CN106883555A - 低介电无溶剂型树脂组合物及基板结构 - Google Patents
低介电无溶剂型树脂组合物及基板结构 Download PDFInfo
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Abstract
本发明提供一种低介电无溶剂型树脂组合物及基板结构体。该低介电无溶剂型树脂组合物包括:(a)20-50重量份的具有式(I)所示结构的共聚物式(I)其中,i、j、k、l、及m分别介于1至10之间;(b)50-80重量份的具有式(II)所示结构的化合物
Description
【技术领域】
本发明涉及低介电无溶剂型树脂组合物及基板结构。
【背景技术】
新时代的电子产品趋向轻薄短小,并适合高频传输,因此电路板的配线走向高密度化,电路板的材料选用走向更严谨的需求。高频电子元件与电路板接合,为了维持传输速率及保持传输讯号完整性,电路板基板材料所使用的孔洞填充材料必须兼具较低的介电常数(dielectric constant、Dk)及耗散因子(dissipation factor、Df)。同时,为了于高温环境下依然维持电子元件正常运作功能,以及确保可应用于共轴(coaxial)填孔制程,孔洞填充材料也必须兼具高耐热特性、良好的填孔性及可钻孔性(punchability)。
由于目前市售或文献所发表的孔洞填充材料其介电常数(dielectric constant、Dk)及耗散因子(dissipation factor、Df)普遍偏高,因此如何在不影响其耐热特性、填孔性及可钻孔性的前提下,改善孔洞填充材料的介电常数及耗散因子,为目前印刷电路板制程的重要课题。
【发明内容】
本发明一实施例提供一种低介电无溶剂型树脂组合物,包含:(a)20-50重量份的具有式(I)所示结构的共聚物
式(I)
其中,i、j、k、l、及m分别介于1至10之间;(b)50-80重量份的具有式(II)所示结构的化合物
式(II);(c)80-100重量份的硬化剂;以及(d)70-100重量份的无机填充物。
根据本发明另一实施例,本发明亦提供一种基板结构,包含:基板,其中该基板具有至少一个孔洞;以及填充材料,填入该孔洞中,其中该填充材料为上述低介电无溶剂型树脂组合物的固化物。
【具体实施方式】
本发明揭露一种低介电无溶剂型树脂组合物、以及包含上述低介电无溶剂型树脂组合物的固化物的基板结构。基于该低介电无溶剂型树脂组合物的特定组成及比例,本发明所述低介电无溶剂型树脂组合物的固化物具有较低的介电常数(dielectric constant、Dk)(可介于2.5至2.98之间)及耗散因子(dissipation factor、Df)(可介于0.013至0.015(于10GHz时))、良好的填孔性、耐热性、耐化性、及可钻孔性,因此该低介电无溶剂型树脂组合物可用于印刷电路板的填孔制程(例如共轴孔洞(coaxial via)制程),解决阻抗失配损耗(impedance mismatch loss)的问题。
本发明一实施方式提供一种低介电无溶剂型树脂组合物,包含:(a)20-50重量份的具有式(I)所示结构的共聚物
式(I)
其中,i、j、k、l、及m分别介于1至10之间,举例来说,i、j、k、l、及m可分别为1、2、3、4、5、6、7、8、9、或10;(b)50-80重量份的具有式(II)所示结构的化合物
式(II);(c)80-100重量份的硬化剂;以及(d)70-100重量份的无机填充物。上述i、j、k、l、及m的范围可由商品选择调整,或由合成单体的比例决定。在这应说明的是,具有式(I)所示结构的共聚物中对应i、j、k、l、及m的重复单元可为有序或无规排列。
