1,3-双-(4-氨基苯氧基)苯(1,3-bis-(4-aminophenoxy)benzene)、1,3-双-(3-氨基苯氧基)苯(1,3-bis-(3-aminophenoxy)benzene)、1-(4-氨基苯氧基)-3-(3-氨基苯氧基)苯(1-(4-aminophenoxy)-3-(3-aminophenoxy)benzene)、1,4-双-(4-氨基苯氧基)苯(1,4-bis-(4-aminophenoxy)benzene)、1,4-双-(3-氨基苯氧基)苯(1,4-bis-(3-aminophenoxy)benzene)、1-(4-氨基苯氧基)-4-(3-氨基苯氧基)苯(1-(4-aminophenoxy)-4-(3-aminophenoxy)benzene)、2,2’-双-[4-(4-氨基苯氧基苯基)]丙烷(2,2-bis-(4-[4-aminophenoxy]phenyl)propane(BAPP))、2,2’-双-(4-氨基苯氧基苯基)]六氟丙烷(2,2’-bis-(4-aminophenyl)-hexafluoro propane)、亚异丙基2,2’-双-(苯氧基苯胺)(2,2’-bis-(4-phenoxy aniline)isopropylidene)、2,4,6-三甲基-1,3-苯二胺(2,4,6-trimethyl-1,3-diaminobenzene)、4,4’-二氨基-2,2’-三氟甲基二苯醚(4,4’-diamino-2,2’-trifluoromethyl diphenyloxide)、3,3’-二氨基-5,5’-三氟甲基二苯醚(3,3’-diamino-5,5’-trifluoromethyl diphenyloxide)、4,4’-三氟甲基-2,2’-二氨基联苯(4,4’-trifluoromethyl-2,2’-diaminobiphenyl)、2,4,6-三甲基-1,3-苯二胺(2,4,6-trimethyl-1,3-diaminobenzene)、4,4’-氧-双-(2-三氟甲基)苯胺(4,4’-oxy-bis-[2-trifluoromethyl)benzene amine])、4,4’-氧-双-(3-三氟甲基)苯胺(4,4’-oxy-bis-[3-trifluoromethyl)benzene amine])、4,4’-硫-双-(2-三氟甲基)苯胺(4,4’-thio-bis-[(2-trifiuoromethyl)benzene-amine])、4,4’-硫-双-(2-三氟甲基)苯胺(4,4’-thiobis[(3-trifluoromethyl)benzene amine])、4,4’-磺酰氧基-双-(2-三氟甲基)苯胺(4,4’-sulfoxyl-bis-[(2-trifiuoromethyl)benzene amine])、4,4’-磺酰氧基-双-(3-三氟甲基)苯胺(4,4’-sulfoxyl-bis-[(3-trifluoromethyl)benzene amine])、4,4’-酮基-双-(2-三氟甲基)苯胺(4,4’-keto-bis-[(2-trifluoromethyl)benzene amine])或前述的组合。
最后,进行步骤S208,加入如方块212所示的酸酐类单体至含聚双马来酰亚胺及双胺类单体的溶液210中,并在室温下充分搅拌,以使双胺类单体及酸酐类单体聚合形成聚酰胺酸,而得到如方块214含互穿型网络聚合物的聚酰胺酸树脂的溶液。在一实施例中,双胺类单体及酸酐类单体的摩尔比可介于约2/3~3/2。需注意的是,步骤S206及S208较佳为在氮气下进行。
