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CN102333908B - 耐热老化特性优良的金属包覆聚酰亚胺树脂基板 - Google Patents

耐热老化特性优良的金属包覆聚酰亚胺树脂基板 Download PDF

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CN102333908B
CN102333908B CN201080009137.3A CN201080009137A CN102333908B CN 102333908 B CN102333908 B CN 102333908B CN 201080009137 A CN201080009137 A CN 201080009137A CN 102333908 B CN102333908 B CN 102333908B
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吉田拓
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Abstract

本发明的课题在于提供在不降低金属包覆聚酰亚胺树脂薄膜与金属层的初期密合力的情况下150℃、168小时老化后的密合力高的金属包覆聚酰亚胺树脂基板。一种金属包覆聚酰亚胺树脂基板，其为在聚酰亚胺树脂薄膜的单面或两面上通过湿法或干法或者它们的组合进行表面改性后，通过湿法形成阻挡层，之后通过湿法或干法形成种子层，并在其表层通过湿法形成导电性被膜而得到的金属包覆聚酰亚胺树脂基板，其特征在于，在对该金属包覆聚酰亚胺树脂基板进行90°剥离试验后的导电性被膜层侧的剥离面上，使用飞行时间二次离子质谱分析装置(TOF-SIMS)进行深度方向分析得到的聚酰亚胺残渣与阻挡金属层残渣的混合层厚度以Si溅射速度换算为2.60nm以下，150℃、168小时老化试验后的剥离强度保持率(150℃、168小时老化后剥离强度/初期剥离强度)为50％以上。

Description

耐热老化特性优良的金属包覆聚酰亚胺树脂基板
技术领域
本发明涉及可以作为柔性印刷板、TAB、COF等电子部件的安装材料使用的无胶粘剂柔性层压材料，特别是耐热老化特性优良的金属包覆聚酰亚胺树脂基板的制造方法。
背景技术
在聚酰亚胺薄膜上层叠有主要由铜构成的金属导体层的FCCL(柔性覆铜箔层压板)，作为电子产业中的电路板的材料广泛使用。其中，在聚酰亚胺薄膜与金属层间不具有胶粘剂层的无胶粘剂柔性层压板(特别是双层柔性层叠体)随着电路布线宽度的细间距化而引起关注。
无胶粘剂柔性层压体、特别是与细间距对应的无胶粘剂柔性层压体的制造方法，有如下方法：通过溅射、CVD、蒸镀等干镀法在聚酰亚胺树脂薄膜上预先形成阻挡层和种子层，然后通过电镀法形成作为导体层的金属层的、所谓的敷金属法(メタライジング法)。
该敷金属法中，为了提高金属层与聚酰亚胺薄膜的密合力，在形成金属层之前，通过等离子体处理对聚酰亚胺树脂薄膜表面进行以提高与阻挡金属的密合性为目的的表面改性(参考专利文献1和专利文献2)。
另外，也提出了通过无电镀法预先在聚酰亚胺树脂薄膜上形成阻挡层和种子层，然后通过电镀法形成作为导体层的金属层的方案。
在该方法中，在形成金属层之前，将聚酰亚胺树脂薄膜浸渍于由碱金属氢氧化物构成的溶液中，进行以提高作为后续的无电镀驱动力的催化剂的吸附及提高与阻挡金属的密合性为目的的表面改性(参考专利文献3)。
