CN1764350A - 树脂掩膜层的除去方法和带焊锡突起的基板的制造方法 - Google Patents
树脂掩膜层的除去方法和带焊锡突起的基板的制造方法 Download PDFInfo
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- CN1764350A CN1764350A CNA2005101135083A CN200510113508A CN1764350A CN 1764350 A CN1764350 A CN 1764350A CN A2005101135083 A CNA2005101135083 A CN A2005101135083A CN 200510113508 A CN200510113508 A CN 200510113508A CN 1764350 A CN1764350 A CN 1764350A
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Abstract
本发明提供一种树脂掩膜层的除去方法,在使用作为感光性树脂的干膜抗蚀剂层在电极周围形成树脂掩膜层的基板上,涂布析出型焊锡组合物,接着对该析出型焊锡组合物进行加热处理,在上述电极表面上析出焊锡之后,除去上述树脂掩膜层,此时使用从二醇醚类和氨基醇类中选择的至少1种,除去加热处理后的树脂掩膜层。这样,不给基板的焊料抗蚀剂和焊锡突起造成损伤,能够在短时间内简单除去加热处理后的树脂掩膜层。
Description
技术领域
本发明涉及在使用析出型焊锡组合物在电子回路基板上表面安装电子构件时,除去使用树脂掩膜法形成焊锡特别是形成焊锡突起情况下的树脂掩膜层的方法以及带焊锡突起的基板的制造方法。
背景技术
近年来,伴随着电子仪器的小型轻量化,电子构件的多插头窄间距化也在进展中,对于导体图案,且在狭窄范围内以极小间隔形成多个导体的细距化也在进展中。因此,为了使电子回路基板与电子构件接合,正广泛采用使用焊锡突起的安装方法来代替以往的引线接合法。另外,在布线的设计方面,也广泛采用在基板上设计通孔的所谓在焊盘上的通孔(via on焊盘)。
作为形成焊锡突起的方法,通常采用的是使用混合了焊锡粉末和助熔剂的钎焊膏的树脂掩膜法。即,以往的树脂掩膜法是在设置了电极的基板上形成树脂膜,通过显影处理形成使电极部露出的开口部。接着,用钎焊膏填充上述开口部,通过加热处理使钎焊膏熔融形成焊锡突起。接着,最终除去树脂掩膜层。
但是,在上述树脂掩膜法中,由于为了形成焊锡突起而进行加热处理(通常为200℃以上),所以通过该加热处理也提高树脂掩膜层的耐剥离性,为此难以完全除去树脂掩膜层。另一方面,如果树脂掩膜层残存于基板上,有可能给其后的电子构件的安装带来坏影响。
另外,作为抗蚀剂的剥离剂,通常使用强碱性溶液,当在这样的强碱性溶液中浸渍基板时,基板的焊料抗蚀剂和焊锡突起有受到损伤的可能性。所以,也有可能在其后的焊锡连接可靠性方面产生问题。
作为树脂掩膜层的除去方法,在特开平7-288372号公报中记载有作为碱可溶型抗蚀剂的剥离剂使用有机碱溶液,特别是使用单乙醇胺。在特开平6-250403号公报中记载有:作为通过水溶性抗蚀剂在基板上形成的镀敷抗蚀剂的剥离液,使用含有三乙醇胺的强碱性水溶液。但是,对于在这些公报中记载的抗蚀剂剥离,在剥离工序前没有进行高加热处理。所以认为抗蚀剂剥离也比较容易。
发明内容
本发明的课题是,提供不对基板的焊料抗蚀剂和焊锡造成损伤并可以在短时间内简单除去被加热处理的树脂掩膜层的树脂掩膜层的除去方法、以及电路基板的制造方法。
本发明人等为了解决上述课题而进行了潜心研究。结果发现了如下所示的新观点,即,在通过树脂掩膜法在电极上形成焊锡的情况下,当使用二醇醚类或氨基醇类除去加热处理后的树脂掩膜层时,可以在短时间内简单除去因加热处理而难以剥离的树脂掩膜层,而且给基板的焊料抗蚀剂或焊锡突起造成的损伤少,所以,可以提高焊锡连接可靠性。
