CN109415558A - 热固性树脂组合物、利用其的预浸料、层叠片及印刷电路基板 - Google Patents

热固性树脂组合物、利用其的预浸料、层叠片及印刷电路基板 Download PDF

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Publication number
CN109415558A
CN109415558A CN201780042735.2A CN201780042735A CN109415558A CN 109415558 A CN109415558 A CN 109415558A CN 201780042735 A CN201780042735 A CN 201780042735A CN 109415558 A CN109415558 A CN 109415558A
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China
Prior art keywords
compositions
thermosetting resin
resin
weight
mentioned
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CN201780042735.2A
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English (en)
Inventor
金武贤
权庭惇
郑东熙
申知澒
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Doosan Corp
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Doosan Corp
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Priority claimed from PCT/KR2017/006946 external-priority patent/WO2018012775A1/ko
Publication of CN109415558A publication Critical patent/CN109415558A/zh
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Abstract

本发明涉及热固性树脂组合物、利用该热固性树脂组合物的预浸料、层叠片及印刷电路基板，上述热固性树脂组合物包含：(a)分子链的两末端具有两个以上选自由乙烯基和烯丙基组成的组中的不饱和取代基的聚苯醚或其低聚物；及(b)氟基聚四氟乙烯填料。

Description

热固性树脂组合物、利用其的预浸料、层叠片及印刷电路基板
技术领域
本发明涉及改善了介电常数和介电损耗的新型热固性树脂组合物、利用该热固性树脂组合物的预浸料、层叠片及印刷电路基板。
背景技术
近年来，包含半导体元件的电子部件以及信息通信设备的信号带出现变高的倾向。此时，电信号的传递损失与介电损耗角正切和频率成比例。由此，随着频率增大，传递损失变大，导致信号的衰减，从而出现信号传递的可靠性降低。此外，传递损失会转变为热，也会引发发热的问题。因此，在高频区域要求介电损耗角正切非常小的绝缘材料。
此外，随着对于半导体元件的高集成化、高精细化、高性能化等的要求变高，要求用于半导体元件的制造的集成度、印刷电路基板的高密度化以及配线间隔的清晰性。为此，优选使信号的传递速度变快，并且使用能够使传递损失减小的低介电特性的物质。
作为这样的物质，以往主要使用具有低介电特性的氟树脂作为基本树脂。但是，氟树脂的价格昂贵，且具有高熔点，因此存在必须要在高温/高压下实施按压(PRESS)的制造上的问题，并且存在利用上述氟树脂制造预浸料时费用变高，成型加工性等下降的问题。
现有技术文献
专利文献
专利文献1：韩国公开专利公报第2007-0011493号
发明内容
所要解决的课题
本发明的目的在于，提供粘接性、耐热性和固化性优异并且具有低介电特性的热固性树脂组合物以解决上述问题。
此外，本发明的目的在于，提供使用了上述热固性树脂组合物的预浸料、层叠片以及包含上述预浸料的印刷电路基板。
解决课题的方法
