CN100473253C - 印刷线路板用半固化片及覆铜层叠板 - Google Patents
印刷线路板用半固化片及覆铜层叠板 Download PDFInfo
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Abstract
一种印刷线路板用半固化片,其特征在于:采用一种溴化环氧树脂,其用红外吸收分光光度计进行测定,其红外线吸收频谱中波数2100~2300cm-1的峰值强度为1600cm-1左右的苯环C=C化合的峰值强度的5%以下,且还采用一种溴化环氧树脂,该溴化环氧树脂的固化物在差示扫描型热量分析计内的转折点为120~150℃,从而可得到一种印刷线路板材料的吸湿性、耐热性及抗污性良好的印刷线路板用半固化片以及采用了该半固化片的覆铜层叠板。
Description
技术领域
本发明涉及一种印刷线路板材料,即吸湿性、耐热性及抗污性良好的印刷线路板用半固化片以及采用了该半固化片的覆铜层叠板。
背景技术
用于制造印刷线路板等的半固化片的生产方法为:首先,将以环氧树脂等热固性树脂为主要成份的树脂组成物作为清漆,使其浸渍到玻璃丝网等基体材料内并使其干燥,从而达到半固化状态(B-级)。这里,上述的树脂组成物从未固体树脂变为半固化树脂。以规定尺寸对该半固化片进行切断,然后,按所需的个数来叠合,并在其单面或双面上叠合铜箔等金属箔,对其进行加热加压,从而层叠成型,由此来制造出用于制造印刷线路板的覆有金属箔的层叠板。在该阶段中,半固化树脂将变为固化树脂,并与基体材料一起形成绝缘层。然后,在该绝缘层中钻孔并进行镀覆,由此形成通孔等,并在绝缘层的单面或双面金属箔上,通过降减法等来形成外层电路,从而制造出印刷线路板。
此外,对在预先形成有内层电路图形的内层用基片的单面或双面上按上述方法制成的半固化片,按规定的尺寸进行切断,然后,按所需的个数来叠合,并在其单面或双面上叠合铜箔等金属箔,对其进行加热加压,从而层叠成型,由此来制造出用于制造多层印刷线路板的多层线路板。与上述同样,在该阶段中,半固化片中的半固化树脂将变为固化树脂,并与基体材料一起形成绝缘层。然后,在该绝缘层中钻孔并进行镀覆,由此形成通孔等,并在绝缘层的单面或双面MP金属箔上,通过降减法等来形成外层电路,从而制造出多层线路板。
发明内容
作为用于制造采用难燃性溴化环氧树脂的半固化片的固化剂,一般主要以双氰胺固化系为主,但在要求低吸湿高耐热这一可靠性的领域中,多采用酚系化合物固化系。对采用酚系化合物固化系而成的半固化片而言,存在着尽管固化物可以固化,但抗污性不佳的质量课题。
在本发明中,将固化物在差示扫描型热量分析计(Differential Scanning Calorimeter:以下称DSC)内的转折点(即玻璃转移温度:以下称Tg)设为120~150℃,由此可解决抗污性的质量课题。
本发明鉴于上述课题,其目的在于,提供一种吸湿性、耐热性及抗污性良好的半固化片、以及采用该半固化片来加热成型的覆铜层叠板。
本发明中权利要求1的发明,是一种印刷线路板用半固化片,其特征在于:采用由红外吸收分光光度计进行测定,其红外线吸收频谱中波数2100~2300cm-1的峰值强度为最接近1600cm-1的苯环C=C化合的峰值强度的5%以下的溴化环氧树脂,且该溴化环氧树脂的固化物在差示扫描型热量分析计内的转折点为120~150℃。
权利要求2的发明,是一种印刷线路板用半固化片,是使上述溴化环氧树脂浸渍于基体材料并干燥,并用固化剂来使其半固化而成的半固化片,其特征在于:对该固化剂而言,采用一种酚系固化剂,该固化剂的分子内平均含有二个以上的与环氧树脂具有反应性的酚性羟基。
权利要求2涉及的环氧树脂组成物以下列物质作为必要成分:即,其分子内平均含有1.8个以上3个以下的与环氧树脂具有反应性的酚性羟基,且具有平均0.8个以上的磷元素的磷化合物;平均粒子直径为30μm以下的无机充填剂;分子内具有平均1.8个以上2.6个以下的环氧基的双官能团环氧树脂;固化剂,其中,双官能团环氧树脂的配合量为环氧树脂整体的51质量%以上,采用分子内具有平均3个以上酚性羟基的多官能团酚系化合物,来作为固化剂,而且磷化合物的酚性羟基当量a与双官能团环氧树脂的环氧基当量c之比a/c为0.3以上0.75以下。
权利要求3的发明是一种印刷线路板用半固化片,其特征在于:作为权利要求2所述的固化剂,采用一种双官能团成分为15%~30%的酚醛树脂。
