CN110129807A - 一种用于铜/铁基材的酸洗缓蚀剂及酸洗液 - Google Patents
一种用于铜/铁基材的酸洗缓蚀剂及酸洗液 Download PDFInfo
- Publication number
- CN110129807A CN110129807A CN201910433032.3A CN201910433032A CN110129807A CN 110129807 A CN110129807 A CN 110129807A CN 201910433032 A CN201910433032 A CN 201910433032A CN 110129807 A CN110129807 A CN 110129807A
- Authority
- CN
- China
- Prior art keywords
- copper
- iron
- based material
- corrosion inhibiter
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000005554 pickling Methods 0.000 title claims abstract description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 41
- 239000010949 copper Substances 0.000 title claims abstract description 41
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000000837 restrainer Substances 0.000 title claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 52
- 238000005260 corrosion Methods 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical class C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 12
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical group SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 7
- PKDBCJSWQUOKDO-UHFFFAOYSA-M 2,3,5-triphenyltetrazolium chloride Chemical compound [Cl-].C1=CC=CC=C1C(N=[N+]1C=2C=CC=CC=2)=NN1C1=CC=CC=C1 PKDBCJSWQUOKDO-UHFFFAOYSA-M 0.000 claims description 7
- 150000003536 tetrazoles Chemical group 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 229910006069 SO3H Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 30
- 230000005764 inhibitory process Effects 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 20
- 239000003814 drug Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000003112 inhibitor Substances 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- -1 phenyltetrazole class compound Chemical class 0.000 abstract description 3
- 238000007747 plating Methods 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 36
- 230000010287 polarization Effects 0.000 description 16
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 11
- 230000003628 erosive effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- PAKWFHYWNFCRCK-CMBBICFISA-M 2,5-diphenyl-3-[4-[(e)-2-phenylethenyl]phenyl]tetrazol-3-ium;chloride Chemical group [Cl-].C=1C=CC=CC=1/C=C/C(C=C1)=CC=C1[N+]1=NC(C=2C=CC=CC=2)=NN1C1=CC=CC=C1 PAKWFHYWNFCRCK-CMBBICFISA-M 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910000975 Carbon steel Inorganic materials 0.000 description 4
