CN104109537B - 使用混合酸液无铬刻蚀有机聚合物的方法 - Google Patents
使用混合酸液无铬刻蚀有机聚合物的方法 Download PDFInfo
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- CN104109537B CN104109537B CN201410245518.1A CN201410245518A CN104109537B CN 104109537 B CN104109537 B CN 104109537B CN 201410245518 A CN201410245518 A CN 201410245518A CN 104109537 B CN104109537 B CN 104109537B
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Classifications
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
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- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
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- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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Abstract
使用混合酸液无铬刻蚀有机聚合物的方法。提供了一种方法，所述方法包括：a.提供包含一种或多种有机聚合物的基材；b.提供一种水性酸溶液，所述水性酸溶液基本由硫酸、一种或多种有机酸以及Mn(II)离子和Mn(III)离子组成；和c.将基材的一种或多种有机聚合物与所述水性酸溶液接触，以刻蚀所述基材的一种或多种有机聚合物。
Description
发明领域
本发明涉及一种使用含锰离子的混合酸溶液无铬刻蚀有机聚合物的方法。更具体地，本发明涉及一种使用包含硫酸和至少一种含锰(II)和(III)离子的有机酸的混合酸液无铬刻蚀有机聚合物的方法。
发明背景
在金属化前，含有机聚合物的基体表面通常进行刻蚀而在基体表面和镀覆的金属之间获得较好的附着性。虽然数年来许多化学供应商和镀覆企业做了许多努力来取代目前使用的有毒的刻蚀液，但是目前在市场上仍然无法获得不含六价铬或Cr(VI)的商品。
含Cr(VI)的化合物被怀疑能够致癌。因此，处理这些化合物需要遵守严格的环境规程。面对释放Cr(VI)的化合物造成的潜在危险，不能排除禁止含Cr(VI)化合物的工业应用。
数年来，在工业上许多化学物质被建议用作湿刻蚀工艺中的无铬氧化剂来改性有机聚合物表面。这些氧化剂包括Mn(VII)、Mn(VI)、Mn(IV)、Ce(IV)、过硫酸盐、H2O2，有机溶剂如二恶烷、Fe、Cu、Ti、Zn和Mg的金属卤化物和氮化物。氧化剂被刻蚀过程或由于氧化剂自身的不稳定性所消耗。因此需要频繁的补充或再生的方法。再生的方式特别适合于工厂。Mn(VII)是最常用的氧化剂。溶液中其通常是MnO4 -离子形式。在碱性溶液中Mn(VII)的电化学再生已用于不同工业，例如用于印制电路板的制造。在酸性介质中，Mn(VII)的再生显得比在碱性介质中更难。在已公开的出版物中鲜见使用如Ag(I)或Bi(III)作为电化学氧化的催化剂。Fleischmann等(J.Appl.Electrochem，第1卷第1页，1971)的研究表明Ag(I)对于电化学氧化有机和无机物而言是一种良好的氧化剂。