权利要求4的发明是一种印刷线路板用半固化片,其特征在于:作为权利要求1、2或3所述的溴化环氧树脂,采用一种环氧当量为300~500g/eq的溴化环氧树脂。
权利要求5的发明是一种覆铜层叠板,其特征在于:所述层叠板通过堆叠若干片根据权利要求1、2、3或4所述的印刷线路板至铜箔上,并加热层压成型而成。
具体实施方式
以下对本发明的实施方式作以说明。
对本发明中所用的溴化环氧树脂而言,只要符合以下条件即可,即:用红外吸收分光光度计进行测定,其红外线吸收频谱中波数2100~2300cm-1的峰值强度为1600cm-1左右的苯环C=C化合的峰值强度的5%以下,且该溴化环氧树脂的固化物在差示扫描型热量分析计内的转折点为120~150℃,这种树脂包括:溴化双酚型环氧树脂、溴化甲醛型环氧树脂、溴化双酚F型环氧树脂、溴化酚醛型环氧树脂、溴化双环戊二烯型环氧树脂等环氧树脂,而且采用由红外吸收分光光度计进行测定,其红外线吸收频谱中波数2100~2300cm-1的峰值强度为1600cm-1左右的苯环C=C化合的峰值强度的5%以下,且该溴化环氧树脂的固化物在差示扫描型热量分析计内的转折点为120~150℃,对这类树脂,可举出比如下述实施例所示的溴化环氧树脂,对这些树脂,可以单独使用一种,也可以混合二种以上来使用。
为达到该溴化环氧树脂固化物的Tg与抗污性的平衡,溴化环氧树脂的环氧当量最好为300~500g/eq。
除了溴化环氧树脂之外,在不损害本发明效果的范围内,也可以采用非溴化环氧树脂。对该非溴化环氧树脂而言,可以举出比如双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、乙内酰脲型环氧树脂、脂环族环氧树脂、联苯型环氧树脂、甲酚醛型环氧树脂、双环戊二烯型环氧树脂等,也可以同时采用二种以上。
在本发明中,作为固化剂,可例举出含有二个以上酚性羟基的酚醛、双酚A酚醛、甲醛等酚系固化剂。此外,为提高覆铜层叠板的成型性,作为固化剂,最好采用双官能团成分为15%以上30%以下的酚醛树脂。此外,溴化环氧树脂的环氧基与酚性羟基的当量比如果是1:1.2~1:0.7,则该溴化环氧树脂固化物的玻璃转移温度及峰值强度等性能的平衡便更好。此外,作为本发明中所用的固化剂,可举出甲醛及双氰胺。
以下,对半固化片的制造作以说明。
为促进固化剂及固化反应,在上述树脂中添加固化促进剂(比如咪唑类),并通过混合搅拌等,使其均匀混合,由此制成树脂组成物。
使所得到的环氧树脂组成物在基体材料中浸渍并干燥,从而制成半固化片。对于使环氧树脂组成物在基体材料中浸渍并干燥的方法没有特别限制,可以采用以下方法:在使基体材料在比如环氧树脂清漆中浸渍后,进行加热并除去溶剂,从而使环氧树脂组成物半固化,由此制成半固化片。
作为基体材料,可举出玻璃丝布、粗纺布、聚酯布、玻璃无纺布、粗纺无纺布、聚酯无纺布、浆纸、棉绒纸等。此外,如果采用玻璃丝布,则层叠板的难燃性将会极佳。
使基体材料浸渍到树脂组成物内的树脂清漆的制作可以采用以下方法:在环氧树脂组成物中采用丁酮(MEK)、甲氧基丙醇(MP)等溶剂。
如此制作出的半固化片的成型品具有低吸湿、高耐热、抗污性良好的质量。
在利用所得到的半固化片来制造覆金属箔层叠板的过程中,使规定数量的该半固化片与金属箔相叠合,用作被压体,并对该被压体进行加热及加压,从而制成覆金属箔层叠板。作为金属箔,可采用铜箔及铝箔等,其厚度一般为0.012~0.070mm。此外,采用铜箔可得到电力特性良好的层叠板。
实施例
以下,通过实施例及比较例,对本发明作具体说明。
实施例1~10,比较例1~5
采用下述化合物,并按表1的比例值,来进行了实施例1~10及比较例1~5的操作。其值均为固体重量比。
对树脂而言,采用了以下树脂:溴化环氧树脂(东都化成公司生产的「YDB-500」:环氧当量500g/eq,大宇化学公司生产的「DER530」:环氧当量430g/eq,大宇化学公司生产的「DER539」:环氧当量450g/eq,长春人造公司生产的「BEB530」:环氧当量438g/eq,长春人造公司生产的「BET539」:环氧当量448g/eq,SHELL公司生产的「EPON-1123」:环氧当量432g/eq,Vantico公司生产的「LZ8008」:环氧当量435g/eq,WUXI DIC EPOXY公司生产的「Epiclon1320」:环氧当量430g/eq,大日本油墨化学工业公司生产的「Epiclon153」:环氧当量400g/eq),甲醛型环氧树脂(大日本油墨化学工业公司生产「N-690」:环氧当量225g/eq),双环戊二烯型环氧树脂(大日本油墨化学工业公司生产「HP-7200H」:环氧当量283g/eq),三官能团环氧树脂(三井化学公司生产「VF2802」:环氧当量380g/eq)。
