CN112440534A - 金属箔积层板、印刷电路板及金属箔积层板的制法 - Google Patents
金属箔积层板、印刷电路板及金属箔积层板的制法 Download PDFInfo
- Publication number
- CN112440534A CN112440534A CN201910886790.0A CN201910886790A CN112440534A CN 112440534 A CN112440534 A CN 112440534A CN 201910886790 A CN201910886790 A CN 201910886790A CN 112440534 A CN112440534 A CN 112440534A
- Authority
- CN
- China
- Prior art keywords
- metal foil
- dielectric layer
- cloth
- filler
- reinforcing cloth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 80
- 239000002184 metal Substances 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title description 14
- 239000004744 fabric Substances 0.000 claims abstract description 112
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 59
- 239000000945 filler Substances 0.000 claims abstract description 54
- 239000003989 dielectric material Substances 0.000 claims abstract description 43
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011737 fluorine Substances 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 45
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 41
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 41
- 229920002313 fluoropolymer Polymers 0.000 claims description 40
- 239000004811 fluoropolymer Substances 0.000 claims description 40
- 239000011521 glass Substances 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- -1 polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymers Polymers 0.000 claims description 21
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- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 239000003365 glass fiber Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
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- 239000000843 powder Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 4
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 3
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- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000271 Kevlar® Polymers 0.000 description 2
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
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- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 238000010295 mobile communication Methods 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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Images
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Abstract
本发明提供一种金属箔积层板、应用该金属箔积层板的印刷电路板及金属箔积层板的制造方法,其中该金属箔积层板包括:一第一介电层,包括第一介电材料且不包括补强布,其中第一介电材料包括20重量%至60重量%的第一氟高分子及40重量%至80重量%的第一填料;一第二介电层,设置于第一介电层的至少一侧,且包括补强布及形成于该补强布表面的第二介电材料,其中该补强布的厚度不大于65微米,且第二介电材料包括55重量%至100重量%的第二氟高分子及0至45重量%的第二填料;以及一金属箔,设置于第二介电层的与第一介电层相对的另一侧。
Description
技术领域
本发明是关于一种金属箔积层板,特别是关于一种氟高分子(fluoropolymer)金属箔积层板以及该氟高分子金属箔积层板的制造方法。本发明的氟高分子金属箔积层板特别适合作为高频技术领域的电路基板,包括射频(RF)应用、微波(microwave)、毫米波(mmwave)、天线(antenna)、雷达(radar)等技术领域,尤其能满足第五代行动通讯(5G)、进阶驾驶人辅助系统(ADAS)、人工智能(AI)等先进应用对高阶材料的要求。
背景技术
随着电子产品的应用逐渐朝高频化、高速化、电子元件小型化及基板线路高密度化等趋势发展,对电子材料的物化性质要求也随之提升,传统的环氧树脂介电材料的特性已不敷使用,取而代之的是以氟高分子(fluoropolymer),例如聚四氟乙烯(polytetrafluoroethylene,PTFE),作为金属箔积层板的介电材料。一般而言,以氟高分子作为金属箔积层板中的介电(dielectric)材料时,所制金属箔积层板除具备极佳的电性之外(介电常数(Dk)、介电耗损因子(Df)皆低),其耐化学酸碱性、耐湿性、难燃性也好。
US 3,556,161最早提出一种无玻布型氟高分子积层板,其中是使用PTFE粉末来制造介电层。随后,US 4,335,180提出另一种积层板,其中是将氟高分子、陶瓷填料、短玻璃纤维(microfiber)、絮凝剂(flocculant)所组成的面团状(dough-like)材料加以挤压(extrusion)成型而得到介电层,再进一步贴合铜箔而制成铜箔积层板。US 4,849,284进一步提出使用偶合剂对陶瓷填料进行表面处理,再将该陶瓷填料添加至氟高分子树脂中,由此所制得的铜箔积层板具有低Dk、低Df等特性。如图1所示,上述积层板的制法是于介电层11上直接压合金属箔12,以形成金属箔积层板1。然而,所制积层板由于不含玻璃纤维布作为补强材料,导致积层板的刚性不足,在后续印刷电路板(printed circuit board,PCB)的钻孔工艺中,积层板容易因钻针下压力而受压变形,从而影响钻孔位置的正确性。
因此,目前仍需要一种可提供具有良好刚性的氟高分子积层板的技术方案。
发明内容