- 239000010962 carbon steel Substances 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 229930186147 Cephalosporin Natural products 0.000 description 3
- 229940124587 cephalosporin Drugs 0.000 description 3
- 150000001780 cephalosporins Chemical class 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000003831 tetrazolyl group Chemical group 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OMAFFHIGWTVZOH-UHFFFAOYSA-N 1-methyltetrazole Chemical group CN1C=NN=N1 OMAFFHIGWTVZOH-UHFFFAOYSA-N 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- UFNOUKDBUJZYDE-UHFFFAOYSA-N 2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol Chemical compound C1=NC=NN1CC(O)(C=1C=CC(Cl)=CC=1)C(C)C1CC1 UFNOUKDBUJZYDE-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 102000008873 Angiotensin II receptor Human genes 0.000 description 1
- 108050000824 Angiotensin II receptor Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005757 Cyproconazole Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000157 blood function Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- MLYYVTUWGNIJIB-BXKDBHETSA-N cefazolin Chemical compound S1C(C)=NN=C1SCC1=C(C(O)=O)N2C(=O)[C@@H](NC(=O)CN3N=NN=C3)[C@H]2SC1 MLYYVTUWGNIJIB-BXKDBHETSA-N 0.000 description 1
- 229960001139 cefazolin Drugs 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/068—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors compounds containing a C=C bond
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/081—Iron or steel solutions containing H2SO4
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/085—Iron or steel solutions containing HNO3
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
本发明属于印制电路板制造领域，涉及铁基材与铜基材电镀前酸洗/微蚀处理工艺及印制电路板棕化工艺中的酸洗工艺，具体提供一种用于铜/铁基材的酸洗缓蚀剂及酸洗液，用以克服现有铜/铁基材酸洗液中缓蚀剂缓蚀效率低、成本高、环境兼容性差的缺陷。本发明采用常规作为医药中间体用的苯基四唑化合物作为缓蚀剂加入铜/铁基材酸洗液，作为缓蚀剂的苯基四唑类化合物用量少，环境危害性小，符合绿色缓蚀剂发展的趋势；且缓蚀效率高、可达到80‑99％，缓蚀性能稳定，在不同的温度和浓度下均具有良好的缓蚀性能；同时，酸洗液中酸液为硝酸、硫酸或盐酸的一种或多种的组合，适和铜基铁基体材料表面酸洗。
Description
技术领域
本发明属于印制电路板制造领域，涉及铁基材与铜基材电镀前酸洗/微蚀处理工艺及印制电路板棕化工艺中的酸洗工艺，具体提供一种用于铜/铁基材的酸洗缓蚀剂及酸洗液，用以防止铁基材及印制电路的铜基材及其制品在酸洗/微蚀过程中酸介质对金属的过腐蚀。
背景技术
铁和铜金属是工业部门不可或缺的金属材料，铁与少量的碳制成合金钢，磁化之后不易去磁，是优良的硬磁材料，同时也是重要的工业材料，在建筑、交通等领域使用广泛。金属铜在电气、电子工业中应用最广、用量最大，占总消费量一半以上；用于各种印刷电路板、电机、变压器、开关以及电缆和导线的制造中。以印制电路板(PCB)为例，PCB作为重要的电子部件，为各种电子元件的安装固定提供支撑，同时又肩负着各元器件之间电路互通的重任。印制电路板制造工艺从基板到成品，前后要经过上百道工序，流程极为繁琐，其中酸洗工序是印制线路板制作工艺中使用最多的工序之一，以PCB棕化工序为例，其工艺流程技术为：酸洗-水洗-碱性除油-水洗-预浸-棕化-纯水洗-烘干-压合，以PCB电镀工序为例，其主要流程为：上板、除油、水洗、酸洗、镀铜、水洗、酸洗、镀锡、水洗、下板等；其中，酸洗的目的是除去棕化工艺或电镀工艺中的印制电路板金属表面的锈垢、氧化膜及其他锈蚀，从而获得良好的金属表面。铜/铁基材表面进行酸洗时通常采用硝酸、硫酸、盐酸等，但金属基材中铜/铁基体表面在酸洗液中去除锈垢、氧化膜及其他锈蚀的同时极易受到酸腐蚀，造成铜/铁基材的金属制品尺寸缩小、表面基体损坏等过腐蚀破坏现象；因此，在酸洗/微蚀过程中为了防止过腐蚀现象，需要在酸洗液中加入缓蚀剂，以降低腐蚀速率、减缓腐蚀过程。
