CN114059050B - 一种聚苯硫醚基材的表面粗化方法及金属化方法 - Google Patents
一种聚苯硫醚基材的表面粗化方法及金属化方法 Download PDFInfo
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- CN114059050B CN114059050B CN202010766563.7A CN202010766563A CN114059050B CN 114059050 B CN114059050 B CN 114059050B CN 202010766563 A CN202010766563 A CN 202010766563A CN 114059050 B CN114059050 B CN 114059050B
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- roughening
- treatment
- base material
- water
- plastic base
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Classifications
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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
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- 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
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
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- C—CHEMISTRY; METALLURGY
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
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- C23C18/26—Roughening, e.g. by etching using organic liquids
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- C—CHEMISTRY; METALLURGY
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- C—CHEMISTRY; METALLURGY
- 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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- C—CHEMISTRY; METALLURGY
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
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Abstract
本申请提供了一种聚苯硫醚塑料基材的表面粗化方法,包括:对含有聚苯硫醚和玻璃纤维的塑料基材依次进行预粗化处理、第二粗化处理、第三粗化处理和中和除膜处理;预粗化处理使用的预粗化液包括五氟丙醇、醚类物质、醇胺类物质、第一无机强碱及水;第二粗化处理使用的第二粗化液包括六价铬源、表面活性剂、硫酸及水;第三粗化处理使用的第三粗化液包括氟离子源、强酸及水;中和除膜处理使用的除膜液包括亚硫酸钠、第二无机强碱及水。该方法可在不明显改变基材表面形貌的情况下,将耐腐蚀性较好的塑料基材的表面充分粗化并使基材亲水,具有优异的上镀性。本申请还提供了聚苯硫醚塑料基材的金属化方法。
Description
技术领域
本发明涉及聚苯硫醚的金属化技术领域,具体涉及一种聚苯硫醚基材的表面粗化方法及金属化方法。
背景技术