即,本发明中的树脂掩膜层的除去方法包括:使用干膜抗蚀剂层在从形成于基板表面的绝缘层的开口部露出的电极的周围形成树脂掩膜层的工序;在上述基板上涂布析出型焊锡组合物的工序;加热处理该析出型焊锡组合物而在上述电极表面析出焊锡的工序;和除去上述树脂掩膜层的工序。加热处理后的上述树脂掩膜层的除去可以使用从二醇醚类和氨基醇类中选择的至少1种进行。
进而,本发明中的带焊锡突起的基板的制造方法包括:使用干膜抗蚀剂层在基板表面的电极周围形成树脂掩膜层的工序;在上述基板上涂布析出型焊锡组合物的工序;加热处理该析出型焊锡组合物而在上述电极表面析出焊锡突起的工序;和使用从二醇醚类和氨基醇类中选择的至少1种除去加热处理后的上述树脂掩膜层的工序。
本发明方法在上述加热处理的温度为200℃以上时特别有效。另外,当基板的绝缘层中的至少1个具有比上述加热处理的温度高的玻璃化温度时,由于加热处理中的基板形状被固定,所以特别有效。
通过本发明,当借助树脂掩膜法在电极上析出焊锡时,可以用更少的工序简单地形成树脂掩膜,而且也可以在短时间内简单除去加热处理后的树脂掩膜层,并且给基板的焊料抗蚀剂或焊锡造成的损伤少,因而具有可以提高焊锡连接可靠性的效果。
通过以下说明可以明确本发明的其它目的和优点。
附图说明
图1是表示本发明方法的一个实施方式的简要工序示意图。
具体实施方式
下面,参照附图对本发明进行说明。图1是表示本发明的一个实施方式中的树脂掩膜层的除去方法的简要示意图。如图1(a)所示,在基板1的表面上形成焊料抗蚀剂膜3(绝缘层),从在该焊料抗蚀剂膜3上形成的开口部露出电极2。在该基板1的表面上,除了电极2的部分以外,还形成树脂掩膜层4(即坝堰:dam)。接着,如图1(b)所示,在基板1的表面上涂布析出型焊锡组合物5,加热,如图1(c)所示,使焊锡在上述电极2的表面上析出,形成焊锡突起6。接着,如图1(d)所示,除去树脂掩膜层4,如图1(e)所示,根据需要,进行修平(flattening)。
电极2在基板1的表面上以规定的间距露出。在焊料抗蚀剂膜3上使用环氧系、丙烯酸系、聚酰亚胺系等树脂,优选环氧系树脂。
从形成均匀膜厚的观点出发,在形成树脂掩膜层4的树脂材料中,优选使用薄膜状的感光性树脂,更优选干膜抗蚀剂。为了通过析出焊锡制作突起,从焊锡析出量的观点出发最好是具有10μm以上、优选30μm以上的厚度的感光性树脂层的干膜抗蚀剂层。还有,感光性树脂层的厚度最好为300μm以下、优选150μm以下,如果厚度超过300μm,则难以使其固化到感光性树脂层的底部。
干膜抗蚀剂层是指在支撑薄膜(carrier film)上层叠感光性树脂并在该感光性树脂层的表面(即,与支撑薄膜相反侧的面)上设置保护薄膜(cover film)而成的3层感光性树脂层叠体。
在本发明中使用的干膜抗蚀剂层,优选具有含特定的配合比而成的感光性树脂作为感光性树脂层。
下面对适合在本发明中使用的感光性树脂进行说明。
本发明中的感光性树脂优选含有:(A1)重均分子量为4万~9万的含有羧基的碱溶性高分子15~35质量%、(A2))重均分子量为10万~15万的含有羧基的碱溶性高分子15~35质量%、(B)加聚性单体15~60质量%、(C)光聚合引发剂0.01~10质量%以及(D)重均分子量为1000~3000的聚环氧丙烷7~30质量%。
从挠性的观点出发,(A1)、(A2)成分的碱溶性高分子优选乙烯基共聚物。进而,从显影性的观点出发,优选含羧基的乙烯基共聚物。在这里,含羧基的乙烯基共聚物是指使从α,β-不饱和羧酸中选择的至少1种的第1单体,与从(甲基)丙烯酸烷基酯、(甲基)丙烯酸羟基烷基酯、(甲基)丙烯酰胺与其氮上的氢被烷基或烷氧基取代的化合物、苯乙烯和苯乙烯衍生物、(甲基)丙烯腈以及(甲基)丙烯酸缩水甘油酯中选择的至少1种的第2单体进行乙烯共聚合得到的化合物。还有,“(甲基)丙烯酸酯”是指甲基丙烯酸酯或丙烯酸酯。