有鉴于上述技术问题,本发明提供一种金属箔积层板,其是通过在氟高分子积层板中组合使用不含补强布的介电层与含补强布的介电层,从而在不影响积层板外观平整度的情况下,改良积层板整体的刚性,解决先前技术中无补强布的氟高分子积层板普遍存在的因刚性不足而导致积层板在后续印刷电路板钻孔工艺中容易变形而影响钻孔位置正确性的问题。
因此,本发明的一目的在于提供一种金属箔积层板,包括:
一第一介电层,包括第一介电材料且不包括补强布,其中第一介电材料包括20重量%至60重量%的第一氟高分子及40重量%至80重量%的第一填料;
一第二介电层,设置于第一介电层的至少一侧,且包括补强布及形成于该补强布表面的第二介电材料,其中该补强布的厚度不大于65微米,且第二介电材料包括55重量%至100重量%的第二氟高分子及0至45重量%的第二填料;以及
一金属箔,设置于第二介电层的与第一介电层相对的另一侧。
于本发明的部分实施方式中,该第一氟高分子及该第二氟高分子各自独立选自以下群组:聚四氟乙烯、四氟乙烯-六氟丙烯共聚物(tetrafluoroethylene-hexafluoropropylene copolymer,FEP)、四氟乙烯-全氟烷基乙烯基醚共聚物(tetrafluoroethylene-perfluorinated alkyl vinyl ether copolymer)及前述的组合。
于本发明的部分实施方式中,该第二氟高分子的熔点低于该第一氟高分子的熔点。
于本发明的部分实施方式中,该补强布是玻璃纤维布。
于本发明的部分实施方式中,该补强布选自以下群组:E-玻璃纤维布(E-glassfabric)、NE-玻璃纤维布(NE-glass fabric)、S-玻璃纤维布(S-glass fabric)、L-玻璃纤维布(L-glass fabric)、D-玻璃纤维布(D-glass fabric)、石英玻璃纤维布(quartz glassfabric)、芳香族聚酰胺纤维布(如克维拉纤维布(Kevlar fabric))、聚四氟乙烯纤维布(polytetrafluoroethylene fabric)、聚酯纤维布及液晶高分子纤维布(liquid crystalpolymer(LCP)fabric)。
于本发明的部分实施方式中,该补强布的厚度不大于40微米。
于本发明的部分实施方式中,第一填料及第二填料各自独立选自以下群组:二氧化硅(包括球型二氧化硅、熔融态二氧化硅、非熔融态二氧化硅、多孔质二氧化硅、中空型二氧化硅、及奈米二氧化硅)、氧化铝、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氮化硼、氢氧化铝、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石、类钻石碳、石墨、煅烧高岭土、白岭土、云母、水滑石、聚四氟乙烯粉末、玻璃珠、陶瓷晶须、奈米碳管、奈米级无机粉体、钛酸锶及前述的组合。
于本发明的部分实施方式中,该金属箔积层板以动态机械分析仪在频率1Hz及温度70℃的条件下测得的储存模数(storage modulus)大于4000MPa。
本发明的另一目的在于提供一种印刷电路板,其是由如上所述的金属箔积层板所制得。
本发明的又一目的在于提供一种金属箔积层板的制造方法,包括:
提供一第一介电层,其包括第一介电材料且不包括补强布,其中第一介电材料包括20重量%至60重量%的第一氟高分子及40重量%至80重量%的第一填料;
提供一第二介电层并设置于第一介电层的至少一侧,其中第二介电层包括补强布及形成于该补强布表面的第二介电材料,该补强布的厚度不大于65微米,且第二介电材料包括55重量%至100重量%的第二氟高分子及0重量%至45重量%的第二填料;
提供一金属箔并设置于第二介电层的与第一介电层相对的另一侧,以提供一层叠物(superimposed object);以及
对该层叠物进行一热压步骤,以提供一金属箔积层板。
为使本发明的上述目的、技术特征及优点能更明显易懂,下文以部分具体实施方式进行详细说明。
附图说明
下面结合附图和具体实施方式对本发明作进一步详细的说明。
图1为现有技术的金属箔积层板的示意图;
图2为本发明金属箔积层板的一实施方式的示意图。
附图标记说明
1、2:金属箔积层板
11:介电层
12、23:金属箔
21:第一介电层