随着电子行业的发展,人们对制备电子线路的原材料的电学性能要求越来越苛刻。其中,聚苯硫醚(PPS)由于其优异的介电性能和相比液晶聚合物(LCP)材料更低廉的价格而备受关注,而添加玻璃纤维(GF)的PPS材料这一工程塑料则具有更加优异的力学性能和耐热性能,目前已开始用于制备5G基站天线的塑料振子中,以实现天线振子的轻量化。
由于PPS工程塑料不导电,为便于天线振子等电子行业的应用,需要在其表面上形成金属层,以实现金属化。为便于实现PPS工程塑料的金属化,通常先对其进行表面粗化,以提高材料表面能,保证金属化后的结合力。目前业界一般采用喷砂等物理粗化方式来实现表面粗糙化,但喷砂对基材的表面损伤较大,极易破坏基材表面台阶、微孔等精细结构,进而影响天线接收或反射信号。
发明内容
鉴于此,本申请针对含玻纤的PPS工程塑料提供了一种新型的化学粗化方法及金属化方法,使粗化后的塑料基材的表面粗糙度不致太高,以避免物理粗化所带来的易破坏精细结构的问题,更好地满足5G基站天线等对表面粗糙度有较高要求的金属化产品的要求。
具体地,第一方面,本申请提供了一种聚苯硫醚塑料基材的表面粗化方法,包括:
采用预粗化液对塑胶基材进行预粗化处理,以使所述塑胶基材的表面溶胀,其中,所述塑料基材含有聚苯硫醚和玻璃纤维;所述预粗化液包括五氟丙醇、醚、醇胺类物质、第一无机强碱及水;
采用第二粗化液对所述预粗化后的塑胶基材进行第二粗化处理,以使溶胀后的塑胶基材表面经氧化后亲水;其中,所述第二粗化液的原料包括六价铬源、表面活性剂、硫酸及水;
采用第三粗化液对所述第二粗化处理后的塑胶基材进行第三粗化处理,以溶解所述塑胶基材表面的玻璃纤维;其中,所述第三粗化液包括氟离子源、强酸及水;
采用除膜液对所述第三粗化处理后的塑胶基材进行除膜处理,以除去含铬残留膜,得到表面粗化后的塑料基材;其中,所述除膜液的原料包括亚硫酸钠、第二无机强碱及水。
可选地,所述塑料基材可以由包括聚苯硫醚(PPS)和玻璃纤维(GS)。的原料经注塑成型获得。可选地,所述塑料基材中,GS的质量占比为1wt%-50wt%。例如为5wt%、10wt%、20wt%或40wt%。优选地,所述塑料基材中,GS的质量占比为40wt%,此时,所述塑胶基材的密度和价格均较低,不易出现起皮等缺陷。
可选地,在进行所述预粗化处理之前,还包括:对所述塑胶基材进行除油处理。其中,所述除油处理可以在热水、热碱水中进行,当然也可以辅以超声波和/或鼓泡装置。进一步地,所述除油处理的温度可以为50-70℃,例如为50-60℃。所述除油处理的时间可以为5-30min。
本申请的所述预粗化液中,五氟丙醇可以对塑胶基材中的玻璃纤维这一无机成分有较好的溶胀作用,醚和有机醇胺类物质可以对PPS这一有机成分有较好的溶胀作用,第一无机强碱和有机醇胺类物质可以共同提高溶胀所需要的碱性环境,提高塑胶基材的表面溶胀效果。可选地,所述预粗化液包括以下含量的各组分:五氟丙醇:10-120g/L,醚类物质:10-120g/L,醇胺类物质:30-100g/L,无机强碱:20-100g/L,以及水。进一步地,所述预粗化液的pH在12以上。该质量配比的预粗化液可使对塑料基材中的PPS、GS同时充分溶胀。
进一步地,所述五氟丙醇、所述醚类物质在所述预粗化液中的含量可以独立地为20、40、50、60、70、80、90、100或110g/L。优选地,所述五氟丙醇在所述预粗化液中的含量为50-90g/L。所述醚类物质在所述预粗化液中的含量可以为30-90g/L。所述醇胺类物质、所述无机强碱在所述预粗化液中的含量可以独立地为30、40、50、60、70、80、90或95g/L。优选地,所述醇胺类物质和所述无机强碱在所述预粗化液中的含量均在40-90g/L的范围内。
其中,所述醇胺类物质可以包括三乙醇胺、二乙醇胺和单乙醇胺中的一种或多种。所述醚类物质可以包括乙二醇乙醚、乙二醇丁醚、乙二醇己醚、二乙二醇乙醚、二乙二醇丁醚、二乙二醇己醚、二乙二醇二乙烯基醚、二乙二醇单乙烯基醚中的一种或多种。所述第一无机强碱包括氢氧化钠、氢氧化钾中的至少一种。
可选地,所述预粗化处理的温度可以为50-70℃,这样可以保证塑料基材充分溶胀,又可避免温度过高而导致基材表面溶胀过度导致过度粗化,进而导致基材表观被严重破坏。所预粗化处理的时间可以为10-60min。
