CN104684259A - 蚀刻或电镀方法以及抗蚀油墨 - Google Patents
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Abstract
本发明涉及蚀刻或电镀方法以及抗蚀油墨。具体地,本发明提供蚀刻或电镀方法,其包括如下步骤:ⅰ)将碱可移除水不溶性热熔喷墨油墨喷墨印刷到基底上,以形成抗蚀图像;ⅱ)在酸性水介质中蚀刻或电镀该基底;和ⅲ)用碱水溶液移除该抗蚀图像。
Description
本专利申请是申请日为2007年8月6日,发明名称为“蚀刻或电镀方法以及抗蚀油墨”的中国专利申请200780036674.5的分案申请。
技术领域
本发明涉及蚀刻或电镀方法——其包括喷墨印刷抗蚀油墨,以及涉及在该方法中使用的抗蚀油墨。
发明背景
一种将期望的图案或图像蚀刻到基底上的熟知的方法,包括首先将被称为抗蚀油墨的油墨印刷到基底上,印刷到不被蚀刻的那些基底部分上,以保护或掩蔽那些区域远离蚀刻介质。带有抗蚀油墨掩蔽的基底随后被暴露于蚀刻介质,例如,酸水溶液,没有被油墨掩蔽的基底区域被蚀刻。在蚀刻步骤之后,该抗蚀油墨例如通过在碱中冲洗被从基底移除。该方法被广泛用于印制电路板的制造中,其中多次沉积、掩蔽和蚀刻步骤被用于建立复杂的结构。在太阳能电池和钢压纹带的制造过程中,抗蚀油墨也被用于蚀刻中。
和蚀刻一样,抗蚀油墨在电镀中具有应用。在此种情况中,抗蚀油墨掩蔽基底的区域远离电镀介质并因此防止在那些区域上的沉积。该方法在一些太阳能电池的生产中被使用。
丝网印刷广泛地被用于将抗蚀油墨应用到基底中。这项技术成本低且可靠。
在抗蚀剂的丝网印刷中使用的油墨经常是光固化的,因此,在它被印刷到基底上之后,该油墨立即可以被固化成硬膜。这样的丝网油墨典型地包括可达40%的碱溶性树脂,以便赋予已固化油墨层碱溶性,因此,它们可以利用碱水溶液从基底中被洗掉。
最近,进行了使用喷墨印刷来印刷抗蚀图像的尝试。喷墨印刷相比丝网印刷具有一些优点,例如,以计算机可读形式存储的图像可以被直接印刷至基底,且可以获得更高的分辨率。但是,采用喷墨作为印刷抗蚀剂的方法受到限制,部分是因为目前可得的喷墨油墨没有同时具有抗蚀油墨所需的包括容易去除这样的性质。
具体地,因为喷墨油墨必须具有非常低的黏度,以便进行适当地喷射,在油墨被固化之前,其趋向于迅速地铺展在基底的表面上,尤其在基底具有不平坦或结构化表面的情况下,因此失去了边缘清晰度(edge definition)。此外,传统的喷墨油墨难于从基底中去除,需要使用有机溶剂和/或机械刮擦或磨蚀。
对改进的抗蚀油墨以及涉及抗蚀油墨的改进的蚀刻和电镀方法仍存在需要。
发明内容
本发明提供蚀刻或电镀方法,其包括以下步骤:
ⅰ)将碱可去除的水不溶性热熔喷墨油墨喷墨印刷到基底上,以形成抗蚀图像;
ⅱ)在酸性水介质中蚀刻或电镀该基底;和
ⅲ)用碱水溶液(aqeous alkali)去除抗蚀图像。
另一方面,本发明提供用作蚀刻或沉积(例如,电镀)抗蚀剂的碱可去除的水不溶性热熔喷墨油墨。
具体实施方式
碱水溶液冲洗目前被广泛用于去除丝网抗蚀油墨,因此本发明方法的抗蚀剂去除步骤通常可以通过该方法的操作员使用传统冲洗设备来进行。此外,使用碱水溶液作为冲洗介质来去除抗蚀油墨避免了使用有机溶剂的需要,由于安全、对环境的影响和成本等原因,这些有机溶剂是不希望的。在本发明的方法中,油墨是碱可去除的,并且通常也不必使用机械方法例如通过摩擦或刮擦来去除该抗蚀油墨。
所述油墨是热熔油墨,也就是说,它在室温即25℃是固体,在打印机内被熔化并被热喷到基底上。本发明人已经发现热熔喷墨油墨产生特别优良的抗蚀图像清晰度,原因在于它们在与基底接触之后非常迅速地冷却且固化,因此抑制了油墨的铺展。传统的热熔油墨主要基于烃蜡,因此在水介质中完全不溶。这样的传统热熔油墨只能通过用有机溶剂冲洗或通过机械刮擦来移除并且没有发现作为抗蚀剂的应用。本发明人已经发现能够配制适于喷墨应用的热熔油墨,并且该热熔油墨通过用碱水溶液冲洗而被容易地去除,同时在蚀刻和电镀所用的酸性介质中是不溶的。
