CN118048666A - Methylsulfonate type pure tin electroplating solution additive and electroplating solution containing same - Google Patents
Methylsulfonate type pure tin electroplating solution additive and electroplating solution containing same Download PDFInfo
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- CN118048666A CN118048666A CN202410194880.4A CN202410194880A CN118048666A CN 118048666 A CN118048666 A CN 118048666A CN 202410194880 A CN202410194880 A CN 202410194880A CN 118048666 A CN118048666 A CN 118048666A
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- pure tin
- methylsulfonate
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- plating solution
- tin plating
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000009713 electroplating Methods 0.000 title claims abstract description 40
- 239000000654 additive Substances 0.000 title claims abstract description 28
- 230000000996 additive effect Effects 0.000 title claims abstract description 26
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 title claims abstract description 17
- 239000002608 ionic liquid Substances 0.000 claims abstract description 33
- -1 halogen ions Chemical class 0.000 claims abstract description 18
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 77
- 238000007747 plating Methods 0.000 claims description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 239000008139 complexing agent Substances 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 12
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 claims description 9
- QJNNHJVSQUUHHE-UHFFFAOYSA-N 2-Methylindole-3-acetic acid Chemical compound C1=CC=C2C(CC(O)=O)=C(C)NC2=C1 QJNNHJVSQUUHHE-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 150000001350 alkyl halides Chemical class 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 7
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- CMQAMENQCKNUPB-UHFFFAOYSA-N NC1CCOP(=O)O1 Chemical compound NC1CCOP(=O)O1 CMQAMENQCKNUPB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 239000011968 lewis acid catalyst Substances 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
- 239000003960 organic solvent Substances 0.000 claims 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004070 electrodeposition Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 125000003884 phenylalkyl group Chemical group 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 14
- OCVXSFKKWXMYPF-UHFFFAOYSA-N 2-chloroimidazole Chemical class ClC1=NC=CN1 OCVXSFKKWXMYPF-UHFFFAOYSA-N 0.000 description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- AXHRGVJWDJDYPO-UHFFFAOYSA-N 2-bromo-1h-imidazole Chemical class BrC1=NC=CN1 AXHRGVJWDJDYPO-UHFFFAOYSA-N 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 4
- 229940073608 benzyl chloride Drugs 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- XJWVCWQKZQENDS-UHFFFAOYSA-N 1-bromopropan-2-ylbenzene Chemical compound BrCC(C)C1=CC=CC=C1 XJWVCWQKZQENDS-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- UPYVYJSWGZMBOU-UHFFFAOYSA-N 1-pentylimidazole Chemical compound CCCCCN1C=CN=C1 UPYVYJSWGZMBOU-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006400 oxidative hydrolysis reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention provides a methylsulfonate pure tin electroplating solution additive and an electroplating solution containing the same, and relates to the technical field of electroplating. The electroplating solution additive comprises halogenated imidazole salt ionic liquid, wherein the molecules of the halogenated imidazole salt ionic liquid contain halogen ions, alkyl groups and phenylalkyl groups. The halogenated ion liquid is used as the additive of the methylsulfonic acid type pure tin electroplating solution, can obviously improve the dispersion performance of the methylsulfonic acid type pure tin electroplating solution and the uniform electrodeposition performance in a high current range, and the electrodeposited coating also has more excellent weldability and effectively optimizes the electroplating process.
Description
Technical Field
The invention relates to the technical field of electroplating, in particular to a methylsulfonate pure tin electroplating solution additive and an electroplating solution containing the same.
Background
In the electroplating technology, the cathode polarization degree is often increased through complexation and additives, and the grain refinement of a plating layer is realized, and meanwhile, the stability of a plating solution is improved. Tin plating is no exception, and complexation is the first choice for improving the polarizability of stannous ions. According to the Lewis acid-base theory, stannous belongs to the boundary acid in the soft and hard acid-base theory, a stable complex is easy to form with medium-hardness base, and O and N atoms are medium-hardness coordination atoms, so that the stable complex can be formed. Sulfite belongs to an acid with medium hardness, and can form a stable complex with stannous in principle, but in a sulfurous acid solution system, when the pH is more than 4 and less than 8, the sulfite can exist stably in a free state, so that the sulfite is the best complexing component of the stannous, and the pH of an acidic tinning solution is generally lower than 1, wherein the sulfite is not suitable as a complexing ligand of the stannous under acidic conditions.