本申请的所述第二粗化液可以将上述塑料基材中PPS中的硫醚键、苯环氧化,暴露出亲水基团,进一步增加粗糙度,便于后续进行镀膜处理获得密合度较好的镀层。其中,所述六价铬源可以提供强氧化性的六价铬,而硫酸可以与六价铬源相配合,在二者的协同作用下起到较好的氧化、粗化效果;表面活性剂可以提高所述第二粗化液对PPS的润湿效果,进而提高粗化形成的孔隙的均匀性。
可选地,所述第二粗化液包括以下含量的各原料:六价铬源:100-400g/L,硫酸:100-400g/L,表面活性剂:0.1-3g/L,及水。可选地,所述第二粗化液的pH为1以下。该原料配比的第二粗化液的性质稳定、对塑料基材的润湿性好、对塑料基材进行处理后可使亲水性官能团充分暴露出来。进一步地,所述六价铬源、所述硫酸在所述第二粗化液的物料体系中的含量可以独立地为120、150、180、200、250、300、320、350或380g/L。优选地,所述六价铬源、所述硫酸在所述第二粗化液的物料体系中的含量可以均在150-350g/L的范围内。而所述表面活性剂在所述第二粗化液中的含量可以为0.5、0.8、1、1.2、1.5、2或2.5g/L。
可选地,所述六价铬源可以包括铬酐、铬酸、铬酸钾、铬酸钠中的一种或多种。基于所述六价铬源有高氧化性,则所述第二粗化液中的表面活性剂为耐氧化表面活性剂,具体可以包括单月桂基硫酸酯、烷基二苯醚二磺酸盐、磺酸盐型碳氟表面活性剂中的一种或多种。其中,对于所述烷基二苯醚二磺酸盐,可以列举十二烷基二苯醚二磺酸钠(C12-MADS)、双十二烷基二苯醚二磺酸钠(C12-DADS)及十六烷基二苯醚二磺酸钠(C16-MADS)等。
可选地,所述第二粗化处理的温度可以为50-70℃,例如为60-70℃。若温度过低会导致粗化效果不明显或失效,温度过高会导致过度粗化进而导致基材与后续镀层的结合力不良。所述第二粗化处理的时间可以为5-30min。
本申请的所述第三粗化液中,在强酸提供的强酸性环境下,所述氟离子源可以提供氟离子,与玻璃纤维中的硅原子进行反应,对玻璃起到刻蚀作用,从而使玻璃纤维较快地溶解,提高粗化效果。可选地,所述第三粗化液的pH在1以下。可选地,所述第三粗化液包括以下含量的各组分:氟离子源:30-200g/L,强酸:100-500g/L。具体地,氟离子源在第三粗化液中的含量可以为40、50、60、70、80、90、100、120、150或180g/L。强酸在第三粗化液中的含量可以为110、150、200、300、400或450g/L。
可选地,所述氟离子源可以包括氢氟酸、氟化铵、氟化氢铵中的一种或多种。其中,在所述氟离子为氢氟酸时,其在第三粗化液中的含量为30-100g/L。
优选地,所述氟离子源为氟化铵和/或氟化氢铵。此时,所述氟离子源在第三粗化液中的含量为50-200g/L。所述氟离子源还可提供含铵离子,含铵离子容易吸附在塑料基材的表面形成铵桥,提高上述塑料基材的表面活性,进而提高粗化效果。可选地,所述强酸为硝酸和盐酸中的至少一种。优选地,所述强酸为盐酸。盐酸还可提供氯离子,加速玻璃纤维的溶解。
进一步地,所述第三粗化液还包括10-60g/L的过氧化氢。含有过氧化氢的第三粗化液对玻璃纤维的溶解速度更高,可更好提高粗化效果。
可选地,所述第三粗化处理的温度可以为15-35℃,例如为20-30℃。若温度过低会导致粗化效果不明显或失效,若温度过高会导致过度粗化进而导致基材与后续镀层的结合力不良。所述第三粗化处理的时间可以为5-30min。
经过上述预粗化、第二粗化处理、第三粗化处理后,塑料基材表面会残留一层含6价铬及氟的有机膜,需要去除该膜以保证后续该塑料基材与金属镀层的结合力及避免漏镀现象。本申请的所述除膜液中,亚硫酸钠作为除膜主力,可以将含Cr残留膜中的六价Cr还原成三价Cr,以便3价Cr被水洗除去,同时还可以将氟从该有机膜中溶解下来进而水洗除去,而第二无机强碱可以中和塑料基材表面的酸根离子,同时可降低亚硫酸钠的水解。
可选地,所述除膜液的原料包括:亚硫酸钠:1-30g/L,第二无机强碱:1-5g/L。其中,所述第二无机强碱可包括氢氧化钠、氢氧化钾中的至少一种。
进一步地,所述除膜液的原料还可以包括:0.1-1g/L的硼氢化钠。加入硼氢化钠可以加速含Cr残留膜中的六价Cr的还原,进一步提高所述除膜液的除膜效果,提高了上镀的活性。此外,所述除膜液中第二无机强碱的存在还可抑制硼氢化钠的水解。
