CN107814961A - 用于选择性金属化的屏蔽涂层 - Google Patents

用于选择性金属化的屏蔽涂层 Download PDF

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CN107814961A
CN107814961A CN201710788790.8A CN201710788790A CN107814961A CN 107814961 A CN107814961 A CN 107814961A CN 201710788790 A CN201710788790 A CN 201710788790A CN 107814961 A CN107814961 A CN 107814961A
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alkyl
straight
branched
polymer
substituted
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陈鸿达
叶家明
陈喆垚
余国伟
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Rohm and Haas Electronic Materials LLC
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Rohm and Haas Electronic Materials LLC
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Abstract

将屏蔽涂层施用到聚合物衬底以用于衬底的选择性金属化。屏蔽涂层包括底涂剂成分和疏水性顶涂层。首先将底涂剂施用到聚合物衬底，随后施用顶涂层成分。随后选择性蚀刻屏蔽涂层以形成所需当前图案的轮廓。将催化剂施用到经图案化的聚合物衬底，随后在经蚀刻的部分进行无电金属镀覆。含有屏蔽涂层的聚合物衬底部分抑制无电金属镀覆。底涂剂含有聚胺并且顶涂层含有疏水性烷基有机化合物。

Description

用于选择性金属化的屏蔽涂层
技术领域
本发明涉及用于与模制互连装置相关的聚合物衬底的选择性金属化的屏蔽涂层。更 确切地说，本发明涉及用于模制互连装置的聚合物衬底的选择性金属化的屏蔽涂层，其中屏蔽涂层充当后续催化剂和无电金属镀覆的阻挡层。
背景技术
激光直接成型工艺(LDS)已经研发并且用于所谓模制互连装置(MID)的模制塑 料材料的选择性镀覆超过10年。通过LDS有可能在复杂3维衬底上获得高度功能性电 路布局。所述工艺的基础涉及掺杂添加剂的热塑性材料或热固性材料与无机填充剂，其 允许借助于激光活化形成电路迹线，随后使用无电镀覆金属化。并入在这类塑料中的含 有金属的添加剂是通过激光束活化并且变得有活性，从而作为催化剂用于在有待镀覆的 塑料表面的经处理区域上无电镀铜。除活化以外，激光处理可产生显微级粗糙表面，使 得铜在金属化期间牢固地锚定于此。然而，这类技术局限于应用在掺杂添加剂的塑料上， 而未掺杂添加剂的一般类型的工程塑料无法被活化用于无电镀铜。
在使用中的另一种技术是连同LDS一起的专用涂法。其是通过首先在塑料部件上喷 涂薄层涂料来进行。LDS工艺随后在涂料涂层上形成电路布局并且同时活化电路上的涂料。塑料将接着经受无电镀铜用于金属化。此方法可在无添加剂掺杂的情况下扩展至塑料。然而，其仍处于原型阶段并且尚未准备用于大量生产。