作为在含羧基的乙烯基共聚物中使用的第1单体,可以举出丙烯酸、甲基丙烯酸、富马酸、肉桂酸、巴豆酸、衣康酸、马来酸半酯等,可以分别单独使用,也可以2种以上组合使用。
在含羧基的乙烯基共聚物中的第1单体的比例优选为15~40质量%,更优选为20~35质量%。为了保持碱显影性,第1单体的比例优选为15质量%以上,从含羧基的乙烯基共聚物的溶解度的观点出发,优选为40质量%以下。
作为在含羧基的乙烯基共聚物中使用的第2单体,可以举出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸2-羟丙酯、(甲基)丙烯酸4-羟丁酯、多乙二醇单(甲基)丙烯酸酯、多丙二醇单(甲基)丙烯酸酯、(甲基)丙烯酰胺、N-羟甲基丙烯酰胺、N-丁氧基甲基丙烯酰胺、苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、对氯苯乙烯、(甲基)丙烯腈、(甲基)丙烯酸缩水甘油酯等,可以分别单独使用,也可以组合2种以上。
在含羧基的乙烯基共聚物中的第2单体的比例优选为60~85质量%,更优选为65~80质量%。
从剥离性和焊锡耐性的平衡的观点出发,含羧基的乙烯基共聚物优选使用具有不同的重均分子量的。进而,感光性树脂优选以感光性树脂总质量基准使用(Al)重均分子量为4万~9万的含有羧基的碱溶性高分子15~35质量%、以感光性树脂总质量基准使用(A2)重均分子量为10万~15万的含有羧基的碱溶性高分子15~35质量%。
(B)成分可以使用公知的加聚性单体。例如可以组合多亚氧烷基单(甲基)丙烯酸酯、多亚氧烷基二(甲基)丙烯酸酯、双酚A亚氧烷基改性二丙烯酸酯、多元醇的亚氧乙基改性多(甲基)丙烯酸酯等1种或2种以上进行使用。配合量以感光性树脂的总质量基准优选为15~60质量%,更优选为20~50质量%。为了使感光性树脂层充分固化并维持作为抗蚀剂的强度,上述含有量优选为15质量%以上。另外,为了防止固化后的裂缝,上述加聚性单体的总含量优选为60质量%以下。
每100g感光性树脂的加聚性双键浓度DT从树脂掩膜的粘附性的观点出发优选为0.07以上,从树脂掩膜的分辨力的观点出发优选为0.12以下,更优选为0.08~0.11。即,优选将每100g感光性树脂的加聚性双键浓度DT为0.07~0.12的感光性树脂层叠于支撑薄膜上,使用在该感光性树脂层的表面上设置保护薄膜而成的干膜抗蚀剂层形成树脂掩膜层。
通过以下计算式得到上述双键浓度DT。
1.对于在感光性树脂中含有加聚性单体[1]为W1的情况,计算双键浓度D1。
D1=(d1/M1) ·····(计算式a)
D1:加聚性单体[1]的双键浓度
d1:具有1个分子加聚性单体[1]的加聚性双键的数目
M1:加聚性单体[1]的数均分子量
例如,关于三乙氧基羟甲基丙烷三丙烯酸酯的双键浓度D,可以以如下所示的方式进行计算。
D=(3/428)=0.00701
2.即使是加聚性单体[2]、[3]、···,也用与计算式a相同的方法分别计算双键浓度D2、D3、···,通过计算式b计算每100g感光性树脂的双键浓度DT。
DT=(D1×W1+D2×W2+D3×W3··)×(100/WT)
···(计算式b)
DT:每100g感光性树脂的双键浓度
W1:感光性树脂中的加聚性单体[1]的质量(g)
W2:感光性树脂中的加聚性单体[2]的质量(g)
W3:感光性树脂中的加聚性单体[3]的质量(g)
WT:感光性树脂的总质量(g)