Park等(J.Electrochem.Soc第151卷，第E265页，2004)披露了在硼掺杂金刚石(BDD)电极上Bi(III)也可充当将Mn(II)氧化为Mn(VII)的电子转移媒介。Boardman(J.Electroanal，Chem，第149卷，第49页，1983)和Comninellis(Electrochimica Acta，第36卷第8期，第1363页，1991)证明了在有Ag(I)存在的硫酸介质中从Mn(II)到Mn(VII)的电化学转变的可能性，以及提高Mn(VII)转变的电流效率的实验环境。US2011/0140035披露了在高锰酸盐酸洗液(permanganate acidic pickling solution)中预处理塑料表面的相似方法。
然而，不论在酸性或碱性介质中，Mn(VII)都不稳定且倾向于还原为低氧化价态，特别是还原为Mn(IV)，因此形成大量不溶性的MnO2而在被处理的聚合物表面造成质量问题。因此在工业级操作中需要频繁去除来自高锰酸盐刻蚀液的MnO2沉淀。因此，就需要不会形成大量不期望的不溶性反应产物的方法以及可在连续操作中再生的氧化剂。
发明内容
方法包括，提供包含一种或多种有机聚合物的基板；提供一种水性酸溶液，所述水性酸溶液基本由硫酸、一种或多种有机酸以及Mn(II)离子和Mn(III)离子组成；和，用包含一种或多种有机聚合物的基板接触水性酸溶液来刻蚀所述基板的一种或多种聚合物。
水性酸液基本由硫酸、一种或多种有机酸以及Mn(II)离子和Mn(III)离子组成。
在金属化前，所述方法和水性酸溶液使用无铬水性酸溶液刻蚀基板的一种或多种聚合物，这样可消除危险的和对环境不良的化合物。所述方法和水性酸溶液使用溶解的Mn(III)离子取代Cr(VI)作为刻蚀剂来粗化一种或多种聚合物。Mn(III)离子在水性酸溶液中比Mn(VII)离子更稳定，而且不会像Mn(VII)那样容易形成不溶性MnO2，同时在刻蚀过程中还原为Mn(II)离子的Mn(III)离子可容易地再生。硫酸和一种或多种有机酸的混合物能提高Mn(II)和Mn(III)离子源的溶解度进而使Mn(II)和Mn(III)离子源完全溶解在水性酸溶液中，从而在溶液中提供足够的Mn(III)氧化剂的浓度以及在生产条件下使用标准溶液循环和过滤系统进行运作。进一步地，已知的是由于硫酸的吸水性，高浓度的硫酸溶液容易吸收大气中的水分。用一种或多种有机酸取代部分硫酸可降低或阻止水分的吸收从而获得良好的刻蚀结果。
附图说明
图1为65℃下的吸水量(g/m2/天)相对于20wt％的H2O和不同的H2SO4含量的混合物中的甲磺酸(wt％)的曲线图。
图2为UV-VIS吸收光谱相对于在1mmol/L的Mn(III)离子溶液和0.1mmol/L的KMnO4溶液中以nm计的波长的曲线图。
图3为UV-VIS吸收光谱相对于在十倍稀释的含49.4mmol的Mn(III)离子的水性酸刻蚀液中的以nm计的波长的曲线图。
图4为25000倍放大的SEM图像，其显示出适合于金属化的粗糙表面。
具体实施方式
除非文中特别清楚地指出，在本说明中使用的简称具有如下含义：℃＝摄氏度；g＝克；L＝升；M＝摩尔浓度或摩尔/升；mM＝毫摩尔浓度；mol＝摩尔；mmol＝毫摩尔；mL＝毫升；g/L＝克每升；m＝米；A＝安培；mA＝毫安；dm＝分米；UV＝紫外线；nm＝纳米；cm＝厘米；wt％＝质量百分比；Tg＝玻璃化转变温度；ASTM＝美国标准测试方法；Mn＝元素锰；Mn(II)＝锰的二价氧化态；Mn(III)＝锰的三价氧化态；Mn(IV)＝锰的四价氧化态；Mn(VI)＝锰的六价氧化态；Mn(VII)＝锰的七价氧化态；Cr(VI)＝铬的六价氧化态；Ag＝银；Bi＝铋；Ce＝铈；Pb＝铅；Ir＝铱；H2SO4＝硫酸；MnO4 -＝高锰酸根；KMnO4＝高锰酸钾；Ag2SO4＝硫酸银；Ag2O＝氧化银；O3＝臭氧；H2O2＝过氧化氢；MSA＝甲磺酸；SEM＝扫描电子显微镜；mbar＝毫巴；吸收度为-log(I/I0)，其中I0＝入射光强度，I＝透射光强度；以及FE-SEM＝高分辨率场发射扫描电子显微镜。
