CN103668138B - A kind of chemical bronze plating liquid and electroless copper plating method - Google Patents
A kind of chemical bronze plating liquid and electroless copper plating method Download PDFInfo
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- CN103668138B CN103668138B CN201210357448.XA CN201210357448A CN103668138B CN 103668138 B CN103668138 B CN 103668138B CN 201210357448 A CN201210357448 A CN 201210357448A CN 103668138 B CN103668138 B CN 103668138B
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- 238000007747 plating Methods 0.000 title claims abstract description 108
- 239000000126 substance Substances 0.000 title claims abstract description 79
- 239000007788 liquid Substances 0.000 title claims abstract description 66
- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 64
- 239000010974 bronze Substances 0.000 title claims abstract description 64
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000010949 copper Substances 0.000 title claims abstract description 60
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 32
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229930024421 Adenine Natural products 0.000 claims abstract description 19
- 229960000643 adenine Drugs 0.000 claims abstract description 19
- LXWJYIBQIPSFSE-UHFFFAOYSA-N dipotassium;nickel(2+);tetracyanide Chemical compound [K+].[K+].[Ni+2].N#[C-].N#[C-].N#[C-].N#[C-] LXWJYIBQIPSFSE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002738 chelating agent Substances 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- -1 mantoquita Substances 0.000 claims abstract description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 5
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 9
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 3
- YLIMHFXLIKETBC-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCC[Na] YLIMHFXLIKETBC-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- 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 claims 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims 1
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 24
- 238000000576 coating method Methods 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 241001156002 Anthonomus pomorum Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical group OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 101000608720 Helianthus annuus 10 kDa late embryogenesis abundant protein Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004531 microgranule Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Chemically Coating (AREA)
Abstract
The invention provides a kind of chemical bronze plating liquid, including mantoquita, chelating agent, PH regulator, reducing agent, adenine and nickel potassium cyanide；Wherein, described chelating agent includes that EDTA and/or EDETATE SODIUM, described reducing agent are formaldehyde.A kind of electroless copper plating method, directly contacts with chemical bronze plating liquid including by workpiece to be plated, obtains plating piece after cleaning-drying；Wherein, described chemical bronze plating liquid is chemical bronze plating liquid disclosed by the invention.When the chemical plating copper plating bath using the present invention to provide carries out electroless copper, ductility and the toughness of coating can be effectively improved.
Description
Technical field
The invention belongs to Nonmetallic Electroless Copper Plating field, particularly relate to a kind of chemical bronze plating liquid and preparation method thereof.
Background technology
Since first the 40's of 20th century Brenner and Ridlell develop electroless copper technology, through the effort of over half a century, this technology is applied in the every field of national economy.Electroless copper occupies highly important status in chemical plating, the various aspects such as electro-magnetic screen layer being the most widely used in the bottom of non-metal electroplating, the hole metallization of printed board and electronic machine.Over nearly 30 years, about the research of electroless copper achieved with a large amount of achievements, but remain many problems at present, such as, how to coordinate stability and plating this contradiction of speed of chemical bronze plating liquid, it is thus achieved that there is certain plating speed and the chemical bronze plating liquid of high stability, the always important topic of this area.
Since electroless copper technology is born, scientist constantly explores the dynamic process of its out-phase surface catalysis deposition；Propose the mechanism of various chemical deposition, hypothesis, it is intended to the experimental fact of electroless copper is made reasonable dismissal, increase the understanding of the essence to electroless copper phenomenon.At present, most of commercial chemistry copper plating solutions use formaldehyde as reducing agent, there are two basic chemical reactions, it may be assumed that Cu2+ in course of reaction
+ 2e → Cu and
2HCHO + 40H- →H2↑+
2H20+2HC00-+2e, chemical reaction occurs on catalytic out-phase surface, there is not exterior power supply and electronics.The net reaction of electroless copper is represented by: Cu2+
+ 2HCHO+40H-→ Cu+H2 ↑+2H20+2HC00-, this reaction equation only represents the relation of reactant and final product, real reaction process is more complex, is divided into two steps or multistep to carry out, and cuprous salt may be had to be formed as the intermediate product of reaction.It is generally believed that the electroless copper reaction mechanism mechanism of reaction is to be occurred by two coherent reactions, i.e. electronics discharges in anode part reacts, and consumes in cathode portion is reacted.