(C)成分可以使用公知的光聚合引发剂。可以使用二苯甲酮衍生物、苄基缩酮(べンジルケタ一ル)衍生物、噻吨酮衍生物、芳基咪唑衍生物等。从粘附性观点出发,优选2-(邻氯苯基)-4,5-二苯基咪唑二聚体。光聚合引发剂的含量以感光性树脂的总质量基准优选含有0.01~20质量%,更优选1~10质量%。即,为了得到充分的灵敏度,优选为0.01质量%以上,为了使感光性树脂层的底的部分充分固化,优选为20质量%以下。
从剥离性观点出发,本发明中的感光性树脂优选含有重均分子量为1000~3000的聚环氧丙烷作为(D)成分。进而,从剥离性和树脂掩膜的分辨力的观点出发,特别优选含有重均分子量为1500~2500的聚环氧丙烷。从剥离性和分辨力的观点出发,(D)成分优选以感光性树脂的总质量基准含有7~30质量%。
为了使用上述干膜抗蚀剂层形成树脂掩膜层,首先从干膜抗蚀剂层剥离保护薄膜,将感光性树脂层压接于上述基板1的表面。接着,在除了电极2的部分以外的感光性树脂层的表面上叠加掩膜。接着,使电极2的部分曝光,剥离支撑薄膜之后,用Na2CO3水溶液等进行显影,由此可以形成在电极2的部分具有开口部的树脂掩膜层4。由于开口部的内径和间距被使用的电极2的大小或个数来决定,所以没有特别限定。
树脂掩膜层4的厚度可以比形成的焊锡突起6的高度高,也可以比其低。具体地说,焊锡突起6的高度相对于树脂掩膜层4的厚度和焊料抗蚀剂膜3的厚度加起来的总厚度为其0.05~3倍,优选为0.1~1.5倍。通常树脂掩膜层4的厚度约为10~300μm,优选为约30~150μm。
作为析出型焊锡组合物5,例如可以举出(a)含有锡粉末和铅、铜、银等的金属盐的析出型焊锡组合物,或者(b)含有从锡粉末和银离子以及铜离子中选择的至少1种与从芳基膦类、烷基膦类以及吡咯类中选择的至少1种的络合物的析出型焊锡组合物。上述(a)的金属盐和(b)的络合物也可以混合使用。在本发明中,特别优选使用不含铅的无铅析出型焊锡组合物。还有,当称为锡粉末时,除了包括金属锡粉末以外,还包括例如含银的锡-银系锡合金粉末、或含铜的锡-铜系锡合金粉末等。作为上述金属盐,可以举出有机羧酸盐、有机次磺酸盐等。
上述组合物中的上述锡粉末与上述金属的盐或络合物的比率(锡粉末的重量:金属的盐或络合物的重量)可以为99∶1~50∶50左右,优选为97∶3~60∶40左右。还有,在本发明中,与金属的盐相比,更优选使用金属的络合物。
在上述组合物中,除了上述成分以外,还可以混合助熔剂成分或溶剂。作为助熔剂成分,通常可以使用用于锡-铅系、锡-银系、锡-铜系等焊锡材料的助熔剂成分,作为溶剂,只要能够溶解组合物中的其它成分并调整粘度或浓度就没有特别限定。
上述焊锡组合物5向基板1上的涂布可以为全涂,或者也可以使用用金属掩膜和刮浆板的涂布方法(用模板印刷)。焊锡组合物5的涂布量可以根据形成的焊锡突起6的大小或高低适当决定。具体地说,只要将涂布量决定为使析出的焊锡合金成为需要的量即可。
在涂布后,用规定的温度加热,使锡焊合金析出。此时,生成的焊锡合金与构成电极2的铜之间的润湿性高,所以在该电极2的表面上选择性地附着而形成焊锡突起6。特别是在使用上述络合物时,有提高电极2向表面的选择性的趋势。因而,在加热后,自然冷却基板1,用溶剂等冲走残存的合金成分等,由此可以防止在电极2以外残留焊锡合金。
如果考虑电路基板的耐热性等,加热温度可以为200℃以上,优选为200~260℃左右。另外,根据组合物的组成等决定加热时间,通常可以为30秒~10分钟左右,优选为1分钟~5分钟左右。可以将焊锡合金的析出处理(涂布和加热处理)分为2次或2次以上进行。加热后,自然冷却基板1,为了不在电极2以外残留焊锡合金,用溶剂等冲走残存的合金成分等。
加热处理后,剥离除去树脂掩膜层4。为此,在本发明中,作为剥离液,使用从二醇醚类和氨基醇类中选择的至少1种溶剂。作为二醇醚类,例如可以举出二醇的单醚类、二醇的二醚类、二醇单醚的酯类等。其中,优选二醇的单醚类,特别优选二甘醇的单醚类(卡必醇类)。