激光重构印刷(LRP)是用于MID应用的另一种创新技术。LRP采用高精度印刷在 工件上产生导电图(银浆料)以形成电路布局。随后激光修整经印刷的工件。在工件上 产生高精度电路结构。此技术涉及对高成本3D打印机的较高启动投资。
另一种技术是半加成工艺(SAP)。第一步是采用现有胶态催化剂和用于在印刷电路 板上金属化的无电铜而在塑料衬底上镀覆无电铜薄层。在塑料衬底上涂布一层电沉积的 负型光刻胶。在曝光和显影后，暴露未覆盖光刻胶的电路图案。经暴露的电路可镀铜以达到所需厚度并且随后镀镍。去除剩余光刻胶。通过微蚀刻去除过量铜层。此技术的一 种优势在于能够将较低成本的电解电镀工艺代替常用无电镀覆工艺应用于完全铜构筑 和镍。塑料衬底已完全镀有一层无电铜。此技术还可应用于未掺杂添加剂的塑料。然而， 由于其不涉及使用激光使电路粗糙化，所以镀覆附着性是一个问题。另外，所述工艺顺 序相当长并且复杂，涉及额外光刻胶工艺。
虽然存在与聚合物和塑料材料的选择性金属化相关的多种工艺，但是仍需要聚合物 和塑料(具体来说，MID)的选择性金属化的改进方法。
发明内容
聚合物衬底的金属化方法包括：提供聚合物衬底；将包括聚胺化合物的底涂剂施用 于聚合物衬底以在聚合物衬底上提供亲水性涂层；直接邻近底涂剂施用疏水性顶涂层以 在衬底上形成屏蔽涂层，疏水性顶涂层包括一种或多种选自烷基醇烷氧基化物、烷基硫醇、非聚合物烷基伯胺和非聚合物烷基仲胺的化合物；选择性蚀刻屏蔽涂层以暴露部分 聚合物衬底；将催化剂提供于包括屏蔽涂层的聚合物衬底；以及选择性无电金属镀覆聚 合物衬底。
屏蔽涂层可通过其排斥水基催化剂的疏水性特征抑制催化剂吸附在塑料衬底上或 可钝化所吸附的催化剂。另外，屏蔽涂层可抑制背景镀覆和过度镀覆。离子催化剂和胶态催化剂均可使用。具有和没有嵌埋式催化剂的聚合物可与本发明一起使用。本发明的 方法可用于在3-D聚合物衬底上形成电路。
附图说明
图1为说明本发明实施例的示意图。
具体实施方式
除非上下文另外明确指示，否则如本说明书通篇所使用，下文给出的缩写具有以下 含义：g＝克；mg＝毫克；mL＝毫升；L＝升；cm＝厘米；m＝米；mm＝毫米； μm＝微米；ppm＝百万分率；mg/L＝毫克/升；M＝摩尔浓度；℃＝摄氏度；RT＝室 温；g/L＝克/升；DI＝去离子；MID＝模制互连装置；3-D＝三(3)维；Pd＝钯； Nd:YAG＝掺杂钕的钇铝石榴石；EO＝氧化乙烯；PO＝氧化丙烯；PO-b-EO＝氧化丙 烯/氧化乙烯嵌段共聚物；Mn＝数目平均分子量；wt％＝重量百分比；ABS＝丙烯腈- 丁二烯-苯乙烯共聚物；White ABS＝白色ABS；PC＝聚碳酸酯聚合物；Black PC＝黑 色PC；GF＝玻璃纤维；以及Tg＝玻璃化转变温度。
术语模制互连装置或MID意思指具有集成电子电路迹线的注射模制热塑性部件，其通常具有3-D形状或形式。术语“背景镀覆”意思指在不打算沉积金属的聚合物或塑料 表面上的随机金属沉积。术语“过度镀覆”意思指在所需电路图案以外的金属镀覆和不能 控制金属镀覆。术语“单体(monomer或monomeric)”意思指可与一个或多个相同或类 似的分子组合的单个分子。术语“寡聚物”意思指组合形成单个分子的两个或三个单体。 术语“聚合物”意思指组合形成单个分子的两个或更多个单体或两个或更多个寡聚物。术 语“聚合物”包括共聚物。术语“邻近”意思指两个不同表面彼此接触形成共同介面的邻接。 术语“印刷电路板”和“印刷线路板”在本说明书通篇可互换使用。术语“镀覆”和“沉积”在 本说明书通篇可互换使用。除非另外指出，否则所有量都是重量百分比。所有数值范围 都包括端点在内并且可按任何次序组合，但逻辑上这类数值范围被限制于总计共100％。