During electroless copper, copper removal ion carries out effective redox reaction at catalytic surface, outside being reduced into metallic copper by formaldehyde, there is also many side reactions.Main side reaction includes: Cannizzaro (Cannizzaro) reaction 2HCHO+OH-→ CH30H
+ HC00-, and on-catalytic type reaction 2Cu2++HCHO+50H-→ Cu20 ↓+2HC00-+3H20, be reduced out by the microgranule of this reaction Red copper oxide, hereafter, Red copper oxide may be reduced into particulate copper again further, i.e. and Cu20+2HCH0+
20H- →2Cu↓+
2HC00-+H2 ↓+H20, these side reactions not only consume the effective ingredient in plating solution, and the Red copper oxide produced suspends in the plating solution with imperceptible powder, very difficult with being filtered to remove, plating solution is easily caused to decompose, if co-depositing with copper, then the copper deposits obtained loosens coarse and basal body binding force is poor.It addition, the internal breakup that the entrance of impurity inevitably causes plating solution produces a large amount of copper powders, cause the irreversible destruction of liquid medicine.
The kind of chemical copper plating solution is a lot, is divided into the thin copper solution of plating and the thick copper solution of plating by the thickness of copper plate；Tartaric acid salt form, EDETATE SODIUM salt form and mixed twine mixture type etc. can be divided into by chelating agent kind；The solution such as formaldehyde, hydrazine, hypophosphites, boron hydride it are divided into by reducing agent used；And according to the purposes of solution, the solution such as plastics metalizing, PCB Hole Metallization can be divided into again.Development through decades, some stabilizers and chelating agent are found to improve chemical bronze plating liquid one after another, modern advanced chemical bronze plating liquid has been realized in continuous high density production, and the thickness of reaction is thicker, have to electroplating technique before instead of a part.
Chemical plating copper layer, for copper electroplating layer, mainly plates speed, ductility and toughness and the most significantly lowers.Although chemical plating copper layer has greater advantage for electro-coppering in some field, such as thickness evenness and be difficult to electroplate hole.But the application being as chemical plating copper layer is increasingly wider, and the requirement to coating performance is more and more higher, such as ductility and Crush tests aspect.So, this respect performance improving electroless copper can expand the application of electroless copper further, solves the technical barrier of this area.
Summary of the invention
It is difficult to improve ductility and the problem of toughness of coating in order to solve chemical bronze plating liquid in prior art, the invention provides a kind of chemical bronze plating liquid, including mantoquita, EDTA, sodium hydroxide, formaldehyde, adenine, nickel potassium cyanide.
Present invention also offers a kind of electroless copper plating method, directly contact with chemical bronze plating liquid including by workpiece to be plated, after cleaning-drying, obtain plating piece；Wherein, the chemical bronze plating liquid that described chemical bronze plating liquid provides for the present invention.
The present inventor is found by substantial amounts of experiment, in the chemical bronze plating liquid that the present invention provides, by adding adenine and nickel potassium cyanide, in course of reaction, the two absorption controls the heavy copper reaction on coating at surface of the work, there is synergism thus greatly increase the toughness of coating in the two, adds cold-hot attack time and the bend test number of times of coating.Adenine in the present invention, is conducive to controlling the grown junction crystal type of copper plate, reduces the copper oxide residual ratio at coating.Nickel potassium cyanide and adenine synergism in chemical bronze plating liquid disclosed by the invention controls the grown junction crystal type of copper plate, reduces the hydrionic residual of coating, reduces the copper oxide residual ratio at coating, thus improves the purity of coating.
Therefore, when the chemical plating copper plating bath using the present invention to provide carries out electroless copper, ductility and the toughness of coating can be effectively improved.
Detailed description of the invention
The invention provides a kind of chemical bronze plating liquid, including mantoquita, chelating agent, PH regulator, reducing agent, adenine and nickel potassium cyanide；Wherein, described chelating agent includes that EDTA, described reducing agent are formaldehyde.