Usually under weakly acidic conditions, the ligand forms a complex with tin, however, weakly acidic conditions plating solutions have poor conductivity, allow lower operating current densities and lower deposition rates. There are studies showing that complex ions such as thiocyanate, acetic acid and tartaric acid can complex with stannous, however, according to the ionization constants of these several organic acids, it was found that when the pH of the solution is < 2, these organic acids are mainly in molecular state in the solution, while considering the smell and stability of the organic acids, these ligands are not viable for use in high-speed electrolytic tinning, so that the acidic tinning solution needs to be added with a stabilizer to control oxidative hydrolysis of stannous.
In addition, tin is a high hydrogen evolution overpotential metal and the metal substrate being plated is often a medium low hydrogen evolution overpotential metal such as iron and copper. To ensure the coverage of the tin layer, a large number of active sites are generated on the surface in the initial tin deposition process, so that the initial tin layer covers the substrate in a short time, the substrate is prevented from being exposed, and the influence of hydrogen evolution on the compactness of the plating layer is eliminated. Therefore, the additive used for tin plating must be capable of uniformly wetting the cathode surface in a short time, and in the initial tin deposition process, a layer of thin tin is rapidly deposited on the cathode surface to realize continuous tin deposition on tin, and meanwhile, the additive needs to meet the requirement of high-current electroplating to improve the deposition rate of a plating layer.
The methanesulfonic acid system acts as a green new system, which can be operated at very high current densities. However, the methanesulfonic acid system is not perfect, and it has a short application time in a high-speed plating system and requires a long verification time. In practical application, the tin mud amount of the plating solution is relatively large, the methanesulfonic acid plating solution realizes electrodeposition of tin, the cathode polarization degree is improved by means of the interface effect of the additive, and the discharge of stannous is inhibited, so that the additive has proper inhibition capability.
Disclosure of Invention
The invention aims to provide a methylsulfonate type pure tin electroplating solution additive and an electroplating solution containing the same, wherein the electroplating solution additive is added into the pure tin electroplating solution, so that the dispersion performance of the electroplating solution and the uniform electrodeposition property in a high current range are obviously improved, and a plating layer obtained by electrodeposition also has more excellent weldability.
The technical scheme adopted by the invention for achieving the purpose is as follows:
A methylsulfonate type pure tin electroplating solution additive comprises halogenated imidazole salt ionic liquid with a structure shown in a formula I:
; wherein R is selected from alkyl with 1-5 carbon atoms, R' is selected from alkyl with 1-5 carbon atoms, alkylene with 1-3 carbon atoms substituted by benzene ring, and X is selected from Cl, br and I.
In some embodiments of the present invention, the preparation method of the halogenated imidazole salt ionic liquid comprises the following steps:
S1: adding alkali metal and absolute ethyl alcohol into a reaction container, adding imidazole after the reaction of the alkali metal and the absolute ethyl alcohol is finished, heating and refluxing for 30-40min, reducing the temperature of a reaction system to 0 ℃, and then dropwise adding haloalkane; reacting for 12-15h at 10-15 ℃, evaporating ethanol and haloalkane after the reaction is finished, washing with a polar solvent, removing precipitate by suction filtration, evaporating the polar solvent in the solution, and finally distilling the residue under reduced pressure, and collecting a fraction of 80-85 ℃/666.7Pa to obtain colorless liquid N-alkyl imidazole;
s2: adding N-alkyl imidazole obtained in S1 into redistilled toluene, slowly dropwise adding benzene alkyl halide or alkyl halide at 35-45 ℃, heating and refluxing for 6-7h to form oily matters insoluble in toluene, decompressing and distilling out solvent and unreacted benzene alkyl halide after the reaction is finished, and washing with ether solvent to obtain viscous liquid, namely the halogenated imidazole salt ionic liquid.