本发明的屏蔽涂层包括底涂剂组合物，其包括一种或多种聚胺并且直接邻近施用于 衬底的聚合物或塑料材料的表面以在聚合物或塑料材料上提供基本上亲水性涂层，随后 除了任选的冲洗步骤之外无任何中间步骤，直接邻近于底涂剂组合物施用疏水性顶涂层 以形成直接邻近于衬底的聚合物材料的屏蔽涂层，所述顶涂层包括烷基醇烷氧基化物、烷基硫醇、非聚合物烷基伯胺和非聚合物烷基仲胺中的一个或多个。因此，屏蔽涂层包 括底涂剂，其包括聚胺，可通过范德华力(Van der Waals force)结合于聚合物；和顶涂 层，其包括烷基醇烷氧基化物、烷基硫醇、非聚合物烷基伯胺和非聚合物烷基仲胺中的 一个或多个。虽然不受理论束缚，但是据相信，疏水性顶涂层中所包括的化合物的亲水 性部分与亲水性底涂剂相互作用或互混并且顶涂层化合物的疏水性部分相反于或远离 衬底的聚合物材料延伸以形成基本上疏水性顶表面，由此在聚合物衬底上形成屏蔽涂 层。图示说明本发明的四个基本步骤。
据设想，在形成本发明的屏蔽涂层时可形成底涂剂的任何聚胺可用于实践本发明。 本发明的聚胺是以0.5g/L至20g/L、优选地1g/L至15g/L、更优选地1g/L至10g/L 的量包括在内。优选地，聚胺选自聚亚烷基聚胺以及直链和支链聚亚烷基亚胺(PAI)。
优选的聚亚烷基聚胺具有以下通式：
其中R1、R2、R3、R4和R5独立地选自氢和直链或支链(C1-C4)烷基，其中a是2至 6并且b是2至6。优选地，R1、R2、R3、R4和R5独立地选自氢和(C1-C2)烷基，a是2 至6并且b是2至6。更优选地，R1和R2是氢并且R3、R4和R5选自氢和甲基，a是2 至3并且b是2至6。最优选地，R1、R2、R3、R4和R5是氢，a是2并且b是2至6。 具有式(I)的示例性聚亚烷基聚胺是二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚 乙基六胺和六亚乙基七胺。
本发明优选的聚亚烷基亚胺(PAI)具有以下通式：
H-(CH2-(CH2)d-NH-)e-H (II)
其中d和e是相同或不同的并且至少是1。优选地，d是1至4并且e是大于25的 值。更优选地，e大于250并且最优选地，e大于2500。最优选的分子量(Mn)是800 和更大，更优选地1500和更大并且最优选地2500和更大。
更优选的聚亚烷基亚胺(PAI)是聚亚乙基亚胺(PEI)。这类PEI被认为具有以下 通式，但在行业内并未确认：
-(NHCH2CH2-)f[-N(CH2CH2NH2)CH2CH2-]g (III)
其中f是1至120,000、优选地2至60,000、更优选地3至24,000并且g是1至60,000、优选地2至30,000、更优选地3至12,000。式(III)的示例性聚亚乙基亚胺是PEI-3、PEI-7、PEI-15、PEI-30、PEI-45、PEI-100、PEI-300、PEI-500、PEI-600、PEI-700、PEI-800、 PEI-1000、PEI-1500、PEI-1800、PEI-2000、PEI-70,000、PEI-500,000和PEI-5,000,000， 其中整数是指聚合物的分子量。像这样命名的PEI可从Aldrich购得。
本发明的聚亚乙基亚胺(PEI)还包括支链质子化聚亚乙基亚胺(PEI盐)。在支链质子化聚亚乙基亚胺(PEI盐)中，每个质子化氮中心的抗衡离子与在中和期间获得的 酸的阴离子平衡。支链质子化聚亚乙基亚胺的实例是PEI-盐酸盐、PEI-硫酸盐、PEI-硝 酸盐、PEI-乙酸盐和PEI-脂肪酸盐。