可选地,所述除膜处理的温度可以为50-70℃,例如为60-70℃,这样可以保证含Cr残留膜被充分除去,同时还可避免温度过高导致除膜液的主要成分氧化分解而大大降低除膜液的效果及寿命。所述除膜处理的时间可以为3-10min。
进一步地,在上述除油处理、预粗化处理、第二粗化处理、第三粗化处理及除膜处理后还分别进行水洗,以免上步处理残留的溶液干扰下一步处理。
本申请第一方面提供的PPS塑料基材的表面粗化方法中,第一步的预粗化处理可溶胀PPS塑料基材的表面,第二步粗化处理可将溶胀后的塑胶基材表面经氧化后亲水,第三步粗化处理可溶解PPS塑胶基材表面的玻璃纤维,这三步粗化工艺是环环相扣、缺一不可,在它们的配合下能在不明显改变基材表面形貌的情况下,将耐腐蚀性较好的PPS塑料基材的表面充分粗化并使基材亲水,避免了采用物理粗化方式所带来的破坏基材表面的台阶、微孔等精细结构的问题。此外,在三步粗化工艺后配合除膜液可除去因三步粗化工艺带来的含铬残留膜。
经过上述四步处理,可使PPS塑料基材具有较高的表面能和优异的上镀性,保证后续的镀层结合力。该表面粗化方法操作简单,较适用于制备对表面粗糙度有较高要求的金属化产品(如5G基站天线的振子等)过程中的粗化。
可选地,经上述表面粗化方法处理后的PPS塑料基材的表面粗糙度Ra为0.5μm-2μm。
第二方面,本申请提供了一种聚苯硫醚塑料基材的金属化方法,包括:
对聚苯硫醚塑料基材按本申请第一方面所述的表面粗化方法进行表面粗化;
对所述表面粗化后的塑料基材进行镀前活化处理后,进行化学镀,以形成镀层;之后对所述镀层进行钝化处理。
可选地,所述镀前活化处理依次包括:浸钯处理和钯还原处理。在本申请一实施方式中,所述浸钯处理所用的浸钯液包括:氯化钯:0.01-0.03g/L,盐酸和/或氯化钠0.02-0.1g/L,氨基吡啶和/或联吡啶:0.02-1g/L。所述浸钯处理可以在表面粗化后的塑料基材上沉积钯离子,以便其后续被还原成金属钯粒子,吸附在塑料基材上,该金属钯粒子作为活化中心,能诱发后续的化学镀反应,得到性能优良、结构完整的化学镀层。可选地,所述浸钯处理的温度为15-35℃,例如为20-30℃。所述浸钯处理的浸泡时间为2-10min。
其中,所述钯还原处理是将所述塑料基材浸泡在还原液中,其中,所述还原液包括:水合肼或二甲胺基硼烷10-20g/L,及水。可选地,所述钯还原处理的温度为15-35℃,例如为20-30℃。所述钯还原处理的浸泡为0.5-5min。
可选地,所述化学镀形成的镀层包括铜层、镍层,或者铜层与镍层的叠层。
可选地,在所述化学镀之后及所述钝化处理之前,还包括:进行电镀处理。在化学镀后再进行电镀处理,可对化学镀的镀层进行加厚,形成较厚的镀层。其中,化学镀、电镀采用本领域的现有手段即可。
本申请中,进行所述钝化处理,可以钝化镀层的表面,提高防腐性能。可选地,所述钝化处理所用的钝化液包括铬酸洗液、或有机钝化剂。进一步地,钝化处理形成的钝化保护膜是导电的,可以包括铬氧化膜或有机物薄膜。
本申请第二方面提供的PPS塑料基材的金属化方法中,在按第一方面所述的方法对PPS塑料基材进行上述表面粗化后,再依次进行镀前活化处理、化学镀、钝化处理,完成金属化的PPS塑料基材中,镀层的附着力强,耐高温高湿和盐雾测试。该方法可在不破坏基材表面细微结构的情况下,实现金属化,便于该基材在电子行业应用。
具体实施方式
以下所述是本申请的示例性实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本申请原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本申请的保护范围。
下面通过具体的实施例对本申请进行进一步的说明。若无特别说明,下面实施例中所采用的试剂皆为市售商品。
实施例1
一种PPS塑料基材的金属化方法,包括:
(1)除油:准备PPS塑料基材,其由PPS和GS注塑成型得到,该PPS塑料基材中GS的质量占比为40%;将该PPS塑料基材在60℃的热水中进行超声浸泡20min;