酸酐类单体可包含3,3’4,4’-二苯甲酮四羧酸二酐(3,3’,4,4’-benzophenonetetracarboxylic dianhydride)、3,3’,4,4’-联苯四羧酸二酐(3,3’,4,4’-biphenyltetracarboxylic dianhydride)、均苯四甲酸二酐(pyromellitic dianhydride,PMDA)、4,4’-氧双邻苯二甲酸酐(4,4’-oxydiphthalic anhydride,ODPA)、3,3,4,4-二苯基砜四羧酸二酸酐(3,3’,4,4’-diphenylsulfonetetracarboxylic dianhydride,DSDA)、2,2’-双(3,4-二羧酸)六氟丙烷二酐(2,2’-bis(3,4-dicarboxyphenyl)hexafluoropropanedianhydride)、苯-1,2,4,5,-四羧酸二酐(1,2,4,5-benzenetetracarboxylic-1,2:4,5-dianhydride)、六环酸酐(1,4,5,8-naphthalene tetracarboxylic dianhydride,NTDA)、3,4,9,10-四羧酸酐(perylene-3,4,9,10-tetracarboxylic acid dianhydride,PTCDA)、2,6-双(3,4-二羧苯氧基)萘二酐(2,6-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride)、2,7-双(3,4-二羧苯氧基)萘二酐(2,7-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride)、联苯四甲酸二酐(4,4’-biphthalic dianhydride)或前述的组合。
由于双胺类单体及酸酐类单体的尺寸皆仅在1埃左右,远小于聚双马来酰亚胺的尺寸(约10~50nm)及其孔洞和间隙所组构的自由体积(约数nm)。因此,双胺类单体及酸酐类单体可自由地渗透进入至此具超分歧结构的聚双马来酰亚胺的孔洞和间隙中,甚至可接近至超分歧结构的核心。因此,双胺类单体及酸酐类单体可在聚双马来酰亚胺的孔洞和间隙中原位(in situ)形成缠绕此双马来酰亚胺的聚酰胺酸,且聚酰胺酸能与此具超分歧结构的聚双马来酰亚胺形成互穿型网络聚合物。本发明中,该互穿网络聚合物可为全互穿型网络聚合物。因此,聚酰胺酸树脂可包含此由聚酰胺酸及聚双马来酰亚胺所形成的互穿型网络聚合物。在一实施例中,双马来酰亚胺超分歧高分子占总体聚酰胺酸树脂的固含量的0.1wt%~50wt%,较佳为1wt%~20wt%。
参见图3,其显示依照本发明另一实施例的形成含互穿型网络聚合物的聚酰胺酸树脂组合物的流程图。
首先,提供方块302所示的双马来酰亚胺单体、巴比土酸及溶剂。进行步骤S302,将双马来酰亚胺单体及巴比土酸加入至溶剂中,并搅拌使其充分溶解,得到如方块304所示的含双马来酰亚胺单体及巴比土酸的溶液。在本实施例中,双马来酰亚胺单体及溶剂可使用与前述实施例相同的双马来酰亚胺单体及溶剂。巴比土酸以如下结构式(III)表示:
其中R3及R4可各自择自氢原子、甲基、苯基、异丙基、异丁基及异戊基。巴比土酸与双马来酰亚胺的摩尔比例可为约1∶1至1∶50。
接着,进行步骤S304,将含双马来酰亚胺单体及巴比土酸的溶液304加热搅拌,以使此溶液中的双马来酰亚胺单体与巴比土酸聚合形成具有超分岐结构的聚双马来酰亚胺,而得到如方块306所示的含聚双马来酰亚胺的溶液。例如,可在40℃~150℃的温度下,搅拌6~96小时。在本实施例中,具有超分岐结构的聚双马来酰亚胺可为马来酰亚胺-巴比土酸共聚物,其可具有10~50nm的平均尺寸及50,000~1,500,000的重量平均分子量。此外,此马来酰亚胺-巴比土酸共聚物具以超分歧结构,并具有许多纳米级的孔洞和孔隙(pore/cage)于其超分歧结构内。
接着,进行步骤S306,加入如方块308所示的双胺类单体至聚双马来酰亚胺的溶液306中,使其完全溶解,得到含聚双马来酰亚胺及双胺类单体的溶液310。在本实施例中,双胺类单体可使用与前述实施例相同的双胺类单体。
最后,进行步骤S308,加入酸酐类单体至含聚双马来酰亚胺及双胺类单体的溶液310中,并在室温下充分搅拌,以使双胺类单体及酸酐类单体聚合形成聚酰胺酸树脂,得到如方块314含互穿型网络聚合物的聚酰胺酸树脂的溶液。在一实施例中,双胺类单体及酸酐类单体的摩尔比可介于约2/3~3/2。需注意的是,步骤S306及S308较佳为在氮气下进行。在本实施例中,酸酐类单体可使用与前述实施例相同的酸酐类单体。