任选地，底涂剂组合物可包括一种或多种金属离子以辅助底涂剂与顶涂层化合物混 合。这类金属离子包括(但不限于)铜离子、镍离子、锰离子和锌离子。这类离子是通 过其水溶性盐添加至底涂剂组合物中。铜盐包括(但不限于)硫酸铜、硝酸铜、氯化铜 和乙酸铜。镍盐包括(但不限于)氯化镍、硫酸镍和氨基磺酸镍。锰盐包括(但不限于) 硫酸锰。锌盐包括(但不限于)硝酸锌。这类盐是以0.5g/L至15g/L、优选地1g/L至 10g/L的量包括在底涂剂中。优选地，所选金属离子是铜和镍。更优选地，所选离子是 铜离子。一般来说，底涂剂溶液中优选地包括一种或多种金属离子；然而，可进行少量 实验以测定所述一种或多种金属离子是否改善顶涂层化合物吸附于特定聚合物材料。
底涂剂可通过将组分按任何次序混合于水中制备。底涂剂的pH值范围可优选地介于7至13、更优选地介于8至12。
在将底涂剂施用于聚合物材料之前，优选地清洁聚合物材料以从聚合物表面去除任 何表面油和残余物。图在步骤1示出了经清洁的衬底。可使用所属领域中已知的常规清洁组合物和方法。清洁通常是在室温下在清洁溶液中，如10％CUPOSITTM Z清洁配制 品(可从马萨诸塞州马波罗的陶氏先进材料(Dow Advanced Materials,Marlborough,MA) 购得)，使用超声波来进行。
可通过将含有聚合物材料的衬底浸没在底涂剂中而直接邻近聚合物材料施用底涂 剂，或其可直接邻近于聚合物材料喷涂。底涂剂优选地在室温至80℃、更优选地30℃至50℃的温度下施用。在聚合物材料与顶涂层接触之前的停留时间介于优选地1分钟至10 分钟、更优选地3分钟至8分钟范围内。
在将底涂剂施用于衬底的聚合物材料之后，在除任选的水冲洗步骤以外在本发明的 方法中无任何中间步骤的情况下，将顶涂层直接邻近于底涂剂施用于聚合物材料上。顶涂层是通过将聚合物材料浸没在顶涂层溶液中或通过直接邻近涂布聚合物材料的底涂 剂喷涂顶涂层而直接邻近于底涂剂施用。顶涂层优选地在室温至80℃、更优选地30℃至 50℃的温度下施用。顶涂层施用的停留时间介于优选地1分钟至10分钟、更优选地3 分钟至8分钟范围内。在将顶涂层施用于底涂剂之后，使顶涂层在底涂剂上干燥以形成 直接邻近于衬底中的聚合物材料的屏蔽涂层。图示说明邻近聚合物衬底的屏蔽涂层。任 选地，顶涂层可通过在室温下吹干而干燥。
顶涂层选自烷基醇烷氧基化物、烷基硫醇和非聚合物伯胺和非聚合物仲胺。其可以 0.5g/L至100g/L、优选地1g/L至30g/L的量包括在内。烷基醇烷氧基化物包括(但不 限于)具有下式的聚乙氧基化醇聚合物：
CH3(CH2)m-(O-CH2-CH2)n-OH (IV)
其中m是7至25；并且n表示1至25的平均乙氧基化程度。优选地，n是7至15 并且m优选地是13至25。烷基醇烷氧基化物还包括具有下式的脂肪族乙氧基化/丙氧 基化共聚物：
R-O-(CH2CH2O)x-(CH2CH2CH2O)y-H (V)或
R-O-(CH2CH2O)x-(CH2CH(CH3)O)y-H (VI)
其中R是具有8至22个碳原子的直链或支链烷基或异十三基，并且x和y独立地 选自1至20。烷基醇烷氧基化物还包括具有下式的丙氧基化/乙氧基化共聚物：
R-O-(CH2CH(CH3)O)x-(CH2CH2O)y-H (VII)或
R-O-(CH2CH2CH2O)x-(CH2CH2O)y-H (VIII)
其中R以及x和y如上文所定义。
烷基硫醇包括(但不限于)具有下式的硫醇：
R6-SH (IX)