In some embodiments of the present invention, in preparing the pure tin plating solution, the molar ratio of the alkali metal, imidazole, and haloalkane added in S1 is (1.1-1.2): 1: (1.05-1.1).
In some embodiments of the present invention, in preparing the pure tin plating solution, the polar solvent in S1 is at least one of dichloromethane, chloroform, and carbon tetrachloride.
In some embodiments of the present invention, the molar ratio of the N-alkylimidazole to the phenylalkylhalide added in S2 is (0.9-1.0): 1 when preparing the pure tin plating solution.
The invention also provides a pure tin electroplating solution containing the methylsulfonate pure tin electroplating solution additive, and the pure tin electroplating solution also contains a complexing agent, a grain control agent and tin methylsulfonate.
In some embodiments of the invention, the complexing agent is a mixture of aminotrimethylene phosphonate and malonic acid in a mass ratio of 1 (0.1-0.3).
In some embodiments of the invention, the grain control agent is a compound prepared by esterification of glycerol diglycidyl ether with 2-methylindole-3-acetic acid.
In some embodiments of the present invention, the method for preparing the grain control agent comprises the steps of:
SS1: uniformly dispersing 2-methylindole-3-acetic acid in a mixed solution of water and dioxane, regulating the pH of the solution to be alkaline, then adding di-tert-butyl dicarbonate, stirring for 2-3h, adding N, N-dimethylethylenediamine into the system, and adding phosphorous acid or citric acid to wash and purify the product to obtain the alkylindole carboxylic acid compound with the amino protected by tert-butoxycarbonyl;
SS2: mixing the product obtained in SS1 with glycerol diglycidyl ether according to the mass ratio of 1.1-1.5:1, adding a Lewis acid catalyst into the mixture, heating to 105-110 ℃, pressurizing to 0.1-0.2MPa for reaction, cooling to room temperature after 5-7h, filtering to remove the catalyst, adding a mixed solution of 1-2M hydrochloric acid and dioxane, stirring for 30-60min, and distilling to remove impurities, thus obtaining the grain control agent.
In some embodiments of the present invention, in the pure tin plating solution, the additive, complexing agent, grain control agent and tin methylsulfonate are mixed in a mass ratio of (1-5): (10-13): (0.5-1): (30-40).
In some embodiments of the invention, the pure tin plating solution may further comprise antioxidants, surfactants, and other additives that facilitate obtaining a pure tin plating layer with excellent properties.
The beneficial effects are that: compared with the prior art, the invention creatively adds the halogenated imidazole salt ionic liquid as the electroplating liquid additive into the methylsulfonate type pure tin electroplating liquid:
1, the halogenated imidazole salt ionic liquid and the complexing agent are in synergistic effect, so that the concentration of stannous and the movement of other metal ions in a system can be stabilized, the deposition rate on a coating of tin grains can be well controlled, meanwhile, the clarification and stability of the plating solution in the long-time electroplating process are maintained, and uniform electrodepositability can be obtained;
2, the halogenated imidazole salt ionic liquid and the grain control agent are in synergistic effect, so that on one hand, the cathode polarization performance of the plating solution can be increased, and on the other hand, the discharge of stannous can be inhibited, so that a fine and smooth tin plating layer is obtained;
And 3, adding the halogenated imidazole salt ionic liquid, the complexing agent and the grain control agent into the methylsulfonate type pure tin electroplating solution, and obtaining the pure tin plating layer with excellent welding performance under the high-current electroplating condition.