所述聚酰亚胺树脂薄膜的表面改性处理，对聚酰亚胺树脂薄膜与金属层的密合性有大的影响，在制造上是特别重要的处理工序。
作为无胶粘剂柔性层压体所要求的机械特性，初期的剥离强度和长期经过后的剥离强度具有重要性，近年来作为高可靠性要求，特别是长期经过后的剥离强度变得重要。
另外，作为长期经过后的剥离强度的评价方法，一般是通过作为加速劣化试验的耐热老化(150℃、168小时)后的剥离测定进行评价。
最近，提出了利用硝酸银水溶液对经改性处理的聚酰亚胺树脂薄膜进行染色后用透射式电子显微镜(TEM)观察断面，根据其改性层的厚度确定初期和耐热老化后的剥离强度的方法(参考专利文献4)。
但是，在实际的聚酰亚胺树脂薄膜的表面改性中，根据处理条件会产生具有包含有助于密合性的官能团的各种分子结构的物质，因此，上述方法只不过是仅用特定的物质对经硝酸银染色的表面改性层进行评价，即使上述评价中的改性层厚度同样，也存在与实际的剥离强度试验结果间产生差异的问题。
现有技术文献
专利文献
专利文献1：日本专利第3173511号公报
专利文献2：日本特表2003-519901号公报
专利文献3：日本特开2005-154895号公报
专利文献4：日本特开2007-318177号公报
发明内容
本申请发明的目的在于提供在不降低金属包覆聚酰亚胺树脂薄膜与金属层的初期密合力的情况下150℃、168小时老化后的密合力高的金属包覆聚酰亚胺树脂基板。
鉴于上述课题，本发明提供如下发明：
1)一种金属包覆聚酰亚胺树脂基板，其为在聚酰亚胺树脂薄膜的单面或两面上通过湿法或干法或者它们的组合进行表面改性后，通过湿法形成阻挡层，之后通过湿法或干法形成种子层，并在其表层通过湿法形成导电性被膜而得到的金属包覆聚酰亚胺树脂基板，其特征在于，
在对该金属包覆聚酰亚胺树脂基板进行90°剥离试验后的导电性被膜层侧的剥离面上，使用飞行时间二次离子质谱分析装置(TOF-SIMS)进行深度方向分析得到的聚酰亚胺残渣与阻挡金属层残渣的混合层厚度以Si溅射速度换算为2.60nm以下，150℃、168小时老化试验后的剥离强度保持率(150℃、168小时老化后剥离强度/初期剥离强度)为50％以上。
另外，本申请发明提供如下发明：
2)如上述1)所述的金属包覆聚酰亚胺树脂基板，其特征在于，所述种子层和导电性被膜为铜，所述阻挡层为镍或它们的合金。
3)如上述1)或2)所述的金属包覆聚酰亚胺树脂基板，其特征在于，
所述聚酰亚胺树脂薄膜上的表面改性通过等离子体、UV、碱金属氢氧化物溶液浸渍或者它们与强酸溶液浸渍的组合来进行。
发明效果
本申请发明的金属包覆聚酰亚胺树脂基板，特别是在不降低聚酰亚胺薄膜与金属层间的层叠后的初期密合力的情况下，可以提高老化后的密合力，从而在形成精细图案方面具有优良效果。
附图说明
图1是表示金属层侧的剥离面上，通过使用飞行时间二次离子质谱分析装置(TOF-SIMS)的深度方向分析对聚酰亚胺残渣和阻挡金属(Ni)层残渣的混合层厚度进行调查所得结果的概要的图。
图2是表示聚酰亚胺混合层的厚度与剥离强度保持率的关系的图。
具体实施方式
一般而言，在聚酰亚胺树脂薄膜的单面或两面上通过湿法或干法进行表面改性后，形成阻挡层，在该阻挡层上形成种子层，并且在该种子层上形成一定厚度的导电性被膜，由此来制造金属包覆聚酰亚胺树脂基板。
这样制造的在聚酰亚胺薄膜与金属层间不具有胶粘剂层的无胶粘剂柔性层压体(特别是两层柔性层叠体)，作为FCCL(柔性覆铜箔层压体)，作为电子产业中的电路板的材料被广泛使用，但是，随着最近的电路布线宽度的细间距化，要求提高金属层与聚酰亚胺薄膜的密合力。