其中R6是具有1至24个碳原子、优选地16至21个碳原子的直链或支链烷基；具 有5至14个碳原子的芳基；和烷芳基，其中烷芳基的烷基是具有1至24个碳原子的直 链或支链并且芳基具有5至14个碳原子。示例性烷基硫醇是乙硫醇、1-丙硫醇、2-丙硫 醇、1-丁硫醇、2-丁硫醇、2-甲基-1-丙硫醇、2-甲基-2-丙硫醇、2-甲基-1-丁硫醇、1-戊 硫醇、2,2-二甲基-1-丙硫醇、1-己硫醇、1,6-己硫醇、1-庚硫醇、2-乙基己硫醇、1-辛硫 醇、1,8-辛硫醇、1-壬硫醇、1,9-壬硫醇、1-癸硫醇、1-十一硫醇、1-十二硫醇、1-十三 硫醇、1-十四硫醇、1-十五硫醇、1-十六硫醇、1-十七硫醇、1-十八硫醇、1-十九硫醇和 1-二十硫醇。优选的示例性烷基硫醇是1-十六硫醇、1-十七硫醇、1-十八硫醇、1-十九 硫醇和1-二十硫醇。
非聚合物伯胺和非聚合物仲胺包括(但不限于)具有下式的胺化合物：
R7-CH2-NH2 (X)或
R8-CH2-NH-CH2-R9 (XI)
其中R7、R8和R9独立地选自氢、经取代或未经取代的直链或支链(C1-C24)烷基、经取代或未经取代的直链或支链(C2-C20)烯基、经取代或未经取代的(C3-C8)环烷基和经取代或未经取代的(C6-C10)芳基，其中取代基包括(但不限于)羟基、羟基(C1-C20)烷基、氨 基、(C1-C20)烷氧基、卤素(如氟、氯和溴)、巯基和苯基。优选地，胺化合物是非聚合 物伯胺，其中R7是经取代或未经取代的直链或支链(C1-C21)烷基，更优选地，胺化合物 是非聚合物伯胺，其中R7是未经取代的直链或支链(C1-C21)烷基。
示例性伯胺包括氨基乙烷、1-氨基丙烷、2-氨基丙烷、1-氨基丁烷、2-氨基丁烷、1-氨基-2-甲基氨基戊烷、2-氨基-2-甲基丙烷、1-氨基戊烷、2-氨基戊烷、3-氨基戊烷、新 戊胺、1-氨基己烷、1-氨基庚烷、2-氨基庚烷、1-氨基辛烷、2-氨基辛烷、1-氨基壬烷、 1-氨基癸烷、1-氨基十二烷、1-氨基十三烷、1-氨基十四烷、1-氨基十五烷、1-氨基十六 烷、1-氨基十七烷和1-氨基十八烷。优选地，示例性伯胺包括1-氨基十六烷、1-氨基十 七烷和1-氨基十八烷。
任选地，顶涂层可包括一种或多种有机溶剂以帮助溶解有机化合物。有机溶剂是以 足以溶解疏水性顶涂层化合物的量包括在内。优选地，一种或多种有机溶剂是以0-60体积％、优选地10体积％至50体积％的量包括在内。这类有机溶剂包括醇、二醇、三 醇和更高级多元醇。合适的醇包括乙醇、丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、乙 二醇、丙-1,2-二醇、丁-1,2-二醇、丁-1,3-二醇、丁-1,4-二醇、丙-1,3-二醇、己-1,4-二醇、 己-1,5-二醇、己-1,6-二醇、2-甲氧基乙醇、2-乙氧基乙醇、2-丙氧基乙醇和2-丁氧基乙 醇。还包括不饱和二醇，如丁烷-二醇、己烷-二醇和炔属物质，如丁炔二醇。合适的三 醇是丙三醇。额外醇包括三乙二醇、二乙二醇、二乙二醇甲醚、三乙二醇单甲醚、三乙 二醇二甲醚、丙二醇、二丙二醇、烯丙醇、呋喃甲醇、四氢呋喃甲醇和聚乙烯与聚乙二 醇的嵌段聚合物。
在衬底的聚合物材料上形成屏蔽涂层之后，选择性蚀刻屏蔽涂层以形成电路图案。 图案可通过在塑料上镀覆行业中已知的常规方法来蚀刻，如(但不限于)激光蚀刻、砂纸蚀刻和等离子蚀刻。优选地，屏蔽涂层是用激光选择性蚀刻，如可从LPKF Laser&Electronics AG购得的Nd:YAG,1064nm LPKF激光器。激光蚀刻能够形成细线电路的细 线图案，因为激光可调节至极细尺寸。这进一步能够使得电路小型化和3-D电子制品小 型化。典型道宽大于或等于150μm并且间距或间隙大于或等于200μm。进行蚀刻以向 下去除屏蔽涂层直至聚合物材料并且使聚合物表面粗糙化，如图步骤3中所示。如果聚 合物材料具有嵌埋式催化剂，那么去除表面足够的聚合物材料以暴露催化剂用于无电金 属镀覆。如果聚合物材料不包括嵌埋式催化剂，那么可将常规离子催化剂或胶态催化剂 施用于聚合物用于无电金属镀覆，如图步骤4中所示。离子或胶态催化剂可通过常规方 式，如通过浸渍或喷涂催化剂而施用在经蚀刻衬底上。可使用常规催化剂参数(如催化 剂溶液的温度、pH值和停留时间)来实践本发明。依据催化剂类型而定，在无电金属 化之前可使用常规后处理活化催化剂。离子催化剂优选地包括催化性离子，如银离子和 钯离子。络合剂通常与金属离子一起被包括以在催化之前稳定金属离子。胶态催化剂优 选地是常规锡/钯。