22:第二介电层。
具体实施方式
以下将具体地描述根据本发明的部分具体实施方式;但是,在不背离本发明的精神下,本发明还可以多种不同形式的方式来实践,不应将本发明保护范围解释为限于说明书所陈述的内容。
除非文中有另外说明,于本说明书中(尤其是在权利要求书中)所使用的“一”、“该”及类似用语应理解为包括单数及复数形式。
除非文中有另外说明,于本说明书中描述溶液、混合物、组合物或胶水(varnish)中所含的成分时,是以固含量(dry weight)计算,即,未纳入溶剂的重量。
除非文中有另外说明,于本说明书中(尤其是在权利要求书中),所使用的“第一”、“第二”及类似用语仅是用于区隔所描述的元件或成分,本身并无特殊涵义,且非意欲指代先后顺序。
除非文中有另外说明,于本说明书中提及“浸渍(impregnate)”作为一技术手段时,应理解,该技术手段包括含浸(dip)、涂布(coat)、喷涂(spray)或其它具有实质上相同功能效果的技术手段。
如前文说明,本发明是通过在氟高分子积层板中组合使用不含补强布的介电层与含补强布的介电层,从而在不影响积层板外观平整度的情况下,改良积层板整体的刚性。现以部分实施方式说明本发明相关技术特征及功效如下。
1.金属箔积层板
本发明的金属箔积层板包括第一介电层、设置于第一介电层的至少一侧的第二介电层及设置于第二介电层的与该第一介电层相对的另一侧的金属箔。图2为本发明金属箔积层板的一实施方式的示意图,为使各元件独立且清晰地呈现,金属箔积层板的堆叠结构以分离形式表示。如图2所示,金属箔积层板2包括第一介电层21、第二介电层22及金属箔23,其中第一介电层21的两侧分别设有一第二介电层22,且各第二介电层22的与该第一介电层21相对的另一侧分别设有金属箔23。
于本发明的部分实施方式中,金属箔积层板以动态机械分析仪在频率1Hz及温度70℃的条件下测得的储存模数大于4000MPa,较佳大于5000Mpa,更佳大于11000Mpa。
1.1.金属箔积层板的第一介电层
第一介电层包括第一介电材料且不包括补强布,其中“补强布”的定义将于下文第1.2.1点中详细描述。于部分实施方式中,第一介电层实质上是由第一介电材料所构成或由第一介电材料所构成。
第一介电材料包括第一氟高分子及第一填料。于部分实施方式中,该第一介电材料实质上是由第一氟高分子及第一填料所构成、或由第一氟高分子及第一填料所构成。以第一介电材料的总重量计,第一氟高分子的含量为20重量%至60重量%,例如21重量%、22重量%、23重量%、24重量%、25重量%、26重量%、27重量%、28重量%、29重量%、30重量%、31重量%、32重量%、33重量%、34重量%、35重量%、36重量%、37重量%、38重量%、39重量%、40重量%、41重量%、42重量%、43重量%、44重量%、45重量%、46重量%、47重量%、48重量%、49重量%、50重量%、51重量%、52重量%、53重量%、54重量%、、55重量%、56重量%、57重量%、58重量%或59重量%。以第一介电材料的总重量计,第一填料的含量为40重量%至80重量%,例如41重量%、42重量%、43重量%、44重量%、45重量%、46重量%、47重量%、48重量%、49重量%、50重量%、51重量%、52重量%、53重量%、54重量%、55重量%、56重量%、57重量%、58重量%、59重量%、60重量%、61重量%、62重量%、63重量%、64重量%、65重量%、66重量%、67重量%、68重量%、69重量%、70重量%、71重量%、72重量%、73重量%、74重量%、75重量%、76重量%、77重量%、78重量%或79重量%。若第一填料的含量低于所述范围(例如低于40重量%),将使得金属箔积层板的尺寸安定性变差;反之,若第一填料的含量高于所述范围(例如高于80重量%),将使得金属箔积层板的厚度均匀性及抗撕强度变差。
第一氟高分子及下文将描述的第二氟高分子是指含有氟原子的同元聚合物(homopolymer)或共聚物(copolymer),特定言之,是指具有多重强碳-氟键的氟碳系(fluorocarbon-based)高分子。一般而言,含氟高分子具有耐溶剂性、耐酸性、耐碱性等特性,且因具有强碳-氟键而具有优良的稳定性。此外,含氟高分子也具有优良的介电特性及宽广的使用温度范围,可应用于电子、化学、机械制造等多种工业或产业上。
