CN1131205A - 有机防锈处理铜箔 - Google Patents

有机防锈处理铜箔 Download PDF

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CN1131205A
CN1131205A CN95120208A CN95120208A CN1131205A CN 1131205 A CN1131205 A CN 1131205A CN 95120208 A CN95120208 A CN 95120208A CN 95120208 A CN95120208 A CN 95120208A CN 1131205 A CN1131205 A CN 1131205A
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copper foil
organic rust
bta
layer
derivatives
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CN1059244C (zh
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横田俊子
土桥诚
端洋志
酒井久雄
高桥进
吉冈敦志
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Mitsui Mining and Smelting Co Ltd
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Abstract

提供了一种有机防锈处理铜箔，该种铜箔既不会降低作为线路板材料用的铜箔的各种性能，又能防止树脂斑点的产生。这种有机防锈处理铜箔的特征是，在该铜箔不与基板粘合的表面上具有金属防锈层，而在该金属防锈层上设置由选自苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中至少2种的混合物构成的有机防锈处理层，或者在所说的金属防锈层上设置铬酸盐处理层，再在其上设置由选自苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中至少2种的混合物构成的有机防锈处理层。

Description

有机防锈处理铜箔
本发明涉及一种有机防锈处理铜箔，更具体地说，涉及一种在基板与铜箔粘合时，能够防止以环氧树脂为主成分的粉尘附着的印刷线路板用的有机防锈处理铜箔。
为了制成印刷线路板，将铜箔与玻璃纤维环氧树脂含浸材料的基板通过加热压合等方法来使其粘合，然后，为了形成导体线路，用酸或碱的蚀刻溶液将不需要的铜箔部分除去。这样形成线路后，在其上面插入电子零件，然后将其在焊锡浴中浸镀，从而将电子零件固定。
通常，作为这类线路板材料使用的铜箔必须满足作为线路板所要求的特性，特别是必须防止在将铜箔与基板加热压合时引起的变色，并且要防锈，为此，采用电沉积的方法形成锌或锌合金的金属防锈层，接着进行铬酸盐处理、硅烷偶合剂处理等表面处理，最后再将其与玻璃纤维环氧树脂等的基板粘合在一起。在这种用途的常规电解铜箔中，通常是将其粗糙面作为与基板的粘合面，而将其光亮面作为非粘合面。
对于这种铜箔不与基板粘合的表面的特性要求是：耐热氧化性、焊锡润湿性、保护层结合牢固性、蚀刻性、化学研磨性等性能均良好。
上述的加热压合操作是将基板与铜箔叠合在一起，以不锈钢板作为隔离板，当重叠数层后，按照预定的压力、温度与时间进行压合。这时，如果基板中的环氧树脂的微粒或空气中的尘埃附着于铜箔不与基板粘合的一侧表面上，就会牢固地粘结于铜箔表面上。这样，在形成导体线路时就会阻碍蚀刻，从而成为引起短路的大问题。人们把这些现象总称为树脂斑点(レジンスポト)。因此，最近提出了要对铜箔的非粘合面增加上述的特性要求，特别是要求克服树脂斑点的问题。
作为对铜及铜合金进行有机防锈处理的方法，过去已知都是广泛地使用苯并三唑(BTA)及其衍生物。另外，作为用于铜箔的有机防锈剂的利用例，有人使用上述的BTA作为保管用的暂时防锈处理措施。
另外，甲苯并三唑(TTA)与BTA一样，也是用于防止铜及铜合金变色的防锈剂的代表性试剂。关于这种TTA，在《防锖管理》，1993年2月号，第1页中有相关的报导。
最近，有人对作为具有耐热性的有机防锈剂的羧基苯并三唑(《防锖管理》，1993年11月号，第11页)和含有3-氨基-1，2，4-三唑的各种BTA衍生物(《防锖管理》，1993年11月号，第6页)进行了研究。
使用BTA或BTA的衍生物来进行铜箔的表面处理可以改善铜箔光亮面的长期保存性(耐湿性)、焊锡润湿性和保护层结合牢固性，其使用方法都是公知的(特开平6-85417号公报、特开平6-85455号公报)。然而，与单独使用BTA或BTA的衍生物相比，将耐热成分的BTA衍生物与氨基三唑混合使用可以改善铜箔的树脂斑点现象，关于这一点却完全未被人们了解。
本发明的目的是要克服先有技术存在的问题，提供一种不会降低作为线路板材料使用的铜箔的各种性能并能防止产生树脂斑点的有机防锈处理铜箔。
本发明的目的是按下述方法达到的，即在铜箔不与基板粘合的表面上设置一层由选自苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中的至少二种的混合物所构成的有机防锈处理层。
