CN114957768A - 化学镀前表面修饰剂及聚苯硫醚基材表面功能化修饰方法 - Google Patents
化学镀前表面修饰剂及聚苯硫醚基材表面功能化修饰方法 Download PDFInfo
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- CN114957768A CN114957768A CN202210812173.8A CN202210812173A CN114957768A CN 114957768 A CN114957768 A CN 114957768A CN 202210812173 A CN202210812173 A CN 202210812173A CN 114957768 A CN114957768 A CN 114957768A
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- Prior art keywords
- polyphenylene sulfide
- base material
- concentration
- treatment
- sulfide base
- Prior art date
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 109
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 98
- 239000000126 substance Substances 0.000 title claims abstract description 38
- 238000007747 plating Methods 0.000 title claims abstract description 35
- 239000003607 modifier Substances 0.000 title claims abstract description 13
- 238000002715 modification method Methods 0.000 title claims abstract description 11
- 238000011282 treatment Methods 0.000 claims abstract description 56
- 238000001465 metallisation Methods 0.000 claims abstract description 10
- -1 phenolic amine compounds Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 73
- 239000000758 substrate Substances 0.000 claims description 42
- 230000004048 modification Effects 0.000 claims description 31
- 238000012986 modification Methods 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 206010042674 Swelling Diseases 0.000 claims description 26
- 230000008961 swelling Effects 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 24
- 239000003431 cross linking reagent Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 230000004913 activation Effects 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 16
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- 238000004140 cleaning Methods 0.000 claims description 14