由于双胺类单体及酸酐类单体的尺寸皆仅在1埃左右,远小于聚双马来酰亚胺的尺寸(约10~50nm)及其孔洞和间隙所组构的自由体积(约数nm)。因此,双胺类单体及酸酐类单体可自由地渗透进入至此具超分歧结构的聚双马来酰亚胺的孔洞和间隙中,甚至可接近至超分歧结构的核心。因此,双胺类单体及酸酐类单体可在聚双马来酰亚胺的孔洞和间隙中原位(in situ)形成缠绕此双马来酰亚胺的聚酰胺酸树脂,且聚酰胺酸树脂能与此具超分歧结构的聚双马来酰亚胺形成互穿型网络聚合物。在一实施例中,此具超分歧结构的聚双马来酰亚胺共聚物占总体聚酰胺酸树脂的固含量的0.1wt%~50wt%,较佳为1wt%~20wt%。
参见图4,将由图2及图3所示的制造流程所得到的含互穿型网络聚合物的聚酰胺酸树脂的溶液214或314(此后简称为混合溶液)涂布于金属基材112上,形成由聚酰亚胺膜114及金属基材112所构成的聚酰亚胺金属层积板。
金属基材112可包含铜箔系、铜铬合金、铜镍合金、铜镍铬合金、铝合金系、或前述的组合。金属基材112的厚度可为5~50μm,热膨胀系数可为15~25ppm/℃。涂布方式可例如为刮刀式涂布、旋转涂布、帘幕式涂布,以及狭缝式涂布(Slot Die)等。例如,可使用刮刀式涂布或狭缝式涂布治具,将混合溶液涂布至金属基材112上之后,并加热以移除溶剂,使聚酰胺酸(聚酰亚胺前驱物)聚合形成聚酰亚胺,形成一以聚酰亚胺为主的聚酰亚胺薄膜。
聚酰亚胺膜114是由含互穿型网络聚合物的聚酰胺酸树脂脱水形成,经涂布于该金属基材上及热烘烤后形成。因此,聚酰亚胺膜114可具有较佳的耐热性及尺寸稳定性。例如,聚酰亚胺膜114的玻璃转化温度可高于300℃以上,较纯聚酰亚胺膜提高了至少约20℃。聚酰亚胺膜114的平均热膨胀系数(30℃至250℃的间)可为约18~21ppm/℃的间,近似于添加无机物(例如二氧化硅纳米颗粒)后的聚酰亚胺膜。
此外,具超分歧结构的聚双马来酰亚胺的末端可为未反应的官能基,包含未反应的双键。此未反应的双键可螯合至金属基材112的表面,可增加聚酰亚胺膜114对金属基材112的接着强度,且互穿型网络结构亦能有效提增聚酰亚胺膜114的结构韧性。因此,聚酰亚胺金属层积板可具有良好的结构强度与韧性,并具有极佳的耐热稳定度和尺寸稳定性。
综上所述,依照本发明实施例提供的含互穿型网络聚合物的聚酰亚胺膜本身就具有极佳的耐热性及尺寸稳定性,且可保持其为有机材料的优点,例如良好的电性绝缘性及较轻的重量。此外,以此含互穿型网络聚合物的聚酰亚胺薄膜与金属基材所形成的聚酰亚胺金属积层板,除了具有含互穿型网络聚合物的聚酰亚胺膜本身的上述优点外,此含互穿型网络聚合物的聚酰亚胺薄膜与金属基材之间也可具有高接着强度。因此,依照本发明实施例所提供的聚酰亚胺金属积层板可足以应用于各种的电子元件中,并提供更优良的性能。
以下将揭示本发明实施例的含互穿型网络聚合物的聚酰亚胺膜及含此聚酰亚胺膜的层积板的详细合成步骤。
【实施例1】
取13.16g(0.037mole)的4,4’-二苯甲烷双马来酰亚胺(4,4’-diphenylmethanebismaleimide)置入于500ml的反应瓶中,加入250g的甲基吡咯烷酮(N-methylpyrollidone,NMP)并进行搅拌,使4,4’-二苯甲烷双马来酰亚胺完全溶解。在氮气环境下,于130℃持续搅拌48小时,得到含5wt%的聚二苯甲烷双马来酰亚胺的NMP溶液。
【实施例2】
取7.60g(0.021mole)的4,4’-二苯甲烷双马来酰亚胺(4,4’-diphenylmethanebismaleimide)和0.14g(0.001mole)的巴比土酸(barbituric acid)置入于500ml的反应瓶中,加入250g的甲基吡咯烷酮(N-methyl pyrollidone,NMP)并进行搅拌,使4,4’-二苯甲烷双马来酰亚胺和巴比土酸能完全溶解。在氮气的环境下,于130℃持续搅拌48小时,得到含3wt%的二苯甲烷双马来酰亚胺-巴比土酸共聚物的NMP溶液。
【实施例3】