作为上述二醇的单醚类,例如可以举出乙二醇单甲醚(甲基溶纤剂)、乙二醇单***(溶纤剂)、乙二醇单异丙醚(异丙基溶纤剂)、乙二醇单正丁醚(丁基溶纤剂)、乙二醇单异丁醚(异丁基溶纤剂)、乙二醇单叔丁醚(叔丁基溶纤剂)、乙二醇单己醚(己基溶纤剂)、二甘醇单甲醚(甲基卡必醇)、二甘醇单***(卡必醇)、二甘醇单异丙醚(异丙基卡必醇)、二甘醇单正丁醚(丁基卡必醇)、二甘醇单异丁醚(异丁基卡必醇)、二甘醇单叔丁醚(叔丁基卡必醇)、二甘醇单己醚(己基卡必醇)、丙二醇单甲醚、丙二醇单***、丙二醇单正丙醚、丙二醇单正丁醚、二丙二醇单甲醚、二丙二醇单***、二丙二醇单正丙醚、二丙二醇单正丁醚、三丙二醇单甲醚、1,3-丁二醇单甲醚(甲氧基丁醇)、3-甲基-甲氧基丁醇(ソルフイツト)等。
作为上述二醇的二醚类,例如可以举出乙二醇二***、二甘醇二甲醚、二甘醇二***、二甘醇二正丁醚、三乙二醇二甲醚、多乙二醇二甲醚、二丙二醇二甲醚等。
作为上述二醇单醚的酯类,例如可以举出乙二醇单***乙酸酯(乙酸溶纤剂)、乙二醇单丁醚乙酸酯(丁基溶纤剂乙酸酯)、二甘醇单***乙酸酯(乙酸卡必醇酯)、二甘醇单丁醚乙酸酯(丁基卡必醇乙酸酯)、丙二醇单甲醚乙酸酯、3-甲基-甲氧基丁基乙酸酯(ソルフイツト乙酸酯)等。
作为氨基醇类(链醇胺类),例如可以举出单乙醇胺(2-乙醇胺、2-氨基乙醇)、二乙醇胺、三乙醇胺、单丙醇胺、二丙醇胺、三丙醇胺、单异丙醇胺、二异丙醇胺、三异丙醇胺、单丁醇胺、二丁醇胺、新戊醇胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N,N-二甲基丙醇胺、N,N-二乙基丙醇胺、N-(β-氨基乙基)乙醇胺、N-甲基乙醇胺、N-甲基二乙醇胺、N-正丁基乙醇胺、N-叔丁基乙醇胺、N-叔丁基二乙醇胺、N,N-二正丁基乙醇胺、N-乙基乙醇胺等,其中,优选使用乙醇胺类,特别优选单乙醇胺。
特别在本发明方法中,优选使用从二醇醚类中选择的至少1种溶剂作为剥离液。这是因为,与氨基醇类相比,二醇醚类给基板的焊料抗蚀剂或焊锡造成的损伤更少。
这些溶剂可以单独使用,或者与其它溶剂例如水、醇等混合使用。当与其它溶剂混合时,从二醇醚类和氨基醇类中选择的至少1种溶剂相对于溶剂总量可以为10质量%以上,优选为15质量%以上。
树脂掩膜层4的除去是通过使利用加热处理形成焊锡突起6的基板1表面的树脂掩膜层4与上述溶剂接触来进行。接触方法包括例如将基板1浸渍于上述溶剂中的浸渍法、将溶剂喷雾于基板1上的喷雾法等。另外,对使用的溶剂的温度没有特别限定,通常可以从1~80℃、优选15~65℃的范围适当选择。另外,除去树脂掩膜层4所需要的时间、即树脂掩膜层4与上述溶剂接触的时间可以约为30秒~2小时,优选为50秒~45分钟。通常处理温度越高则越能够缩短处理时间。
另外,也可以将基板1浸渍于上述溶剂中进行超声波清洗。这样,能够更进一步缩短处理时间。
本发明中的焊锡突起6的高度通常为40~100μm。通过本发明方法,可以以狭窄间距排列该焊锡突起6,也可以对应约80μm左右的间距。
还有,在该实施方式中,举例说明只在一面上设置电极2(布线层)的基板,本发明方法也同样可以应用于在两面上设置了电极(布线层)的基板、或除了在一面或两面以外在内部也设置了电极(布线层)的基板。具体地说,本发明方法除了可以用于多片组件、通过各种封装(package)向电极(导体图案)向表面上的预涂敷的突起的形成,组合(build-up)技术基板向在焊盘上的通孔的预备焊锡、细距突起的形成以外,也可以应用于TCP(Tape Carrier Package)搭载用焊锡预涂敷、QFP(Quad FlatPackage)搭载用大容量预涂敷等。另外,在本发明中所谓的绝缘层中,不只包括基板,也包括焊料抗蚀剂膜。