目前，酸洗液中铜缓蚀剂大部分为苯并三氮唑(BTA)及甲巯基苯并噻唑(MBT)、基苯并三氮唑(TTA)、BTM等衍生物；三唑类铜缓蚀剂存在溶解度低、熔点低(如BTA熔点98.5℃)、毒性大、气味大、可降解性差及环境兼容性差等缺陷，且苯并三氮唑及其衍生物作为中性或偏碱性铜缓蚀剂，在酸洗液中缓蚀性能明显下降，导致其应用受到了限制；且三氮唑及其衍生物易导致水环境缺氧和富营养化，人体接触后易致癌并破坏血液功能系统。公开号为CN103388152.A的专利文献中公开了含有环唑醇作为酸洗缓蚀剂，具有用量少、缓蚀效率高、廉价易得、能够在阳光下自然降解，不存在使用后的环境问题等，符合现代绿色生产的理念，但该专利所选择的缓蚀剂主要是以铜基材酸洗为主。公开号为CN106521520.A的专利文献中公开了一种氨基磺酸作为高温酸洗缓蚀剂及其制备方法，能有效的阻止酸洗介质对碳钢和锌基体的腐蚀，缓蚀率可达90％以上；但同时能作为铜、铁基材的酸洗缓蚀剂鲜有报道。
四氮唑类化合物是含有四个氮原子的五元芳杂环化合物，是一类在有机合成中极其重要的中间体，可用来合成医药、衣药及工业用的发泡剂等产品；此外，可用来取代药物中的羧基以缓解羧基在体内引起的不良反应，提高药物的脂溶性，进而增加药物的生物利用度；如头孢菌素的7－位酰胺基是抗菌谱的决定基团，用N-甲基四氮唑取代，合成了第一代头孢菌素、头孢唑林，扩人了抗菌谱并提高了活性；5-位取代四氮唑具有显著的生物活性，常川于头孢菌素类杭生素，血管紧张素受体抑制剂及抗肿瘤药物等的修饰改造，故近年来四氮唑类芳杂环化合物在医药领域的应用越来越广泛；被科学家认为是最具发展前景的一类。
发明内容
本发明的目的在于针对背景技术中铜/铁基材酸洗液中缓蚀剂缓蚀效率低、成本高、环境兼容性差的缺陷，提供一种用于铜/铁基材的酸洗缓蚀剂及酸洗液，用于为印制电路板制造中的电镀、棕化工艺中酸洗/微蚀处理工艺提供一种高效、环保、廉价、易得的具有缓蚀效果的铜/铁基材酸洗缓蚀剂及酸洗液。
为实现上述目的，本发明采用的技术方案为：
一种用于铜/铁基材的酸洗缓蚀剂，其特征在于，所述缓蚀剂为苯基四唑化合物，其分子结构为：
其中，X1、X2、X3、X4均为取代基，具体为巯基-SH、羧基-COOH、磺酸基-SO3H、胺基-NH、苯基或萘基。
进一步的，所述缓蚀剂为四氮唑紫，其分子结构为：
进一步的，所述缓蚀剂为2,5二苯基-3-(4苯乙烯基苯基)氯化四氮唑，其分子结构为：
进一步的，所述缓蚀剂为2,3二苯基-5-(4甲氧苯基)氯化四氮唑，其分子结构为：
进一步的，所述缓蚀剂为1-苯基-5-巯基-1H-四唑，其分子结构为：
一种包含上述酸洗缓蚀剂的铜/铁基材酸洗液，包括酸液和缓蚀剂；其特征在于，所述缓蚀剂的量为10-5～10-3mol/L；酸液为强酸，浓度为0.5～3mol/L。
进一步的，所述缓蚀剂为四氮唑紫、2,5二苯基-3-(4苯乙烯基苯基)氯化四氮唑、1-苯基-5-巯基-1H-四唑、2,3二苯基-5-(4甲氧苯基)氯化四氮唑中的一种或多种。
所述强酸为硝酸、硫酸、盐酸中的一种或多种。
本发明的有益效果在于：
本发明采用常规作为医药中间体用的苯基四唑化合物作为缓蚀剂加入铜/铁基材酸洗液，配制得具有缓蚀效果的铜/铁基材酸洗液；该酸洗液中作为缓蚀剂的苯基四唑类化合物用量少，环境危害性小，符合绿色缓蚀剂发展的趋势；且缓蚀效率高、可达到80-99％，缓蚀性能稳定，在不同的温度和浓度下均具有良好的缓蚀性能；同时，酸洗液中酸液为硝酸、硫酸或盐酸的一种或多种的组合，适和铜基铁基体材料表面酸洗。
附图说明
图1为实施例1电化学阻抗谱测试所得奈奎斯特图。
图2为实施例1动电位极化曲线测试所得动电位极化曲线图。
图3为实施例2电化学阻抗谱测试所得奈奎斯特图。
图4为实施例2动电位极化曲线测试所得动电位极化曲线图。
图5为实施例3电化学阻抗谱测试所得奈奎斯特图。
图6为实施例3动电位极化曲线测试所得动电位极化曲线图。
图7为实施例4电化学阻抗谱测试所得奈奎斯特图。
图8为实施例4动电位极化曲线测试所得动电位极化曲线图。
图9为实施例5电化学阻抗谱测试所得奈奎斯特图。
图10为实施例5动电位极化曲线测试所得动电位极化曲线图。
具体实施方式
下面结合附图和实施例对本发明做进一步详细说明。
本发明按照GB10124－88《金属材料实验室均匀腐蚀全浸试验方法》进行失重试验，失重实验使用的覆铜板铜箔(99.9％)尺寸为：100mm×100mm×2mm，所用Q235钢尺寸为30mm×15mm×15mm，并以未添加任何缓蚀剂的酸洗液配方作为空白对照。
电化学实验使用CHI760E电化学工作站，采用三电极体系，大面积铂片(20mm×20mm)为辅助电极，带有毛细管的饱和硫酸亚汞电极为参比电极，有效直径1cm的紫铜(99.999％)及有效直径1.5cm的Q235碳钢分别作为工作电极；极化曲线测试的扫描速率为1mV/s，扫面范围为-250mV～+250mV；交流阻抗(EIS)测试采用正弦波作为激励信号，振幅为5mV，扫描频率为100kHz～1mHz。
实施例1
酸洗液中酸液为稀硫酸，浓度为0.5mol/L，酸洗液用量为1L，加入四唑氮紫10- 4mol/L，2,5二苯基-3-(4苯乙烯基苯基)氯化四氮唑10-4mol/L，在25℃条件下将待清洗的金属铜浸没在酸洗处理液中失重实验浸没2天；电化学测试浸泡1小时。