如果催化剂是离子催化剂，那么在将催化剂施用于聚合物之后并且在金属化之前， 将一种或多种还原剂施用于催化的聚合物以使金属离子还原至其金属态。可使用已知使 金属离子还原成金属的常规还原剂。这类还原剂包括(但不限于)二甲胺硼烷、硼氢化钠、抗坏血酸、异抗坏血酸、次磷酸钠、水合肼、甲酸和甲醛。还原剂是以使基本上所 有金属离子还原成金属的量包括在内。这类量一般是常规量并且是所属领域的技术人员 所熟知的。
本发明的方法可用于无电金属镀覆各种衬底，如印刷电路板和MID。优选地，本发明的方法用于选择性无电金属镀覆MID，其通常具有3-D配置而非平面配置的衬底，如 印刷电路板。这类3-D配置的衬底由于其3-D配置而难以无电金属电镀连续和均一的电 路，其中电路需要按照MID配置表面的不规律轮廓。这类印刷电路板和MID可包括以 下聚合材料：热固性树脂、热塑性树脂及其组合，包括纤维(如玻璃纤维)和前述浸渍 实施例。
热塑性树脂包括(但不限于)缩醛树脂、丙烯酸树脂(如丙烯酸甲酯)、纤维素树 脂(如乙酸乙酯、丙酸纤维素、乙酸丁酸纤维素和硝酸纤维素)、聚醚、尼龙(nylon)、 聚乙烯、聚苯乙烯、苯乙烯掺合物(如丙烯腈苯乙烯和共聚物和丙烯腈-丁二烯苯乙烯共 聚物)、聚碳酸酯、聚氯三氟乙烯以及乙烯基聚合物和共聚物(如乙酸乙烯酯、乙烯醇、 乙烯基缩丁醛、氯乙烯、氯乙烯-乙酸酯共聚物、偏二氯乙烯和乙烯基缩甲醛)。
热固性树脂包括(但不限于)邻苯二甲酸烯丙酯、呋喃、三聚氰胺-甲醛、酚-甲醛和酚-糠醛共聚物(单独的或与丁二烯丙烯腈共聚物或丙烯腈-丁二烯-苯乙烯共聚物复合)、聚丙烯酸酯、硅酮、脲甲醛、环氧树脂、烯丙基树脂、邻苯二甲酸甘油酯和聚酯。
本发明的方法可用于镀覆具有低和高Tg树脂的衬底。低Tg树脂的Tg低于160℃并且高Tg树脂的Tg是160℃和更高。通常，高Tg树脂的Tg是160℃至280℃或如170℃至 240℃。高Tg聚合物树脂包括(但不限于)聚四氟乙烯(PTFE)和聚四氟乙烯掺合物。 这类掺合物包括例如具有聚苯醚和氰酸酯的PTFE。其它类别的包括高Tg树脂的聚合物 树脂包括(但不限于)环氧树脂，如双官能和多官能环氧树脂、双马来酰亚胺/三嗪和环 氧树脂(BT环氧树脂)、环氧树脂/聚苯醚树脂、丙烯腈丁二烯苯乙烯、聚碳酸酯(PC)、 聚苯醚(PPO)、聚亚苯基醚(PPE)、聚苯硫醚(PPS)、聚砜(PS)、聚酰胺、聚酯(如 聚对苯二甲酸乙二酯(PET)和聚对苯二甲酸丁二酯(PBT))、聚醚酮(PEEK)、液晶 聚合物、聚氨基甲酸酯、聚醚酰亚胺、环氧树脂以及其复合物。
虽然据设想本发明可用于无电沉积任何可无电镀覆的金属，但是金属优选地选自铜、铜合金、镍或镍合金。可商购的无电镀铜浴的实例是CIRCUPOSITTM 880无电铜浴 (可从马萨诸塞州马波罗的陶氏先进材料购得)。可商购的无电镀镍浴的另一个实例是DURAPOSITTM SMT 88(可从马萨诸塞州马波罗的陶氏先进材料购得)。可商购的无电 镍浴的实例是DURAPOSITTM SMT 88无电镍(可从马萨诸塞州马波罗的陶氏先进材料 购得)。