为避免在填孔过程中,因溶剂的挥发会造成气孔的产生,导致所得固化物孔柱不连续,进而影响后续的加工性,本发明所述的低介电无溶剂型树脂组合物不包含溶剂(例如水或有机溶剂)。因此,本发明所用的硬化剂为液态硬化剂,例如为甲基六氢邻苯二甲酸酐(methyl hexahydrophthalic anhydride)、甲基四氢邻苯二甲酸酐(methyltetrahydrophthalic anhydride)、马来酸酐(maleic anhydride、HA)、苯乙烯-共聚-马来酸酐(polystyrene-co-maleic anhydride、SMA)、或上述的组合。本发明添加该无机填充物目的在于降低热膨胀系数,该无机填充物可例如为二氧化硅、硫酸钡、碳酸钙、或上述的组合。
在本发明的实施方式中,具有式(I)所示结构的共聚物及具有式(II)所示结构的化合物的总重为100重量份。若具有式(I)所示结构的共聚物的添加量较低时(例如小于20重量份),则介电常数会偏高;若具有式(I)所示结构的共聚物的添加量较高时(例如大于50重量份),则玻璃态转化温度会降低。此外,本发明所述的硬化剂的添加量可为80-100重量份(其中具有式(I)所示结构的共聚物及具有式(II)所示结构的化合物的总重为100重量份)。若硬化剂的添加量不在上述范围中时,则该低介电无溶剂型树脂组合物的固化物的耐化性及可钻孔性下降。本发明所述的无机填充物的添加量可为70-100重量份(其中具有式(I)所示结构的共聚物及具有式(II)所示结构的化合物的总重为100重量份)。若无机填充物的添加量不在上述范围中时,则该低介电无溶剂型树脂组合物的固化物具有较差的硬度及较高的耗散因子。
根据本发明的实施方式,本发明所述的低介电无溶剂型树脂组合物,可还包含1-60重量份的添加剂,其中该添加剂可例如为催化剂、平坦剂、色料、消泡剂、耐燃剂、或上述的组合。
根据本发明的实施方式,本发明亦提供一种基板结构,包含:基板(例如印刷电路板),其中该基板具有孔洞(可例如具有孔洞尺寸介于100μm至2mm之间);以及填充材料,填入该孔洞中,其中该填充材料为上述低介电无溶剂型树脂组合物的固化物。本发明所述的低介电无溶剂型树脂组合物可例如以填孔机网印于该基板上,并在一制程温度(例如150℃~200℃)下进行固化。
为了让本发明的上述和其他目的、特征、和优点能更明显易懂,下文特举数实施例及比较实施例,作详细说明如下:
低介电无溶剂型树脂组合物
实施例1
将15g的具有式(I)所示结构的共聚物(重均分子量为1300、环氧当量介于260-330克/当量之间,酸值为1.74(meq/g))、15g的具有式(II)所示结构的化合物(商品编号为ERL-4221,由Dow贩售)、24g的甲基六氢邻苯二甲酸酐(methyl hexahydrophthalic anhydride、MEHHPA)均匀混合。接着,将21g的二氧化硅无机粉体(商品编号为525、由Sibelco贩售)、0.9g的熔凝氧化硅(fused silica)(商品编号为TS-720、由Cabot贩售)、以及1g的消泡剂(商品编号为KS-66、由信越化学贩售)加入上述混合物中,并以三滚轮研磨机(triple-rollmill)进行分散研磨,然后加入1g的催化剂(4-二甲氨基吡啶、DMAP),得到低介电无溶剂型树脂组合物(1)。
实施例2
将10g的具有式(I)所示结构的共聚物(重均分子量为1300、环氧当量介于260-330克/当量之间,酸值为1.74(meq/g))、20g的具有式(II)所示结构的化合物(商品编号为ERL-4221,由Dow贩售)、28g的甲基六氢邻苯二甲酸酐(methyl hexahydrophthalic anhydride、MEHHPA)均匀混合。接着,将23g的二氧化硅无机粉体(商品编号为525、由Sibelco贩售)、1g的熔凝氧化硅(fused silica)(商品编号为TS-720、由Cabot贩售)、以及1.2g的消泡剂(商品编号为KS-66、由信越化学贩售)加入上述混合物中,并以三滚轮研磨机(thriple-rollmill)进行分散研磨,然后加入1.1g的催化剂(4-二甲氨基吡啶、DMAP),得到低介电无溶剂型树脂组合物(2)。
实施例3