In the present invention, described mantoquita is the main salt of electroless copper, is used for providing bivalent cupric ion, follow-up be reduced agent reduction and form metallic copper, and is deposited on unplated piece surface, forms chemical plating copper layer.Wherein, described mantoquita is various water solublity mantoquita commonly used in the prior art, including, but not limited to any one in copper sulfate, copper chloride, copper sulphate pentahydrate, anhydrous cupric sulfate, copper chloride, copper nitrate.
The inventor of invention is found by substantial amounts of experiment, in the chemical bronze plating liquid that invention provides, by adding adenine and nickel potassium cyanide, in course of reaction, the two absorption controls the heavy copper reaction on coating at surface of the work, there is synergism thus greatly increase the toughness of coating in the two, adds cold-hot attack time and the bend test number of times of coating.Adenine in the present invention, is conducive to controlling the grown junction crystal type of copper plate, reduces the copper oxide residual ratio at coating.Nickel potassium cyanide and adenine synergism in chemical bronze plating liquid disclosed by the invention controls the grown junction crystal type of copper plate, reduces the hydrionic residual of coating, reduces the copper oxide residual ratio at coating, thus improves the purity of coating.
In the present invention, described reducing agent is formaldehyde, and its content is in the usual range of existing formaldehyde reduction system chemical bronze plating liquid, and the present invention is not particularly limited.Such as, in described chemical bronze plating liquid, the content of reducing agent is 1-5g/L.
Described stabilizer is various stabilizers common in chemical bronze plating liquid, such as, can be selected from one or more in potassium ferrocyanide, bipyridyl, methanol.As a kind of preferred implementation of the present invention, described stabilizer is the mixture of potassium ferrocyanide and bipyridyl.In the case of more preferably, described stabilizer is potassium ferrocyanide and bipyridyl, and in described chemical bronze plating liquid, the content of potassium ferrocyanide is 0.001-0.1g/L, and the content of described bipyridyl is 0.001-0.025g/L。
Described pH adjusting agent, for regulating the pH value of plating solution；It can be selected from one or more in sodium carbonate, sodium hydroxide, boric acid.Under preferable case, in described chemical bronze plating liquid, the content of pH adjusting agent is 5-20g/L.
A kind of preferred implementation as the present invention, chelating agent in described chemical bronze plating liquid also includes sodium tartrate, stable complex is formed with copper ion, avoid the formation of Copper hydrate precipitation under highly alkaline conditions, being also prevented from direct the reaction with formaldehyde of copper causes plating solution to lose efficacy, and is conducive to controlling the carrying out of copper facing reaction simultaneously.
As a kind of preferred implementation of the present invention, possibly together with surfactant in described chemical bronze plating liquid.Surfactant, can reduce the volatilization of reducing agent formaldehyde, on the one hand ensures chemical bronze plating liquid component stability, it is ensured that its service life, on the other hand can avoid affecting in formaldehyde volatilization process the consistency of coating, it is ensured that quality of coating.One or more in dodecylbenzene sodium sulfonate, sodium lauryl sulphate, n-octyl sodium sulfate, polyoxyethylene ene-type surfactant of described surfactant.Under preferable case, in described chemical bronze plating liquid, the content of surfactant is 0.001-0.1g/L.
According to the present invention, described each constituent content can be more preferably: mantoquita 10-12g/L, EDTA20-30g/L, sodium hydroxide 10-15g/L, formaldehyde 3-4g/L, bipyridyl 0.005-0.02g/L, potassium ferrocyanide 0.005-0.05g/L, adenine 0.003-0.005g/L, nickel potassium cyanide 0.003-0.005g/L.Adenine and nickel potassium cyanide excessive concentration quality of coating can be deteriorated on the contrary, and both synergism need to embody in certain concentration range.
Present invention also offers a kind of electroless copper plating method, directly contact with chemical bronze plating liquid including by workpiece to be plated, after cleaning-drying, obtain plating piece；Wherein, the chemical bronze plating liquid that described chemical bronze plating liquid provides for the present invention.
In accordance with the present invention it is preferred that, the temperature of described chemical bronze plating liquid is 45-55 DEG C, and described time of contact is 60-300 minute.