具体而言,第一氟高分子及下文将描述的第二氟高分子可各自独立为选自以下群组的单体的同元聚合物、选自以下群组的单体的两种或多种的共聚物、或选自以下群组的单体与其他共单体的共聚物:四氟乙烯、偏二氟乙烯(vinylidene fluoride)、氟乙烯、全氟醚(perfluoroether)、三氟氯乙烯(chlorotrifluoroethylene)及六氟丙烯(hexafluoropropylene)。全氟醚包括含有烯基的全氟醚类,例如全氟烷基乙烯基醚。全氟烷基乙烯基醚的实例包括但不限于全氟甲基乙烯基醚(perfluoromethyl vinyl ether)。其他共单体的实例包括但不限于全氟丁基乙烯(perfluorobutyl ethylene)、乙烯、丙烯及丁烯。
第一氟高分子或下文将描述的第二氟高分子的实例包括聚四氟乙烯(PTFE)、四氟乙烯-六氟丙烯共聚物(FEP)、四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)、四氟乙烯-六氟丙烯-全氟烷基乙烯基醚共聚物、聚三氟氯乙烯(PCTFE)、聚偏二氟乙烯、聚氟乙烯、及四氟乙烯-乙烯共聚物。各氟高分子可单独使用或任意组合使用。于本发明的部分实施方式中,该第一氟高分子及该第二氟高分子各自独立为聚四氟乙烯、四氟乙烯-六氟丙烯共聚物、四氟乙烯-全氟烷基乙烯基醚共聚物或前述的任意组合。
第一填料及下文将描述第二填料的种类并无特殊限制,可由本发明所属技术领域普通技术人员视需要选择,以针对性改善金属箔积层板的性质,如机械强度、导热性或尺寸安定性,此外,第一填料及第二填料可相同或不同。第一填料及第二填料的实例包括但不限于二氧化硅(包括球型二氧化硅、熔融态二氧化硅、非熔融态二氧化硅、多孔质二氧化硅、中空型二氧化硅、及奈米二氧化硅)、氧化铝、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氮化硼、氢氧化铝、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石、类钻石碳、石墨、煅烧高岭土、白岭土、云母、水滑石、中空二氧化硅、聚四氟乙烯粉末、玻璃珠、陶瓷晶须、奈米碳管、奈米级无机粉体及钛酸锶。前述填料可单独使用或任意组合使用。于后附实施例中,第一填料是二氧化硅。
1.2.金属箔积层板的第二介电层
第二介电层包括补强布及形成于该补强布表面的第二介电材料。于部分实施方式中,该第二介电层实质上由补强布及第二介电材料所构成或由补强布及第二介电材料所构成。第二介电层设置于第一介电层的至少一侧,于部分实施方式中,第二介电层设置于第一介电层的两侧。
1.2.1.补强布
补强布是指由纤维材料所构成的布状(fabric)结构增强材,形式包括织布(wovenfabric)及不织布(non-woven fabric)。补强布的实例包括但不限于E-玻璃纤维布、NE-玻璃纤维布、S-玻璃纤维布、L-玻璃纤维布、D-玻璃纤维布、石英玻璃纤维布、芳香族聚酰胺纤维布(如克维拉纤维布)、聚四氟乙烯纤维布、聚酯纤维布、芳香族聚酯纤维布及液晶高分子纤维布等热稳定性高的材料。
为避免金属箔积层板太厚且外观平整度不佳,补强布的厚度较佳不大于65微米,更佳不大于45微米。具体而言,补强布的实例包括以下型号的E-玻璃纤维布或NE-玻璃纤维布的织造玻璃纤维布(woven glass fabric):1080型(64微米)、1086型(50微米)、1078型(40微米)、106型(32微米)、1067型(35微米)、1037型(30微米)及1035型(30微米)。
1.2.2.第二介电材料