通过失重试验测试获得的最高缓蚀效率为90.1％，电化学阻抗谱测试结果显示缓蚀效率为98.8％、如图1所示，动电位极化曲线测试结果显示缓蚀效率为98.7％、如图2所示，酸洗处理液中缓蚀剂显示为高效的缓蚀剂。
实施例2
酸洗液中酸液为稀盐酸和稀硫酸，浓度分别为0.5mol/L，酸洗液用量为5L加入四唑氮紫10-4mol/L，2,5二苯基-3-(4苯乙烯基苯基)氯化四氮唑10-4mol/L，在15℃条件下将待清洗的覆铜板浸没在酸洗处理液中浸没5天。
通过失重试验测试获得的最高缓蚀效率为84.1％，电化学阻抗谱测试结果显示缓蚀效率为89.1％、如图3所示，动电位极化曲线测试结果显示缓蚀效率为88.9％、如图4所示，酸洗处理液中缓蚀剂显示为高效的缓蚀剂。
实施例3
酸洗液中酸液为稀硫酸，浓度为0.5mol/L，酸洗液用量为2L，加入四唑氮紫10- 4mol/L，2,3二苯基-5-(4甲氧苯基)氯化四氮唑10-4mol/L，1-苯基-5-巯基-1H-四唑10-4mol/L，在25℃条件下将待清洗的Q235碳钢浸没在酸洗处理液中失重实验浸没3天；电化学测试浸泡1小时。
通过失重试验测试获得的最高缓蚀效率为81.7％，电化学阻抗谱测试结果显示缓蚀效率为88.2％、如图5所示，动电位极化曲线测试结果显示缓蚀效率为87.7％、如图6所示，酸洗处理液中缓蚀剂显示为高效的缓蚀剂。
实施例4
酸洗液中酸液为稀盐酸，浓度为1mol/L，酸洗液用量为10L，加入四氮唑紫10-4mol/L、2,5二苯基-3-(4苯乙烯基苯基)氯化四氮唑10-4mol/L、1-苯基-5-巯基-1H-四唑10-3mol/L，在35℃条件下将待清洗的Q235碳钢浸没在酸洗处理液中2天，电化学测试浸泡2小时。
通过失重试验测试获得的最高缓蚀效率为81.7％，电化学阻抗谱测试结果显示缓蚀效率为88.2％、如图7所示，动电位极化曲线测试结果显示缓蚀效率为92.1％、如图8所示，酸洗处理液中缓蚀剂显示为高效的缓蚀剂。
实施例5
酸洗液中酸液为稀硫酸，浓度为0.5mol/L，酸洗液用量为5L，加入四氮唑紫10- 3mol/L、1-苯基-5-巯基-1H-四唑10-4mol/L，在45℃条件下将待清洗的金属铜浸没在酸洗处理液中失重实验浸没1天；电化学测试浸泡1小时。
通过失重试验测试获得最高缓蚀效率为90.1％，电化学阻抗谱测试结果显示缓蚀效率为98.4％、如图9所示，动电位极化曲线测试结果显示缓蚀效率为95.7％、如图10所示，酸洗处理液中缓蚀剂显示为高效的缓蚀剂。
以上所述，仅为本发明的具体实施方式，本说明书中所公开的任一特征，除非特别叙述，均可被其他等效或具有类似目的的替代特征加以替换；所公开的所有特征、或所有方法或过程中的步骤，除了互相排斥的特征和/或步骤以外，均可以任何方式组合。
Claims (8)
1.一种用于铜/铁基材的酸洗缓蚀剂，其特征在于，所述缓蚀剂为苯基四唑化合物，其分子结构为：
其中，X1、X2、X3、X4均为取代基，具体为巯基-SH、羧基-COOH、磺酸基-SO3H、胺基-NH、苯基或萘基。
2.按权利要求1所述用于铜/铁基材的酸洗缓蚀剂，其特征在于，所述缓蚀剂为四氮唑紫。
3.按权利要求1所述用于铜/铁基材的酸洗缓蚀剂，其特征在于，所述缓蚀剂为2,5二苯基-3-(4苯乙烯基苯基)氯化四氮唑。
4.按权利要求1所述用于铜/铁基材的酸洗缓蚀剂，其特征在于，所述缓蚀剂为2,3二苯基-5-(4甲氧苯基)氯化四氮唑。
5.按权利要求1所述用于铜/铁基材的酸洗缓蚀剂，其特征在于，所述缓蚀剂为1-苯基-5-巯基-1H-四唑。
6.一种包含权利要求1所述用于铜/铁基材的酸洗缓蚀剂的铜/铁基材酸洗液，包括酸液和缓蚀剂；其特征在于，所述缓蚀剂的量为10-5～10-3mol/L；酸液为强酸，浓度为0.5～3mol/L。
7.按权利要求6所述铜/铁基材酸洗液，其特征在于，所述缓蚀剂为四氮唑紫、2,5二苯基-3-(4苯乙烯基苯基)氯化四氮唑、1-苯基-5-巯基-1H-四唑、2,3二苯基-5-(4甲氧苯基)氯化四氮唑中的一种或多种。
8.按权利要求6所述铜/铁基材酸洗液，其特征在于，所述强酸为硝酸、硫酸、盐酸中的一种或多种。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910433032.3A CN110129807A (zh) | 2019-05-23 | 2019-05-23 | 一种用于铜/铁基材的酸洗缓蚀剂及酸洗液 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910433032.3A CN110129807A (zh) | 2019-05-23 | 2019-05-23 | 一种用于铜/铁基材的酸洗缓蚀剂及酸洗液 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110129807A true CN110129807A (zh) | 2019-08-16 |
Family
ID=67572632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910433032.3A Pending CN110129807A (zh) | 2019-05-23 | 2019-05-23 | 一种用于铜/铁基材的酸洗缓蚀剂及酸洗液 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110129807A (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111485264A (zh) * | 2020-05-11 | 2020-08-04 | 江西旅游商贸职业学院 | 一种具有缓蚀功能的电镀铜前处理液及前处理工艺 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101688145A (zh) * | 2007-05-24 | 2010-03-31 | 千代田化学株式会社 | 功能性流体 |