术语“化学计量的”表示一种数量关系，通常表示两种或多种发生物理或化学变化的化学物质的比率；其对应化学反应完成或稳定状态。所有数值范围都包括在内并以任何顺序组合，除了在逻辑上会相加大于100％的数值范围。除非特别指出，所有含量都以重量百分比计，所有比率都以重量比计。属于“一”和“一个”可认为包括单数和复数。
溶液基本由Mn(II)离子和Mn(III)离子、硫酸和一种或多种有机酸组成。在所述溶液中，用于刻蚀和粗化一种或多种聚合物的活性刻蚀成分为溶解的Mn(III)离子。Mn(II)和Mn(III)离子在溶液中的最大浓度由其在给定的酸的浓度和温度下的溶解度决定。可进行辅助实验来确定其对于给定组分溶液的饱和浓度。溶液中包含的一种或多种Mn(II)和Mn(III)离子源可高达刚好低于它们的饱和浓度。所述水性酸溶液不是悬浮液、分散液或胶质溶液。所述水性酸溶液的所有溶质都基本上全部溶解在溶剂中。所述溶液是无铬的。加足量的水使溶液达到100wt％。加水量可最高达溶液的45wt％，优选最高达到25wt％。如果水含量过高，那么溶液的刻蚀表现和Mn(III)离子在溶液中的稳定性会大打折扣。
Mn(II)离子的存在能使Mn(III)离子在高于Mn(II)的氧化态下基本成为唯一的Mn形式。在酸性介质中，如果在溶液中存在具有比Mn(III)更高氧化态形式的Mn，那么其将以如下氧化还原反应还原为Mn(III)：
Mn(VII)+4Mn(II)→5Mn(III) 反应式1
Mn(VI)+3Mn(II)→4Mn(III) 反应式2
Mn(IV)+Mn(II)→2Mn(III) 反应式3
刻蚀组合物的pH值从小于1到6，优选从小于1到3，更优选为小于1。由于存在Mn(II)离子，溶液中基本不含Mn(VI)、Mn(VII)和不溶的MnO2。
优选地，Mn(II)离子的浓度为0.1mmol/L到刚好低于形成Mn(II)盐沉淀或结晶的浓度，更优选地，Mn(II)离子的浓度为1mmol/L到刚好低于形成Mn(II)盐沉淀的浓度。最优选地，Mn(II)离子的浓度为1mmol/L到50mmol/L。Mn(II)离子在溶液中的最大浓度取决于温度和组合物中的酸含量而不同；然而，这可以通过溶液进行肉眼观测随后用原子吸收光谱仪(AAS)测量Mn的总浓度来容易地确定。Mn(II)离子在溶液中的浓度随后通过比对溶液中Mn总浓度和在波长530nm到520nm之间的UV-VIS分析仪得到的溶液中的Mn(III)离子浓度之差得到。UV-VIS和AAS是现有技术中公知的和最常用的用于分析溶液中金属浓度的分析方法。
优选地，Mn(III)离子的浓度为0.01mmol/L到刚好低于形成Mn(III)盐沉淀的浓度，更优选地，Mn(III)离子的浓度为1mmol/L到刚好低于形成Mn(III)盐沉淀的浓度。最优选地，Mn(III)离子的浓度为1mmol/L到70mmol/L。Mn(III)离子在溶液中的最大浓度取决于温度和组合物中的酸含量而不同；然而，这可通过肉眼观测溶液，随后用前述方法使用UV-VIS分析仪测量Mn(III)的浓度而容易地确定。
溶液中Mn(III)离子源包括，但不局限于Mn(III)-硫酸盐、Mn(III)-乙酸盐、Mn(III)-乙酰丙酮化物、Mn(III)-氟化物、Mn(III)-甲磺酸盐、Mn(III)-氧化物、Mn(III)-氧基氢氧化物(oxyhydroxide)、Mn(III)-磷酸盐、具有氮-螯合物的Mn(III)物质，例如卟吩，如5，10，15，20-四苯基-21H，23H-卟吩和2，3，7，8，12，13，17，18-八乙基21H-23H-卟吩和酚菁。上述化合物在现有技术或出版物中都是公知的，其中一些可商业获得。它们在溶液中的含量足以给溶液提供所需浓度的Mn(III)离子。