第二介电材料包括第二氟高分子及视需要的第二填料。于部分实施方式中,该第二介电材料实质上由第二氟高分子及第二填料所构成、或由第二氟高分子及第二填料所构成。以该第二介电材料的总重量计,第二氟高分子的含量为55重量%至100重量%,例如56重量%、57重量%、58重量%、59重量%、60重量%、61重量%、62重量%、63重量%、64重量%、65重量%、66重量%、67重量%、68重量%、69重量%、70重量%、71重量%、72重量%、73重量%、74重量%、75重量%、76重量%、77重量%、78重量%、79重量%、80重量%、81重量%、82重量%、83重量%、84重量%、85重量%、86重量%、87重量%、88重量%、89重量%、90重量%、91重量%、92重量%、93重量%、94重量%、95重量%、96重量%、97重量%、98重量%或99重量%。以该第二介电材料的总重量计,第二填料的含量为0至45重量%,例如1重量%、2重量%、3重量%、4重量%、5重量%、6重量%、7重量%、8重量%、9重量%、10重量%、11重量%、12重量%、13重量%、14重量%、15重量%、16重量%、17重量%、18重量%、19重量%、20重量%、21重量%、22重量%、23重量%、24重量%、25重量%、26重量%、27重量%、28重量%、29重量%、30重量%、31重量%、32重量%、33重量%、34重量%、35重量%、36重量%、37重量%、38重量%、39重量%、40重量%、41重量%、42重量%、43重量%或44重量%。若第二填料的含量高于所述范围(例如高于45重量%),将使得金属箔积层板的厚度均匀性及抗撕强度变差。
第二氟高分子的定义及实例如前文说明。第一氟高分子与第二氟高分子的种类可相同或不同。于本发明的部分实施方式中,第二氟高分子与第一氟高分子不同,且第二氟高分子的熔点低于该第一氟高分子的熔点,例如第一氟高分子的熔点可为约325℃至约340℃,而第二氟高分子的熔点可为约250℃至约320℃,俾使得第二氟高分子在热压过程中的流胶(resin flow)特性优于第一氟高分子,由此可提高介电层与金属箔之间的黏着性能。具体言之,第一氟高分子可为聚四氟乙烯(PTFE,熔点约330℃),且第二氟高分子可为四氟乙烯-全氟甲基乙烯基醚共聚物(熔点约310℃)或四氟乙烯-六氟丙烯共聚物(FEP,熔点约260℃),四氟乙烯-全氟甲基乙烯基醚共聚物与四氟乙烯-六氟丙烯共聚物在热压时可提供相较于聚四氟乙烯更佳的流胶特性。有关四氟乙烯-全氟甲基乙烯基醚共聚物与四氟乙烯-六氟丙烯共聚物的流胶特性及其他性质的资讯可参考生益科技公司的CN 101838431B、CN103102627B等专利文献,这些文献全文并于此以供参考。
第二填料的定义及实例如前文说明。于后附实施例中,是使用二氧化硅作为第二填料。
1.3.金属箔积层板的金属箔
金属箔的实例包括但不限于铜、不锈钢、铝、锌、铁、镍、金、银、过渡金属、或前述两种或多种的合金等具有良好导电性的材料。于本发明部分实施方式中是使用铜箔,所述铜箔的表面可经粗化或未经粗化。铜箔的实例包括但不限于高温延展性(High TemperatureElongation,HTE)铜箔(表面粗糙度Ra:6微米至10微米)、反转处理铜箔(ReverseTreatment Foil,RTF)(Ra:2微米至5微米)、超低棱线(Very Low Profile,VLP)铜箔(Ra:小于2微米)、极低棱线(Hyper Very Low Profile,HVLP)铜箔(Ra:小于1.5微米)。
2.印刷电路板
本发明金属箔积层板可通过进一步图案化其外侧的金属箔,而形成印刷电路板,因此本发明也提供一种印刷电路板,其是通过进一步图案化本发明积层板的外侧的金属箔所制得,其中图案化金属箔的方法并无特殊限制,其实例包括但不限于光蚀刻法、网版印刷法及喷墨印刷法。
3.金属箔积层板的制造方法
本发明金属箔积层板的制造方法包括如下步骤:
提供一第一介电层,其包括第一介电材料且不包括补强布,其中第一介电材料包括20重量%至60重量%的第一氟高分子及40重量%至80重量%的第一填料;
提供一第二介电层并设置于第一介电层的至少一侧,其中第二介电层包括补强布及形成于该补强布表面的第二介电材料,该补强布的厚度不大于65微米,且第二介电材料包括55重量%至100重量%的第二氟高分子及0至45重量%的第二填料;
提供一金属箔并设置于第二介电层的与第一介电层相对的另一侧,以提供一层叠物(superimposed object);以及
对该层叠物进行一热压步骤,以提供一金属箔积层板。
其中补强布、第一介电材料、第二介电材料及金属箔的定义如前文说明。