也就是说，本发明的有机防锈处理铜箔，其特征在于，在铜箔不与基板粘合的表面上具有金属防锈层，或者直接在该金属防锈层上设置一层由选自苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中的至少2种的混合物所构成的有机防锈处理层，或者先在该金属防锈层上设置铬酸盐处理层，再在该铬酸盐处理层上设置一层由选自苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中的至少2种的混合物所构成的有机防锈处理层。
本发明的有机防锈处理铜箔在铜箔不与基板粘合的表面上设置有金属防锈层。作为这种金属防锈层，优选是锌或锌合金层。为了形成这类锌或锌合金层，可以使用镀敷等各种各样的公知方法，不管使用哪一种镀敷方法都可以。另外，如果进行以锌作为主要成分的镀敷，还可以添加微量的第3种金属等。
以下示出此处使用的锌镀浴的组成及镀敷条件的一个例子。这里只不过是举出了这种锌镀浴的组成及镀敷条件的一个例子，只要是能在铜箔上获得同样的锌层或锌合金层的镀敷方法，不管使用哪一种方法都可以获得同样的结果。
<锌电镀>
焦磷酸锌                         1-10g/l
焦磷酸钾                          100g/l
pH                                  9-12
液温                                室温
电流密度                      0.1-1A/dm2
另外，本发明的铜箔，在不与基板粘合的一面上设置的上述金属防锈层上也可以再形成一层铬酸盐处理层。作为铬酸盐处理方法，可以使用电解铬酸盐的方法，也可以使用浸渍铬酸盐的方法，凡是通常使用的铬酸盐处理方法都可以使用。
以下示出此处所用的铬酸盐处理液的组成及处理条件的一个例子。这里只不过是举出了铬酸盐处理液的组成及处理条件的一个例子，只要是能在锌层或锌合金层上获得同样的铬酸盐处理层即可。
<铬酸盐处理>
铬酸                              0.05-10g/L
pH                                      9-13
电流密度                          0.1-5A/dm2
本发明的铜箔，或者直接在不与基板粘合的一面上设置的上述金属防锈层上，或者在铬酸盐处理层上，设置一层由选自苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中的至少2种的混合物所构成的有机防锈处理层。使用由选自苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中的至少2种的混合物进行的有机防锈处理，是使用这些试剂的水溶液来处理，可以使用浸渍、喷涂或滚筒涂敷等任何一种方法。
作为在这里使用的苯并三唑的衍生物，可以使用例如含有耐热成分的羧基苯并三唑、甲苯并三唑和羧基苯并三唑、甲苯并三唑的钠盐和各种胺盐，例如单乙醇胺、环己胺、二异丙胺盐、吗啉盐等的物质。
作为氨基三唑的异构体，可以使用3-氨基-1，2，4-三唑、2-氨基-1，3，4-三唑、4-氨基-1，2，4-三唑、1 -氨基-1，3，4-三唑。
作为氨基三唑的衍生物，可以使用含有钠盐、各种胺盐，例如一元醇胺、环己胺、二异丙胺盐、吗啉盐等的物质。
下面示出这里使用的有机防锈处理液中各种试剂的成分浓度的一个例子。
苯并三唑                         0.01-2重量％
甲苯并三唑                       0.01-1重量％
羧基苯并三唑                 0.01-0.035重量％
氨基三唑                        0.01-25重量％
所说的有机防锈处理液是将这些成分中的至少2种以上混合，作为混合物使用。
在制备本发明的有机防锈处理铜箔时使用的铜箔，可以使用电解铜箔、轧制铜箔等任何一种，至于铜箔的厚度没有特殊的限定。
本发明的铜箔不与基板粘合的表面可按通常的方法进行处理。即，首先在铜箔要与基板粘合的表面上形成粒状铜层，然后进行金属镀敷处理，以形成锌或锌合金层等合金防锈层，再在其上面形成作为用于改善其耐化学品性能的铬酸盐处理层。这种金属防锈层和铬酸盐处理层的形成，通常是在铜箔与基板粘合的表面和不粘合的表面同时地进行。然后，在铜箔与基板粘合的表面上不进行有机防锈处理。
在进行上述的处理后，使其干燥，从而获得本发明的有机防锈处理铜箔，在将该铜箔与作为线路板的基板粘合时，不会产生树脂斑点，而且不与基板粘合的表面的其他性能也优良。
以下根据实施例来具体地解释本发明。
实施例1-10
取一块一般的电解铜箔，在其不与基板粘合的表面上镀敷20mg/m2的锌层，水洗后，再进行电解铬酸盐处理。然后，使用选自在表1中示出的苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中的至少2种的混合物组成的有机防锈处理液对上述那些铜箔进行有机防锈处理，然后使其干燥，提供作为树脂斑点试验之用。所说的有机防锈处理液，按各种有机防锈剂的成分浓度为0.1重量％，将2-3种混合在一起，在常温下进行涂敷。
另外，树脂斑点的试验方法是在铜箔不与基板粘合的一侧表面，与通常的情况相反，将该表面与基板加热压合而使其粘合在一起，根据这时的剥离试验，按照下述的标准来评价在不与基板粘合的表面上的树脂斑点(灰尘等的粘附)。
○：良好，△：稍差，X：差
结果示于表1中。另外，在表1中，各种缩写符号表示下列化合物。
ATA：氨基三唑；BTA：苯并三唑；