Mn(II)离子源包括但不局限于Mn(II)-硫酸盐、Mn(II)-磷酸盐、Mn(II)-磷酸氢盐、Mn(II)-连二磷酸盐、Mn(II)-碳酸盐、Mn(II)-氧化物、Mn(II)-氢氧化物、Mn(II)-卤化物、Mn(II)-氮化物、Mn(II)-乙酸盐、Mn(II)-乳酸盐、Mn(II)-草酸盐、Mn(II)-柠檬酸盐、Mn(II)-乙酰丙酮化物、Mn(II)-硫化物、Mn(II)-甲酸盐、Mn(II)-乙二胺四乙酸络合物(EDTA)、Mn(II)-次氮基三乙酸(nitrilo triacetic acid，NTA)络合物、具有氮-螯合物的Mn(II)物质，例如卟吩，如5，10，15，20-四苯基21H，23H-卟吩和2，3，7，8，12，13，17，18-八乙基-21H-23H-卟吩和酚菁。上述锰化合物在现有技术或出版物都是公知的，其中一些可商业获得。它们在溶液中的含量，足以给溶液提供所需浓度的Mn(III)离子。
Mn(III)物质还可以在刻蚀液中用一种或多种Mn(II)化合物和一种或多种氧化剂化学反应提供。氧化剂包括但不局限于KMnO4、MnO2、如碱金属的过硫酸盐的过硫酸盐、包括铵和、过氧化氢或其他无机过氧化物，例如碱金属和碱土金属过氧化物、有机过氧化物、如过氧羧酸(peroxycarbonic acid)或氢过氧化物、亚氯酸盐如碱金属和碱土金属亚氯酸盐、亚氯酸银或亚氯酸铅、氯酸盐如碱金属和碱土金属氯酸盐、高氯酸盐如碱金属和碱土金属高氯酸盐，包括高氯酸铵、高氯酸四丁基铵、高氯酸银、高氯酸铜、高氯酸镍、高氯酸锆、高氯酸镉、高氯酸铅、高氯酸汞或高氯酸铁，以及如碱金属和碱土金属次氯酸盐的次氯酸盐、四氧化锇、银(II)-氧化物、臭氧、铈(IV)如铵铈(IV)-硝酸盐、铈(IV)-氧化物、铈(IV)-硫酸盐、铈(IV)-氟化物或二水合硫酸铵铈(IV)、以及醋酸铅。溶液中加入的氧化剂或其混合物总含量低于按化学计量比确定的Mn(II)化合物的含量，这样产生的Mn(III)离子的量为0.01mmol/L到刚好低于形成Mn(II)盐沉淀的量，优选地，Mn(II)离子浓度为0.1mmol/L到刚好低于能在氧化剂基本全反应后形成沉淀的量。最优选地，包含在溶液中的氧化剂能使Mn(II)离子浓度范围为1mmol/L到50mmol/L。
Mn(III)离子还能通过电解作用由Mn(II)离子得到。一种或多种Mn(II)化合物加入到包括硫酸和一种或多种有机酸的酸性水溶液中。电解可以在单室电解槽或双室电解槽中进行，其中阳极电解液和阴极电解液用膜或多孔陶瓷管或板隔开。阳极电解液包括Mn(II)离子、硫酸和一种或多种有机酸，而阴极电解液包括硫酸和一种或多种有机酸。可以使用不同材料的阳极和阴极，例如，但不局限于硼掺杂的金刚石(BDD)、石墨、铂、镀铂钛、镀铂铌、铅、铅合金、PbO2、IrO2或混合阳极氧化物。进行电解直到得到为后续的金属化做准备而刻蚀有机聚合物所需的Mn(III)离子的量。根据电极材料和Mn(III)离子产生的速率，电流密度可以是不同的。通常，电流密度为0.1A/dm2到100A/dm2。当Mn(III)离子低于所需值时，再次开始电解直到达到刻蚀液所需Mn(III)离子量。电解降低或消除了需要在操作过程中补充刻蚀液的问题，例如在产业上设定的时间、效率和成本对于特定企业是十分重要的参数。而且使用电解方法，装置的安装成本也降低了。使用一种或多种氧化剂、电解以及一种或多种Mn(II)和Mn(III)盐源的组合也可以用来获得所需Mn(II)/Mn(III)离子浓度。