如本文所使用的术语“碱可去除的”是指使用在蚀刻和电镀工艺中通常使用的碱水溶液条件,油墨可以容易地从基底去除。
如本文所使用的术语“水不溶性”是指油墨在中性水中(pH7.0-6.5)以及在蚀刻和电镀工艺通常使用的酸性水介质中是不溶的,因此,在蚀刻或电镀步骤过程中或在任何相关的水漂洗步骤中,该油墨将不会从基底中移除。
如本文所使用的术语“水可洗性”和“碱可洗性”以及类似术语是指按照下面给出的试验方法所测定的水和碱可洗性。
任选地,该油墨具有至少80%,优选地至少90%,更优选地至少95%,以及特别优选地至少99%的碱可洗性。
任选地,该油墨具有少于20%,优选地少于10%,更优选地少于5%,以及特别优选地少于1%的水可洗性。
使用适于印刷热熔油墨的任何喷墨打印机,该油墨可以被施用到基底上。适于印刷热熔油墨的打印头可以从Spectra获得。
蚀刻或电镀工艺可以是任何这样的工艺,其包括将基底与中性水或酸水溶液(aqeous acid)接触。
该工艺可以包括用酸水溶液蚀刻基底。蚀刻可以包括“PAWN”溶液(即,包含磷酸、乙酸、水和硝酸的溶液)。PAWN溶液适合于蚀刻铜和铝。该工艺可以包括用含有过氧化氢以及任选还有硫酸的溶液蚀刻基底。在太阳能电池生产中,这样的溶液适于蚀刻例如钛-钨层。该工艺可以包括用包含氟化氢和/或氟化物盐的溶液蚀刻二氧化硅。该工艺可以是将金属例如铜或锡电镀到基底上的工艺。基底可以是印制电路板的基底。在太阳能电池的生产中,该工艺可以是蚀刻或电镀的工艺。该工艺可以是蚀刻钢压纹带,例如一种被用于将木纹图案压印到木质材料上的类型的带的工艺。
油墨典型地包括溶解或分散在碱水溶液例如5%氢氧化钾水溶液中的组分。这有助于避免油墨以薄片或条的形式被去除,这些薄片或条可阻塞滤器设备和排水管。优选地,该油墨主要由碱溶性的成分或在碱水溶液中分散成直径小于10微米(μm)的颗粒的成分组成。例如,许多颜料不溶于碱水溶液,但是当该油墨从基底上被冲洗时,其将会分散成直径小于10微米(μm)的颗粒(也就是说,它们穿过10微米的滤网)。优选地,该油墨包括至少95wt%,更优选地至少98wt%,以及特别优选地至少99wt%在碱水溶液中可溶的成分。优选地,该油墨包括至少95wt%,更优选地至少98wt%,以及特别优选地至少99wt%的成分,其每一种成分具有至少80%,优选地至少90%,更优选地至少95%,以及特别优选地至少99%的碱可洗性。
油墨可含有碱溶性蜡。该碱溶性蜡可以是有机酸,例如羧酸。合适的碱溶性蜡是肉豆蔻酸、硬脂酸、棕榈酸、月桂酸和其它酸官能蜡例如来自Baker Petrolite的Unicid系列。肉豆蔻酸是优选的。该蜡优选地具有至少80%,更优选地至少90%,特别优选地至少95%,以及最优选地至少99%的碱可洗性。该油墨任选地包含至少30wt%,优选地至少50wt%的一种或多种碱溶性蜡。任选地,该油墨包含不超过99wt%,优选地不超过90wt%的碱溶性蜡或多种碱溶性蜡。
优选地,所述油墨包括一种或多种熔点在从40到80℃范围内的碱溶性蜡。如果在冲洗阶段中使用的碱水溶液被加热到等于或大于蜡的熔点的温度,该蜡将在冲洗期间熔化,并且油墨将会更加快速地冲洗掉。当然,如果蚀刻或电镀步骤是涉及高温的步骤,则应该对油墨的成分进行选择,使得油墨在该高温下不会熔化或软化。