将10g的具有式(I)所示结构的共聚物(重均分子量为1300、环氧当量介于260-330克/当量之间,酸值为1.74(meq/g))、30g的具有式(II)所示结构的化合物(商品编号为ERL-4221,由Dow贩售)、40g的甲基六氢邻苯二甲酸酐(methyl hexahydrophthalic anhydride、MEHHPA)均匀混合。接着,将32g的二氧化硅无机粉体(商品编号为525、由Sibelco贩售)、1.6g的熔凝氧化硅(fused silica)(商品编号为TS-720、由Cabot贩售)、以及1.5g的消泡剂(商品编号为KS-66、由信越化学贩售)加入上述混合物中,并以三滚轮研磨机(thriple-roll mill)进行分散研磨,然后加入1.6g的催化剂(4-二甲氨基吡啶、DMAP),得到低介电无溶剂型树脂组合物(3)。
实施例4
将10g的具有式(I)所示结构的共聚物(平均重量分子量为1300、环氧当量介于260-330克/当量之间,酸值为1.74(meq/g))、40g的具有式(II)所示结构的化合物(商品编号为ERL-4221,由Dow贩售)、50g的甲基六氢邻苯二甲酸酐(methyl hexahydrophthalicanhydride、MEHHPA)均匀混合。接着,将50g的二氧化硅无机粉体(商品编号为525、由Sibelco贩售)、2g的熔凝氧化硅(fused silica)(商品编号为TS-720、由Cabot贩售)、以及2g的消泡剂(商品编号为KS-66、由信越化学贩售)加入上述混合物中,并以三滚轮研磨机(thriple-roll mill)进行分散研磨,然后加入2g的催化剂(4-二甲氨基吡啶、DMAP),得到低介电无溶剂型树脂组合物(4)。
比较实施例1
将30g的具有式(II)所示结构的化合物(商品编号为ERL-4221,Dow贩售)、33g的甲基六氢邻苯二甲酸酐(methyl hexahydrophthalic anhydride、MEHHPA)均匀混合。接着,将33g的二氧化硅无机粉体(商品编号为525、由Sibelco贩售)、1.5g的熔凝氧化硅(fusedsilica)(商品编号为TS-720、由Cabot贩售)、以及1.2g的消泡剂(商品编号为KS-66、由信越化学贩售)加入上述混合物中,并以三滚轮研磨机(thriple-roll mill)进行分散研磨,然后加入1.1g的催化剂(4-二甲氨基吡啶、DMAP),得到低介电无溶剂型树脂组合物(5)。
比较实施例2
将30g的环氧树脂(商品编号为Epikot 828,由Dow贩售)、24g的甲基六氢邻苯二甲酸酐(methyl hexahydrophthalic anhydride、MEHHPA)均匀混合。接着,将22g的二氧化硅无机粉体(商品编号为525、由Sibelco贩售)、0.9g的熔凝氧化硅(fused silica)(商品编号为TS-720、由Cabot贩售)、以及1g的消泡剂(商品编号为KS-66、由信越化学贩售)加入上述混合物中,并以三滚轮研磨机(thriple-roll mill)进行分散研磨,然后加入1g的催化剂(4-二甲氨基吡啶、DMAP),得到低介电无溶剂型树脂组合物(6)。
低介电无溶剂型树脂组合物其固化物的性质测试
将实施例1-4及比较实施例1-2所得的低介电无溶剂型树脂组合物(1)-(6)分别填入位于印刷电路版内的孔洞中(洞孔直径为800μm)。接着,对上述低介电无溶剂型树脂组合物(1)-(6)进行固化制程(在180℃下加热60分钟),分别得到固化物(1)-(6)。以扫描式电子显微镜(scanning electron microscope、SEM)对固化物(1)-(4)进行观察,未发现由该固化物(1)-(4)所形成的孔柱具有任何气泡及缝隙。接着,测量固化物(1)-(6)的玻璃态转化温度(Tg)、介电常数(dielectric constant、Dk)、及耗散因子(dissipation factor、Df),并对该等固化物(1)-(6)进行钻孔性评估(评估方式为以机械方式对固化物进行钻孔,未发生掉落或破裂的状况视为通过),结果如表1所示。