(2)预粗化:将除油后的PPS塑料基材置于预粗化液中,在60℃下浸泡40min,其中,该预粗化液包括:五氟丙醇:60g/L,三乙醇胺:50g/L,氢氧化钠:70g/L,乙二醇丁醚:40g/L,以及水;
(3)第二粗化:将步骤(2)处理后的PPS塑料基材经水洗后置于第二粗化液中,在65℃下浸泡10min,其中,第二粗化液的配置过程如下:将铬酐与水混合,再加入硫酸,最后加入单月桂基硫酸酯进行搅拌,直至容器底部无明显沉淀;其中,在组成第二粗化液的物料体系中,铬酐的用量为300g/L,单月桂基硫酸酯的用量为1g/L;硫酸的用量为300g/L;
(4)第三粗化:将步骤(3)处理后的PPS塑料基材经水洗后置于第三粗化液中,在20℃下浸泡15min,其中,第三粗化液的配置过程如下:先用水溶解氟化氢铵,再加入硝酸,最后加入50wt%的双氧水进行搅拌,直至容器底部无明显沉淀;其中,该第三粗化液包括以下含量的各组分:氟化氢铵:120g/L,硝酸:200g/L,过氧化氢:30g/L;
(5)中和除膜:将步骤(4)处理后的PPS塑料基材经水洗后置于除膜液中,在65℃下浸泡5min,之后进行超声水洗,完成表面粗化处理;其中,该除膜液的配置原料包括:无水亚硫酸钠:5g/L,氢氧化钠:2g/L,硼氢化钠:0.5g/L及水;
(6)浸钯:将步骤(5)处理后的PPS塑料基材置于浸钯液中,在20℃下浸泡5min,其中,该浸钯液包括:氯化钯:0.02g/L,盐酸:0.05g/L,氨基吡啶:0.06g/L,及水;
(7)钯还原:将步骤(6)处理后的PPS塑料基材经水洗后置于浓度为15g/L的水合肼水溶液中,在20℃下浸泡5min;
(8)化学镀:将步骤(7)处理后的PPS塑料基材经水洗后进行化学镀铜,以形成铜化镀层;
(9)电镀:将步骤(8)处理后的PPS塑料基材经水洗后,在上述铜化镀层上电镀铜,以形成铜电镀层;
(10)钝化:将步骤(9)处理后的PPS塑料基材经水洗后,采用铬酸洗液对上述铜电镀层进行钝化处理,以提高铜镀层的防腐性,完成金属化。
实施例2
一种PPS塑料基材的金属化方法,其与实施例1的区别在于:预粗化液的成分包括:五氟丙醇:10/L,三乙醇胺:30g/L,氢氧化钠:20g/L,乙二醇丁醚:10g/L,及水;第二粗化液的原料包括:铬酐:100g/L,单月桂基硫酸酯:0.1g/L,硫酸:100g/L,及水;第三粗化液的成分包括:氟化氢铵:50g/L,硝酸:100g/L,过氧化氢:10g/L,及水;除膜液的原料包括:无水亚硫酸钠:1g/L,硼氢化钠:0.1g/L,氢氧化钠:1g/L,及水。
实施例3
一种PPS塑料基材的金属化方法,其与实施例1的区别在于:第三粗化液不含过氧化氢,其成分为:氟化氢铵:120g/L,硝酸:200g/L及水;除膜液的原料不包括硼氢化钠,其原料为:无水亚硫酸钠:5g/L,氢氧化钠:1g/L,及水。
实施例4
一种PPS塑料基材的金属化方法,其与实施例2的区别在于:将实施例2的第三粗化液中含量为50g/L的氟化氢铵替换成含量为30g/L的氢氟酸。
实施例5
一种PPS塑料基材的金属化方法,其与实施例1的区别在于:预粗化处理是在70℃下浸泡10min。
实施例6
一种PPS塑料基材的金属化方法,其与实施例1的区别在于:预粗化处理是在50℃下浸泡60min。
实施例7
一种PPS塑料基材的金属化方法,其与实施例1的区别在于:将第二粗化液中的铬酐替换为铬酸;第二粗化处理是在70℃下浸泡5min。并将铬酐改为铬酸
实施例8
一种PPS塑料基材的金属化方法,其与实施例1的区别在于:将第二粗化液中的铬酐替换为铬酸钠;第二粗化处理是在60℃下浸泡30min。
实施例9
一种PPS塑料基材的金属化方法,其与实施例1的区别在于:第三粗化处理是在35℃下浸泡5min。
实施例10
一种PPS塑料基材的金属化方法,其与实施例1的区别在于:第三粗化处理是在15℃下浸泡30min。
实施例11
一种PPS塑料基材的金属化方法,其与实施例1的区别在于:中和除膜处理是在35℃下进行5min。
实施例12
一种PPS塑料基材的金属化方法,其与实施例1的区别在于:中和除膜处理是在15℃下进行30min。
为突出本申请实施例的技术方案带来的有益效果,现设置以下对比例:
对比例1
一种PPS塑料基材的金属化方法,其与实施例1的区别在于:将PPS塑料基材通过物理喷砂进行表面粗化,水洗后直接进行步骤(6)-(10)的处理。