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- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 12
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 12
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 12
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 12
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 230000003064 anti-oxidating effect Effects 0.000 claims description 6
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- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 4
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- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 4
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 claims description 2
- OGSPWJRAVKPPFI-UHFFFAOYSA-N Alendronic Acid Chemical compound NCCCC(O)(P(O)(O)=O)P(O)(O)=O OGSPWJRAVKPPFI-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 229960004343 alendronic acid Drugs 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 229940039009 isoproterenol Drugs 0.000 claims description 2
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- QNIVIMYXGGFTAK-UHFFFAOYSA-N octodrine Chemical compound CC(C)CCCC(C)N QNIVIMYXGGFTAK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 2
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 abstract description 85
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- 238000001338 self-assembly Methods 0.000 abstract 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
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- 239000010949 copper Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 9
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明涉及表面预处理技术以及聚苯硫醚基材表面金属化技术领域,公开了一种化学镀前表面修饰剂及聚苯硫醚基材表面功能化修饰方法。目的在于解决保证聚苯硫醚基材表面较小粗糙度的条件下难以沉积高质量金属层的问题,主要方案为:先通过微蚀刻对聚苯硫醚基材进行预处理以改善其表面性能,再将微蚀刻后的基材通过酚胺类化合物自发进行的迈克尔加成与席夫碱氧化聚合反应在其表面自组装形成单分子功能层,并通过适当的紫外辐照处理诱导活性氧产生加速单分子功能层沉积效率,从而可在基材表面引入能与金属粒子产生强键合作用的活性基团,进而实现聚苯硫醚基材与化学沉积的金属层之间的高界面结合强度。