Detailed Description
The invention is described in further detail below with reference to examples. The following examples and comparative examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
Example 1
S1: 7.59g (0.33 mol) of alkali metal sodium and 150ml of absolute ethyl alcohol are added into a reaction vessel, 20.4g (0.3 mol) of imidazole is added after the reaction of the alkali metal sodium and the absolute ethyl alcohol is finished, the heating reflux is carried out for 30min, the temperature of the reaction system is reduced to 0 ℃, and then 15.9g (0.315 mol) of chloromethane is added dropwise; reacting for 12h at 10 ℃, evaporating ethanol and methyl chloride after the reaction is finished, washing with dichloromethane, removing precipitate by suction filtration, evaporating dichloromethane in the solution, and finally distilling the residue under reduced pressure, and collecting a fraction of 80-85 ℃/666.7Pa to obtain colorless liquid N-methylimidazole;
S2: adding 7.38g (0.09 mol) of N-methylimidazole obtained by S1 into 50ml of redistilled toluene, slowly dropwise adding 113.4g (0.9 mol) of benzyl chloride at 35 ℃, heating and refluxing for 6 hours to form an oily substance insoluble in toluene, and after the reaction is finished, decompressing and distilling toluene and unreacted phenylalkyl halide, and washing with diethyl ether to obtain a viscous liquid, namely the chloroimidazole salt ionic liquid, wherein the structural formula of the chloroimidazole salt ionic liquid is shown as the formula I-1:
。
example 2
S1: 8.28g (0.36 mol) of alkali metal sodium and 150ml of absolute ethyl alcohol are added into a reaction vessel, 20.4g (0.3 mol) of imidazole is added after the reaction of the alkali metal sodium and the absolute ethyl alcohol is finished, the heating reflux is carried out for 35min, the temperature of the reaction system is reduced to 0 ℃, and then 39.9g (0.324 mol) of 1-bromopropane is added dropwise; reacting for 13h at 15 ℃, evaporating ethanol and bromopropane after the reaction is finished, washing with dichloromethane, removing precipitate by suction filtration, evaporating dichloromethane in the solution, and finally distilling the residue under reduced pressure, and collecting a fraction of 80-85 ℃/666.7Pa to obtain colorless liquid N-propylimidazole;
S2: 59.4g (0.54 mol) of N-propylimidazole obtained by S1 is added into 50ml of toluene which is redistilled, 73.8g (0.6 mol) of benzyl chloride is slowly added dropwise under the condition of 40 ℃, heating reflux is carried out for 6 hours, oily matters which are insoluble in toluene are generated, after the reaction is finished, toluene and unreacted benzyl chloride are distilled out under reduced pressure, and the obtained mixture is washed by diethyl ether, so that viscous liquid is obtained, namely the chloroimidazole salt ionic liquid, and the structural formula of the chloroimidazole salt ionic liquid is shown as formula I-2:
。
Example 3
S1: 8.28g (0.36 mol) of alkali metal sodium and 150ml of absolute ethyl alcohol are added into a reaction vessel, 20.4g (0.3 mol) of imidazole is added after the reaction of the alkali metal sodium and the absolute ethyl alcohol is finished, the heating reflux is carried out for 35min, the temperature of the reaction system is reduced to 0 ℃, and then 36.3g (0.33 mol) of 1-bromopentane is added dropwise; reacting for 15h at 15 ℃, evaporating ethanol and bromopentane after the reaction is finished, washing with dichloromethane, removing precipitate by suction filtration, evaporating dichloromethane in the solution, and finally distilling the residue under reduced pressure, and collecting a fraction of 80-85 ℃/666.7Pa to obtain colorless liquid N-amyl imidazole;
S2: adding 41.4g (0.3 mol) of 1-n-amyl imidazole obtained by S1 into 50ml of redistilled toluene, slowly dropwise adding 59.7g (0.3 mol) of 1-bromo-2-phenylpropane at the temperature of 40 ℃, heating and refluxing for 7h, generating oily matters insoluble in toluene, decompressing and distilling toluene and unreacted 1-bromo-2-phenylpropane after the reaction is finished, and washing with diethyl ether to obtain viscous liquid, namely the bromoimidazole salt ionic liquid, wherein the structural formula of the bromoimidazole salt ionic liquid is shown as formula I-3:
。
Example 4
The preparation process is the same as in example 3, except that 1-bromo-2-phenylpropane in S2 is replaced by bromobutane, and the structural formula of the obtained bromoimidazole salt ionic liquid is shown as formula I-4:
。
Example 5