为对本申请实施例的技术方案带来的有益效果进行有力支持,提供按各实施例中提及的表面粗化方法及对比例1的喷砂方式对PPS+40%GS的PPS塑料基材进行表面粗化处理后的粗糙度Ra测试结果。此外,还提供按各实施例及对比例的金属化方法对PPS+40%GS的PPS塑料基材进行处理后,进行百格测试、高温高湿测试、盐雾测试等测试,结果汇总在下表1中。
表1各实施例与对比例1的结果汇总
上述各测试指标是分别采用以下方法测试。其中,百格测试:用百格刀在钝化后金属镀层上划1*1mm的格子,要求划穿到基材表面,然后用3M-600胶带粘牢,避免胶带与镀层间有气泡,然后匀速拉起胶带,看是否有镀层脱落以及镀层脱落的面积大小来判断镀层等级。无脱落代表镀层的百格测试等级为5B,切口的相交处有小片剥落,格子内实际破损小于5%为4B等级,切口边缘或相交处有剥落,面积大于5%小于15%脱落为3B等级,脱落大于15%小于35%为2B等级,脱落大于35%小于65%为1B等级。其中,百格测试等级在3B以上才符合一般应用要求。
高温高湿测试:将金属化后的PPS塑料基材置于湿度为85%、温度为85℃的高温高湿箱中,放置48小时,取出后观察外观是否有变化。具体是观察是否出现溶胶、镀层是否鼓包、起泡、是否变色严重,若均无,则记录为“OK”。
盐雾测试:按GB/T 1771-2007进行中性盐雾测试,在盐雾箱内放置,看放置多久后镀层的外观才会发生变化(如,变色、鼓包、起泡等)。
从表1可以看出,采用本申请实施例中提及的四步式表面粗化工艺对PPS塑料基材处理后的粗糙度Ra明显低于采用对比例1的喷砂方式进行表面粗化处理后的粗糙度,且不会出现不同区域粗糙度不均匀的现象。这进一步验证了上述四步式的表面粗化处理几乎不会破坏PPS塑料基材原有的表面细微结构,进而不会影响金属化后的PPS塑料基材在电子行业的应用,例如在其作为天线振子时,不会影响天线功能的发挥。此外,采用本申请实施例提供的PPS塑料基材的金属化方法所形成的镀层的耐盐雾性也较优于喷砂粗化后所形成的镀层的耐盐雾性。
以上所述是本申请的示例性实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本申请原理的前提下,还可以对其做出若干改进和润饰,这些改进和润饰也视为本申请的保护范围。
Claims (13)
1.一种聚苯硫醚塑料基材的表面粗化方法,其特征在于,包括:
提供塑料基材,对所述塑料基材依次进行预粗化处理、第二粗化处理、第三粗化处理和中和除膜处理;其中,所述塑料基材含有聚苯硫醚和玻璃纤维;
所述预粗化处理使用的预粗化液包括以下含量的各组分:五氟丙醇:10-120g/L、醚类物质:10-120g/L、醇胺类物质:30-100g/L、第一无机强碱:20-100g/L及水;
所述第二粗化处理使用的第二粗化液的原料包括六价铬源、表面活性剂、硫酸及水;
所述第三粗化处理使用的第三粗化液包括氟离子源、强酸及水;
所述中和除膜处理使用的除膜液的原料包括亚硫酸钠、第二无机强碱及水。
2.如权利要求1所述的表面粗化方法,其特征在于,所述醇胺类物质包括三乙醇胺、二乙醇胺和单乙醇胺中的一种或多种;所述醚类包括乙二醇乙醚、乙二醇丁醚、乙二醇己醚、二乙二醇乙醚、二乙二醇丁醚、二乙二醇己醚、二乙二醇二乙烯基醚、二乙二醇单乙烯基醚中的一种或多种。
3.如权利要求1所述的表面粗化方法,其特征在于,所述第二粗化液包括以下含量的各原料:六价铬源:100-400g/L,硫酸:100-400g/L,表面活性剂:0.1-3g/L,及水;其中,所述六价铬源包括铬酐、铬酸、铬酸钾和铬酸钠中的一种或多种。
4.如权利要求3所述的表面粗化方法,其特征在于,所述表面活性剂包括单月桂基硫酸酯、烷基二苯醚二磺酸盐和磺酸盐型碳氟表面活性剂中的一种或多种。
5.如权利要求1所述的表面粗化方法,其特征在于,所述第三粗化液包括以下含量的各组分:氟离子源:30-200g/L,强酸:100-500g/L,过氧化氢:0-60g/L。
6.如权利要求5所述的表面粗化方法,其特征在于,所述过氧化氢在所述第三粗化液中的含量为10-60g/L。
7.如权利要求1所述的表面粗化方法,其特征在于,所述除膜液的原料包括:亚硫酸钠:1-30g/L,第二无机强碱:1-5g/L,0-1g/L的硼氢化钠。