下面,举出实施例对本发明进行更详细的说明,但本发明不被这些实施例所限定。
实施例
实施例1
(基板)
作为基板,表面被厚10μm的焊料抗蚀剂膜覆盖,使用从形成于该焊料抗蚀剂膜的开口部(直径:80μm)露出焊盘(非电解镍金镀敷电极)的基板。焊盘是以150μm间距形成于基板上。
(干膜抗蚀剂层(a)的作成)
混合以下成分作成感光性树脂溶液。
甲基丙烯酸甲酯65重量%、甲基丙烯酸25重量%、丙烯酸丁酯10
重量%的三元共聚物的甲基乙基甲酮溶液(固体成分浓度34%、重
均分子量8万、酸当量340)······················65g
甲基丙烯酸甲酯65重量%、甲基丙烯酸25重量%、丙烯酸丁酯10
重量%的三元共聚物的甲基乙基甲酮溶液(固体成分浓度34%、重
均分子量12万、酸当量340)·····················88g
三乙氧基羟甲基丙烷丙烯酸酯····················10g
在已加成了平均8摩尔的环氧丙烷的多丙二醇上进一步在两端分别
加成平均3摩尔的环氧乙烷的二醇的二甲基丙烯酸酯····7g
对壬基苯氧基七乙氧基二丙氧基丙烯酸酯················5g
2-(邻氯苯基)-4,5-二苯基咪唑二聚体·················3g
4,4’-双(二乙基氨基)二苯甲酮···················0.14g
金刚石绿·····························0.04g
无色(leuco)结晶紫·························0.5g
多丙二醇(日本油酯(株)制ユニ才一ルD-2000)··10g
对甲苯磺酰胺····························5g
甲基乙基甲酮····························10g
(每100g感光性树脂的加聚性双键浓度DT:0.106)
接着,按照下述步骤生成干膜抗蚀剂层(a)。
使用棒涂机将上述感光性树脂涂布于厚19μm的聚对苯二甲酸乙二醇酯薄膜上,得到支撑薄膜和感光性树脂的层叠体。在90℃下干燥上述层叠体3分钟。涂布感光性树脂并使干燥后的感光性树脂厚度为38μm。在与支撑薄膜相反侧的感光性树脂面上层叠保护薄膜,得到干膜抗蚀剂层(a)。
(树脂掩膜层的制作)
从上述干膜抗蚀剂层(a)剥离保护薄膜,将感光性树脂层压接于上述基板表面,接着,在感光性树脂层的表面上配置掩膜。接着,使各焊盘及其周围曝光,然后剥离支撑薄膜,用Na2CO3水溶液显影,形成在焊盘部分以150μm间距具有内径为130μm的开口部的厚度38μm的树脂掩膜层。
(析出型焊锡组合物)
混炼下述组合物,得到焊锡组合物。
Sn/Pb合金粉末 75质量%
(Sn/Pb=70/30,平均粒径10μm)
环烷酸铅 10质量%
助熔剂 15质量%
使用的助熔剂是混合下述配方的成分,在120℃下使其加热熔融后冷却至室温的产物。
松香树脂 70质量%
己基卡必醇(溶剂) 25质量%
固化蓖麻油(触变剂) 5质量%
(焊锡析出处理)
通过用模板印刷,在上述基板的各开口部填充在上述得到的焊锡组合物。接着,通过在240℃以上加热1分钟,在各焊盘上形成焊锡突起。(树脂掩膜层剥离液的调制)
在室温下使2-乙醇胺溶液(三菱瓦斯化学公司制)17ml和蒸馏水83ml混合,调制剥离液100ml。
(树脂掩膜层的剥离处理)
向200ml烧杯中加入上述调制的剥离液100ml,通过热板加热到约40℃之后,将已形成焊锡突起的上述基板浸渍于剥离液中1~2分钟,除去坝堰。
实施例2
向超声波清洗装置中加入已加热至约60℃的丁基卡必醇1L,与实施例1一样在其中浸渍已形成了焊锡突起的带树脂掩膜层的基板,进行3~5分钟的超声波清洗,除去树脂掩膜层。