| CN101994124A (zh) * | 2009-08-21 | 2011-03-30 | 中国科学院海洋研究所 | 一种杂环类碳钢酸洗缓蚀剂及其应用 |
| CN103725745A (zh) * | 2012-10-10 | 2014-04-16 | 苏州四同医药科技有限公司 | 霉菌酵母菌显色计数培养基 |
| CN103820795A (zh) * | 2014-01-22 | 2014-05-28 | 西南林业大学 | 一种高效复配缓蚀剂及其制备方法与应用 |
| CN109576722A (zh) * | 2019-01-31 | 2019-04-05 | 深圳市华星光电技术有限公司 | 铜清洗剂 |
-
2019
- 2019-05-23 CN CN201910433032.3A patent/CN110129807A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101688145A (zh) * | 2007-05-24 | 2010-03-31 | 千代田化学株式会社 | 功能性流体 |
| CN101994124A (zh) * | 2009-08-21 | 2011-03-30 | 中国科学院海洋研究所 | 一种杂环类碳钢酸洗缓蚀剂及其应用 |
| CN103725745A (zh) * | 2012-10-10 | 2014-04-16 | 苏州四同医药科技有限公司 | 霉菌酵母菌显色计数培养基 |
| CN103820795A (zh) * | 2014-01-22 | 2014-05-28 | 西南林业大学 | 一种高效复配缓蚀剂及其制备方法与应用 |
| CN109576722A (zh) * | 2019-01-31 | 2019-04-05 | 深圳市华星光电技术有限公司 | 铜清洗剂 |
Non-Patent Citations (2)
| Title |
|---|
| HTTPS://WWW.CHEMICALBOOK.COM/PRODUCTCHEMICALPROPERTIESCB5431496.: "https://www.chemicalbook.com/ProductChemicalPropertiesCB5431496.htm", 《HTTPS://WWW.CHEMICALBOOK.COM/PRODUCTCHEMICALPROPERTIESCB5431496.HTM》 * |
| HTTPS://WWW.TCICHEMICALS.COM/CN/ZH/P/B0339: "https://www.tcichemicals.com/CN/zh/p/B0339", 《HTTPS://WWW.TCICHEMICALS.COM/CN/ZH/P/B0339》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111485264A (zh) * | 2020-05-11 | 2020-08-04 | 江西旅游商贸职业学院 | 一种具有缓蚀功能的电镀铜前处理液及前处理工艺 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Frignani et al. | Inhibition of AZ31 Mg alloy corrosion by anionic surfactants | |
| Varvara et al. | Evaluation of some non-toxic thiadiazole derivatives as bronze corrosion inhibitors in aqueous solution | |
| Sherif et al. | Effects of 2-amino-5-ethylthio-1, 3, 4-thiadiazole on copper corrosion as a corrosion inhibitor in aerated acidic pickling solutions | |
| Ma et al. | Impedance spectroscopic study of corrosion inhibition of copper by surfactants in the acidic solutions | |
| Bentiss et al. | Inhibition of acidic corrosion of mild steel by 3, 5-diphenyl-4H-1, 2, 4-triazole | |
| Zhang et al. | Electrochemical behavior of anodized Mg alloy AZ91D in chloride containing aqueous solution | |
| Oguzie et al. | Effect of 2-amino-3-mercaptopropanoic acid (cysteine) on the corrosion behaviour of low carbon steel in sulphuric acid | |