优选地,所述油墨包含碱溶性树脂。一般而言,树脂增加对基底的粘附。优选地,该树脂具有至少80%,更优选地至少90%,特别优选地至少95%,以及最优选地至少99%的碱可洗性。适合的碱溶性树脂包括酸官能松香、改性松香以及具有残留酸值的改性松香酯,以及还包括这样的产物,如来自Lawter的Ennesin M57w、Ennesin PM45/HMP、Ennesin FM65,来自Hexion的Prince 2000、Prince 6500,以及其它来自Hercules、Pinova等的产品。具有酸值的松香酯树脂是优选的碱溶性树脂。在它们增加对基底的粘附的同时——这是期望的,树脂往往也增加油墨的熔体粘度,这使其更难喷射。任选地,该油墨包含可达40wt%重量,优选地可达20wt%的碱溶性树脂或碱溶性树脂的混合物。优选地,该油墨包含至少2wt%,更优选地至少5wt%的碱溶性树脂或此类树脂的混合物。
当在油墨中包含着色剂不是必需的同时,该油墨优选地包含着色剂,例如颜料或染料或荧光剂,以使抗蚀图像容易检测。有利的是,本发明的方法包括抗蚀图像检测及评估的步骤。这样的步骤允许排除具有明显缺陷的抗蚀图像,从而增强整体工艺技术。优选地,检测和评估是自动的。着色剂可以是染料,例如,任何可溶于油墨的染料,如来自Ciba的Orasol溶剂可溶性染料,或适合的脂肪/油可溶性染料,如来自BASF的Oilsol。包含荧光剂的油墨特别适合于自动检测和评估。
该油墨进一步包括常规油墨添加剂,诸如稳定剂和湿润剂。优选地,该油墨包括至少一种稳定剂、着色剂、染料、抗氧化剂或湿润剂。
在一些应用中,尤其是基底容易被破坏的那些应用中,还优选的是该油墨不含微粒材料,诸如二氧化硅。优选地,该油墨包含1wt%以下,更优选地少于0.01wt%以下的二氧化硅。
为了使油墨被有效地喷射,所述油墨优选地具有低熔体粘度。优选地,在从50到125℃范围的温度下,该油墨具有不超过20mPas,更优选地不超过12mPas的粘度。有利的是,该油墨适合于通过Spectra Nova256或S-等级打印头印刷。
冲洗步骤可以包括通过浸渍或喷雾使已蚀刻或电镀的基底与碱水溶液接触。优选地,油墨和冲洗条件可使油墨完全溶解,而不是留下微粒残留物或薄片,它们可能阻塞机器管道、过滤网或排水管。
用于评估油墨和油墨成分碱可洗性的试验方法
1)取一片铜片(大约25mm×75mm×1mm厚)并称重至4个小数位,得到重量(基础)
2)用待测试的油墨涂覆半个铜片,油墨层厚度为大约15-30微米。这可使用24微米的刮板(Meyer棒)实现。在上述范围内的精确涂层厚度不是严格的。
3)称重涂覆的铜片,得到重量(基础+油墨)
4)在50℃的温度下,将涂覆的铜片浸入到含有5%KOH水溶液的烧杯中。通过在KOH溶液中左右移动该铜片,将该铜片在溶液中搅动5分钟。
5)从该KOH溶液中移走该铜片,在流动的水下冲洗。将冲洗水收集在烧杯中。
6)在40℃的烤箱中干燥该铜片30分钟
7)称重铜片,得到重量(基础+残余)
8)如下计算碱可洗性:
碱可洗性=(重量(基础+油墨)-重量(基础+残余))/(重量(基础+油墨)-重量(基础))×100
优选地,油墨或油墨成分可使KOH溶液和冲洗溶液不含块、薄片和碎片形式的大(<1mm)片油墨。
用于评估油墨和油墨成分水可洗性的试验方法
1)取一片铜片(大约25mm×75mm×1mm厚)并称重至4个小数位,得到重量(基础)
2)用待测试的油墨涂覆半个铜片,油墨层厚度为大约15-30微米。这可使用24微米的刮板(Meyer棒)实现。在上述范围内的精确涂层厚度不是严格的。
3)称重涂覆的铜片,得到重量(基础+油墨)
4)在50℃的温度下,将涂覆的铜片浸入到含有水的烧杯中。通过在水中左右移动该铜片,将该铜片在溶液中搅动5分钟。
5)从水中移走铜片,在流动的水下冲洗。将冲洗水收集在烧杯中。
6)在40℃的烤箱中干燥该铜片30分钟
7)称重铜片,得到重量(基础+残余)
8)如下计算水可洗性:
水可洗性=(重量(基础+油墨)-重量(基础+残余))/(重量(基础+油墨)-重量(基础))×100
实施例
本发明的具体实施方式现在将被描述,仅仅为了示例的目的。
制备具有表中所示成分的油墨。随后测试油墨的碱和水可洗性,并且结果也在该表中给出。
注意(1)=Ennesin M57W来自Lawter