作为其评价方法，一般而言，通过测定常态剥离强度(初期剥离强度)以及作为加速劣化试验的耐热老化(150℃、168小时老化)后的剥离强度来进行。
如上所述，作为高可靠性要求，特别是长期经过后的剥离强度变得重要，因此要求尽量提高150℃、168小时老化试验后的剥离强度保持率(耐热剥离强度/常态剥离强度)。
为了提高这样的剥离强度保持率，已知优选通过湿法或干法对聚酰亚胺树脂薄膜的表面进行表面改性处理，但是，这种表面改性处理通过何种机理或现象增加剥离强度尚未充分理解，另外，改性处理本身也是通过试错来实施的，因此存在难以保持恒定的改性水平的问题。
因此，本申请发明人对金属包覆聚酰亚胺树脂基板的90°剥离中金属层侧剥离面的深度方向的结构进行了详细调查。结果发现，存在表面改性处理后形成的阻挡层(镍、其合金层)与聚酰亚胺的混合层。
虽然也依赖于聚酰亚胺树脂的改性处理方法，但是，一般而言，改性处理过量时，阻挡层金属在聚酰亚胺改性层中的混入增加，从而阻挡层金属与聚酰亚胺的混合层增厚。
而且发现，耐热老化后的剥离强度下降起因于初期剥离的剥离面上金属层侧的聚酰亚胺与阻挡层金属的混合层的厚度。
即发现，聚酰亚胺与阻挡层金属的混合层越厚，则具有催化剂氧化作用的铜越容易通过该混合层扩散到聚酰亚胺层中，从而耐热老化中的剥离强度下降。
因此可以看出，通过调节初期的剥离中金属层侧剥离面的聚酰亚胺与金属混合层的厚度，可以保持较高的耐热老化后的剥离强度，并且可以由初期的金属层侧剥离面的聚酰亚胺与金属混合层的厚度预测耐热老化后的剥离强度。
图1中表示在金属层侧的剥离面上，通过使用飞行时间二次离子质谱分析装置(TOF-SIMS)的深度方向分析对聚酰亚胺残渣和阻挡金属(Ni)层残渣的混合层厚度进行调查所得结果的概要。
如图1所示，聚酰亚胺残渣(C-C)以溅射Si换算在深度2nm附近形成峰，另一方面，阻挡金属(Ni)以溅射Si换算在深度4.5nm附近形成峰。其中间为聚酰亚胺与金属的混合层。
由后述的实施例和比较例明显可以看出，该混合层为造成剥离强度保持率下降的原因。
根据以上内容，本申请发明人通过大量研究发现，当金属层侧剥离面上聚酰亚胺与阻挡金属层的混合层厚度以通过TOF-SIMS的深度方向分析得到的Si溅射速度换算为2.60nm以下时，可以增加150℃、168小时老化试验后的剥离强度保持率(耐热剥离强度/常态剥离强度)。而且，此时，可以实现剥离强度保持率为50％以上。
实施例
以下，基于实施例和比较例进行说明。需要注意的是，本实施例仅仅是一例，本发明不限于该例。即，本发明还包括其它方式或变形。
(实施例1)
作为聚酰亚胺树脂薄膜，使用杜邦公司的カプトン150EN。作为表面改性法，将该聚酰亚胺树脂薄膜浸渍到氢氧化钾水溶液中，并用纯水洗涤。然后，作为催化剂施加工序，浸渍到预先使含有具有金属捕捉能力的官能团的硅烷偶联剂与贵金属化合物混合或反应而得到的溶液中，并用纯水洗涤。
该处理后，作为无电镀工序，使用无电解镍-硼系镀液，形成0.15μm的镍层，用纯水洗涤后，进行150℃的热处理，形成0.05μm的镍层然后用纯水洗涤，共计形成0.20μm的镍层。接着，在无电解铜镀液中在镍层上形成无电解铜种子层，然后通过电镀形成8μm的铜导体层。
对这样形成的金属包覆聚酰亚胺树脂基板，进行90°剥离强度测定，并且使用飞行时间二次离子质谱分析装置(TOF-SIMS)的深度方向分析测定金属层侧剥离面的聚酰亚胺与阻挡层金属的混合层的厚度。
上述测定的结果如表1所示。
表1