为了实现上述目的，本发明提供一种热固性树脂组合物，其包含(a)分子链的两末端具有两个以上选自由乙烯基和烯丙基组成的组中的不饱和取代基的聚苯醚或其低聚物、以及(b)聚四氟乙烯(PTFE)填料。
本发明中，相对于整体组合物100重量份，上述聚四氟乙烯(PTFE)填料的含量可以为10～60重量份范围。
本发明中，上述聚四氟乙烯(PTFE)填料的平均粒径可以为0.2～20μm，且比表面积可以为1～15m2/g，优选地，平均粒径可以为1～10μm，且比表面积可以为1.5～12m2/g范围。
本发明的热固性树脂组合物可以进一步包含选自由(c)无机填料、(d)交联结合性固化剂、以及(e)阻燃剂组成的组中的一种以上。
此外，本发明提供一种预浸料，其包含由含乙烯基硅烷偶联剂进行了表面处理的纤维基材、以及使上述热固性树脂组合物含浸于上述纤维基材而得的树脂。
此外，本发明提供一种层叠片，其包含金属箔或高分子膜基材、以及形成于上述金属箔或上述高分子膜基材的一面或两面上且由上述热固性树脂组合物固化而成的树脂层。
本发明中，上述层叠片的基于IPC TM 6502.5.5.9的频率1GHz时的介电损耗(Df)系数可以为0.0025以下，介电常数(Dk)可以为3.75以下。
并且，本发明提供包含上述预浸料的印刷电路基板。
发明效果
本发明的热固性树脂组合物的玻璃化转变温度(Tg)高，耐热性及加工性优异，且表现出低介电特性，因此能够在制造用于收发1GHz以上(尤其10GHz)的高频信号的移动通信设备或其基站装置、服务器、路由器等网络相关电子设备以及大型计算机等各种电气电子设备的印刷电路基板时有效地使用。
具体实施方式
以下，对本发明进行说明。
本发明提供能够有效用于印刷电路基板、尤其高频用途的多层印刷电路基板的热固性树脂组合物。
电信号的介电损耗与形成电路的绝缘层的相对介电常数的平方根、介电损耗角正切及电信号的频率的乘积成比例，因此电信号的频率越高，介电损耗越大。由此，为了用于高频印刷电路基板的绝缘层，要求使用介电常数和介电损耗因子(介电损耗)低的物质。
以往，为了满足低介电常数和低介电损耗特性，主要使用具有低介电特性的氟系树脂，但这样的氟系树脂由于高熔点而要求300℃以上的高温挤出成型，因此导致高制造费用和成型加工性降低。
对此，本发明的特征在于，作为构成热固性树脂组合物的树脂成分，以介电特性优异的聚(苯醚)树脂(以下称为“PPE”)为基础，且向其中以填料(filler)形态而非树脂(resin)形态添加氟系之一的聚四氟乙烯(PTFE)进行混合使用。
如上所述，混合使用了PPE树脂和PTFE填料的本发明的热固性树脂组合物可以直接应用本领域通常的预浸料(prepreg)制造工序、比如在热固性树脂组合物中含浸玻璃纤维后加压的工序(压力：35kgf/cm2，温度：200℃条件)来代替以往使用氟系树脂时不得不必须实施的300℃以上的高温挤出成型工序，因此能够减少制造工序的费用以及增大加工的容易性。
此外，本发明中，通过以介电特性低且加工性容易的PPE树脂为基础，且向其中以特定配合比调节并应用介电常数为2.1水平的聚四氟乙烯(PTFE)填料，从而能够不对PPE树脂所具有的固有的特性造成影响地发挥优异的低介电常数(Dk)和低介电损耗(Df)特性，同时能够提供高玻璃化转变温度(Tg)和优异的耐热性(T-288)等。
1.热固性树脂组合物
本发明提供能够有效用于印刷电路基板、尤其高频用途的多层印刷电路基板的热固性树脂组合物。以下，更具体地对其进行说明。
上述热固性树脂组合物作为非环氧系热固性树脂组合物，包含(a)在分子链的两末端具有两个以上选自由乙烯基和烯丙基组成的组中的不饱和取代基的聚苯醚或其低聚物；及(b)作为氟基填充剂的聚四氟乙烯填料。此时，视需要，可以进一步包含(c)无机填料、(d)交联结合性固化剂、(e)阻燃剂、或它们的一种以上的混合物。
(a)聚苯醚
本发明的热固性树脂组合物所包含的聚苯醚(PPE)或其低聚物可以使用在分子链的两末端具有两个以上的不饱和双键性部分的物质。上述不饱和双键性部分可以无限制地使用本领域已知的通常的部分，例如，可以为乙烯基、烯丙基或它们两者。
这里，考虑到本发明的热固性树脂组合物的物性，上述聚苯醚优选为下述化学式1所表示的化合物。这是因为，下述化学式1所表示的化合物在两末端导入有两个以上的乙烯基，因而玻璃化转变温度高，热膨胀系数低，且因羟基(OH)减少而耐湿性和介电特性优异。
[化学式1]
上述化学式1中，