取44.12g的实施例1的的含5wt%的二苯甲烷双马来酰亚胺的NMP溶液置入于500ml的反应瓶中,加入208.18g的甲基吡咯烷酮(N-methyl pyrollidone,NMP),通入氮气并进行搅拌使溶液呈现均匀状态。取12.60g(0.070mole)的对苯二胺(p-phenylene diamine,p-PDA)及3.50g(0.018mole)的4,4’-二胺基二苯基醚(4,4’-oxydianiline,4,4’-ODA)加入至上述溶液中,并在氮气的环境下进行搅拌,使对苯二胺及4,4’-二胺基二苯基醚完全溶解。随后,取4,4″-联苯四酸二酐(bis(phenylene dicarboxylic acid)dianhydride,BPDA)25.82g(0.088mole),以间隔30分钟的时频,分批加料加入于反应瓶内,并持续搅拌。待4,4″-联苯四酸二酐完全加入至反应瓶后,再持续搅拌3小时,得到固含量为约15wt%的含聚二苯甲烷双马来酰亚胺及酰亚胺酸的NMP溶液-I。
【实施例4】
取44.12g的实施例1的的含5wt%的二苯甲烷双马来酰亚胺的NMP溶液置入于500ml的反应瓶中,加入208.18g的甲基吡咯烷酮(N-methyl pyrollidone,NMP(,通入氮气并进行搅拌使溶液呈现均匀状态。取13.47g(0.067mole)的对苯二胺(p-phenylene diamine,p-PDA)及2.64g(0.013mole)的4,4’-二胺基二苯基醚(4,4’-oxydianiline,4,4’-ODA)加入至上述溶液中,并在氮气的环境下进行搅拌,使对苯二胺及4,4’-二胺基二苯基醚完全溶解。随后,取20.70g(0.070mole)的4,4″-联苯四酸二酐(bis(phenylene dicarboxylic acid)dianhydride,BPDA)和5.10g(0.016mole)的3,3’,4,4’-二苯二酸酐酮(3,3’,4,4’-benzophenonetetracarboxylic dianhydride,BTDA),且以间隔30分钟的时频,分批加料加入于反应瓶内,并持续搅拌。待4,4″-联苯四酸二酐及3,3’,4,4’-二苯二酸酐酮完全加料置入反应瓶后,再持续搅拌3小时,得到固含量为约15wt%的含聚二苯甲烷双马来酰亚胺及酰亚胺酸的NMP溶液-II。
【实施例5】
取147.06g的实施例2的含3wt%的二苯甲烷双马来酰亚胺-巴比土酸共聚物的NMP溶液置入于500ml的反应瓶中,加入107.35g的甲基吡咯烷酮(N-methyl pyrollidone,NMP),通入氮气并进行搅拌使溶液呈现均匀状态。取11.93g(0.066mole)的对苯二胺(p-phenylene diamine,p-PDA)及3.32g(0.017mole)的4,4’-二胺基二苯基醚(4,4’-oxydianiline,4,4’-ODA)加入至上述溶液中,并在氮气的环境下进行搅拌,使对苯二胺及4,4’-二胺基二苯基醚完全溶解。的后再取24.46g(0.083mole)的4,4″-联苯四酸二酐(bis(phenylene dicarboxylicacid)dianhydride,BPDA),且以间隔30分钟的时频,分批加料加入于反应瓶内,并持续搅拌。待4,4″-联苯四酸二酐完全加料置入反应瓶后,再持续搅拌3小时,得到固含量为约15wt%的含二苯甲烷双马来酰亚胺-巴比土酸共聚物及酰亚胺酸的NMP溶液-III。
【实施例6】
取73.67g的实施例2的的含3wt%的二苯甲烷双马来酰亚胺-巴比土酸共聚物的NMP溶液置入于500ml的反应瓶中加入178.54g的甲基吡咯烷酮(N-methyl pyrollidone,NMP),通入氮气并进行搅拌使溶液呈现均匀状态。取13.47g(0.067mole)的对苯二胺(p-phenylene diamine,p-PDA)及2.64g(0.013mole)的4,4’-二胺基二苯基醚(4,4’-oxydianiline,4,4’-ODA)加入至上述溶液中,并在氮气的环境下进行搅拌,使对苯二胺及4,4’-二胺基二苯基醚完全溶解。随后,再取20.70g(0.070mole)的4,4″-联苯四酸二酐(bis(phenylene dicarboxylicacid)dianhydride,BPDA)和5.10g(0.016mole)的3,3’,4,4’-二苯二酸酐酮(3,3’,4,4’-benzophenone tetracarboxylic dianhydride,BTDA),且以间隔30分钟的时频,分批加料加入于反应瓶内,并持续搅拌。待4,4″-联苯四酸二酐和3,3’,4,4’-二苯二酸酐酮完全加料置入反应瓶后,再持续搅拌3小时,得到固含量为约15wt%的含二苯甲烷双马来酰亚胺-巴比土酸共聚物及酰亚胺酸的NMP溶液-IV。