(2)来自Baker Petrolite
(3)来自Ciba
如所见,实施例油墨1到4每个具有适于喷墨印刷的熔体粘度。它们都是高度碱可洗的而不是水可洗的。
比较实施例1是典型的传统热熔喷墨油墨配方。如从表中可见,它不是碱可移除的。因此,其通过用碱水溶液冲洗是不可从基底移除的。
比较实施例2是水溶性热熔喷墨油墨。如从表中可见,其通过碱水溶液还有通过水是可移除的。因此,其在蚀刻或电镀步骤期间或在与此步骤相关的水冲洗中将被移除。
Claims (25)
1.蚀刻或电镀的方法,包括下述步骤:
ⅰ)将碱可移除的水不溶性热熔喷墨油墨喷墨印刷到基底上,以形成抗蚀图像;
ⅱ)在酸性水介质中蚀刻或镀所述基底;和
ⅲ)用碱水溶液移除所述抗蚀图像。
2.如权利要求1所述的方法,其中所述油墨包含碱溶性树脂和至少30wt%的碱溶性蜡,该碱溶性蜡包括有机酸,和其中所述油墨包括95wt%或以上的碱溶性成分。
3.如权利要求1或2所述的方法,其中在移除步骤中,所述抗蚀油墨分散在所述碱水溶液中形成溶液,在该溶液中,小于5wt%的所述抗蚀油墨是将被10微米滤器保留的颗粒的形式。
4.如权利要求1至3中任一项所述的方法,其是蚀刻方法,并且步骤ii)涉及用酸性水介质蚀刻所述基底。
5.如权利要求4所述的方法,其中使用“PAWN”蚀刻溶液蚀刻金属。
6.如权利要求4所述的方法,其中使用包含硫酸和过氧化氢的溶液蚀刻金属。
7.如权利要求4所述的方法,其中使用包含氢氟酸的溶液蚀刻二氧化硅。
8.如权利要求1至3中任一项所述的方法,其是将铜或锡电镀到所述基底上的方法。
9.如权利要求1至8中任一项所述的方法,其是在电路板生产中蚀刻或电镀的方法。
10.如权利要求1到8中任一项所述的方法,其是在太阳能电池生产中蚀刻或电镀的方法。
11.如权利要求1到4中任一项所述的方法,其是蚀刻钢压纹带的方法。
12.用作蚀刻或沉积抗蚀剂的碱可移除的水不溶性热熔喷墨油墨。
13.如权利要求12所述的油墨,其包含95wt%或以上的碱溶性成分。
14.如权利要求12或权利要求13所述的油墨,其包含碱溶性蜡。
15.如权利要求14所述的油墨,其包含从50wt%到95wt%的碱溶性蜡。
16.如权利要求14所述的油墨,其还包含碱溶性树脂,其中所述油墨包含至少30wt%的碱溶性蜡,其中所述碱溶性蜡包括有机酸。
17.如权利要求14至16中任一项所述的油墨,其中所述碱溶性蜡具有从45到60℃范围内的熔点。
18.如权利要求12到15中任一项所述的油墨,其包含碱溶性树脂。
19.如权利要求12到18中任一项所述的油墨,其包含着色剂。
20.如权利要求12到19中任一项所述的油墨,其包含荧光剂。
21.如权利要求12到20中任一项所述的油墨,其基本不含微粒。
22.如权利要求12到21中任一项所述的油墨,其在125℃下具有100mPas或更少的熔体粘度。
23.如权利要求12所述的油墨,其具有至少80%的碱可洗性和小于20%的水可洗性。
24.喷墨打印机,其包括如权利要求12到23任一项所述的油墨。
25.用于蚀刻或电镀工艺的基底,其在至少一个表面上具有如权利要求12到23中任一项所述的油墨的抗蚀图像。
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EP1630600A3 (en) * | 2004-07-29 | 2006-03-22 | Rohm and Haas Electronic Materials, L.L.C. | Hot melt composition and method involving forming a masking pattern |
CN101142148A (zh) | 2005-02-18 | 2008-03-12 | 格拉沃贝尔公司 | 玻璃制品表面的选择性蚀刻方法 |