Description
技术领域
本发明主要涉及到表面预处理以及聚苯硫醚表面金属化技术领域,特别涉及到一种化学镀前表面修饰剂及聚苯硫醚基材表面功能化修饰方法。
背景技术
聚苯硫醚基材具有较好的力学性能、尺寸稳定性、耐腐蚀性、低介电性、低介电损耗、使用频率范围广、耐温阻燃等较好物理化学性质,通过在其表面镀覆金属层能够实现其表面具有导电、导热等相关金属特性,可广泛应用于电子通信、新能源汽车、精密仪器、石油化工、航空国防等领域。
由于聚苯硫醚基材表面粗糙度较小、自由能较低、表面呈疏水性以及缺乏吸附金属粒子的活性官能团,难以实现表面金属化,且表面制备的金属层与聚苯硫醚基材结合强度较弱。为了实现聚苯硫醚基材表面金属化以及提高表面金属层与基材的界面结合强度,需在化学镀前对聚苯硫醚进行表面修饰,目前针对聚苯硫醚等有机聚合物基材改性方法主要包括溶胀处理、离子体处理、喷砂处理、聚合物辅助功能化修饰等。公开号为CN104017231A的中国专利《一种塑料表面处理工艺》中公开了一种通过刻蚀与溶胀相结合对塑料进行表面预处理的方法。公开号为CN110639362A的中国专利《一种低温等离子体改性的催化纤维滤料制备方法》中公开了静电纺丝技术与低温等离子体改性相结合制备纤维滤料的方法。虽然上述方法都能适当改善有机聚合物表面性能,但是过度溶胀处理会破坏基材表面形貌从而影响基材力学及电学性能,等离子体处理所需设备昂贵、能耗成本高,喷砂处理易导致基材表面均匀性较差,因此聚合物辅助功能化修饰成为一种简单有效的表面改性途径。
在选择表面修饰剂的时需具备“双性”结构,一是具有能与聚苯硫醚基材形成高强度附着的分子结构或官能团;二是具有能保证后续反应顺利完成的分子结构或官能团;公开号为CN101126156A的中国专利《一种用于ABS塑料基材化学镀前处理的工艺》中利用壳聚糖及其衍生物对钯催化剂的鳌合作用,以化学键合作用取代传统非导电基材表面化学镀前处理对钯催化剂的物理键合作用。然而,壳聚糖仅可溶于部分酸性溶液,且在不同pH值和温度条件下,其分子结构会发生较大变化,限制了壳聚糖在聚苯硫醚基材等有机聚合物基材上的使用。公开号为CN110540662A的中国专利《一种聚多巴胺改性碳纤维/莫来石晶须增强树脂基摩擦材料的制备方法》中公开了通过聚多巴胺表面修饰的方法明显改善了碳纤维/莫来石晶须的界面结合强度,提高了该复合材料的摩擦磨损性能、耐热性能及力学性能。然而多巴胺成本高昂且聚合时间较长限制其进一步的工业应用。
在此情况下,为简单高效、低成本实现聚苯硫醚基材表面金属化,寻求一种工艺流程简单、设备成本低廉、适用性强、沉积金属层与聚苯硫醚基材界面强度高的化学镀前表面修饰方法显得尤为重要。
发明内容
本发明提供了一种化学镀前表面修饰剂及通过该化学镀前表面修饰剂对聚苯硫醚基材进行表面功能化修饰方法,目的在于能够有效的解决聚苯硫醚基材表面难以实现金属化以及与金属层结合力较差的问题,具有简单高效、经济环保的优势。
为解决上述问题本发明提供的技术方案如下:
一种化学镀前表面修饰剂,主体成分包括基质表面交联剂A和基质表面交联剂B,其中:
基质表面交联剂A为阿仑膦酸钠、三羟甲基氨基甲烷、邻苯二酚、对羟基苯酚、异丙肾上腺素中的一种或任意几种组合,物质的量浓度为5~55mmol/L,pH调节至9.5。
基质表面交联剂B为1,5-二甲基己胺、聚氧乙烯二胺、二乙烯三胺、四乙烯五胺、间二甲苯二胺中的一种或任意几种组合,物质的量浓度为5~40mmol/L。
本发明还公开了一种功能化修饰聚苯硫醚基材表面的方法,包括如下步骤;
步骤(1)、将清洗后的聚苯硫醚基材浸入碱性膨润液中进行膨润处理;
步骤(2)、将经步骤(1)处理后的聚苯硫醚基材表面进行微蚀刻处理,并中和表面残余微蚀刻副产物;
步骤(3)、将经步骤(2)处理后的聚苯硫醚基材浸入由基质表面交联剂A、基质表面交联剂B和去离子水所配置的化学镀前表面修饰剂并结合紫外辐照进行功能化修饰,取出冲洗、烘干,酚胺类试剂结合紫外辐照后其自发聚合效率更高、成本更低。
步骤(4)、将经完成表面功能化修饰后的聚苯硫醚基材进行活化及金属化处理,结束后进行抗氧化处理,清洗、干燥得到最终样品;