【实施例7】
将实施例3的NMP溶液-I涂布于铜箔基板上,并在氮气环境下分别经过120℃/30分钟、250℃/30分钟,及350℃/60分钟的三阶段烘烤程序,以使酰亚胺酸完成聚合化作用,制备出聚酰亚胺膜/铜箔双层板。
【实施例8】
将实施例4的NMP溶液-II涂布于铜箔基板上,并在氮气环境下分别经过120℃/30分钟、250℃/30分钟,及350℃/60分钟的三阶段烘烤程序,以使酰亚胺酸完成聚合化作用,制备出聚酰亚胺膜/铜箔双层板。
【实施例9】
将实施例5的含15wt%的NMP溶液-III涂布于铜箔基板上,并在氮气环境下分别经过120℃/30分钟、250℃/30分钟,及350℃/60分钟的三阶段烘烤程序,以使酰亚胺酸完成聚合化作用,制备出聚酰亚胺膜/铜箔双层板。
【实施例10】
将合成实施例6的含15wt%的NMP溶液-IV涂布于铜箔基板上,并在氮气环境下分别经过120℃/30分钟、250℃/30分钟,及350℃/60分钟的三阶段烘烤程序,以使酰亚胺酸完成聚合化作用,制备出聚酰亚胺膜/铜箔双层板。
【比较例1】
取8.34g(0.046mole)的对苯二胺(p-phenylene diamine,p-PDA)及2.32g(0.011mole)的4,4’-二胺基二苯基醚(4,4’-oxydianiline,4,4’-ODA)置入于500ml的反应瓶中,加入250g的二甲基乙酰胺(dimethyl acetamide,DMAC)后,通入氮气并进行搅拌,使对苯二胺及4,4’-二胺基二苯基醚完全溶解。取17.09g(0.058mole)的4,4″-联苯四酸二酐(bis(phenylene dicarboxylic acid)dianhydride,BPDA),且以间隔30分钟的时频,分批加料加入于反应瓶内,并持续搅拌。待4,4″-联苯四酸二酐完全加料置入于反应瓶后,再持续搅拌3小时,得到含10wt%的酰亚胺酸的DMAC溶液-I。
【比较例2】
取14.18g(0.079mole)的对苯二胺(p-phenylene diamine,p-PDA)及2.78g(0.014mole)的4,4’-二胺基二苯基醚(4,4’-oxydianiline,4,4’-ODA)置入于500ml的反应瓶中,加入250g的甲基吡咯烷酮(N-methyl pyrollidone,NMP)后,通入氮气并进行搅拌,使对苯二胺及4,4’-二胺基二苯基醚能完全溶解。取21.79g (0.074mole)的4,4″-联苯四酸二酐(bis(phenylene dicarboxylicacid)dianhydride,BPDA)和5.37g(0.017mole)的3,3’,4,4’-二苯二酸酐酮(3,3’,4,4’-Benzophenone tetracarboxylic dianhydride,BTDA),且以间隔30分钟的时频,分批加料加入于反应瓶内,并持续搅拌。待4,4″-联苯四酸二酐和3,3’,4,4’-二苯二酸酐酮完全加料置入反应瓶后,再持续搅拌3小时,得到含15wt%的酰亚胺酸的DMAC溶液-II。
【比较例3】
取比较例1的含10wt%的聚酰胺酸的DMAC溶液-I 100g,加入0.53克的氧化硅粉末(占总固含量的5wt%),并置于三滚轮式碾磨机(three-roller mill)中充分混合,得到含无机添加剂(silica)及酰亚胺酸的DMAC溶液-I。
【比较例4】
取比较例2的含15wt%的聚酰胺酸的DMAC溶液-II 100g,加入0.79克的氧化硅粉末(占总固含量的5wt%),并置于三滚轮式碾磨机(three-roller mill)中充分混合,得到含有无机添加剂(silica)及酰亚胺酸的DMAC溶液-II。
【比较例5】
将比较例1的含10wt%的聚酰胺酸的DMAC溶液-I涂布于铜箔基板(copper foil)上,并在氮气气氛下,并在氮气环境下分别经过120℃/30分钟、250℃/30分钟,及350℃/60分钟的三阶段烘烤程序,以完成聚合化作用,制备出聚酰亚胺膜/铜箔双层板。
【比较例6】