于本发明的部分实施方式中,金属箔积层板以下述方法制备。
首先,将第一氟高分子、第一填料及视需要的添加剂(如偶合剂、黏度调整剂)混合并搅拌均匀,使其成为一面团状(dough-like)混合物;之后,将该面团状混合物通过挤制(extrusion)方式成膜,得到膜状或片状的不含补强布的第一介电层。关于不含补强布的第一介电层的制备方法,另可参考US 3,556,161、US 4,335,180及US 4,849,284,这些文献全文并于此以供参考。
随后,将第二氟高分子与第二填料混合并分散于溶剂中,以形成一胶水,并将补强布(如玻璃纤维布)浸渍该含胶水;之后,在不低于第二氟高分子的熔点的温度下熟成(sintering)该经浸渍的补强布,以得到第二介电层胶片。
之后,将第一介电层、第二介电层胶片及金属箔(例如:铜箔)层叠以提供层叠物,并对该层叠物进行热压,以得到本发明的氟高分子金属箔积层板,其中,热压温度较佳高于第一氟高分子与第二氟高分子的熔点,第一介电层可使用单片或预先叠合多片,第二介电层胶片及相应的金属箔可设置于第一介电层的一侧或两侧(图2所示为两侧设置的情形)。
4.实施例
4.1.测量方式说明
现以下列具体实施方式进一步例示说明本发明,其中,所采用的测量仪器及方法如下:
[储存模数的测量]
将本发明金属箔金层板蚀刻去除铜层,得到不含铜的测试样品。根据参照IPC-TM-650 2.4.24.4所述的方法,以动态机械分析仪(Dynamic Mechanical Analyzer,DMA),在频率1Hz及温度70℃的条件下,进行储存模数的测量,单位为MPa,储存模数的值越高,代表基板的刚性越好(耐压不变形)。
4.2.实施例与比较例所用的原物料资讯列表
表1:原物料资讯列表
原物料 | 说明及来源 |
DISP30 | PTFE分散液,购自科慕公司(Chemours) |
填料 | SiO<sub>2</sub>陶瓷填料,购自联瑞新材(Novoray)型号为1040的产品 |
HTE铜箔 | 高温延展性铜箔,购自长春(CCP)型号为PLS的产品 |
4.3.金属箔积层板的制备
[实施例1]
取PTFE分散液(PTFE固含量60重量%)666.67克与SiO2填料600克混合均匀以形成第一胶水(即胶水固含量中,填料占60重量%)。将第一胶水进一步搅拌形成面团状(dough-like),并进行挤压成型工艺而得到一片状材料,经过烘除原先存在于PTFE分散液中的水分与界面活性剂,然后以高温360℃进行烘烤,得到不含补强布的PTFE介电层(第一介电层)。
另外,取PTFE分散液(PTFE固含量60重量%)1333.33公克与SiO2填料200公克混合均匀以形成第二胶水(即胶水固含量中,填料占20重量%)。将1080型E-玻璃纤维布(厚度64微米)含浸该第二胶水,共进行两次含浸以达足够量的树脂,经高温360℃烘烤后得到含补强布的PTFE介电层(第二介电层)。
于不含补强布的PTFE介电层(第一介电层)两侧各叠置一含补强布的PTFE介电层(第二介电层),最后在上下两侧再各放1张半盎司(half-oz)的HTE铜箔,接着使用真空高温热压机于380℃、3MPa条件下压合90分钟,制得实施例1的金属箔积层板。
[实施例2]
取PTFE分散液(PTFE固含量60重量%)666.67克与SiO2填料600克混合均匀以形成第一胶水(即胶水固含量中,填料占60重量%)。将第一胶水进一步搅拌形成面团状(dough-like),并进行挤压成型工艺而得到一片状材料,经过烘除原先存在于PTFE分散液中的水分与界面活性剂,然后以高温360℃进行烘烤,得到不含补强布的PTFE介电层(第一介电层)。
另外,取PTFE分散液(PTFE固含量60重量%)1333.33克与SiO2填料200克混合均匀以形成第二胶水(即胶水固含量中,填料占20重量%)。将1067型的E-玻璃纤维布(厚度35微米)含浸第二胶水,共进行两次含浸以达足够量的树脂,经高温360℃烘烤后得到含补强布的PTFE介电层(第二介电层)。
于不含补强布的PTFE介电层(第一介电层)两侧各叠置一含补强布的PTFE介电层(第二介电层),最后在上下两侧再各放1张半盎司的HTE铜箔,接着使用真空高温热压机于380℃、3MPa条件下压合90分钟,制得实施例2的金属箔积层板。