Present invention also offers the preparation method of chemical bronze plating liquid of the present invention, first by each component respectively with water dissolution, then the mantoquita after dissolving and the aqueous solution of chelating agent, add the aqueous solution of PH regulator, add other component after stirring and i.e. can get chemical bronze plating liquid of the present invention.
When the chemical plating copper plating bath using the present invention to provide carries out electroless copper, ductility and the toughness of coating can be effectively improved.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1-5
Chemical bronze plating liquid S1-S5 is prepared respectively by the formula in table 1.
Table 1
| Component | Embodiment 1/ (g/L) | Embodiment 2/ (g/L) | Embodiment 3/ (g/L) | Embodiment 4/ (g/L) | Embodiment 5/ (g/L) |
| Copper sulphate pentahydrate | 15 | 7 | / | 16 | 8 |
| Copper nitrate | / | / | 10 | / | / |
| EDTA | / | 10 | / | / | / |
| EDETATE SODIUM | 30 | / | 42 | 40 | 20 |
| Sodium hydroxide | 16 | / | 21 | 5 | 12 |
| Adenine | 0.005 | 0.001 | 0.012 | 0.01 | 0.007 |
| Nickel potassium cyanide | 0.005 | 0.001 | 0.01 | 0.012 | 0.008 |
| Formaldehyde | 4 | 1 | 6 | 5 | 3 |
| Rocchelle's salt | / | 20 | 10 | 40 | 8 |
| Potassium ferrocyanide | 0.005 | 0.003 | 0.02 | 0.02 | / |
| Bipyridyl | 0.005 | 0.003 | / | 0.01 | 0.005 |
| Sodium lauryl sulphate | / | 0.005 | 0.001 | 0.1 | / |
| Dodecylbenzene sodium sulfonate | / | 0.005 | / | / | 0.12 |
| Sodium carbonate | / | 20 | / | / | / |
Comparative example 1
Compared with Example 1, lacking component adenine and nickel potassium cyanide, other are same as in Example 1, obtain chemical bronze plating liquid DS1.
Comparative example 2
Compared with Example 1, replacing adenine with 2-mercaptobenzothiazole, other are same as in Example 1, obtain chemical bronze plating liquid DS1.
Comparative example 3
Use the chemical bronze plating liquid DS3 as this comparative example of the electroless copper plating solution described in embodiment 1 of CN 201210266830.X.
Comparative example 4
Use " electrochemical research that electroless copper is affected by chelating agent and additive " (electrochemistry；The 1st phase of volume 10；In February, 2004；Article is numbered: 1006-3471(2004) 01-0014-06；Gu Xin, Wang Zhoucheng, Lin Changjian) in chemical bronze plating liquid disclosed in experimental technique: CuSO4 5H2O
15g/L, EDETATE SODIUM
28g/L, triethanolamine (TEA) 15ml/L, 2,2 '-bipyridyl 5mg/L, HCHO 3g/L, surfactant 0.005g/L, NaOH 13g/L, agents useful for same is analytical pure；Chemical bronze plating liquid DS4 as this comparative example.
Embodiment 6
Take the ABS plastic part of 10cm × 10cm, it is first dipped in degreasing fluid (NaOH 1mol/L, Na2CO3 of 50 DEG C
1mol/L, dodecyl sodium sulfate 0.1mol/L), soak 8 minutes, wash after taking-up.ABS plastic part after cleaning proceeds to roughening agent (the chromic anhydride 150g/L of 60 DEG C, sulphuric acid 150g/L) the middle immersion 15min time, then proceed to the 10wt% oxalic acid solution of 30 DEG C soaks the 3min time, wash after taking-up, and proceed to the hydrochloric acid of 30wt% presoaks 1min, then 25 DEG C of colloidal pd activation solutions (colloidal pd activation solution: take Atotech Noviganth Activator PL liquid medicine 6ml/L is proceeded to, it is added into being dissolved with 8g/L stannous chloride, 300g/L salt aqueous acid stirs) middle immersion 3min, proceed to the 10wt% hydrochloric acid of 45 DEG C soaks 3min after washing, wash after taking-up, obtain unplated piece.Then unplated piece entirety being put in 200mL chemical plating bath S1, electroless plating time is 20min.After chemical plating completes, it is washed with deionized surface, obtains plating piece, be designated as S10.