实施例3
与实施例1一样,将已形成了焊锡突起的带树脂掩膜层的基板浸渍于20℃的在实施例1得到的剥离液中30分钟,除去树脂掩膜层。
比较例1
将用与实施例1相同的方法得到的已形成了焊锡突起的带树脂掩膜层的基板浸渍于40℃的NaOH水溶液中2分钟,除去树脂掩膜层。
比较例2
将用与实施例1相同的方法得到的已形成了焊锡突起的带树脂掩膜层的基板浸渍于20℃的NaOH水溶液中30分钟,除去树脂掩膜层。
对在各实施例、比较例中得到的焊锡突起,进行如下评价。
(评价方法)
1.焊料抗蚀剂的外观检查和树脂掩膜层残渣的有无
使用显微镜(キ一エンス公司制VH-6300),确认树脂掩膜层在剥离处理前后有无焊料抗蚀剂颜色的变化以及在树脂掩膜层剥离处理后的基板抗蚀剂上有无树脂掩膜层残渣。评价标准如下所示。
焊料抗蚀剂变色:○=无变色、×=有变色
树脂掩膜层残渣:○=无残渣、×=有残渣
2.焊锡突起的外观检查
使用显微镜(キ一エンス公司制VH-6300),确认坝堰剥离处理后的各焊锡突起的形状、光泽。
评价标准:○=表面光滑而且有焊锡光泽的半球状突起
△=在表面上有凹凸不平或者没有焊锡光泽的半球状突
起
×=没有焊锡光泽的扁圆形状突起
3.焊锡突起的焊锡接合性
在坝堰剥离处理后,在焊锡突起上涂布助熔剂,进而在其上搭载焊锡球,在240℃以上加热1分钟之后,通过显微镜确认焊锡球是否与焊锡突起接合。
评价标准:○=接合良好、×=接合不良
将这些试验结果显示于表1。
表1
焊料抗蚀剂变色 | 树脂掩膜层残渣 | 焊锡突起的外观 | 焊锡接合性 | |
实施例1 | ○ | ○ | ○ | ○ |
实施例2 | ○ | ○ | ○ | ○ |
实施例3 | ○ | ○ | ○ | ○ |
比较例1 | × | × | × | × |
比较例2 | × | × | △ | × |
从表1可知:与使用强碱溶液作为剥离液的比较例相比,实施例很少给焊料抗蚀剂或焊锡突起造成损伤,也不会损害焊锡接合性。
Claims (14)
1.一种树脂掩膜层的除去方法,其特征在于,包括:
使用干膜抗蚀剂层在从形成于基板表面的绝缘层的开口部露出的电极的周围形成树脂掩膜层的工序,
在所述基板上涂布析出型焊锡组合物的工序,
对该析出型焊锡组合物进行加热处理并在所述电极表面上析出焊锡的工序,和
除去所述树脂掩膜层的工序;
加热处理后的所述树脂掩膜层的除去,可以使用从二醇醚类和氨基醇类中选择的至少1种进行。
2.根据权利要求1所述的树脂掩膜层的除去方法,其特征在于,
所述加热处理的温度为200℃以上。
3.根据权利要求1所述的树脂掩膜层的除去方法,其特征在于,
在含有从所述二醇醚类和氨基醇类中选择的至少1种的剥离液中,浸渍已形成了所述树脂掩膜层的基板,除去所述树脂掩膜层。
4.根据权利要求1所述的树脂掩膜层的除去方法,其特征在于,
在含有从所述二醇醚类和氨基醇类中选择的至少1种的剥离液中,浸渍已形成了所述树脂掩膜层的基板,进行超声波清洗。
5.根据权利要求1所述的树脂掩膜层的除去方法,其特征在于,
所述二醇醚类为二醇的单醚类,所述氨基醇类为乙醇胺类。
6.根据权利要求1所述的树脂掩膜层的除去方法,其特征在于,
所述干膜抗蚀剂层是在支撑薄膜上按顺序层叠了感光性树脂层和保护薄膜的感光性树脂层叠体。
7.根据权利要求6所述的树脂掩膜层的除去方法,其特征在于,形成所述树脂掩膜层的工序包括:
从所述干膜抗蚀剂层剥下保护薄膜并将感光性树脂层压接于所述基板的表面的工序;
在除了电极的部分之外的感光性树脂层的表面上叠加掩膜的工序;
使电极的部分曝光的工序;和
剥下所述支撑薄膜并用显影液进行显影而形成在电极的部分具有开口部的树脂掩膜层的工序。
8.根据权利要求6所述的树脂掩膜层的除去方法,其特征在于,