Y选自由双酚A型、双酚F型、双酚S型、萘型、蒽、联苯型、四甲基联苯型、苯酚酚醛清漆型、甲酚酚醛清漆型、双酚A酚醛清漆型和双酚S酚醛清漆型树脂组成的组，
m和n各自为3～20的整数。
本发明的聚苯醚或其低聚物虽被定义为在分子链的两末端具有两个以上的乙烯基和/或烯丙基，但除了上述乙烯基和/或烯丙基以外，本领域公知的具有不饱和双键性部分(moiety)的聚苯醚或其低聚物也包含在本发明的范畴之内。
另一方面，聚苯醚由于本质上熔点高而包含其的树脂组合物的熔化物粘性高，因此难以以多层生产层叠片。由此，本发明中，优选使用通过再分配反应而改性成低分子量的聚苯醚来代替以往直接使用高分子量的聚苯醚。这里，本发明中，作为用于聚苯醚的再分配反应的催化剂，使用烷基(Alkyl)含量和芳香族环基(Aromatic)含量增加了的特定双酚(Bisphenol)衍生物，因此能够提高热固性树脂组合物的低介电特性。
即，以往在将高分子量的聚苯醚改性成低分子量的聚苯醚时，使用苯酚衍生物或双酚A之类的化合物，该情况下，由于分子结构上能够旋转，因而在改善介电特性方面存在局限。具体而言，以往，通过将高分子量的聚苯醚以多酚和自由基引发剂为催化剂进行再分配反应从而改性成两末端具有羟基的低分子量的聚苯醚后进行使用，但由于再分配反应中所使用的作为多酚的双酚A的结构特性以及两末端所导入的羟基的高极性，在降低介电常数和介电损耗方面存在局限。
但是，本发明中，作为再分配反应中所使用的多酚，使用烷基(Alkyl)含量和芳香族环基(Aromatic)含量增加了的特定双酚衍生物来进行再分配反应，从而使用两末端导入了极性低的乙烯基和/或烯丙基的低分子量的聚苯醚来代替极性高的羟基，这样的低分子量的聚苯醚与以往的聚苯醚衍生物相比，分子量小，烷基(alkyl)含量高，因此在将其添加于热固性树脂组合物中的情况下，与现有的环氧树脂等的相容性优异，能够提供操作性以及介电特性改善了的热固性树脂组合物。
上述烷基(alkyl)含量和芳香族环基(aromatic)含量增加了的特定双酚衍生物没有特别限定，优选除了双酚A[BPA，2,2-双(4-羟基苯基)丙烷(2,2-Bis(4-hydroxyphenyl)propane)]以外的双酚系化合物。
本发明中，作为特定双酚衍生物的具体例，可以举出双酚AP(1,1-双(4-羟基苯基)-1-苯基-乙烷(1,1-Bis(4-hydroxyphenyl)-1-phenyl-ethane))、双酚AF(2,2-双(4-羟基苯基)六氟丙烷(2,2-Bis(4-hydroxyphenyl)hexafluoropropane))、双酚B(2,2-双(4-羟基苯基)丁烷(2,2-Bis(4-hydroxyphenyl)butane))、双酚BP(双(4-羟基苯基)二苯基甲烷(Bis-(4-hydroxyphenyl)diphenylmethane))、双酚C(2,2-双(3-甲基-4-羟基苯基)丙烷(2,2-Bis(3-methyl-4-hydroxyphenyl)propane))、双酚C(双(4-羟基苯基)-2,2-二氯乙烯(Bis(4-hydroxyphenyl)-2,2-dichlorethylene))、双酚G(2,2-双(4-羟基-3-异丙基-苯基)丙烷(2,2-Bis(4-hydroxy-3-isopropyl-phenyl)propane))、双酚M(1,3-双(2-(4-羟基苯基)-2-丙基)苯(1,3-Bis(2-(4-hydroxyphenyl)-2-propyl)benzene))、双酚P(双(4-羟基苯基)砜(Bis(4-hydroxyphenyl)sulfone))、双酚PH(5,5'-(1-甲基亚乙基)-双[1,1'-(双苯基)-2-醇]丙烷(5,5'-(1-Methylethyliden)-bis[1,1'-(bisphenyl)-2-ol]propane))、双酚TMC(1,1-双(4-羟基苯基)-3,3,5-三甲基-环己烷(1,1-Bis(4-hydroyphenyl)-3,3,5-trimethyl-cyclohexane))、或双酚Z(1,1-双(4-羟基苯基)-环己烷(1,1-Bis(4-hydroxyphenyl)-cyclohexane))等。上述成分可以单独或将两种以上混合使用。本发明中，在使用上述例示的特定双酚衍生物进行再分配反应的情况下，上述化学式1的Y可以为衍生自上述特定双酚衍生物化合物的2价基团。