进一步的上述技术方案中,所述步骤(1)中的碱性膨润液溶剂为去离子水,溶质由N-甲基吡咯烷酮、乙酰乙酸乙酯、乙二醇二***、乙二醇丁醚、氢氧化钠中的一种或几种组成,N-甲基吡咯烷酮浓度为20~80mL/L,乙酰乙酸乙酯0~15mL/L,乙二醇二***浓度为0~10mL/L,乙二醇丁醚5~40mL/L,氢氧化钠浓度为30~60g/L,膨润温度为30~70℃,膨润时间为5~30min。
进一步的上述技术方案中,所述步骤(2)中的微蚀刻处理所使用的微蚀刻液为二氧化锰、高锰酸钾、焦磷酸钠、浓硫酸、氢氧化钾中的一种或几种组成的混合溶液,二氧化锰浓度为30~80g/L,高锰酸钾浓度为0~30g/L,焦磷酸钠浓度为30~60g/L,浓硫酸浓度为350~800mL/L,氢氧化钾浓度为30~60g/L,微蚀刻温度为40~80℃,微蚀刻时间为5~40min。
进一步的上述技术方案中,所述步骤(2)中的中和表面残余微蚀刻副产物的溶液为草酸,浓度为10~50g/L,中和温度为30~70℃,中和时间为5~40min。
进一步的上述技术方案中,所述步骤(3)中的聚苯硫醚浸入化学镀前表面修饰剂中,其中基质表面交联剂A量浓度为5~55mmol/L,基质表面交联剂B量浓度为5~40mmol/L,去离子水为溶剂,处理温度为20~50℃,处理时间为1~9h,超声功率为50~200W。
进一步的上述技术方案中,所述步骤(4)中的活化处理所使用的为可溶性银盐,浓度为1~4g/L,活化温度为25~45℃,活化时间为5~25min。
进一步的上述技术方案中,所述步骤(4)中金属化处理所使用的化学镀液包含硫酸铜、硫酸镍、亚铁***、氢氧化钾、稳定剂还原剂及络合剂;
所述的稳定剂为联吡啶和硫脲中的一种;
所述的还原剂为硼氢化钠、甲醛以及次氯酸钠中的一种;
所述的络合剂为柠檬酸钠、酒石酸钾钠、乙二胺、乙二胺四乙酸二钠中的一种或几种;
处理温度为35~60℃,处理时间为20~80min;
与现有技术相比,本发明的有益效果如下:
一、本发明的基质表面交联剂A与基质表面交联剂B经自氧化可发生迈克尔加成与席夫碱反应生成两种低聚物,通过交联耦合可在聚苯硫醚基材表面形成高粘附强度自组装单分子层,同时可引入大量的羟基和氨基两种活性基团从而提高聚苯硫醚基材表面活性;
二、本发明在聚苯硫醚基材表面所制备的金属铜层平整光亮、均匀致密、纯度极高且结晶性较好,同时具有优异的机械性能、电学性能以及粘附强度。将铜层暴露于空气中72天仍能达到初始导电率的90%以上,相较于一般的化学镀前表面化学接枝改性处理,本发明在聚苯硫醚基材表面所制备的铜层纯度更高、导电性更好、粘附强度更优。
三、本发明的聚苯硫醚基材表面功能化修饰方法工艺流程简单高效且成本低廉,通过基质表面交联剂A与基质表面交联剂B发生迈克尔加成与席夫碱反应可在基材表面自组装形成单分子功能层,同时引入了能与化学沉积液中的金属离子产生鳌合作用的氨基和羟基两种活性基团,最终制备出高质量金属铜层。有效解决了聚苯硫醚基材表面难以金属化的问题,具有简单高效、低成本且绿色环保的优点。
四、本发明通过酚类物质的酚羟基与胺类物质的胺基在弱碱性条件下自发发生迈克尔加成反应与席夫碱反应生成两种不同低聚物,两种低聚物通过交联耦合形成富含酚羟及与胺基的交联网络,能国牢固的吸附在基材表面,从而能够改变基材表面极性与生物活性,因此可在基材表面负载大量活性金属银离子,从而在其表面可沉积附着力较好的金属层。
附图说明
图1是本发明在聚苯硫醚基材上实现表面功能化修饰及金属化的流程示意图;
图2是聚苯硫醚未经过表面功能化修饰活化后和经过本发明表面功能化修饰活化后得到的表面X射线光电子能谱图(XPS);
图3是聚苯硫醚未经过表面功能化修饰和经过本发明表面功能化修饰后化学镀得到的表面铜层光学显微形貌对比。
具体实施方式
下面结合具体实施例和说明书附图对本发明进一步详细的说明。
本发明的具体实例以聚苯硫醚(PPS)为基材,二氧化锰-焦磷酸钠-浓硫酸作为典型的微蚀刻溶液,其表面修饰及金属化工艺流程如图1所示。
实施例1
表面膨润:依次将氢氧化钠、乙二醇丁醚、N-甲基吡咯烷酮加入到去离子水中,充分搅拌后得到膨润液,其中氢氧化钠浓度为45g/L,乙二醇丁醚浓度为20mL/L,N-甲基吡咯烷酮浓度为40mL/L,膨润液加热至50℃后将聚苯硫醚(PPS)基材放入该溶液中处理15min,取出洗净干燥。该步骤的作用主要是在基材内部产生微孔结构,由于该基材耐酸碱腐蚀性较强,直接进行微蚀刻效果不明显,通过膨润处理可在其内部形成微孔,有利于微蚀液与基材进行充分接触,增加微蚀面积,有利于产生有效微蚀刻!