8.如权利要求7所述的表面粗化方法,其特征在于,所述硼氢化钠在所述除膜液中的含量为0.1-1g/L。
9.如权利要求1-8任一项所述的表面粗化方法,其特征在于,所述预粗化处理、第二粗化处理和除膜处理分别在50-70℃的温度下进行,所述第三粗化处理在15-35℃的温度下进行。
10.一种聚苯硫醚塑料基材的金属化方法,其特征在于,包括以下步骤:
按权利要求1-9任一项所述的表面粗化方法对聚苯硫醚塑料基材进行表面粗化;
对所述表面粗化后的塑料基材进行镀前活化处理后,进行化学镀,以形成镀层;之后对所述镀层进行钝化处理。
11.如权利要求10所述的金属化方法,其特征在于,所述镀前活化处理依次包括浸钯处理和钯还原处理。
12.如权利要求10所述的金属化方法,其特征在于,所述钝化处理所用的钝化液包括铬酸洗液。
13.如权利要求10-12任一项所述的金属化方法,其特征在于,在所述化学镀之后和所述钝化处理之前,还包括:进行电镀处理。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4941940A (en) * | 1988-11-07 | 1990-07-17 | Jp Laboratories, Inc. | Pre-swelling and etching of plastics for plating |
JPH05112872A (ja) * | 1991-10-21 | 1993-05-07 | Okuno Seiyaku Kogyo Kk | ポリイミド系樹脂の無電解めつき方法及びプリエツチング用組成物 |
CN103572263A (zh) * | 2012-07-28 | 2014-02-12 | 比亚迪股份有限公司 | 塑料表面金属化的方法和表面具有金属图案的塑料产品 |
KR101422616B1 (ko) * | 2013-06-21 | 2014-07-23 | 정한영 | 무선통신 단말기용 인테나의 무전해 도금방법 |
CN104894537A (zh) * | 2015-07-01 | 2015-09-09 | 常德鑫鸿金属材料有限公司 | 一种单面导电的聚酰亚胺复合材料及其制备方法 |
-
2020
- 2020-08-03 CN CN202010766563.7A patent/CN114059050B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4941940A (en) * | 1988-11-07 | 1990-07-17 | Jp Laboratories, Inc. | Pre-swelling and etching of plastics for plating |
JPH05112872A (ja) * | 1991-10-21 | 1993-05-07 | Okuno Seiyaku Kogyo Kk | ポリイミド系樹脂の無電解めつき方法及びプリエツチング用組成物 |
CN103572263A (zh) * | 2012-07-28 | 2014-02-12 | 比亚迪股份有限公司 | 塑料表面金属化的方法和表面具有金属图案的塑料产品 |
KR101422616B1 (ko) * | 2013-06-21 | 2014-07-23 | 정한영 | 무선통신 단말기용 인테나의 무전해 도금방법 |
CN104894537A (zh) * | 2015-07-01 | 2015-09-09 | 常德鑫鸿金属材料有限公司 | 一种单面导电的聚酰亚胺复合材料及其制备方法 |
Non-Patent Citations (1)
Title |
---|
Metallizing Polyetherimide Resin Reinforced with Glass Fibers;Maher A. Alodan;《Journal of King Saud University - Engineering Sciences》;20040615;第17卷(第2期);第251-259页 * |
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