通常，铜离子源包括(但不限于)铜的水溶性卤化物、硝酸盐、乙酸盐、硫酸盐和 其它有机和无机盐。可使用这类铜盐中的一种或多种的混合物提供铜离子。实例包括硫 酸铜(如五水合硫酸铜)、氯化铜、硝酸铜、氢氧化铜以及氨基磺酸铜。组合物中可使 用常规量的铜盐。
无电组合物中还可包括一种或多种合金金属。这类合金金属包括(但不限于)镍和锡。铜合金的实例包括铜/镍和铜/锡。通常，铜合金是铜/镍。
镍和镍合金无电浴的镍离子源可包括一种或多种常规水溶性镍盐。镍离子源包括(但不限于)硫酸镍和卤化镍。镍离子源可以常规量包括在无电合金组合物中。锡离子 源包括(但不限于)硫酸锡、氯化锡和有机锡盐，如烷基磺酸锡。锡盐可以常规量包括 在无电合金组合物中。
无电金属镀覆参数(如温度和时间)可以是常规的并且是所属领域中众所周知的。无电金属镀覆浴的pH值通常是碱性的。
在所暴露聚合物材料的选择性无电金属镀覆期间，涂布有屏蔽涂层的聚合物材料部 分抑制无电金属镀覆，如图步骤5中所示。抑制在涂布有屏蔽涂层的聚合物部分上的不当背景镀覆和过度镀覆，使得金属镀覆基本上发生在聚合物的经蚀刻部分。屏蔽涂层能 够按照3-D物品的轮廓形成金属电路，同时抑制可产生缺陷制品的背景镀覆和过度镀覆。 能够进行细线电路图案化的激光蚀刻与屏蔽涂层的组合使得能够在3-D聚合物衬底的不 规律表面上形成连续微型化电路，从而形成微型化电子制品。
以下实例并不打算限制本发明的范围，而是进一步说明本发明。
实例1
提供多个聚合物衬底。根据下表1中所公开的方法处理每个衬底并且选择性无电镀 铜。大部分衬底具有尖晶石重金属氧化物或重金属络合物的嵌埋式催化剂。发生无电镀铜的屏蔽涂层部分用碳化硅类型P220砂纸去除。如果衬底不具有嵌埋式催化剂，那么 在无电镀覆之前将离子催化剂水溶液施用到衬底。离子催化剂水溶液包括200ppm钯离 子和1,020ppm 2,6-二甲基吡嗪。还原剂是在1g/L浓度下的二甲胺硼烷。使用可从陶氏 先进材料购得的CUPOSITTM 71HS无电铜浴进行无电镀铜。
表1
表2
在每个聚合物衬底被无电镀铜之后，在室温下用去离子水冲洗衬底并且分析铜沉积 物的质量。所有铜沉积物呈现为均匀和明亮的。在任一个衬底上都未观察到背景镀覆或过度镀覆。
实例2
根据下表3中所公开的方法，用铜选择性无电镀覆多个白色ABS和黑色PC(XANTARTM 3730)聚合物衬底。
表3
针对铜沉积质量以及任何背景镀覆，分析聚合物衬底。所有铜沉积物呈现为明亮和 平滑的。下表4公开与背景镀覆和底涂剂组合物中氯化铜的浓度相关的结果。
表4
除在含有四亚乙基五胺的底涂剂中不包括氯化铜的情况下黑色PC具有轻微背景镀 覆之外，所有聚合物样品都未出现任何背景镀覆。
实例3
根据下表5中所公开的方法，选择性无电镀覆白色ABS和黑色PC(XANTARTM 3730)。
表5
针对铜沉积质量以及任何背景镀覆，分析聚合物衬底。所有铜沉积物呈现为明亮和 平滑的。下表6公开与背景镀覆和底涂剂组合物中氯化铜的浓度相关的结果。
表6
虽然在0.015M和0.03M的氯化铜浓度下存在轻微背景镀覆，但是在底涂剂组合物包括聚亚乙基亚胺时添加氯化铜显著抑制背景镀覆。

Claims (18)

1.一种聚合物衬底金属化的方法，包含：
a)提供聚合物衬底；
b)将包含聚胺化合物的底涂剂施用于所述聚合物衬底以在所述聚合物衬底上提供亲水性涂层；
c)直接邻近所述底涂剂施用疏水性顶涂层以在所述衬底上形成屏蔽涂层，所述疏水性顶涂层包含一种或多种选自烷基醇烷氧基化物、烷基硫醇、非聚合物烷基伯胺和非聚合物烷基仲胺的化合物；
d)选择性蚀刻所述屏蔽涂层以暴露部分所述聚合物衬底；
e)将催化剂提供于包含所述屏蔽涂层的所述聚合物衬底；以及
f)选择性无电金属镀覆所述聚合物衬底。