任选地，当实施电解方法时，可在溶液中加入一种或多种催化剂。浓度为0.01mmol/L到1mmol/L的一种或多种催化剂可用于提高Mn(II)/Mn(III)氧化反应的阳极电流效率，并提高组合物的刻蚀活性。这样的催化剂包括但不局限于Ag(I)、Bi(III)、Ce(III)和Pb(II)离子。这些催化剂离子的来源在现有技术和出版物中是公知的，而且大多数可商业获得。
刻蚀液中的无机酸优选限定为硫酸。优选地，包括硫酸盐的无机酸盐不包含在溶液中。包含在水性酸溶液中的硫酸的量为1wt％到89wt％，优选从15wt％到70wt％。有机酸包括但不局限于链烷磺酸，如甲磺酸、乙磺酸和丙磺酸；芳基磺酸，如苯磺酸和萘磺酸；羧酸，如乙酸、乳酸、柠檬酸、甲酸和抗坏血酸。优选地，有机酸为链烷磺酸和芳基磺酸。更优选地，有机酸为链烷磺酸。最优选地，有机酸为乙磺酸和甲磺酸。包含在水性酸溶液中的有机酸的量为1wt到89wt％，优选地，为15wt％到70wt％。优选地，硫酸和有机酸在溶液中的浓度不相同。优选地，其中一种的浓度高于另一种从而防止水含量发生变化。有机酸盐优选地不包含在水性酸溶液中。
具有一种或多种有机聚合物的基板浸入水性酸溶液中，或将所述溶液喷到基板上。对有机聚合物的刻蚀的溶液温度为10℃到135℃，优选为20℃到100℃，更优选为30℃到80℃。
有机聚合物包括但不局限于热固性树脂、热塑性树脂、低Tg树脂、高Tg树脂以及它们的组合。热塑性树脂包括但不局限于缩醛树脂，丙烯酸，如丙烯酸甲酯，纤维素树脂，例如乙酸乙酯、纤维素丙酸酯、纤维素醋酸酯、丁酸酯和硝化纤维，聚醚，尼龙，聚乙烯，聚丙烯，聚苯乙烯，苯乙烯共混物如丙烯腈苯乙烯共聚物，和丙烯腈-丁二烯-苯乙烯(ABS)共聚物，聚碳酸酯(PC)，聚三氟氯乙烯，和乙烯基聚合物及其共聚物例如乙酸乙烯酯、乙烯醇、乙烯缩丁醛、氯乙烯、氯乙烯-乙酸酯共聚物、偏二氯乙烯和乙烯缩甲醛(vinyl formal)。
热固性树脂包括但不局限于邻苯二甲酸烯丙酯、呋喃、密胺甲醛、酚醛和苯酚-糠醛共聚物，它们单独或与丁二烯丙烯腈共聚物或丙烯腈-丁二烯-苯乙烯(ABS)共聚物，聚丙烯酸酯，硅氧烷、脲甲醛，环氧树脂，烯丙树脂，邻苯二甲酸甘油酯和聚酯混合。
所述溶液也可用于刻蚀低和高Tg树脂。低Tg树脂具有低于160℃的Tg温度，而高Tg树脂具有为160℃或更高的Tg温度。通常高Tg树脂具有160℃到280℃的Tg温度。高Tg树脂包括但不局限于聚四氟乙烯(PTFE)和聚四氟乙烯共混物。这种共混物包括，例如具有聚苯醚和氰酸酯的PTFE。包括具有高Tg的树脂的其他聚合物树脂种类包括但不局限于环氧树脂，如双官能和多官能环氧树脂，二马来酰亚胺/三嗪和环氧树脂(BT环氧)，环氧/聚苯醚树脂，丙烯腈-丁二烯-苯乙烯(ABS)，聚碳酸酯(PC)，聚苯醚(PPO)，聚亚苯基醚(PPE)，聚苯硫醚(PPS)，聚砜(PSU)，聚酰胺(PA)，聚酯如聚对苯二甲酸乙二醇酯(PET)和聚对苯二甲酸丁二酯(PBT)，聚醚醚酮(PEEK)，液晶聚合物(LCP)，聚氨酯(PU)，聚醚酰亚胺(PEI)，它们的环氧化物和复合物。
具有有机聚合物的基板用溶液处理10秒到30分钟，优选2分钟到15分钟。基板的有机聚合物被刻蚀后，用水冲洗基板，然后进一步用常规方法进行准备金属化的处理。随后用常规镀金属方法和金属镀浴如无电镀镍和无电镀铜将其金属化。
以下实施例用于进一步说明本发明而目的不是在于限定其范围。
实施例1(对比例)
四种不同的H2SO4/MSA混合物含20wt％的水但具有不同含量的H2SO4和MSA，它们是混合H2O，18M H2SO4和9.8MSA得到的，获得如下表所示的1.8升水性酸混合物：
表1