表面微蚀刻:依次将二氧化锰、焦磷酸钠、浓硫酸(98%)加入到去离子水中,充分搅拌得到粗化液,其中二氧化锰浓度为55g/L,焦磷酸钠浓度为60g/L,浓硫酸浓度为600mL/L,粗化液加热至50℃后将聚苯硫醚基材放入该溶液处理25min。然后配置草酸浓度为35g/L、硫酸浓度为120mL/L的中和溶液,将微蚀刻后的基材洗净烘干后浸入溶液中,在60℃条件下处理15min,取出洗净干燥。
表面功能化修饰:将三羟甲基氨基甲烷(Tris)缓冲试剂加入去离子水中,用稀盐酸将溶液pH调节至9.5左右,然后将邻苯二酚和四乙烯五胺加入到缓冲溶液中充分搅拌得到基质表面交联剂,其中Tris试剂浓度为15mmol/L,邻苯二酚浓度为20mmol/L,四乙烯五胺浓度为10mmol/L。然后将中和处理后清洗干净的聚苯硫醚浸入该溶液,在150W超声强度常温浸泡3h,然后将其放入波长为365nm的紫外箱中辐照处理1h,上述处理结束后洗净干燥得到完成表面功能化修饰的聚苯硫醚基材。
活化:将浓度为2.5g/L的硝酸银加入到去离子中搅拌得到活化液,将表面功能化修饰的聚苯硫醚放入其中于35℃处理10min。上述处理结束后用去离子水多次超声清洗,将其烘干后得到活化后的聚苯硫醚基材。
化学镀:制备化学镀液,将化学镀液加热至50℃,将活化后的聚苯硫醚基材放入镀液中处理30min,取出基材用去离子水洗净并放入6g/L的苯并三氮唑溶液中进行防氧化处理,然后高温退火得到表面金属化的聚苯硫醚基材。
实施例1在聚苯硫醚基材表面所制备的金属铜层具有明显金属光泽、均匀且致密,基材与铜层之间的附着力得到较大提升,可达到ASTM-D3359标准中的5B级别。
实施例2
表面膨润:依次将氢氧化钠、乙二醇丁醚、N-甲基吡咯烷酮加入到去离子水中,充分搅拌后得到膨润液,其中氢氧化钠浓度为30g/L,乙二醇丁醚浓度为0mL/L,N-甲基吡咯烷酮浓度为20mL/L,膨润液加热至30℃后将聚苯硫醚(PPS)基材放入该溶液中处理5min,取出洗净干燥。
表面微蚀刻:依次将二氧化锰、焦磷酸钠、浓硫酸(98%)、高锰酸钾、氢氧化钾加入到去离子水中,充分搅拌得到粗化液,其中二氧化锰浓度为30g/L,焦磷酸钠浓度为30g/L,高锰酸钾浓度为0g/L,氢氧化钾浓度为30g/L,浓硫酸浓度为350mL/L,粗化液加热至40℃后将聚苯硫醚基材放入该溶液处理5min。然后配置草酸浓度为10g/L、硫酸浓度为120mL/L的中和溶液,将微蚀刻后的基材洗净烘干后浸入溶液中,在30℃条件下处理5min,取出洗净干燥。
表面功能化修饰:将三羟甲基氨基甲烷(Tris)缓冲试剂加入去离子水中,用稀盐酸将溶液pH调节至9.5左右,然后将邻苯二酚和四乙烯五胺加入到缓冲溶液中充分搅拌得到基质表面交联剂,其中Tris试剂浓度为15mmol/L,邻苯二酚浓度为5mmol/L,四乙烯五胺浓度为5mmol/L。然后将中和处理后清洗干净的聚苯硫醚浸入该溶液,在50W超声强度常温浸泡1h,然后将其放入波长为365nm的紫外箱中辐照处理1h,上述处理结束后洗净干燥得到完成表面功能化修饰的聚苯硫醚基材。
活化:将浓度为1g/L的硝酸银加入到去离子中搅拌得到活化液,将表面功能化修饰的聚苯硫醚放入其中于25℃处理5min。上述处理结束后用去离子水多次超声清洗,将其烘干后得到活化后的聚苯硫醚基材。
化学镀:制备化学镀液,将化学镀液加热至35℃,将活化后的聚苯硫醚基材放入镀液中处理20min,取出基材用去离子水洗净并放入6g/L的苯并三氮唑溶液中进行防氧化处理,然后高温退火得到表面金属化的聚苯硫醚基材。
实施例2在聚苯硫醚基材表面所制备的金属铜层具有明显金属光泽、均匀且致密,基材与铜层之间的附着力得到较大提升,可达到ASTM-D3359标准中的3B级别。
实施例3
表面膨润:依次将氢氧化钠、乙二醇丁醚、N-甲基吡咯烷酮加入到去离子水中,充分搅拌后得到膨润液,其中氢氧化钠浓度为60g/L,乙二醇丁醚浓度为40mL/L,N-甲基吡咯烷酮浓度为80mL/L,膨润液加热至70℃后将聚苯硫醚(PPS)基材放入该溶液中处理30min,取出洗净干燥。
表面微蚀刻:依次将二氧化锰、焦磷酸钠、浓硫酸(98%)、高锰酸钾、氢氧化钾加入到去离子水中,充分搅拌得到粗化液,其中二氧化锰浓度为80g/L,焦磷酸钠浓度为60g/L,高锰酸钾浓度为30g/L,氢氧化钾浓度为60g/L,浓硫酸浓度为800mL/L,粗化液加热至80℃后将聚苯硫醚基材放入该溶液处理40min。然后配置草酸浓度为50g/L、硫酸浓度为120mL/L的中和溶液,将微蚀刻后的基材洗净烘干后浸入溶液中,在70℃条件下处理40min,取出洗净干燥。