2.根据权利要求1所述的方法，其中所述聚胺选自聚亚烷基聚胺和直链或支链聚亚烷基亚胺。
3.根据权利要求2所述的方法，其中所述聚亚烷基聚胺具有以下通式：
其中R1、R2、R3、R4和R5独立地选自氢和直链或支链(C1-C4)烷基，其中a是2至6并且b是2至6。
4.根据权利要求3所述的方法，其中所述聚亚烷基聚胺选自二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺和六亚乙基七胺。
5.根据权利要求2所述的方法，其中所述直链聚亚烷基亚胺具有下式：
H-(CH2-(CH2)d-NH-)e-H(II)
其中d和e是相同或不同的并且至少是1。
6.根据权利要求2所述的方法，其中所述直链或支链聚亚烷基亚胺具有下式：
-(NHCH2CH2-)f[-N(CH2CH2NH2)CH2CH2-]g(III)
其中f是1至120,000并且g是1至60,000。
7.根据权利要求2所述的方法，其中所述支链聚亚烷基亚胺是质子化聚亚乙基亚胺(PEI盐)。
8.根据权利要求1所述的方法，其中所述烷基醇烷氧基化物是具有下式的聚乙氧基化醇聚合物：
CH3(CH2)m-(O-CH2-CH2)n-OH(IV)
其中m是7至25；并且n表示1至25的平均乙氧基化程度。
9.根据权利要求1所述的方法，其中所述烷基醇烷氧基化物是具有下式的脂肪族乙氧基化/丙氧基化共聚物：
R-O-(CH2CH2O)x-(CH2CH2CH2O)y-H(V)或
R-O-(CH2CH2O)x-(CH2CH(CH3)O)y-H(VI)
其中R是具有8至22个碳原子的直链或支链烷基或异十三基，并且x和y独立地选自1至20。
10.根据权利要求1所述的方法，其中所述烷基醇烷氧基化物是具有下式的脂肪族丙氧基化/乙氧基化共聚物：
R-O-(CH2CH(CH3)O)x-(CH2CH2O)y-H(VII)或
R-O-(CH2CH2CH2O)x-(CH2CH2O)y-H(VIII)
其中R是具有8至22个碳原子的直链或支链烷基或异十三基，并且x和y独立地选自1至20。
11.根据权利要求1所述的方法，其中所述烷基硫醇具有下式：
R6-SH(IX)
其中R6是具有1至24个碳原子的直链或支链烷基、具有5至14个碳原子的芳基或烷芳基，其中所述烷芳基的烷基是具有1至24个碳原子的直链或支链并且芳基具有5至14个碳原子。
12.根据权利要求1所述的方法，其中所述非聚合物伯胺具有下式：
R7-CH2-NH2(X)
其中R7独立地选自氢、经取代或未经取代的直链或支链(C1-C20)烷基、经取代或未经取代的直链或支链(C2-C20)烯基、经取代或未经取代的(C3-C8)环烷基或经取代或未经取代的(C6-C10)芳基。
13.根据权利要求1所述的方法，其中所述非聚合物仲胺具有下式：
R8-CH2-NH-CH2-R9(XI)
其中R8和R9独立地选自氢、经取代或未经取代的直链或支链(C1-C20)烷基、经取代或未经取代的直链或支链(C2-C20)烯基、经取代或未经取代的(C3-C8)环烷基或经取代或未经取代的(C6-C10)芳基。
14.根据权利要求1所述的方法，其中所述底涂剂另外包含一种或多种金属离子。
15.根据权利要求14所述的方法，其中所述一种或多种金属离子选自铜、镍、锰和锌。
16.根据权利要求1所述的方法，其中所述疏水性顶涂层另外包含一种或多种有机溶剂。
17.根据权利要求16所述的方法，其中所述一种或多种有机溶剂选自醇、二醇、三醇和更高级多元醇。
18.根据权利要求1所述的方法，其中金属是铜。
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