所述感光性树脂是含有下述而成的,即,(A1)重均分子量为4万~9万的含有羧基的碱溶性高分子15~35质量%、(A2)重均分子量为10万~15万的含有羧基的碱溶性高分子15~35质量%、(B)加聚性单体15~60质量%、(C)光聚合引发剂0.01~10质量%、以及(D)重均分子量为1000~3000的聚环氧丙烷7~30质量%。
9.根据权利要求1所述的树脂掩膜层的除去方法,其特征在于,
将每100g感光性树脂的加聚性双键浓度DT为0.07以上0.12以下的感光性树脂层叠于支撑薄膜上,使用在该感光性树脂层的表面上设置保护薄膜而成的干膜抗蚀剂层形成树脂掩膜层。
10.一种带焊锡突起的基板的制造方法,其特征在于,包括:
使用干膜抗蚀剂层在基板表面的电极周围形成树脂掩膜层的工序;
在所述基板上涂布析出型焊锡组合物的工序;
对该析出型焊锡组合物进行加热处理而在所述电极表面上析出焊锡突起的工序;和
使用从二醇醚类和氨基醇类中选择的至少1种除去加热处理后的所述树脂掩膜层的工序。
11.根据权利要求10所述的制造方法,其特征在于,
所述基板由至少1个布线层和至少2个绝缘层构成,至少1个绝缘层的玻璃化温度比所述加热处理的温度高。
12.根据权利要求11所述的制造方法,其特征在于,
所述加热处理的温度为200℃以上。
13.根据权利要求10所述的制造方法,其特征在于,
在含有从所述二醇醚类和氨基醇类中选择的至少1种的剥离液中,浸渍已形成了所述树脂掩膜层的基板,除去所述树脂掩膜层。
14.根据权利要求10所述的制造方法,其特征在于,
所述干膜抗蚀剂层是在支撑薄膜上按顺序层叠了感光性树脂层和保护薄膜的感光性树脂层叠体。
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CN101460015B (zh) * | 2007-12-12 | 2013-04-24 | 三星电子株式会社 | 用于安装至少两种类型的电子元件的方法和设备 |
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2004
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CN105032874A (zh) * | 2014-04-30 | 2015-11-11 | 旭硝子株式会社 | 树脂层的去除方法 |
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CN106324922A (zh) * | 2016-08-29 | 2017-01-11 | 贵州乾萃科技有限公司 | 一种在基片上快速制备所需形状功能电极层的方法 |
CN109939977A (zh) * | 2017-12-21 | 2019-06-28 | 花王株式会社 | 树脂掩模剥离清洗方法 |
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KR20060051910A (ko) | 2006-05-19 |
JP4855667B2 (ja) | 2012-01-18 |
TW200619874A (en) | 2006-06-16 |
KR101143071B1 (ko) | 2012-05-08 |
JP2006114735A (ja) | 2006-04-27 |
US7291517B2 (en) | 2007-11-06 |
CN100551207C (zh) | 2009-10-14 |
US20060110907A1 (en) | 2006-05-25 |
TWI398203B (zh) | 2013-06-01 |
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