将比较例2的含15wt%的聚酰胺酸的DMAC溶液-II涂布于铜箔基板上,并在氮气环境下分别经过120℃/30分钟、250℃/30分钟,及350℃/60分钟的三阶段烘烤程序,以完成聚合化作用,制备出聚酰亚胺膜/铜箔双层板。
【比较例7】
将比较例3的含无机添加剂(silica)及酰亚胺酸的DMAC溶液-I涂布于铜箔基板上,并在氮气环境下分别经过120℃/30分钟、250℃/30分钟,及350℃/60分钟的三阶段烘烤程序,以使酰亚胺酸完成聚合化作用,制备出聚酰亚胺膜/铜箔双层板。
【比较例8】
将比较例4的含无机添加剂(silica)及酰亚胺酸的DMAC溶液-II涂布于铜箔基板上,并在氮气环境下分别经过120℃/30分钟、250℃/30分钟,及350℃/60分钟的三阶段烘烤程序,以使酰亚胺酸完成聚合化作用,制备出聚酰亚胺膜/铜箔双层板。
图5显示以胶体渗透层析仪分析二苯甲烷双马来酰亚胺的单体的NMP溶液及实施例1的含5wt%的聚二苯甲烷双马来酰亚胺的NMP溶液。在图5中,二苯甲烷双马来酰亚胺的单体的NMP溶液是以虚线表示,实施例1的含5wt%的聚二苯甲烷双马来酰亚胺的NMP溶液是以实线表示。可观察到的是,双马来酰亚胺的单体在约40分钟时出现,NMP分子约在52.4分钟时出现,且实施例1的NMP溶液中的大部分的双马来酰亚胺的单体几乎都已消失,并在约25分钟的地方有新的波峰出现。因此,可由此推测实施例1的NMP溶液中的大部分的双马来酰亚胺的单体均已聚合成聚二苯甲烷双马来酰亚胺,且二苯甲烷双马来酰亚胺单体的聚合反应转换率超过95%。
表1显示了实施例7-10及比较例5-8的聚酰亚胺膜/铜箔双层板的性能测试结果。
表1
a:以热机械分析仪测试;b:依照IPC-TM-650(2.4.9)标准;c:将层积结构裁切成A4尺寸的测试工作件;d:依照IPC-TM-650(2.4.13)标准;e:依照IPC-TM-650(2.5.17)标准。
由表1可得知的是,由实施例7-10所得到的含互穿型网络聚合物的聚酰亚胺薄膜可具有的玻璃转化温度皆为在300℃以上,显见其耐热性大幅提高,甚至超过如比较例3-4的加入无机物(氧化硅)的聚酰亚胺膜。此外,由实施例7-10所得到的含互穿型网络聚合物的聚酰亚胺薄膜的平均热膨胀系数均仅在19~22ppm/℃,远低于纯聚酰亚胺薄膜,且近似于如比较例3-4的加入无机物(氧化硅)的聚酰亚胺膜。其它例如电气绝缘特性及焊锡耐热性等性质,由实施例7-10所得到的含互穿型网络聚合物的聚酰亚胺薄膜也可通过标准测试(例如IPC-TM-650(2.4.13)、IPC-TM-650(2.5.17))。
此外,由表1可看出,在实施例7-10的聚酰亚胺金属积层板的层积结构中,聚酰亚胺膜与铜箔之间具有良好的剥离强度,且无论是在铜箔蚀刻前及铜箔蚀刻后,皆具有良好的表面平坦度,不会产生卷曲。
虽然本发明已以数个较佳实施例揭露如上,然其并非用以限定本发明,任何所属技术领域中具有通常知识者,在不脱离本发明的精神和范围内,当可作任意的更动与润饰,因此本发明的保护范围当视后附的权利要求书所界定的范围为准。
Claims (12)
1.一种含互穿型网络聚合物的聚酰胺酸树脂的溶液,包括:
一聚酰胺酸树脂溶于一溶剂中,其中该聚酰胺酸树脂包含一互穿型网络聚合物,该互穿型网络聚合物是由一具超分岐结构的聚双马来酰亚胺及一缠绕该聚双马来酰亚胺的聚酰胺酸形成,其中该具超分岐结构的聚双马来酰亚胺包含双马来酰亚胺高分子、双马来酰亚胺寡聚物、巴比土酸-双马来酰亚胺共聚物、或前述的组合。
2.如权利要求1所述的含互穿型网络聚合物的聚酰胺酸树脂的溶液,其中该双马来酰亚胺的聚合物及该双马来酰亚胺的寡聚物是由具有下列结构式(I)或(II)的双马来酰亚胺单体聚合形成:
其中在上述式(I)中,R1可为:
-R-CH2-R-、-R-NH2-R-、-C(O)-、-C(O)CH2-,-CH2OCH2-、-C(O)-、-R-C(O)-R-、-O-、-O-O-、-S-、-S-S-、-S(O)-、-R-S(O)-R-、-(O)S(O)-、-R-(O)S(O)-R-、-C6H4-、-R-(C6H4)-R-、-R(C6H4)(O)-、-(C6H4)-(C6H4)-、-R-(C6H4)-(C6H4)-R-或-R-(C6H4)-(C6H4)-O-,其中R为C1-8的烷撑基、(C6H4)为苯撑基,及(C6H4)-(C6H4)为联苯撑基;