| Sherif | Effects of 2-amino-5-(ethylthio)-1, 3, 4-thiadiazole on copper corrosion as a corrosion inhibitor in 3% NaCl solutions | |
| Yang et al. | Galvanic corrosion behavior between AZ91D magnesium alloy and copper in distilled water | |
| Sherif et al. | Corrosion of magnesium/manganese alloy in chloride solutions and its inhibition by 5-(3-aminophenyl)-tetrazole | |
| US11982002B2 (en) | Method for anti-corrosion treatment of metallic copper-containing materials | |
| Bazzaoui et al. | Environmentally friendly process for nickel electroplating of ABS | |
| He et al. | Conjugated polymers for corrosion control: scanning vibrating electrode studies of polypyrrole-aluminum alloy interactions | |
| Sherif et al. | Corrosion and corrosion inhibition of high strength low alloy steel in 2.0 M sulfuric acid solutions by 3-amino-1, 2, 3-triazole as a corrosion inhibitor | |
| Radovanović et al. | Protection of copper surface in acidic chloride solution by non-toxic thiadiazole derivative | |
| Shao et al. | N-[2-(3-indolyl) ethyl]-cinnamamide synthesized from cinnamomum cassia presl and alkaloid tryptamine as green corrosion inhibitor for Q235 steel in acidic medium | |
| Shi et al. | Corrosion protection of AZ91D magnesium alloy with sol–gel coating containing 2-methyl piperidine | |
| Sherif | Inhibition of copper corrosion reactions in neutral and acidic chloride solutions by 5-ethyl-1, 3, 4-thiadiazol-2-amine as a corrosion inhibitor | |
| Saranya et al. | Electrodeposition of Ni–Cu alloys from a protic ionic liquid medium-voltammetric and surface morphologic studies | |
| Zhang et al. | The effect of quaternary ammonium-based ionic liquids on copper electrodeposition from acidic sulfate electrolyte | |
| Arenas et al. | Synthesis and electrochemical evaluation of polypyrrole coatings electrodeposited onto AA-2024 alloy | |
| CN110129807A (zh) | 一种用于铜/铁基材的酸洗缓蚀剂及酸洗液 | |
| Ma et al. | Pyrazole acylhydrazone Schiff bases as magnesium alloy corrosion inhibitor: synthesis, properties and mechanism investigation | |
| Lin et al. | Through-hole filling in a Cu plating bath with functional insoluble anodes and acetic acid as a supporting electrolyte | |
| Al-Esary | Influence of additives on electrodeposition of metals from deep eutectic solvents |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190816 |
|
| RJ01 | Rejection of invention patent application after publication |