TTA：甲苯并三唑；C-BTA：羧基苯并三唑。
比较例1
使用与实施例1同样的普通电解铜箔，在其不与基板粘合的表面上仅仅进行了与实施例1同样的20mg/m2的锌层镀敷处理。与实施例1同样评价该铜箔的树脂斑点，其结果示于表1中。
比较例2：
使用与实施例1同样的普通电解铜箔，在其不与基板粘合的表面上镀敷20mg/m2的锌层后，与实施例1同样进行电解铬酸盐处理。与实施例1同样评价该铜箔的树脂斑点，其结果示于表1中。
比较例3-6
使用与实施例1同样的普通铜箔，在其不与基板粘合的表面上镀敷20mg/m2的锌层后，与实施例1同样进行铬酸盐处理。然后使用选自苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中的至少一种组成的有机防锈处理液对该铜箔进行有机防锈处理，最后将其干燥。所说的有机防锈处理液，使各种有机防锈剂的成分浓度为0.1重量％，在常温下进行涂布。与实施例1同样评价这些铜箔的树脂斑点，其结果示于表1中。
                            表1
实施例比较例        有机防锈处理 树脂斑点
实施例1           ATA＋BTA     ○
实施例2           ATA＋TTA     ○
实施例3          ATA＋C－BTA     ○
实施例4           BTA＋TTA     ○
实施例5           BTA＋C－BTA     ○
实施例6           TTA＋C－BTA     ○
实施例7          ATA＋BTA＋TTA     ○
实施例8        ATA＋BTA＋C-BTA     ○
实施例9        ATA＋TTA＋C－BTA     ○
实施例10       ATA＋BTA＋C-BTA＋TTA     ○
比较例1          无(仅镀锌)     ×
比较例2      无(镀锌＋电解铬酸盐处理)     ×
比较例3             BTA     △
比较例4             ATA     △
比较例5             TTA     △
比较例6             C－BTA     △
实施例11-20
在一种普通铜箔的不与基板粘合的表面上镀敷20mg/m2的锌，水洗后，使用选自表2中所示苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中至少2种混合物组成的有机防锈处理液进行有机防锈处理后，使其干燥，提供作为树脂斑点试验用。所说的有机防锈处理液，是使各种有机防锈剂的成分浓度为0.1重量％，将其2-3种成分混合，在常温下进行涂布。与实施例1同样评价该铜箔的树脂斑点，其结果示于表2中。
比较例7-10
使用与实施例1同样的普通铜箔，在其不与基板粘合的表面上镀敷20mg/m2的锌后，使用选自苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中的1种组成的有机防锈处理液进行有机防锈处理后，使其干燥。所说的有机防锈处理液，使各种有机防锈剂的成分浓度为0.1重量％，在常温下进行涂布。与实施例1同样评价这些铜箔的树脂斑点，其结果示于表2中。
                                  表2
实施例比较例     有机防锈处理 树脂斑点
实施例11         ATA＋BTA     ○
实施例12         ATA＋TTA     ○
实施例13         ATA＋C－BTA     ○
实施例14         BTA＋TTA     ○
实施例15         BTA＋C－BTA     ○
实施例16         TTA＋C－BTA     ○
实施例17 ATA＋BTA＋TTA ○
实施例18       ATA＋BTA＋C－BTA     ○
实施例19       ATA＋TTA＋C－BTA     ○
实施例20     ATA＋BTA＋C－BTA＋TTA     ○
比较例7            BTA     △
比较例8            ATA     △
比较例9            TTA     △
比较例10            C－BTA     △
从表1-2的结果可以判断，使用选自苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中至少2种的混合物组成的有机防锈处理液进行过有机防锈处理的铜箔在树脂斑点方面显示出其效果。
将本发明的有机防锈处理铜箔与线路板用铜箔的基板粘合时，可以克服粉尘等附着到非粘合面上的问题，从而可以防止由于树脂斑点引起的短路等问题。

Claims (2)

1.一种有机防锈处理铜箔，其特征在于，在铜箔不与基板粘合的表面上具有金属防锈层，在该金属防锈层上设置一层由选自苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中至少2种的混合物构成的有机防锈处理层。
2.一种有机防锈处理铜箔，其特征在于，在铜箔不与基板粘合的表面上具有金属防锈层，在该金属防锈层上设置铬酸盐处理层，再在该铬酸盐处理层上设置由选自苯并三唑或其衍生物、氨基三唑或其异构体或其衍生物中至少2种的混合物构成的有机防锈处理层。
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