The preparation process is the same as in example 2, except that benzyl chloride in S2 is replaced by 2-chloropropane, and the structural formula of the obtained chloroimidazole salt ionic liquid is shown as formula I-5:
。
application example 1
Mixing the chloroimidazole salt ionic liquid obtained in the example 1 with a complexing agent, a grain control agent and tin methylsulfonate according to the mass ratio of 1:10:0.5:30, and uniformly dispersing with water; the complexing agent is a mixture of amino trimethylene phosphonate and malonic acid according to the mass ratio of 1:0.1; the preparation method of the grain control agent comprises the following steps:
SS1: uniformly dispersing 2-methylindole-3-acetic acid in a mixed solution of water and dioxane, regulating the pH of the solution to be alkaline, then adding di-tert-butyl dicarbonate, stirring for 2-3h, adding N, N-dimethylethylenediamine into the system, and adding phosphorous acid or citric acid to wash and purify the product to obtain the alkylindole carboxylic acid compound with the amino protected by tert-butoxycarbonyl;
SS2: mixing the product obtained in SS1 with glycerol diglycidyl ether according to the mass ratio of 1.1:1, adding ferric chloride, heating to 105 ℃, pressurizing to 0.2MPa for reaction, cooling to room temperature after 5 hours, filtering to remove the catalyst, adding a mixed solution of 1M hydrochloric acid and dioxane according to the volume ratio of 1:1, stirring for 30 minutes, and distilling to remove impurities to obtain the grain control agent;
and then regulating the pH value of the solution system to be neutral to obtain the electroplating solution.
Application example 2
Mixing the chloroimidazole salt ionic liquid obtained in the example 2 with a complexing agent, a grain control agent and tin methylsulfonate according to the mass ratio of 2:11:0.6:35, and uniformly dispersing with water; the complexing agent is a mixture of amino trimethylene phosphonate and malonic acid according to the mass ratio of 1:0.2; the preparation method of the grain control agent comprises the following steps:
SS1: uniformly dispersing 2-methylindole-3-acetic acid in a mixed solution of water and dioxane, regulating the pH of the solution to be alkaline, then adding di-tert-butyl dicarbonate, stirring for 2-3h, adding N, N-dimethylethylenediamine into the system, and adding phosphorous acid or citric acid to wash and purify the product to obtain the alkylindole carboxylic acid compound with the amino protected by tert-butoxycarbonyl;
SS2: mixing the product obtained in SS1 with glycerol diglycidyl ether according to the mass ratio of 1.2:1, adding ferric chloride, heating to 110 ℃, pressurizing to 0.1MPa for reaction, cooling to room temperature after 6 hours, filtering to remove the catalyst, adding a mixed solution of 2M hydrochloric acid and dioxane according to the volume ratio of 1:1, stirring for 50 minutes, and distilling to remove impurities, thus obtaining the grain control agent.
And then regulating the pH value of the solution system to be neutral to obtain the electroplating solution.
Application example 3
Mixing the bromoimidazole salt ionic liquid obtained in the example 3 with a complexing agent, a grain control agent and tin methylsulfonate according to the mass ratio of 3:13:0.7:40, and uniformly dispersing with water; the complexing agent is a mixture of amino trimethylene phosphonate and malonic acid according to the mass ratio of 1:0.3; the preparation method of the grain control agent comprises the following steps:
SS1: uniformly dispersing 2-methylindole-3-acetic acid in a mixed solution of water and dioxane, regulating the pH of the solution to be alkaline, then adding di-tert-butyl dicarbonate, stirring for 2-3h, adding N, N-dimethylethylenediamine into the system, and adding phosphorous acid or citric acid to wash and purify the product to obtain the alkylindole carboxylic acid compound with the amino protected by tert-butoxycarbonyl;
SS2: mixing the product obtained in SS1 with glycerol diglycidyl ether according to the mass ratio of 1.3:1, adding ferric chloride, heating to 110 ℃, pressurizing to 0.1MPa for reaction, cooling to room temperature after 7 hours, filtering to remove the catalyst, adding a mixed solution of 2M hydrochloric acid and dioxane according to the volume ratio of 1:1, stirring for 60 minutes, and distilling to remove impurities to obtain the grain control agent;
and then regulating the pH value of the solution system to be neutral to obtain the electroplating solution.