Figure BPA00001424012800071
如表1所示，常态剥离强度为0.55kN/m，耐热剥离强度为0.45kN/m，剥离强度保持率(耐热剥离强度/常态剥离强度)为82％。而且，此时通过TOF-SIMS测定的Ni与聚酰亚胺的混合层为0.51nm。
该Ni与聚酰亚胺混合层的厚度小，满足本申请发明的条件，结果，剥离强度保持率为82％，显示出良好的特性。
(实施例2)
作为聚酰亚胺树脂薄膜，使用杜邦公司的カプトン150EN。作为表面改性法，将该聚酰亚胺树脂薄膜进行UV照射后浸渍到硫酸中，然后用纯水洗涤。然后，作为催化剂施加工序，浸渍到预先使含有具有金属捕捉能力的官能团的硅烷偶联剂与贵金属化合物混合或反应而得到的溶液中，并用纯水洗涤。
该处理后，作为无电镀工序，使用无电解镍-硼系镀液，形成0.2μm的镍层，并用纯水洗涤。接着，在无电解铜镀液中在镍层上形成无电解铜种子层，然后通过电镀形成8μm的铜导体层。
对这样形成的金属包覆聚酰亚胺树脂基板，进行90°剥离强度测定，并且使用飞行时间二次离子质谱分析装置(TOF-SIMS)的深度方向分析测定金属层侧剥离面的聚酰亚胺与阻挡层金属的混合层的厚度。
上述测定的结果如表1所示。
如表1所示，常态剥离强度为0.61kN/m，耐热剥离强度为0.55kN/m，剥离强度保持率(耐热剥离强度/常态剥离强度)为90％。而且，此时通过TOF-SIMS测定的Ni与聚酰亚胺的混合层为0.13nm。
该Ni与聚酰亚胺混合层的厚度满足本申请发明的条件，结果，剥离强度保持率为90％，显示出非常良好的特性。
(实施例3)
作为聚酰亚胺树脂薄膜，使用杜邦公司的カプトン150EN。作为表面改性法，将该聚酰亚胺树脂薄膜进行UV照射后浸渍到硝酸中，然后用纯水洗涤。然后，作为催化剂施加工序，浸渍到预先使含有具有金属捕捉能力的官能团的硅烷偶联剂与贵金属化合物混合或反应而得到的溶液中，并用纯水洗涤。
该处理后，作为无电镀工序，使用无电解镍-硼系镀液，形成0.15μm的镍层，用纯水洗涤后，进行150℃的热处理，形成0.05μm的镍层然后用纯水洗涤，共计形成0.20μm的镍层。接着，在无电解铜镀液中在镍层上形成无电解铜种子层，然后通过电镀形成8μm的铜导体层。
对这样形成的金属包覆聚酰亚胺树脂基板，进行90°剥离强度测定，并且使用飞行时间二次离子质谱分析装置(TOF-SIMS)的深度方向分析测定金属层侧剥离面的聚酰亚胺与阻挡层金属的混合层的厚度。
上述测定的结果如表1所示。
如表1所示，常态剥离强度为0.56kN/m，150℃、168小时耐热剥离强度为0.39kN/m，剥离强度保持率(耐热剥离强度/常态剥离强度)为70％。而且，此时通过TOF-SIMS测定的Ni与聚酰亚胺的混合层为1.60nm。
该Ni与聚酰亚胺混合层的厚度极小，满足本申请发明的条件，结果，剥离强度保持率为70％，显示出良好的特性。
(比较例1)
作为聚酰亚胺树脂薄膜，使用杜邦公司的カプトン150EN。作为表面改性法，将该聚酰亚胺树脂薄膜浸渍到氢氧化钾水溶液中，然后用纯水洗涤。然后，作为催化剂施加工序，浸渍到预先使含有具有金属捕捉能力的官能团的硅烷偶联剂与贵金属化合物混合或反应而得到的溶液中，并用纯水洗涤。
该处理后，作为无电镀工序，使用无电解镍-硼系镀液，形成0.2μm的镍层，并用纯水洗涤。接着，在无电解铜镀液中在镍层上形成无电解铜种子层，然后通过电镀形成8μm的铜导体层。
对这样形成的金属包覆聚酰亚胺树脂基板，进行90°剥离强度测定，并且使用飞行时间二次离子质谱分析装置(TOF-SIMS)的深度方向分析测定金属层侧剥离面的聚酰亚胺与阻挡层金属的混合层的厚度。