表面功能化修饰:将三羟甲基氨基甲烷(Tris)缓冲试剂加入去离子水中,用稀盐酸将溶液pH调节至9.5左右,然后将邻苯二酚和四乙烯五胺加入到缓冲溶液中充分搅拌得到基质表面交联剂,其中Tris试剂浓度为15mmol/L,邻苯二酚浓度为55mmol/L,四乙烯五胺浓度为40mmol/L。然后将中和处理后清洗干净的聚苯硫醚浸入该溶液,在200W超声强度常温浸泡9h,然后将其放入波长为365nm的紫外箱中辐照处理1h,上述处理结束后洗净干燥得到完成表面功能化修饰的聚苯硫醚基材。
活化:将浓度为4g/L的硝酸银加入到去离子中搅拌得到活化液,将表面功能化修饰的聚苯硫醚放入其中于45℃处理25min。上述处理结束后用去离子水多次超声清洗,将其烘干后得到活化后的聚苯硫醚基材。
化学镀:制备化学镀液,将化学镀液加热至60℃,将活化后的聚苯硫醚基材放入镀液中处理80min,取出基材用去离子水洗净并放入6g/L的苯并三氮唑溶液中进行防氧化处理,然后高温退火得到表面金属化的聚苯硫醚基材。
实施例3在聚苯硫醚基材表面所制备的金属铜层具有明显金属光泽、均匀且致密,基材与铜层之间的附着力得到较大提升,但并未达到ASTM-D3359标准中的4B级别。
对比例
表面膨润:依次将氢氧化钠、乙二醇丁醚、N-甲基吡咯烷酮加入到去离子水中,充分搅拌后得到膨润液,其中氢氧化钠浓度为45g/L,乙二醇丁醚浓度为20mL/L,N-甲基吡咯烷酮浓度为40mL/L,膨润液加热至50℃后将聚苯硫醚(PPS)基材放入该溶液中处理15min,取出洗净干燥。
表面微蚀刻:依次将二氧化锰、焦磷酸钠、浓硫酸(98%)加入到去离子水中,充分搅拌得到粗化液,其中二氧化锰浓度为55g/L,焦磷酸钠浓度为60g/L,浓硫酸浓度为600mL/L,粗化液加热至50℃后将聚苯硫醚基材放入该溶液处理25min。然后配置草酸浓度为35g/L、硫酸浓度为120mL/L的中和溶液,将微蚀刻后的基材洗净烘干后浸入溶液中,在60℃条件下处理15min,取出洗净干燥。
活化:将浓度为2.5g/L的硝酸银加入到去离子中搅拌得到活化液,将表面修饰的聚苯硫醚放入其中于35℃处理10min。上述处理结束后用去离子水多次超声清洗,将其烘干后得到活化后的聚苯硫醚基材。
化学镀:制备化学镀液,将化学镀液加热至50℃,将活化后的聚苯硫醚基材放入镀液中处理30min,取出基材用去离子水洗净并放入6g/L的苯并三氮唑溶液中进行防氧化处理,然后高温退火得到表面金属化的聚苯硫醚基材。
图2是对比例中未经过表面功能化修饰的聚苯硫醚活化后的XPS以及实施例中经过表面功能化修饰的聚苯硫醚活化后的XPS。通过对比可以得出:未经过功能化修饰的聚苯硫醚表面峰杂乱无章,未检测到银特征峰,而经过功能化修饰的聚苯硫醚基材表面可以检测到明显的银特征峰。
图3是对比例中未经过表面功能化修饰的聚苯硫醚化学镀后的铜层形貌以及实施例中经过表面功能化修饰的聚苯硫醚化学镀后的铜层形貌。通过对比可知,未经表面功能化修饰的聚苯硫醚化学镀后表面未镀覆完整铜层,而经过表面功能化修饰的聚苯硫醚化学镀后表面铜层光亮致密、均匀平整。
Claims (8)
1.一种化学镀前表面修饰剂,其特征在于,主体成分包括基质表面交联剂A和基质表面交联剂B,其中:
基质表面交联剂A为阿仑膦酸钠、三羟甲基氨基甲烷、邻苯二酚、对羟基苯酚、异丙肾上腺素中的一种或任意几种组合,物质的量浓度为5~55mmol/L,pH调节至9.5;
基质表面交联剂B为1,5-二甲基己胺、聚氧乙烯二胺、二乙烯三胺、四乙烯五胺、间二甲苯二胺中的一种或任意几种组合,物质的量浓度为5~40mmol/L。
2.一种聚苯硫醚基材的表面功能化修饰方法,其特征在于,包括如下步骤:
步骤(1)、将清洗后的聚苯硫醚基材浸入碱性膨润液中进行膨润处理;
步骤(2)、将经步骤(1)处理后的聚苯硫醚基材表面进行微蚀刻处理,并中和表面残余微蚀刻副产物;
步骤(3)、将经步骤(2)处理后的聚苯硫醚基材浸入由基质表面交联剂A、基质表面交联剂B和去离子水所配置的化学镀前表面修饰剂并结合紫外辐照进行功能化修饰,取出冲洗、烘干;
步骤(4)、将经完成表面功能化修饰后的聚苯硫醚基材进行活化及金属化处理,结束后进行抗氧化处理,清洗、干燥得到最终样品。