Application example 4
Mixing the bromoimidazole salt ionic liquid obtained in the example 4 with a complexing agent, a grain control agent and tin methylsulfonate according to the mass ratio of 4:13:0.8:38, and uniformly dispersing with water; the complexing agent is a mixture of amino trimethylene phosphonate and malonic acid according to the mass ratio of 1:0.3; the preparation method of the grain control agent comprises the following steps:
SS1: uniformly dispersing 2-methylindole-3-acetic acid in a mixed solution of water and dioxane, regulating the pH of the solution to be alkaline, then adding di-tert-butyl dicarbonate, stirring for 2-3h, adding N, N-dimethylethylenediamine into the system, and adding phosphorous acid or citric acid to wash and purify the product to obtain the alkylindole carboxylic acid compound with the amino protected by tert-butoxycarbonyl;
SS2: mixing the product obtained in SS1 with glycerol diglycidyl ether according to the mass ratio of 1.4:1, adding ferric chloride, heating to 110 ℃, pressurizing to 0.1MPa for reaction, cooling to room temperature after 7 hours, filtering to remove the catalyst, adding a mixed solution of 2M hydrochloric acid and dioxane according to the volume ratio of 1:1, stirring for 60 minutes, and distilling to remove impurities to obtain the grain control agent;
and then regulating the pH value of the solution system to be neutral to obtain the electroplating solution.
Application example 5
Mixing the chloroimidazole salt ionic liquid obtained in the example 5 with a complexing agent, a grain control agent and tin methylsulfonate according to the mass ratio of 5:13:1:32, and uniformly dispersing with water; the complexing agent is a mixture of amino trimethylene phosphonate and malonic acid according to the mass ratio of 1:0.3; the preparation method of the grain control agent comprises the following steps:
SS1: uniformly dispersing 2-methylindole-3-acetic acid in a mixed solution of water and dioxane, regulating the pH of the solution to be alkaline, then adding di-tert-butyl dicarbonate, stirring for 2-3h, adding N, N-dimethylethylenediamine into the system, and adding phosphorous acid or citric acid to wash and purify the product to obtain the alkylindole carboxylic acid compound with the amino protected by tert-butoxycarbonyl;
SS2: mixing the product obtained in SS1 with glycerol diglycidyl ether according to the mass ratio of 1.5:1, adding ferric chloride, heating to 110 ℃, pressurizing to 0.1MPa for reaction, cooling to room temperature after 7 hours, filtering to remove the catalyst, adding a mixed solution of 2M hydrochloric acid and dioxane according to the volume ratio of 1:1, stirring for 60 minutes, and distilling to remove impurities to obtain the grain control agent;
and then regulating the pH value of the solution system to be neutral to obtain the electroplating solution.
Application example 6
The same as in application example 1, except that the mixing mass ratio of the additive to the complexing agent, grain control agent, and tin methylsulfonate was 0.9:10:0.5:30.
Application example 7
The same as in application example 5, except that the mixing mass ratio of the additive to the complexing agent, grain control agent, and tin methylsulfonate was 5.1:13:1:32.
Application example 8
The procedure is as in application example 5, except that no complexing agent is added.
Application example 9
The same as in application example 5 was conducted except that the grain control agent was not added.
Application example 10
The same as in application example 5 was found except that the halogenated imidazole salt ionic liquid was not added.