这样的本发明的聚苯醚可以为将数均分子量(Mn)为10,000～30,000范围的高分子量聚苯醚在上述双酚衍生物(其中，双酚A除外)的存在下进行再分配反应而改性成数均分子量(Mn)为1,000～10,000范围的低分子量后得到的聚苯醚，优选数均分子量(Mn)可以为1,000～5,000范围，更优选可以为1,000～3,000范围。
此外，本发明的聚苯醚的分子量分布(Mw/Mn)优选为3以下，更优选为1.5～2.5。
这样的本发明的聚苯醚或其低聚物的含量没有特别限定，但考虑到热固性树脂组合物的物性，以该热固性树脂组合物100重量％为基准，可以为20～45重量％范围，优选为25～40重量％范围。
(b)聚四氟乙烯(PTFE)填料
本发明的热固性树脂组合物所包含的聚四氟乙烯(PTFE)填料发挥降低热固性树脂组合物的介电特性的作用。
这样的PTFE填料是介电常数大致2.1水平的氟基材料，因此能够发挥低介电特性。此外，由于以填料(filler)形态添加，因此能够在没有高温加压成型工序的情况下实现绝缘层制造工序的容易性。
另一方面，在热固性树脂组合物中，随着聚四氟乙烯(PTFE)填料均匀地分散，能够改善热固性树脂组合物的介电特性，而且也适合于用于制造CCL的玻璃纤维含浸工艺以及加压成型工艺。由此，本发明中，优选以将聚四氟乙烯填料的平均粒径、比表面积和/或其含量分别调节至特定范围。
具体而言，本发明的聚四氟乙烯填料的平均粒径可以为0.2～20μm范围，比表面积可以为1～15m2/g范围，优选地，平均粒径可以为1～10μm，比表面积可以为1.5～12m2/g范围。在具有上述的粒径和比表面积的情况下，由于在热固性树脂组合物内没有凝集现象地均匀分散，因而适合于制造印刷电路基板用预浸料绝缘层。
本发明中，上述聚四氟乙烯(PTFE)填料可以将具有特定粒径和比表面积的PTFE填料单独使用，或者将粒径和比表面积不同的两种以上的PTFE填料混合使用。
根据本发明的优选的一例，将上述聚四氟乙烯(PTFE)填料可以将(i)平均粒径为1～9μm、比表面积为1.5～3m2/g的第一聚四氟乙烯填料；(ii)平均粒径为1～10μm、比表面积为5～10m2/g的第二聚四氟乙烯填料；(iii)平均粒径为1～5μm、比表面积为8～11m2/g的第三聚四氟乙烯填料分别单独使用，或者将它们混合使用。
这样的本发明的聚四氟乙烯填料的含量没有特别限定，例如，以该热固性树脂组合物100重量％为基准，可以为10～60重量％范围。考虑到本发明的热固性树脂组合物的物性，以该树脂组合物100重量％为基准，优选可以为10～57重量％范围，更优选可以为10～50重量％。
(c)无机填料
本发明的热固性树脂组合物可以进一步包含无机填料以提高机械强度并且使利用该树脂组合物形成的树脂层与相邻的其他层间的热膨胀系数差异最小化。
这样的无机填料只要是本领域公知的物质就没有特别限定，例如，优选为由含乙烯基硅烷偶联剂进行了表面处理的无机填料。这是因为，表面被含乙烯基硅烷偶联剂处理的无机填料与上述的具有乙烯基和/或烯丙基的聚苯醚的相容性优异，能够改善热固性树脂组合物的介电特性、耐热性、加工性等。
上述为了用含乙烯基硅烷偶联剂进行表面处理而使用的无机填料没有特别限定，可以举出天然二氧化硅(natural silica)、熔融二氧化硅(Fused silica)、无定形二氧化硅(amorphous silica)、结晶二氧化硅(crystalline silica)等二氧化硅类；勃姆石(boehmite)、氧化铝、滑石(Talc)、球形玻璃、碳酸钙、碳酸镁、氧化镁、粘土、硅酸钙、氧化钛、氧化锑、玻璃纤维、硼酸铝、钛酸钡、钛酸锶、钛酸钙、钛酸镁、钛酸铋、锆酸钡、锆酸钙、氮化硼、氮化硅或云母(mica)等。上述的成分可以单独或将两种以上混合使用。
此外，无机填料的粒径没有特别限定，考虑到分散性，平均粒径优选为约0.5～5μm。
上述将无机填料用含乙烯基硅烷偶联剂进行表面处理的方法没有特别限定，可以举出在包含含乙烯基硅烷偶联剂的溶液中投入无机填料后进行干燥的方法。
这样的本发明的无机填料的含量没有特别限定，例如，以该热固性树脂组合物100重量％为基准，可以为0～30重量％范围。考虑到本发明的热固性树脂组合物的物性，以该热固性树脂组合物100重量％为基准，优选为5～30重量％，更优选为10～30重量％。
(d)交联结合性固化剂
本发明的热固性树脂组合物可以进一步包含交联结合性固化剂以改善上述聚苯醚的结合结构。