[比较例1]
取PTFE分散液(PTFE固含量60重量%)666.67克与SiO2填料600克混合均匀以形成第一胶水(即胶水固含量中,填料占60重量%)。将第一胶水进一步搅拌形成面团状(dough-like),并进行挤压成型工艺而得到一片状材料,经过烘除原先存在于PTFE分散液中的水分与界面活性剂,然后以高温360℃进行烘烤,得到不含补强布的PTFE介电层。于该不含补强布的PTFE介电层上下两侧各放1张半盎司的HTE铜箔,接着使用真空高温热压机于380℃、3MPa条件下压合90分钟,制得比较例1的金属箔积层板。
4.4.金属箔积层板的性质测量
将实施例1至2与比较例1所制得的金属箔积层板进行蚀刻以去除铜层,然后进行储存模数的测量,测量结果如下表2所示。
表2:
如表2所示,根据本发明的实施例1及2的金属箔积层板的储存模数明显高于比较例1的金属箔积层板,显示在刚性上获得显著改善。
上述实施例仅为例示性说明本发明的原理及其功效,并阐述本发明的技术特征,而非用于限制本发明的保护范畴。任何本领域技术人员在不违背本发明的技术原理及精神下,可轻易完成的改变或安排,均属本发明所主张的范围。因此,本发明的权利保护范围如权利要求书中所列。
Claims (10)
1.一种金属箔积层板,其特征在于,包括:
一第一介电层,包括第一介电材料且不包括补强布,其中第一介电材料包括20重量%至60重量%的第一氟高分子及40重量%至80重量%的第一填料;
一第二介电层,设置于第一介电层的至少一侧,且包括补强布及形成于该补强布表面的第二介电材料,其中该补强布的厚度不大于65微米,且第二介电材料包括55重量%至100重量%的第二氟高分子及0至45重量%的第二填料;以及
一金属箔,设置于第二介电层的与第一介电层相对的另一侧。
2.如权利要求1所述的金属箔积层板,其特征在于,该第一氟高分子及该第二氟高分子各自独立选自以下群组:聚四氟乙烯、四氟乙烯-六氟丙烯共聚物、四氟乙烯-全氟烷基乙烯基醚共聚物及前述的组合。
3.如权利要求1所述的金属箔积层板,其特征在于,该第二氟高分子的熔点低于该第一氟高分子的熔点。
4.如权利要求1中所述的金属箔积层板,其特征在于,该补强布是玻璃纤维布。
5.如权利要求1所述的金属箔积层板,其特征在于,该补强布选自以下群组:E-玻璃纤维布、NE-玻璃纤维布、S-玻璃纤维布、L-玻璃纤维布、D-玻璃纤维布、石英玻璃纤维布、芳香族聚酰胺纤维布、聚四氟乙烯纤维布、聚酯纤维布及液晶高分子纤维布。
6.如权利要求1至5中任一项所述的金属箔积层板,其特征在于,该补强布的厚度不大于40微米。
7.如权利要求1至5中任一项所述的金属箔积层板,其特征在于,第一填料及第二填料各自独立选自以下群组:二氧化硅、氧化铝、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氮化硼、氢氧化铝、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石、类钻石碳、石墨、煅烧高岭土、白岭土、云母、水滑石、聚四氟乙烯粉末、玻璃珠、陶瓷晶须、奈米碳管、奈米级无机粉体、钛酸锶及前述的组合。
8.如权利要求1至5中任一项所述的金属箔积层板,其特征在于,其以动态机械分析仪在频率1 Hz及温度70℃的条件下测得的储存模数大于4000 MPa。
9.一种印刷电路板,其特征在于,其是由权利要求1至8中任一项所述的金属箔积层板所制得。
10.一种金属箔积层板的制造方法,其特征在于,包括:
提供一第一介电层,其包括第一介电材料且不包括补强布,其中第一介电材料包括20重量%至60重量%的第一氟高分子及40重量%至80重量%的第一填料;
提供一第二介电层并设置于第一介电层的至少一侧,其中第二介电层包括补强布及形成于该补强布表面的第二介电材料,该补强布的厚度不大于65微米,且第二介电材料包括55重量%至100重量%的第二氟高分子及0至45重量%的第二填料;
提供一金属箔并设置于第二介电层的与第一介电层相对的另一侧,以提供一层叠物;以及
对该层叠物进行一热压步骤,以提供一金属箔积层板。
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