Performance testing
Plating solution dispersibility measurement: the test method for measuring the dispersibility test parameters of the plating solution by adopting a far-near cathode method comprises the following steps: a Halin tank with the specification of 240X 60X 125mm, the plating solution sample volume is 500mL, and a single tin anode (pre-treatment is carried out): uniformly punching and then placing the middle position; double cathode (150×60mm specification pre-treated brass sheet): placing two ends to form a far cathode and a near cathode, wherein the distance ratio of the cathodes to the anodes at the two ends is 1:5. the electroplating process parameters comprise: the plating time was 30 minutes with a current density of 2.55A/dm 2. And after the completion, taking out the cathode test piece from the plating solution, washing with water for 5 times, washing with acetone for 3 times, drying to constant weight, and weighing the mass of the test piece. And finally, respectively calculating the mass m Far distance 、m Near-to-near of the coating on the far and near cathode test pieces according to the mass of the test pieces, and calculating a formula of the dispersion capacity: s= (H-M)/(k+m-2) ×100%, where S represents a dispersing ability; m=m Near-to-near /m Far distance ; h represents the distance ratio of the near-far cathode to the anode, and h=5 is taken in the test;
Plating solution stability: the formulation of each application example was expanded to 5L of plating solution in equal proportion, and the plating test was performed, and the same frequency was used, so that the plating solution remained clear, and the phenomenon of no turbidity or formation of tetravalent tin colloid was excellent. After the continuous test for 3 months, the application example 6 is slightly turbid, after the continuous test for 4 months, the application example 7 is slightly turbid, and the continuous test for 6 months carried out by the application examples 1-5 still keeps clear, thus proving that the plating solution has excellent stability and oxidation resistance;
Welding performance: according to national standard of the people's republic of China, GB/T2423.28-2005 environmental test of Electrical and electronic products, part 2: test method test T: the tin soldering is judged by visual inspection, the tin soldering is smooth and bright, only a small amount of scattered defects such as pinholes, non-wetting or weak wetting are allowed, the defects are not concentrated together, and the tin soldering area is more than 95% of the immersed area, so that the tin soldering is qualified;
Microscopic crystalline phase: and photographing and amplifying the crystal phase diagram by 1000 times and 2000 times by using a scanning electron microscope, wherein the crystal phase is clear, the crystal is fine and smooth, and the grain size is less than 5 mu m, so that the product is qualified.
The test results are shown in the following table:
。
as can be seen from the results in Table 1, the plating solutions obtained in application examples 1 to 5 all meet the application requirements of the plating layer in terms of dispersibility, stability and solderability, and the tin crystal grains formed are small, and the plating layer is uniform and compact.
As is clear from the results of comparative application example 5 and application examples 1 to 4, the group (alkyl and/or phenylalkyl) on the imidazole ring in the molecule of the halogenated imidazole salt ionic liquid has a certain influence on the dispersibility of the obtained plating solution: in the chloroimidazole salt ionic liquid molecule used in application example 5, ethyl and propyl were substituted on the imidazole ring, and the dispersibility of the plating solution of application example 5 was weaker than that of application example 2 (in the chloroimidazole salt ionic liquid molecule used, benzyl and propyl were substituted on the imidazole ring), and application example 4 (in the chloroimidazole salt ionic liquid molecule used, pentyl and butyl were substituted on the imidazole ring).
As is apparent from the results of application examples 6 to 7, the use of the halogenated imidazole salt ionic liquid as an additive to a pure tin plating solution of methylsulfonate type requires a proper use ratio, and when the use amount is too low or too high, the dispersibility and stability of the resulting plating solution are lowered and the solderability thereof is also deteriorated.
From the results of application examples 8 to 10, it is understood that the complexing agent, the grain control agent and the halogenated imidazole salt ionic liquid are essential for achieving good stability, dispersibility, solderability and plating compactness of the methylsulfonate type pure tin plating solution.
In conclusion, the halogenated imidazole salt ionic liquid prepared by adopting the technical scheme provided by the invention is applied to the methylsulfonate type pure tin electroplating liquid together with the specific complexing agent and the grain control agent, the obtained electroplating liquid has excellent performance, and the prepared plating layer has uniform and compact structure and has considerable application prospect in the field of methylsulfonate type pure tin electroplating liquid.