对固化剂而言,采用了以下固化剂:双酚A型酚醛(大日本油墨化学工业公司生产「VH4170」:双官能团成分25%,羟基当量118),甲醛(大日本油墨化学工业公司生产「KA-163」:双官能团成分5%,羟基当量118),双氰胺(分子量84,理论活性氢当量21)。
作为固化促进剂,采用了咪唑(2E4MZ,四国化成公司生产)。
作为溶剂,采用了丁酮(MEK)及甲氧基丙醇(MP)。
基体材料中所浸渍的树脂清漆按以下方法来制作。
对环氧树脂及固化剂进行定量计量,并投入到MEK及MP中。用(调节MEK及MP的量,从而达到70质量%)的分散机进行二个小时的搅拌。
作为基体材料,采用玻璃丝布(日东纺织者公司生产7628型丝布),并在室温下,使该玻璃丝布浸渍按上述调整的树脂组成物的清漆,然后,用非接触型加热装置,以大约130~170℃的温度来加热,由此使装置中的溶剂干燥并除去,从而使树脂组成物半固化,由此而制成半固化片。
树脂量调整成:100重量份玻璃丝布配用100重量份树脂。
用FT-IR(日本分光公司生产FT/IR-350),来测定按上述方法制成的半固化片(340mm×510mm)的树脂部分的红外线吸收频谱,并确认红外线吸收频谱中波数2100~2300cm-1的峰值强度是否为1600cm-1左右的苯环C=C化合的峰值强度的5%以下。其结果如表1所示。
将8片按上述方法制作的半固化片(340mm×510mm)进行层叠,并在其两面进行层叠,从而使铜箔(厚度为18μ,GT箔,古河电路箔公司生产)的粗面成为半固化片侧,并在180℃、2.94MPa的压力下加热加压90分钟,从而层叠成型,由此制作出覆铜层叠板。在制作出覆铜层叠板后,通过蚀刻来除去铜箔,并进行固化后树脂的DSC(井户电子工业公司生产DSC-220C)分析,其结果如表1所示。
对上述获得的半固化片,进行了以下所示的物理性能评估。其结果如表1所示。
(1)成型性
用上述的印刷线路板用半固化片制造方法,来制作融化粘度不同的半固化片,将8片按上述方法制作的半固化片(340mm×510mm)进行层叠,并在其两面进行层叠,从而使铜箔(厚度为18μ,GT箔,古河电路箔公司生产)的粗面成为半固化片侧,并在180℃、2.94MPa的压力下加热加压90分钟,从而层叠成型,由此制作出覆铜层叠板。在制作出覆铜层叠板后,通过蚀刻来除去铜箔,并观察有无孔隙及缺陷。用「○」来表示无孔隙及缺陷的板材,用「×」来表示有孔隙及缺陷的板材。
在较大的融熔范围内没有孔隙及缺陷的板材,是成型性良好的板材。
按下列方法来测定融熔粘度。
将上述制作的半固化片加工成粉末(为除去玻璃纤维等异物,采用60目筛滤器),并利用造粒挤压机来制成粒状。采用高融化式流量试验仪(岛津制作所生产CTF-100),对该颗粒进行了融熔粘度测定。测定条件为:温度130±0.2℃,喷口:0.5φ×10mm,负重:20kg/cm2,搅杆面积:1.0cm2,预加热:30秒。
(2)基于TGA的热分解温度测定
将8片按上述方法制作的半固化片(340mm×510mm)进行层叠,并在其两面进行层叠,从而使铜箔(厚度为18μ,GT箔,古河电路箔公司生产)的粗面成为半固化片侧,并在180℃、2.94MPa的压力下加热加压90分钟,从而层叠成型,由此制作出覆铜层叠板。在制作出覆铜层叠板后,通过蚀刻来除去铜箔,并进行固化树脂的TGA(岛津制作所生产TGA50/50H)分析,且测定了5%减重条件下的温度。
(3)吸收性
将8片按上述方法制作的半固化片(340mm×510mm)进行层叠,并在其两面进行层叠,从而使铜箔(厚度为18μ,GT箔,古河电路箔公司生产)的粗面成为半固化片侧,并在180℃、2.94MPa的压力下加热加压90分钟,从而层叠成型,由此制作出覆铜层叠板。在制作出覆铜层叠板后,通过蚀刻来除去铜箔,并按下列条件来进行了评估。
吸水率条件为:E-1/105+PCT处理(121℃100%90分钟处理)。
(4)耐热性