上述交联结合(cross-linking)性固化剂是使上述聚苯醚进行三维交联结合而形成网状结构的物质，由此，能够提高包含改性成低分子量的聚苯醚的本发明的热固性树脂组合物的耐热性。此外，还能够增加本发明的热固性树脂组合物的流动性，提高与其他基材(例如，铜箔)的剥离强度。
本发明中可使用的交联结合性固化剂没有特别限定，例如优选使用含有三个以上官能团的固化剂。
上述含有三个以上官能团的固化剂没有特别限定，具体可以举出三烯丙基异氰脲酸酯(triallyl isocyanurate，TAIC)或1,2,4-三乙烯基环己烷(1,2,4-trivinylcyclohexane，TVCH)等。上述的成分可以单独或将两种以上混合使用。
这里，作为上述三烯丙基异氰脲酸酯(triallyl isocyanurate，TAIC)，优选使用下述化学式2所表示的化合物。
[化学式2]
这样的交联结合性固化剂的含量没有特别限定，考虑到热固性树脂组合物的物性，以该热固性树脂组合物100重量％为基准，可以为5～20重量％，优选可以为10～20重量％范围。
(e)阻燃剂
本发明的热固性树脂组合物可以进一步包含阻燃剂以提高阻燃性。
上述阻燃剂只要是本领域公知的阻燃剂就没有特别限定，例如，可以举出含有溴或氯的卤素阻燃剂；磷酸三苯酯、磷酸三甲苯酯、三二氯丙基磷酸酯、磷腈等磷系阻燃剂；三氧化二锑等锑系阻燃剂；氢氧化铝、氢氧化镁等金属氢氧化物等无机物的阻燃剂等。
本发明中，优选使用与聚苯醚不发生反应性，且不降低耐热性和介电特性的溴化阻燃剂。具体而言，本发明通过使用溴邻苯二甲酰亚胺(Bromophthalimide)、溴苯基(Bromophenyl)添加型溴化阻燃剂或者末端烷基化形态的四溴双酚A(Tetrabromobisphenol A)、二乙烯基苯酚(Divinylphenol)形态的阻燃性固化剂，从而能够同时改善固化剂特性以及阻燃性。此外，也可以使用溴化有机化合物。作为这样的溴化有机化合物的例子，可以举出十溴二苯基乙烷(decabromodiphenylethane)、4,4-二溴联苯、或亚乙基双四溴邻苯二甲酰亚胺(ethylenbistetrabromophthalimide)等。
这样的本发明的阻燃剂的含量没有特别限定，考虑到热固性树脂组合物的物性，以该热固性树脂组合物100重量％为基准，可以为1～15重量％范围，优选可以为5～10重量％范围。
根据本发明的优选的一例，上述热固性树脂组合物以该组合物100重量％为基准，可以包含聚苯醚或其低聚物20～45重量％；聚四氟乙烯填料10～60重量％；无机填料0～30重量％；交联结合性固化剂5～20重量％；以及阻燃剂1～15重量％。
另一方面，本发明的热固性树脂组合物视需要可以进一步包含反应引发剂和/或固化促进剂等。
上述反应引发剂能够使上述聚苯醚与上述交联结合性固化剂的固化反应加速，能够提高热固性树脂组合物的耐热性。作为这样的反应引发剂的非限制性例子，可以举出α,α′-双(叔丁基过氧化间异丙基)苯、2,5-二甲基-2,5-二(叔丁基过氧化)-3-己炔(hexyne)、过氧化苯甲酰、3,3′,5,5′-四甲基-1,4-二苯氧基醌、氯醌、2,4,6-三叔丁基苯酚、叔丁基过氧化单碳酸异丙酯、或偶氮二异丁腈(azobisisobutylonitrile)等，也可以追加使用金属碳酸盐。
上述固化促进剂没有特别限定，例如，可以举出包含选自由铁、铜、锌、钴、铅、镍、锰和锡组成的组中的一种以上的金属的有机金属盐或有机金属络合物等。
作为上述有机金属盐或有机金属络合物的具体例，可以举出环烷酸(napthenates)铁、环烷酸铜、环烷酸锌、环烷酸钴、环烷酸镍、环烷酸锰、环烷酸锡、辛酸(octanoate)锌、辛酸锡、辛酸铁、辛酸铜、2-乙基己酸锌、乙酰丙酮铅、乙酰丙酮钴、或马来酸二丁基锡等，可以将上述成分单独或将两种以上混合使用。
上述的反应引发剂和/或固化促进剂的含量可以在本领域已知的通常范围内适宜调节。例如，上述反应引发剂和/或固化促进剂的含量分别以该热固性树脂组合物100重量％为基准可以为0.1～10重量％范围。
除此以外，本发明的热固性树脂组合物在不损害其物性的范围内视需要可以进一步包含上述未提及的其他热固性树脂或热塑性树脂及它们的低聚物等之类的多种多样的高分子；固态橡胶粒子；或紫外线吸收剂、抗氧化剂、聚合引发剂、染料、颜料、分散剂、增稠剂、流平剂等添加剂等。
2.预浸料