ATE516693T1 (de) * | 2008-11-04 | 2011-07-15 | Rohm & Haas Elect Mat | Verbesserte schmelzzusammensetzungen |
JP5734734B2 (ja) * | 2010-05-18 | 2015-06-17 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | 半導体上に電流トラックを形成する方法 |
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- 2006-08-07 GB GBGB0615650.9A patent/GB0615650D0/en not_active Ceased
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- 2007-08-06 EP EP07800023.9A patent/EP2055156B1/en active Active
- 2007-08-06 US US12/375,506 patent/US8999185B2/en active Active
- 2007-08-06 CN CN201510083767.XA patent/CN104684259A/zh active Pending
- 2007-08-06 MY MYPI20090475A patent/MY148485A/en unknown
- 2007-08-06 CN CNA2007800366745A patent/CN101524005A/zh active Pending
- 2007-08-06 WO PCT/US2007/075253 patent/WO2008021780A1/en active Application Filing
- 2007-08-06 KR KR1020097004656A patent/KR101473689B1/ko not_active IP Right Cessation
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105163509A (zh) * | 2015-08-26 | 2015-12-16 | 江门崇达电路技术有限公司 | 一种在pcb上整板沉镍金的表面处理方法 |
CN105163509B (zh) * | 2015-08-26 | 2018-05-01 | 江门崇达电路技术有限公司 | 一种在pcb上整板沉镍金的表面处理方法 |
CN116732518A (zh) * | 2023-06-06 | 2023-09-12 | 上海奢藏科技有限公司 | 一种异型多面铝材表面花纹蚀刻处理工艺 |
Also Published As
Publication number | Publication date |
---|---|
US8999185B2 (en) | 2015-04-07 |
WO2008021780A1 (en) | 2008-02-21 |
EP2055156A1 (en) | 2009-05-06 |
MY148485A (en) | 2013-04-30 |
CN101524005A (zh) | 2009-09-02 |
GB0615650D0 (en) | 2006-09-13 |
KR101473689B1 (ko) | 2014-12-18 |
US20110020970A1 (en) | 2011-01-27 |
EP2055156B1 (en) | 2017-05-24 |
KR20090074730A (ko) | 2009-07-07 |
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