所述混合物在敞开于环境(23℃，20％相对湿度)的2升烧杯中于65℃轻轻搅动24小时，在每个溶液中由于酸混合物的吸水性造成的重量增加通过测量24小时前后的溶液重量差来确定。由于MSA和H2SO4的蒸汽压远远小于水的蒸汽压(MSA0.07mbar，H2SO40.005mbar，H2O250mbar，65℃)，因此溶液的重量变化主要来自于从大气中吸收的水分或从刻蚀液中蒸发的水分。图1示出了不同混合物测量到的吸水量作为MSA含量的函数。正值表示重量增加，例如吸湿水增量，而负值表示重量减小，例如水分蒸发。不包括任何MSA的混合物具有约为2100g/m2/天吸水量。相反，包含MSA的混合物具有负的吸水值，从刚刚低于0g/m2/天到约-1300g/m2/天。数据清楚地表明用20wt％到40wt％的MSA替代部分H2SO4，混合物的吸水量或吸水性降低。
实施例2(对比例)
将4.97g MnSO4·H2O(29.6mmol)溶解于120mL水中制备出Mn(III)离子原液。将585mL9.6M的H2SO4加入得到700ml溶液，其中在8M H2SO4中含29.6mmol Mn(II)离子(溶液A)。将1.162g(7.3mmol)KMnO4溶解于35mL水中形成水溶液(溶液B)。在搅拌中将溶液B逐滴地加入溶液A。搅拌在室温下持续2小时。在这段时间中MnSO4与KMnO4发生反应式1的反应，得到在7.6M的硫酸中具有50mM的Mn(III)离子的血红色溶液。
将一等份2mL的Mn(III)离子原液和35.3mL的浓硫酸(18M)加入100mL容量的烧瓶中，再加入14M的硫酸至满，配置出1mmol/L的Mn(III)离子溶液。溶液的pH值小于1。从1mM的Mn(III)溶液中取出10mL的一等份放入石英比色皿中。随后将比色皿置于双光束UV-VIS光谱仪(日立U-2010光谱仪)中检测溶液的吸光度。UV吸收度在700nm至350nm之间扫描，测量520nm至525nm之间的吸光度。1mM的Mn(III)离子溶液的吸光度光谱在图2中用虚线示出。
将粉末状KMnO4溶解于一升去离子水中制备10mmol(1.58g)KMnO4水性原液，得到10mmol/L的Mn(VII)离子溶液。将一等份10mL的原液引入1升容量的烧瓶中，然后加入去离子水至满得到0.1mmol/L的Mn(VII)离子溶液。将10mL的01mmol/L的溶液置于石英比色皿中，再放入UV-VIS色谱仪中检测其吸光度。UV吸光度在350nm至700nm之间扫描，测量450nm至600nm之间的吸光度。0.1mmol/L的Mn(III)离子溶液的吸光度光谱在图2中用实线示出。虽然每种形态的锰的峰值都位于相同的450nm至600nm光谱范围中，但MnO4 -的特征振动结构和Mn(III)在波长低于400nm时强烈的吸光度使得这两种形态能够被区分。
实施例3
将镀铂钛制成的阳极置于无色溶液中，所述溶液是将10.14g(60mmol)的MnSO4·H2O和0.36g(1.15mmol)Ag2SO4在65℃加入含有18mL的H2O、639mL的9.8M甲磺酸和18M硫酸的混合酸得到的，得到的溶液具有39.72wt％的硫酸、39.72wt％的甲磺酸、19.93wt％的水和0.6wt％的MnSO4。将铂丝制成的阴极置于一个单独的含14M硫酸的电解槽中。使用多孔陶瓷管分隔阳极电解液和阴极电解液，并允许电流在电解槽之间通过。电极连接在常规的整流器上提供电源。当施加的阳极电流密度为8A/dm2时，溶液从无色变为深蓝紫色，表明Mn(III)离子正在产生。Mn(III)离子浓度达到49.4mM后关闭电流。没有迹象表明Mn(III)或Mn(II)离子开始从溶液中以不溶性盐的形式沉淀。对具有14M硫酸的10倍稀释液的UV-VIS分析表明其在525nm-535nm范围内具有单一的吸收峰，如图3所示其峰值在531nm处。这揭示了在电解液中没有Mn(VII)态形成。图3可与图2中实线表明的出现Mn(VII)离子进行对比。