本发明提供利用上述的热固性树脂组合物制造的预浸料(prepreg)。具体而言，本发明的预浸料包含由含乙烯基硅烷偶联剂进行了表面处理的纤维基材、以及使上述的热固性树脂组合物含浸于上述纤维基材而得的树脂。此时，上述热固性树脂组合物可以为溶解或分散于溶剂的形态的树脂清漆形态。
在使上述热固性树脂组合物含浸于上述由含乙烯基硅烷偶联剂进行了表面处理的纤维基材的情况下，由于上述纤维基材和上述热固性树脂组合物所包含的成分分别具有乙烯基，因此纤维基材与热固性树脂组合物之间的相容性(Compatibility)优异，由此能够提供介电特性被改善、且耐热性和加工性提高了的高频用材料。
本发明中，上述纤维基材只要是将本领域公知的纤维基材用含乙烯基硅烷偶联剂进行了表面处理的纤维基材就没有特别限定，可以以想要使用的用途或性能为基准来选择要进行表面处理的纤维基材。
具体而言，作为上述纤维基材的非限制性例子，可以使用E-玻璃、D-玻璃、S-玻璃、NE-玻璃、T-玻璃、Q-玻璃等玻璃纤维之类的无机纤维；聚酰亚胺、聚酰胺、聚酯、芳族聚酰胺纤维、芳香族聚酯、氟树脂等有机纤维；以及上述无机纤维与有机纤维的混合物；由上述无机纤维和/或有机纤维构成的纸、无纺布、织物、纸等、和粗纱(roving)、短切毡(choppedstrand mat)、表面毡(surfacing mat)等毡类等。它们均由含乙烯基硅烷偶联剂进行了表面处理，可以单独或将两种以上混合使用。此时，在混用增强的纤维基材的情况下，能够提高预浸料的刚性、尺寸稳定性。
根据本发明的一例，作为上述纤维基材，可以使用玻璃纤维、玻璃纸、玻璃纤维无纺布(glass web)、玻璃织物(glass cloth)、芳族聚酰胺纤维、芳族聚酰胺纸(aramidpaper)、聚酯纤维、碳纤维、无机纤维、有机纤维及它们的混合物。
这样的纤维基材的厚度没有特别限定，可以为约0.01～0.3㎜。
将这样的纤维基材用含乙烯基硅烷偶联剂进行表面处理的方法没有特别限定，例如，可以应用与上述的将无机填料用含乙烯基硅烷偶联剂进行表面处理的方法相同的方法。
另一方面，本发明的预浸料可以通过本领域公知的方法来制造。具体而言，本发明的预浸料是指，对由含乙烯基硅烷偶联剂进行了表面处理的纤维基材涂布或含浸上述的热固性树脂组合物后，通过加热而使之固化至B-阶段(B-stage(半固化状态))，从而在纤维基材内含浸有树脂的片状的材料。此时，将含浸有热固性树脂组合物的纤维基材进行加热的温度及时间没有特别限定，温度优选为约20～200℃(具体为70～170℃)，时间优选为约1～10分钟。除了这样的方法以外，本发明的预浸料也可以通过溶剂法、热熔法等方法来制造。
上述溶剂法是使混合了热固性树脂组合物和有机溶剂的树脂清漆含浸于纤维基材后进行干燥的方法。此时，使树脂清漆含浸于纤维基材的方法没有特别限定，可以举出将纤维基材浸渍于树脂清漆的方法、利用各种涂布机将树脂清漆涂布于纤维基材的方法、喷洒树脂清漆而喷射于纤维基材的方法等。这里，在将纤维基材浸渍于树脂清漆的情况下，能够提高对于纤维基材的树脂清漆的含浸性，因而优选使用上述的方法。
为了制造上述树脂清漆而使用的有机溶剂没有特别限定，可以举出丙酮、甲基乙基酮、环己酮等酮类；乙酸乙酯、乙酸丁酯、乙酸溶纤剂、丙二醇单甲基醚乙酸酯、卡必醇乙酸酯等乙酸酯类；溶纤剂、丁基卡必醇等卡必醇类；甲苯、二甲苯等芳香族烃类；二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、四氢呋喃等，它们可以单独或两种以上混合使用。
上述热熔法是将热固性树脂组合物涂布于脱模纸后，将其层压于片状的纤维基材或利用模涂机进行直接涂布的方法。此外，将由热固性树脂组合物形成的粘接膜配置于片状的纤维基材的两面后，进行加热及加压而连续层压的方法也可以称为热熔法。
这样的本发明的预浸料包含上述的热固性树脂组合物固化而成的树脂，因此能够在粘接性、耐热性和固化性优异的同时显示出改善了的低介电特性。
3.层叠片
本发明提供利用上述的热固性树脂组合物制造的层叠片。具体而言，本发明的层叠片包含金属箔或高分子膜基材、以及形成于上述金属箔或高分子膜基材的一面或两面上且由上述的热固性树脂组合物固化而成的树脂层。
作为这样的本发明的层叠片的一例，可以举出包含金属箔、以及形成于上述金属箔的一面或两面上且由上述的热固性树脂组合物固化而成的树脂层的铜箔层叠片(或铜箔层叠体)。