表1
固化物(1) | 固化物(2) | 固化物(3) | 固化物(4) | 固化物(5) | 固化物(6) | |
玻璃态转化温度(℃) | 180 | 200 | 211 | 223 | 240 | 150 |
介电常数 | 2.72 | 2.81 | 2.90 | 2.98 | 3.0 | 4.2 |
耗散因子(10GHz) | 0.013 | 0.014 | 0.014 | 0.015 | 0.016 | 0.025 |
钻孔性评估 | 通过 | 通过 | 通过 | 通过 | 未通过 | 通过 |
由表1可得知,在本发明所述组成比例范围内的低介电无溶剂型树脂组合物(1)-(4),由于具有特定的成分及比例,因此由本发明所述的低介电无溶剂型树脂组合物所得的固化物具有较低的介电常数(dielectric constant、Dk)(可介于2.5至2.98之间)、耗散因子(dissipation factor、Df)(可介于0.013至0.015(于10GHz时))、良好的填孔性、以及可钻孔性,因此可进一步应用于印刷电路板的填孔制程(例如共轴孔洞(coaxial via)制程),解决阻抗失配损耗(impedance mismatch loss)的问题。
虽然本发明已以数个实施例揭露如上,然其并非用以限定本发明,任何本领域技术技术人员在不脱离本发明的精神和范围内,应可作任意的更动与润饰,因此本发明的保护范围以应所附权利要求书所界定的范围为准。
Claims (11)
1.一种低介电无溶剂型树脂组合物,包括:
(a)20-50重量份的具有式(I)所示结构的共聚物
其中,i、j、k、l、及m分别为1至10;
(b)50-80重量份的具有式(II)所示结构的化合物
(c)80-100重量份的硬化剂;以及
(d)70-100重量份的无机填充物。
2.如权利要求1所述的低介电无溶剂型树脂组合物,其中该具有式(I)所示结构的共聚物的重均分子量为1000-2000。
3.如权利要求1所述的低介电无溶剂型树脂组合物,其中该具有式(I)所示结构的共聚物的环氧当量为200克/当量至600克/当量。
4.如权利要求1所述的低介电无溶剂型树脂组合物,其中该硬化剂为甲基六氢邻苯二甲酸酐(methyl hexahydrophthalic anhydride)、甲基四氢邻苯二甲酸酐(methyltetrahydrophthalic anhydride)、马来酸酐(maleic anhydride、HA)、苯乙烯-共聚-马来酸酐(polystyrene-co-maleic anhydride、SMA)、或上述的组合。
5.如权利要求1所述的低介电无溶剂型树脂组合物,其中该无机填充物为二氧化硅、硫酸钡、碳酸钙、或上述的组合。
6.如权利要求1所述的低介电无溶剂型树脂组合物,其中(a)具有式(I)所示结构的共聚物及(b)具有式(II)所示结构的化合物的总重为100重量份。
7.如权利要求1所述的低介电无溶剂型树脂组合物,还包含:
(e)1-60重量份的添加剂。
8.如权利要求7所述的低介电无溶剂型树脂组合物,其中该添加剂系催化剂、平坦剂、色料、消泡剂、耐燃剂、或上述的组合。
9.如权利要求1所述的低介电无溶剂型树脂组合物,其中该组合物不包含溶剂。
10.如权利要求1所述的低介电无溶剂型树脂组合物,其中该低介电无溶剂型树脂组合物的固化物具有2.5至2.98的介电常数(dielectric constant、Dk),以及于10GHz时具有0.013至0.015的耗散因子(dissipation factor、Df)。
11.一种基板结构,包含:
基板,其中该基板具有至少一个孔洞;以及
填充材料,填入该孔洞中,其中该填充材料为权利要求1所述的低介电无溶剂型树脂组合物的固化物。
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