将ABS/PC聚合物(已知的BAYBLENDTM T45PG的共混聚合物(可由拜耳公司获得))注塑成型样片于65℃浸入上述所述溶液中10分钟，用于刻蚀所述样片的表面。用常规pH测量仪测量所述溶液的pH值小于1。刻蚀后的样片随后用去离子水冲洗，然后浸入30℃的CONDUCTRONTM DP-H催化胶体钯溶液(可由马萨诸塞州马堡的陶氏先进材料获得)3分钟。随后用去离子水冲洗样片，然后浸入45℃的ACCELERATORTM PM-964溶液(可由陶氏先进材料获得)5分钟。用去离子水冲洗样片后将其浸入30℃的NIPOSITTM PM980无电镀镍浴(可由陶氏先进材料获得)10分钟，在样片上形成导电金属层。该镀镍样片冲洗后接着镀铜，使用的是含110g/L焦磷酸铜，400g/L焦磷酸钾，10g/L柠檬酸和3g/L铵离子的常规焦磷酸铜电镀浴，在pH值为8.5、电流密度1A/dm2、40℃镀6分钟。附加的薄铜层增加了无电镀镍层的导电性，使下一阶段在更高电流密度下电镀铜更容易。使用COPPER GLEAMTM DL900电镀铜浴(可由陶氏先进材料获得)在焦磷酸铜层上电镀另一铜层。电镀铜在5A/dm2的电流密度下持续50分钟完成。样片表明镍被完整覆盖。使用ASTM D3359交叉分析和胶带测试法对ABS/PC样片上金属层的附着性进行测试。观测到ABS/PC和金属层之间具有良好的附着性。将胶带从样片表面的金属层上揭下后未观察到其上残留金属。
实施例4
将7g MnSO4·H2O(42mmol)溶解在200mL水中。由于反应的放热性而将162mL的9.8M甲磺酸和564mL的18M的H2SO4缓慢加入上述溶液中。然后，在强烈搅拌下将1.26gKMnO4(8mmol)加入75mL水中。所述8mmol KMnO4和32mmol MnSO4发生如下反应：
8MnSO4·H2O+2KMnO4+8H2SO4→5Mn2(SO4)3+K2SO4+8H2O
从而在具有64.53wt％H2SO4，9.93wt％甲磺酸和24.88t％H2O的混合酸液中产出40mmol的Mn(III)离子和10mM的Mn(II)离子。该溶液具有深蓝紫的颜色，其UV-VIS光谱与图3所示的实质相同，具有峰值为530nm的处单一峰。这为证明Mn(III)是唯一具有高于+2的氧化价态的Mn形态提供了确实证据。
将可由苯领集团公司(Styrolution Group Corporation)获得的NOVODURTMP2MC ABS聚合物注塑成型样片于65℃浸在酸液中10分钟，然后用去离子水冲洗。在室温下干燥后，使用Blazers Union SCD040，金源，电流15mA溅射2分钟在其上溅射沉积金层，以获得能够得到SEM图像的导电表面。使用蔡司(Zeiss)的西格玛VP FE-SEM在放大25000倍下获得的SEM图像如图4所示，其揭示了酸液提供的粗化表面适于金属化。
实施例5
将NOVODURTM P2MC ABS聚合物注塑成型样片于65℃浸入实施例4所述水性酸液中10分钟用于刻蚀样片表面。被刻蚀的样品随后用去离子水冲洗，然后用实施例3所述工艺镀覆。用ASTM D3359交叉分析和胶带测试法对ABS样片上金属层的附着性进行测试。观察到在ABS和金属层之间良好的覆盖性和附着性。将胶带从样片表面的金属层上揭下后未观察到其上残留金属。
Claims (7)
1.一种用于刻蚀有机聚合物的方法，所述方法包括：
a.提供包含一种或多种有机聚合物的基材；