上述金属箔可以使用本领域公知的金属或合金，具体而言，可以为铜箔。此时，作为可使用的铜箔的例子，可以举出卢森堡电路铜箔(CFL)(TZA_B、HFZ_B)、三井(HSVSP、MLS-G)、日矿(RTCHP)、古河、ILSIN等。此外，上述铜箔可以应用通过压延法或电解法制造的所有铜箔。而且，上述铜箔可以被防锈处理以防止表面被氧化腐蚀。
上述金属箔在与本发明的热固性树脂组合物固化而成的树脂层接触的一面可以形成有表面粗糙度(Rz)。此时，表面粗糙度(Rz)范围没有特别限定，优选为0.6～3.0μm。
这样的金属箔的厚度没有特别限定，考虑到层叠片的厚度和机械特性，优选小于5μm，更优选为1～3μm。
另一方面，本发明的层叠片所包含的高分子膜基材只要是本领域公知的绝缘膜就没有特别限定，可以举出聚酰亚胺膜、环氧树脂膜等。
这样的本发明的层叠片包含上述的热固性树脂组合物固化而成的树脂层，因此能够在粘接性、耐热性和固化性优异的同时显示出改善了的低介电特性。
4.印刷电路基板
本发明提供包含上述的预浸料的印刷电路基板。
具体而言，本发明的印刷电路基板包含将两个以上上述的预浸料彼此重叠后，按照通常的条件将其进行加热及加压而形成的层叠板。上述层叠板在印刷电路基板中发挥绝缘层、粘接层或覆盖层等的作用。
这样的本发明的印刷电路基板可以通过本领域公知的方法来制造。具体而言，可以如下制造：在上述的预浸料的一面或两面层叠铜箔并进行加热及加压而形成铜箔层叠板后，在铜箔层叠板上形成通孔且进行通孔镀敷，然后对铜箔进行蚀刻而形成电路。
这样的本发明的印刷电路基板利用包含上述的热固性树脂组合物固化而成的树脂的预浸料来制造，因此热膨胀系数(CTE)低，玻璃化转变温度(Tg)高，耐热性优异，并且介电常数和介电损耗低。由此，本发明的印刷电路基板能够作为用于收发1GHz以上的频率信号的移动通信设备或其基站装置、服务器、路由器等网络相关电子设备以及大型计算机等各种电气电子设备的印刷电路基板有效地使用。
以下，通过实施例来详细说明本发明，具体如下。但是，下述实施例仅例示本发明，本发明不受下述实施例的限定。
[实施例1-6和比较例1-2]
1)热固性树脂组合物的制造
根据下述表1中记载的组成，将上述聚苯醚溶解于甲苯后，与交联结合性固化剂、阻燃剂混合，并搅拌2小时。在树脂组合物中投入无机填料和有机填料之前，将甲苯或MEK溶剂搅拌后，利用均质器(Honogenizer)使凝集最小化。将利用均质器使分散性尽可能提高的有机填料和无机填料与树脂组合物混合，并搅拌2小时，进一步添加引发剂并搅拌1小时，从而制造树脂组合物。下述表1中各组合物的使用量单位为重量份。
2)层叠片的制造
使上述制造的树脂组合物含浸于玻璃纤维后，在160℃干燥3～10分钟，从而制造预浸料。将上述预浸料进行1ply层叠后，进行按压，从而制作0.1mm厚度的层叠薄板。
[表1]
(注)1)烯丙基化PPE：MX-9000(数均分子量：2000～3000)
2)TAIC(日本化成(NIPPON KASEICHEMICAL))
3)阻燃剂：Saytex8010(雅宝朝野公司(Albemarle Asano Corporation))
4)引发剂：Perbutyl P(日油公司(NOF Corporation))
5)无机填料：SC-5200SQ(雅都玛(Admatechs))
6)聚四氟乙烯填料1：MP1200(杜邦(Dupont))
7)聚四氟乙烯填料2：MP1100(杜邦(Dupont))
8)聚四氟乙烯填料3：L-2(大金(DAIKIN))
9)DCPD环氧树脂：XD-1000(日本化药(Nippon kayaku))
10)酚醛清漆固化剂：KC-2070(江南化学(kangnam chemical))
[实验例1]层叠片的物性评价
按照如下方法评价上述实施例1-6和比较例1中制造的各个层叠片的物性，并将其结果示于下述表2中。
1)玻璃化转变温度(Tg)的测定
玻璃化转变温度(Tg)利用动态力学分析(Dynamic Mechanical Analysis，DMA)、TA公司的Q800并依据IPC-TM-650-2.4.24.4(DMA法)进行测定。
2)耐热性
根据IPC TM-6502.4.13评价标准，将层叠片漂浮(Floating)于焊锡(Solder)288℃，测定直至绝缘层与铜箔层、或绝缘层之间的分离现象出现时的时间并进行评价。
3)T-288评价