将8片按上述方法制作的半固化片(340mm×510mm)进行层叠,并在其两面进行层叠,从而使铜箔(厚度为18μ,GT箔,古河电路箔公司生产)的粗面成为半固化片侧,并在180℃、2.94MPa的压力下加热加压90分钟,从而层叠成型,由此制作出覆铜层叠板。按JIS-C6481标准来评估了该层叠板,并将发生膨胀的温度设为大气耐热性温度。
(5)发生膨胀
将8片按上述方法制作的半固化片(340mm×510mm)进行层叠,并在其两面进行层叠,从而使铜箔(厚度为18μ,GT箔,古河电路箔公司生产)的粗面成为半固化片侧,并在180℃、2.94MPa的压力下加热加压90分钟,从而层叠成型,由此制作出覆铜层叠板。按IPC-TM-650标准来评估了该层叠板,并将发生膨胀的时间设为T-288小时。
(6)抗污性
将8片按上述方法制作的半固化片(340mm×510mm)进行层叠,并在其两面进行层叠,从而使铜箔(厚度为18μ,GT箔,古河电路箔公司生产)的粗面成为半固化片侧,并在180℃、2.94MPa的压力下加热加压90分钟,从而层叠成型,由此制作出覆铜层叠板。在制作出覆铜层叠板后,通过蚀刻来除去铜箔,并按10cm角来切断,且将抗污性处理前后的重量变化作为抗污性指标(mg/dm2)。
按下列条件来进行了评估。
在抗污性处理前,在120℃温度下风干一小时,并测定初始重量,然后利用标示剂公司生产的抗污性液,进行膨润工序(示踪剂9204)35℃三分钟处理~过锰酸工序(示踪剂9275)75℃七分钟处理~中和工序(示踪剂9279)43℃五分钟处理,且进行了120℃一小时风干,并进行了处理后的重量测定。
如表1所示,根据本发明,作为印刷线路板材料,可获得一种采用吸湿性、耐热性及抗污性良好的印刷线路板用半固化片以及采用了该半固化片的覆铜层叠板。
Claims (5)
1.一种印刷线路板用半固化片,其特征在于:采用由红外吸收分光光度计进行测定,其红外线吸收频谱中波数2100~2300cm-1的峰值强度为最接近1600cm-1的苯环C=C化合的峰值强度的5%以下的溴化环氧树脂,且该溴化环氧树脂的固化物在差示扫描型热量分析计内的转折点为120~150℃。
2.根据权利要求1所述的印刷线路板用半固化片,其特征在于:所述半固化片是使所述溴化环氧树脂浸渍于基体材料并干燥,并用固化剂来使其半固化而成,对该固化剂而言,采用一种酚系固化剂,该固化剂的分子内平均含有二个以上的与环氧树脂具有反应性的酚性羟基。
3.根据权利要求2所述的印刷线路板用半固化片,其特征在于:所述的固化剂,采用双官能团成分为15%~30%的酚醛树脂。
4.根据权利要求1、2或3所述的印刷线路板用半固化片,其特征在于:所述的溴化环氧树脂,采用环氧当量为300~500g/eq的溴化环氧树脂。
5.一种覆铜层叠板,其特征在于:所述覆铜层叠板通过堆叠若干片根据权利要求1、2、3或4所述的半固化片至铜箔上,并加热层压成型而成。
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AU608627B2 (en) * | 1987-08-10 | 1991-04-11 | Dow Chemical Company, The | Curing agent compositions, laminating varnishes containing same and laminates prepared therefrom |
US4868059A (en) * | 1987-11-16 | 1989-09-19 | The Dow Chemical Company | Curable composition containing a difunctional epoxy resin, a polyfunctional epoxy resin, a difunctional phenol and a polyfunctional phenol |
JPH0780994A (ja) * | 1993-09-10 | 1995-03-28 | Toshiba Chem Corp | 銅張積層板 |
JPH0812858A (ja) * | 1994-06-28 | 1996-01-16 | Matsushita Electric Works Ltd | エポキシ樹脂組成物、このエポキシ樹脂組成物を用いたプリプレグ、及びこのプリプレグを用いた積層板 |
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