b.提供一种水性酸溶液，所述水性酸溶液由硫酸、一种或多种有机酸以及Mn(II)离子和Mn(III)离子、水和一种或多种氧化剂组成，所述氧化剂选自下组：KMnO4、过硫酸盐、无机过氧化物、有机过氧化物、亚氯酸盐、氯酸盐、高氯酸盐、次氯酸盐、四氧化锇、银(II)-氧化物、臭氧、铈(IV)和醋酸铅，其中包含在溶液中的氧化剂能使Mn(II)离子浓度范围为1mmol/L到50mmol/L；和
c.将基材的一种或多种有机聚合物与所述水性酸溶液接触，以刻蚀所述基材的一种或多种有机聚合物。
2.根据权利要求1的方法，其中硫酸的浓度为1wt％-89wt％。
3.根据权利要求1的方法，其中有机酸的浓度为1wt％-89wt％。
4.如权利要求1所述的方法，其特征在于，所述一种或多种有机酸选自甲磺酸、乙磺酸和丙磺酸。
5.如权利要求3所述的方法，其特征在于，所述有机酸的浓度为15wt％-70wt％。
6.如权利要求1所述的方法，其特征在于，所述Mn(III)离子的浓度为1mmol/L到70mmol/L。
7.如权利要求1所述的方法，其特征在于，所述氧化剂为高氯酸铵。
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| KR20170008309A (ko) | 2014-07-10 | 2017-01-23 | 오꾸노 케미칼 인더스트리즈 컴파니,리미티드 | 수지 도금 방법 |
| EP3323910B1 (en) * | 2016-11-22 | 2018-11-14 | MacDermid Enthone GmbH | Chromium-free plating-on-plastic etch |
| US20190009185A1 (en) * | 2017-07-10 | 2019-01-10 | Srg Global, Inc. | Hexavalent chromium free etch manganese vacuum evaporation system |
| KR102172092B1 (ko) * | 2017-09-19 | 2020-10-30 | 주식회사 엘지화학 | 열가소성 수지 조성물, 이의 제조방법 및 성형품 |
| ES2646237B2 (es) * | 2017-09-28 | 2018-07-27 | Avanzare Innovacion Tecnologica S.L. | Formulación para el mordentado de materiales poliméricos previo al recubrimiento de los mismos |
| JP6477831B1 (ja) * | 2017-10-31 | 2019-03-06 | 栗田工業株式会社 | ポリフェニレンサルファイド樹脂の親水化処理方法 |
| JP6477832B1 (ja) * | 2017-10-31 | 2019-03-06 | 栗田工業株式会社 | ポリプロピレン樹脂の親水化処理方法 |
| FR3074808B1 (fr) | 2017-12-13 | 2020-05-29 | Maxence RENAUD | Outillage de galvanoplastie |
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| US10889905B2 (en) * | 2018-12-11 | 2021-01-12 | Rohm And Haas Electronic Materials Llc | Methods of generating manganese (III) ions in mixed aqueous acid solutions using ozone |
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