分层时间(Time to delamination)利用热力学分析(Thermo mechanicalanalysis，TMA)、TA公司的2940并依据IPC TM-6502.4.24.1(T-288法)进行测定。
4)TGA Td(5％损失(loss))
5％损失重量变化测定利用热重分析(Thermo gravimetric analysis，TGA)、TA公司的Q500并依据IPC-TM-650-2.4.24.6(TGA法)进行测定。
5)介电常数和介电损耗
根据IPC TM 6502.5.5.9评价标准，将层叠片含浸于铜液而将铜箔层去除，利用介电常数测定装置(射频阻抗/材料分析仪(RF Impedence/Material Analyzer)；Agilent)分别测定频率1GHz时的介电常数和介电损耗。
6)阻燃性
将层叠片含浸于铜蚀刻液而将铜箔层去除，以长127mm、宽12.7mm制造样品后，依据UL94的试验法(V法)进行评价。
7)铜箔粘接性(剥离强度(Peel Strength)，P/S)
根据IPC-TM-6502.4.8的评价标准，将层叠片的铜箔层以90°方向拉起，测定直至铜箔层被剥离时的时间并进行评价。
[表2]
实验结果，利用本发明的聚四氟乙烯(PTFE)填料制造的印刷电路基板在介电常数和介电损耗方面显示出优异的特性(参照表2)。具体而言，实施例1～9的层叠片与以往在环氧树脂基体中使用PTFE填料的比较例2相比，不仅显示出优异的玻璃化转变温度、耐热性和低介电常数特性，而且发挥了至少10倍以上的优秀的低介电损耗(Df)特性。
特别是，实施例7～9是没有使用无机填料而单独使用PTFE填料形成的印刷电路基板。可知，不仅低介电损耗(Df)明显优异，在其他物性方面也显示出与混合使用无机填料和PTFE填料的实施例1～6同等的特性。
由此判断，本发明日后能够制造在超高频区域中介电特性优异的多层印刷电路基板，可作为要求低介电特性的通信用设备及半导体元件的构成材料有效地使用。

Claims (10)

1.一种热固性树脂组合物，其包含：
(a)分子链的两末端具有两个以上选自由乙烯基和烯丙基组成的组中的不饱和取代基的聚苯醚或其低聚物、以及
(b)聚四氟乙烯(PTFE)填料。
2.根据权利要求1所述的热固性树脂组合物，相对于整体组合物100重量份，所述聚四氟乙烯填料的含量为10～60重量份范围。
3.根据权利要求1所述的热固性树脂组合物，所述聚四氟乙烯填料的平均粒径为0.2～20μm，比表面积为1～15m2/g。
4.根据权利要求1所述的热固性树脂组合物，所述聚四氟乙烯填料的平均粒径为1～10μm，比表面积为1.5～12m2/g范围。
5.根据权利要求1所述的热固性树脂组合物，所述聚苯醚为下述化学式1所表示的化合物，
[化学式1]
所述化学式1中，
Y选自由双酚A型树脂、双酚F型树脂、双酚S型树脂、萘型树脂、蒽树脂、联苯型树脂、四甲基联苯型树脂、苯酚酚醛清漆型树脂、甲酚酚醛清漆型树脂、双酚A酚醛清漆型树脂和双酚S酚醛清漆型树脂组成的组，
m和n各自为3～20的整数。
6.根据权利要求1所述的热固性树脂组合物，其进一步包含选自由(c)无机填料、(d)交联结合性固化剂、和(e)阻燃剂组成的组中的一种以上。
7.根据权利要求6所述的热固性树脂组合物，所述热固性树脂组合物以该热固性树脂组合物100重量％为基准，包含：
聚苯醚或其低聚物20～45重量％；
聚四氟乙烯填料10～60重量％；
无机填料0～30重量％；
交联结合性固化剂5～20重量％；以及
阻燃剂1～15重量％。
8.一种预浸料，其包含：
由含乙烯基硅烷偶联剂进行了表面处理的纤维基材、以及
使权利要求1～7中任一项所述的热固性树脂组合物含浸于所述纤维基材而得的树脂。
9.一种层叠片，其包含：
金属箔或高分子膜基材、以及
形成于所述金属箔或所述高分子膜基材的一面或两面上且由权利要求1～7中任一项所述的热固性树脂组合物固化而成的树脂层。
10.一种印刷电路基板，其包含权利要求8所述的预浸料。
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CN104774476A (zh) * 2015-03-10 2015-07-15 广东生益科技股份有限公司 含磷阻燃组合物以及使用它的含磷聚苯醚树脂组合物、预浸料和层压板

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