Claims (10)
1. The methylsulfonate pure tin electroplating solution additive is characterized by comprising halogenated imidazole salt ionic liquid with a structure shown in a formula I:
; wherein R is selected from alkyl with 1-5 carbon atoms, R' is selected from alkyl with 1-5 carbon atoms, alkylene with 1-3 carbon atoms substituted by benzene ring, and X is selected from Cl, br and I.
2. The methylsulfonate pure tin plating solution additive according to claim 1, wherein the preparation method of the halogenated imidazole salt ionic liquid comprises the following steps:
S1: adding alkali metal and absolute ethyl alcohol into a reaction container, adding imidazole after the reaction of the alkali metal and the absolute ethyl alcohol is finished, heating and refluxing for 30-40min, reducing the temperature of a reaction system to 0-2 ℃, and then dropwise adding haloalkane; reacting for 12-15h at 10-15 ℃, evaporating ethanol and haloalkane after the reaction is finished, washing with a polar solvent, removing precipitate by suction filtration, evaporating the polar solvent in the solution, and finally distilling the residue under reduced pressure, and collecting a fraction of 80-85 ℃/666.7Pa to obtain colorless liquid N-alkyl imidazole;
s2: adding N-alkyl imidazole obtained in S1 into redistilled toluene, slowly dropwise adding benzene alkyl halide or alkyl halide at 35-45 ℃, heating and refluxing for 6-7h to form oily matters insoluble in toluene, decompressing and distilling out solvent and unreacted benzene alkyl halide after the reaction is finished, and washing with ether solvent to obtain viscous liquid, namely the halogenated imidazole salt ionic liquid.
3. The additive for the pure tin plating solution according to claim 2, wherein the molar ratio of the alkali metal, imidazole to haloalkane added in S1 is (1.1-1.2): (1.05-1.1).
4. The methylsulfonate pure tin plating solution additive of claim 2, wherein the polar solvent in S1 is at least one of dichloromethane, chloroform, carbon tetrachloride.
5. The additive for pure tin plating solution according to claim 2, wherein the molar ratio of N-alkylimidazole to phenylalkylhalide added in S2 is (0.9-1.0): 1.
6. A pure tin plating solution comprising the methylsulfonate pure tin plating solution additive according to any one of claims 1 to 5, further comprising a complexing agent, a grain control agent, and tin methylsulfonate.
7. The pure tin plating solution of claim 6, wherein the complexing agent is a mixture of aminotrimethylene phosphonate and malonic acid in the range of 1 (0.1-0.3).
8. The pure tin plating solution according to claim 6, wherein the grain control agent is a compound obtained by esterification of glycerol diglycidyl ether with 2-methylindole-3-acetic acid.
9. The pure tin plating solution of claim 8, wherein the method of preparing the grain control agent comprises the steps of:
SS1: uniformly dispersing 2-methylindole-3-acetic acid in a mixed solution of water and dioxane, regulating the pH of the solution to be alkaline, then adding di-tert-butyl dicarbonate, stirring for 2-3h, adding N, N-dimethylethylenediamine into the system, and adding phosphorous acid or citric acid to wash and purify the product to obtain the alkylindole carboxylic acid compound with the amino protected by tert-butoxycarbonyl;
SS2: mixing the product obtained in SS1 with glycerol diglycidyl ether according to the mass ratio of 1.1-1.5:1, adding a Lewis acid catalyst into the mixture, heating to 105-110 ℃, pressurizing to 0.1-0.2MPa for reaction, cooling to room temperature after 5-7h, filtering to remove the catalyst, adding a mixed solution of 1-2M hydrochloric acid and dioxane, stirring for 30-60min, and distilling to remove the organic solvent to obtain the grain control agent.
10. The pure tin plating solution according to claim 6, wherein the mixing mass ratio of the additive, the complexing agent, the grain control agent and the tin methylsulfonate is (1-5): (10-13): (0.5-1): (30-40).
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