其中在上述式(II)中,R2可为:
-R-、-O-、-O-O-、-S-、-S-S-、-C(O)-、-S(O)-或-(O)S(O)-,其中X1、X2、X3、X4、X5、X6、X7、X8可各自择自卤素、氢原子、C1-8的烷基、C1-8的环烷基或C1-8的硅烷基。
4.如权利要求1所述的含互穿型网络聚合物的聚酰胺酸树脂的溶液,其中该聚酰胺酸由一双胺类单体及一酸酐类单体聚合形成。
5.如权利要求4所述的含互穿型网络聚合物的聚酰胺酸树脂的溶液,其中该酸酐类单体为3,3’4,4’-二苯甲酮四羧酸二酐、3,3’,4,4’-联苯四羧酸二酐、均苯四甲酸二酐、4,4’-氧双邻苯二甲酸酐、3,3,4,4-二苯基砜四羧酸二酸酐、2,2’-双(3,4-二羧酸)六氟丙烷二酐、苯-1,2,4,5,-四羧酸二酐、六环酸酐、3,4,9,10-四羧酸酐、2,6-双(3,4-二羧苯氧基)萘二酐、2,7-双(3,4-二羧苯氧基)萘二酐、联苯四甲酸二酐、或前述的组合。
6.如权利要求4所述的含互穿型网络聚合物的聚酰胺酸树脂的溶液,其中该双胺类单体为对苯二胺、间苯二胺、三氟甲基-2,4-苯二胺、三氟甲基-3,5-苯二胺、2,5-二甲基-1,4-苯二胺、2,2-双-(4-胺基苯基)-丙烷、4,4’-二氨基-联苯、4,4’-二氨基二苯甲酮、4,4’-二氨基二苯甲烷、4,4-二氨基二苯硫醚、4,4’-二氨基二苯砜、3,3’-二氨基二苯砜、4,4’-双(4-氨基苯氧基)二苯砜、4,4’-双(3-氨基苯氧基)联苯、4,4`-二氨基二苯醚、3,4`-二氨基二苯醚、2,2-双-(3-胺基苯基)-丙烷、N,N-双-(4-胺基苯基)-正丁基胺、N,N-双-(4-胺基苯基)-甲基胺)、1,5-二氨基萘、4,4’-二氨基-3,3’-二甲基联苯、m-胺基苯甲酰-p-胺基苯胺、4-氨基苯基-3-胺基苯甲酸甲酯、N,N-双-(4-胺基苯基)-苯胺、2,4-二氨基甲苯、2,5-二氨基甲苯、2,6-二氨基甲苯、2,4-二氨基-5-氯甲苯、2,4-二氨基-6-氯甲苯、2,4-双-(β-氨基叔丁基)甲苯、双-(对-β-氨基叔丁基苯基)醚、对-双-2(2-甲基-4-氨基戊基)苯、间苯二甲胺、对苯二甲胺、1,2-双-(4-氨基苯氧基)苯、1,3-双-(4-氨基苯氧基)苯、1,3-双-(3-氨基苯氧基)苯、1-(4-氨基苯氧基)-3-(3-氨基苯氧基)苯、1,4-双-(4-氨基苯氧基)苯、1,4-双-(3-氨基苯氧基)苯、1-(4-氨基苯氧基)-4-(3-氨基苯氧基)苯、2,2’-双-[4-(4-氨基苯氧基苯基)]丙烷、2,2’-双-(4-氨基苯氧基苯基)]六氟丙烷、亚异丙基2,2’-双-(苯氧基苯胺)、2,4,6-三甲基-1,3-苯二胺、4,4’-二氨基-2,2’-三氟甲基二苯醚、3,3’-二氨基-5,5’-三氟甲基二苯醚、4,4’-三氟甲基-2,2’-二氨基联苯、2,4,6-三甲基-1,3-苯二胺、4,4’-氧-双-(2-三氟甲基)苯胺、4,4’-氧-双-(3-三氟甲基)苯胺、4,4’-硫-双-(2-三氟甲基)苯胺、4,4’-硫-双-(2-三氟甲基)苯胺、4,4’-磺酰氧基-双-(2-三氟甲基)苯胺、4,4’-磺酰氧基-双-(3-三氟甲基)苯胺、4,4’-酮基-双-(2-三氟甲基)苯胺、或前述的组合。
7.如权利要求1所述的含互穿型网络聚合物的聚酰胺酸树脂的溶液,其中该互穿网络聚合物为全互穿型网络聚合物。
8.如权利要求1所述的含互穿型网络聚合物的聚酰胺酸树脂的溶液,其中该聚双马来酰亚胺超分歧高分子占聚酰亚胺膜总重的0.1wt%至50wt%。
9.一种聚酰亚胺金属积层板,包括:
一金属基材;以及
一聚酰亚胺膜覆于该金属基材上,其中该聚酰亚胺膜由权利要求1所述的含互穿型网络聚合物的聚酰胺酸树脂的溶液经涂布于该金属基材上及热烘烤后形成。
10.如权利要求9所述的聚酰亚胺金属积层板,其中该双马来酰亚胺的聚合物及该双马来酰亚胺的寡聚物是由具有下列结构式(I)或(II)的双马来酰亚胺单体聚合形成:
其中在上述式(I)中,R1可为:
-R-CH2-R-、-R-NH2-R-、-C(O)-、-C(O)CH2-,-CH2OCH2-、-C(O)-、-R-C(O)-R-、-O-、-O-O-、-S-、-S-S-、-S(O)-、-R-S(O)-R-、-(O)S(O)-、-R-(O)S(O)-R-、-C6H4-、-R-(C6H4)-R-、-R(C6H4)(O)-、-(C6H4)-(C6H4)-、-R-(C6H4)-(C6H4)-R-或-R-(C6H4)-(C6H4)-O-,其中R为C1-8的烷撑基、(C6H4)为苯撑基,及(C6H4)-(C6H4)为联苯撑基;
其中在上述式(II)中,R2可为:
-R-、-O-、-O-O-、-S-、-S-S-、-C(O)-、-S(O)-或-(O)S(O)-,其中X1、X2、X3、X4、X5、X6、X7、X8可各自择自卤素、氢原子、C1-8的烷基、C1-8的环烷基或C1-8的硅烷基。
12.如权利要求8所述的聚酰亚胺金属积层积结构板,其中该金属基材为铜箔系、铜铬合金、铜镍合金、铜镍铬合金、铝合金系、或前述的组合。
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CN103965770A (zh) * | 2014-05-26 | 2014-08-06 | 常熟理工学院 | 耐高温聚酰亚胺漆包线漆及其制备方法 |
CN108948354A (zh) * | 2017-05-26 | 2018-12-07 | 昆山国显光电有限公司 | 改性聚酰亚胺树脂及其制备方法、以及应用 |
CN117533001A (zh) * | 2023-10-25 | 2024-02-09 | 江门建滔积层板有限公司 | 一种耐冲击阻燃覆铜板及其制备方法 |
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JP6352791B2 (ja) * | 2014-12-11 | 2018-07-04 | Ckd株式会社 | コイル用シート、コイル、及びコイルの製造方法 |
TWI718728B (zh) | 2019-10-29 | 2021-02-11 | 南亞塑膠工業股份有限公司 | 改性雙馬來醯亞胺樹脂及其製備方法、預浸材、銅箔基板及印刷電路板 |
US20220145030A1 (en) * | 2020-01-21 | 2022-05-12 | Quantum MicroMaterials, Inc. | Coating substrate by polymerization of amine compound and apparatus having polymer coated substrate |
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US6828390B2 (en) * | 2002-06-24 | 2004-12-07 | E.I. Du Pont De Nemours And Company | Polyimide substrates having an interpenetrating network morphology and methods relating thereto |
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CN103965770A (zh) * | 2014-05-26 | 2014-08-06 | 常熟理工学院 | 耐高温聚酰亚胺漆包线漆及其制备方法 |
CN103965770B (zh) * | 2014-05-26 | 2016-02-10 | 常熟理工学院 | 耐高温聚酰亚胺漆包线漆及其制备方法 |
CN108948354A (zh) * | 2017-05-26 | 2018-12-07 | 昆山国显光电有限公司 | 改性聚酰亚胺树脂及其制备方法、以及应用 |
CN117533001A (zh) * | 2023-10-25 | 2024-02-09 | 江门建滔积层板有限公司 | 一种耐冲击阻燃覆铜板及其制备方法 |
CN117533001B (zh) * | 2023-10-25 | 2024-05-10 | 江门建滔积层板有限公司 | 一种耐冲击阻燃覆铜板及其制备方法 |
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