3.根据权利要求2所述的一种聚苯硫醚基材的表面功能化修饰方法,其特征在于,所述步骤(1)中的碱性膨润液溶剂为去离子水,溶质由N-甲基吡咯烷酮、乙酰乙酸乙酯、乙二醇二***、乙二醇丁醚、氢氧化钠中的一种或几种组成,N-甲基吡咯烷酮浓度为20~80mL/L,乙酰乙酸乙酯0~15mL/L,乙二醇二***浓度为0~10mL/L,乙二醇丁醚5~40mL/L,氢氧化钠浓度为30~60g/L,膨润温度为30~70℃,膨润时间为5~30min。
4.根据权利要求2所述的一种聚苯硫醚基材的表面功能化修饰方法,其特征在于,所述步骤(2)中的表面微蚀刻处理所使用的微蚀液为二氧化锰、高锰酸钾、焦磷酸钠、浓硫酸、氢氧化钾中的一种或几种组成的混合溶液,二氧化锰浓度为30~80g/L,高锰酸钾浓度为0~30g/L,焦磷酸钠浓度为30~60g/L,浓硫酸浓度为350~800mL/L,氢氧化钾浓度为30~60g/L,微蚀刻温度为40~80℃,微蚀刻时间为5~40min。
5.根据权利要求2所述的一种聚苯硫醚基材的表面功能化修饰方法,其特征在于,所述步骤(2)中的中和表面残余微蚀刻副产物的溶液为草酸,浓度为10~50g/L,中和温度为30~70℃,中和时间为5~40min。
6.根据权利要求2所述的一种聚苯硫醚基材的表面功能化修饰方法,其特征在于,所述步骤(3)中的基质表面交联剂A量浓度为5~55mmol/L,基质表面交联剂B量浓度为5~40mmol/L,去离子水为溶剂,处理温度为20~50℃,处理时间为1~9h,超声功率为50~200W。
7.根据权利要求2所述的一种聚苯硫醚基材的表面功能化修饰方法,其特征在于,所述步骤(4)中的活化处理所使用的为可溶性银盐,浓度为1~4g/L,活化温度为25~45℃,活化时间为5~25min。
8.根据权利要求2所述的一种聚苯硫醚基材的表面功能化修饰方法,其特征在于,所述步骤(4)中金属化处理所使用的化学镀液包含硫酸铜、硫酸镍、亚铁***、氢氧化钾、稳定剂还原剂及络合剂;
所述的稳定剂为联吡啶和硫脲中的一种;
所述的还原剂为硼氢化钠、甲醛以及次氯酸钠中的一种;
所述的络合剂为柠檬酸钠、酒石酸钾钠、乙二胺、乙二胺四乙酸二钠中的一种或几种;
处理温度为35~60℃,处理时间为20~80min。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106436306A (zh) * | 2016-06-14 | 2017-02-22 | 北京化工大学 | 一种纤维的表面改性方法 |
CN111501030A (zh) * | 2020-05-26 | 2020-08-07 | 电子科技大学 | 化学镀前表面修饰体系及双重修饰聚合物基材表面的方法 |
-
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106436306A (zh) * | 2016-06-14 | 2017-02-22 | 北京化工大学 | 一种纤维的表面改性方法 |
CN111501030A (zh) * | 2020-05-26 | 2020-08-07 | 电子科技大学 | 化学镀前表面修饰体系及双重修饰聚合物基材表面的方法 |
Non-Patent Citations (1)
Title |
---|
CHENGYUAN FENG ET AL.: "Metallization of Polyphenylene Sulfide by Low-Cost Mussel-Inspired Catechol/Polyamine Surface Modification", 《ACS APPLIED POLYMER MATERIALS》 * |
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---|---|---|---|---|
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CN116782516B (zh) * | 2023-07-13 | 2024-01-23 | 南华大学 | 一种基于均相离子型催化油墨制备铜印刷电路的普适工艺 |
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