上述测定的结果如表1所示。
如表1所示，常态剥离强度为0.63kN/m，耐热剥离强度为0.28kN/m，剥离强度保持率(耐热剥离强度/常态剥离强度)为44％。而且，此时通过TOF-SIMS测定的Ni与聚酰亚胺的混合层为2.87nm。
该Ni与聚酰亚胺混合层的厚度大，不满足本申请发明的条件，而且，剥离强度保持率为44％，变差。
以上的实施例和比较例的阻挡层和聚酰亚胺混合层的厚度与剥离强度保持率的关系如图2所示。
从该图2明显可以看出，随着通过TOF-SIMS测定的Ni与聚酰亚胺的混合层的厚度增大，具有剥离强度保持率(耐热剥离强度/常态剥离强度)下降的倾向，可以确认：聚酰亚胺残渣与阻挡金属层残渣的混合层厚度以Si溅射速度换算为2.60nm以下对于使剥离强度保持率为50％以上是必要的。
产业实用性
本申请发明提供一种金属包覆聚酰亚胺树脂基板，其在聚酰亚胺树脂薄膜的单面或两面上通过湿法或干法或者它们的组合进行表面改性后，通过湿法形成阻挡层，之后通过湿法或干法形成种子层，并在其表层通过湿法形成导电性被膜，其特征在于，在对该金属包覆聚酰亚胺树脂基板进行90°剥离试验后的导电性被膜层侧的剥离面上，使用飞行时间二次离子质谱分析装置(TOF-SIMS)进行深度方向分析得到的聚酰亚胺残渣与阻挡金属层残渣的混合层厚度以Si溅射速度换算为2.60nm以下，150℃、168小时老化试验后的剥离强度保持率(耐热剥离强度/常态剥离强度)为50％以上。本申请发明特别是在不降低聚酰亚胺薄膜与金属层间的层叠后的初期密合力的情况下，可以提高老化后的密合力，因此在形成精细图案的方面具有优良效果。本申请发明作为用作柔性印刷板、TAB、COF等电子部件的安装材料的无胶粘剂柔性层压材料、特别是剥离强度保持率优良的金属包覆聚酰亚胺树脂基板有用。

Claims (3)

1.一种金属包覆聚酰亚胺树脂基板，其为在聚酰亚胺树脂薄膜的单面或两面上通过湿法或干法或者它们的组合进行表面改性后，通过湿法形成阻挡层，之后通过湿法或干法形成种子层，并在其表层通过湿法形成导电性被膜而得到的金属包覆聚酰亚胺树脂基板，其特征在于，
在对该金属包覆聚酰亚胺树脂基板进行90°剥离试验后的导电性被膜层侧的剥离面上，使用飞行时间二次离子质谱分析装置(TOF-SIMS)进行深度方向分析得到的聚酰亚胺残渣与阻挡金属层残渣的混合层厚度以Si溅射速度换算为1.60nm以下，150℃、168小时老化试验后的剥离强度保持率(150℃、168小时老化后剥离强度/初期剥离强度)为70％以上。
2.如权利要求1所述的金属包覆聚酰亚胺树脂基板，其特征在于，
所述种子层和导电性被膜为铜，所述阻挡层为镍或它们的合金，且通过无电镀法形成。
3.如权利要求1或2所述的金属包覆聚酰亚胺树脂基板，其特征在于，
所述聚酰亚胺树脂薄膜上的表面改性通过等离子体、UV、碱金属氢氧化物溶液浸渍处理或者它们与强酸溶液浸渍处理的组合来进行。
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EP2402485A1 (en) 2012-01-04
SG173595A1 (en) 2011-09-29
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EP2402485A4 (en) 2012-09-19
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