Embodiment 7-10
Using method same as in Example 6 to prepare plating piece S20-S40, difference is the S1 being respectively adopted in chemical bronze plating liquid S2-S5 alternate embodiment 6.
Comparative example 5-8
Using method same as in Example 6 to prepare plating piece DS10-DS40, difference is the S1 being respectively adopted in chemical bronze plating liquid DS1-DS4 alternate embodiment 6.
Performance test
1, resist bending experiment: the chemical plating copper layer on bending copper coin repeatedly, layers of copper plane is bent to 60 degree by 180 degree, alternating bending, until chemical plating copper layer occurs that number of bends during crackle occur in crackle, record, number of times is the most, and ductility and toughness are the best.
Test result is as shown in table 2.
Table 2:
| Experimental program | Resist bending experimental result |
| S10 | 15 times |
| S20 | 12 times |
| S30 | 8 times |
| S40 | 10 times |
| S50 | 13 times |
| DS10 | 4 times |
| DS20 | 4 times |
| DS30 | 5 times |
| DS40 | 4 times |
During from the test result of upper table 2 it can be seen that the chemical plating copper plating bath using the present invention to provide carries out electroless copper, adenine and the synergism of nickel potassium cyanide, ductility and the toughness of coating can be greatly improved.And other is combined, we find no identical effect at present.The present invention can meet the demand changing the application that copper ductility has higher requirements.Wherein, the adenine being previously mentioned in the document of comparative example 4 is intended only as stabilizer or accelerator, the technical issues that need to address of the present invention cannot be solved, and the present invention is it is mentioned that the chemical cooperated effect of adenine and nickel potassium cyanide, play increase coating ductility and the effect of toughness, be not used as stabilizer or accelerator uses.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, should be included within the scope of the present invention.
Claims (12)
1. a chemical bronze plating liquid, including mantoquita, chelating agent, pH adjusting agent, reducing agent, adenine and nickel potassium cyanide；Described chelating agent includes that EDTA and/or EDETATE SODIUM, described reducing agent are formaldehyde；On the basis of the total amount of described chemical bronze plating liquid, described each constituent content is: mantoquita 7-15g/L, chelating agent 10-40g/L, pH adjusting agent 5-20g/L, formaldehyde 1-5g/L, adenine 0.001-0.01g/L, nickel potassium cyanide 0.001-0.01g/L.
Chemical bronze plating liquid the most according to claim 1, it is characterised in that one or more in copper sulfate, copper chloride, copper nitrate, anhydrous cupric sulfate, copper sulphate pentahydrate of described mantoquita.
Chemical bronze plating liquid the most according to claim 1, it is characterised in that the pH value range of described chemical bronze plating liquid is 12-13.
4. according to the chemical bronze plating liquid described in any one of claim 1-3, it is characterised in that described chelating agent also includes sodium potassium tartrate tetrahydrate.
Chemical bronze plating liquid the most according to claim 4, it is characterised in that on the basis of the total amount of described chemical bronze plating liquid, described Soluble tartar. sodium content is 10-40g/L.
6. according to the chemical bronze plating liquid described in any one of claim 1-3, it is characterised in that described chemical bronze plating liquid also includes stabilizer, one or more in potassium ferrocyanide, bipyridyl, methanol of described stabilizer.
Chemical bronze plating liquid the most according to claim 6, it is characterized in that, described stabilizer is potassium ferrocyanide and bipyridyl, on the basis of the total amount of described chemical bronze plating liquid, the content of described potassium ferrocyanide is 0.001-0.1g/L, and the content of described bipyridyl is 0.001-0.025g/L.
8. according to the chemical bronze plating liquid described in any one of claim 1-3, it is characterized in that, also include surfactant, one or more in dodecylbenzene sodium sulfonate, sodium lauryl sulphate, n-octyl sodium sulfate, polyoxyethylene ene-type surfactant of described surfactant.
Chemical bronze plating liquid the most according to claim 8, it is characterised in that on the basis of the total amount of described chemical bronze plating liquid, the content of described surfactant is 0.001-0.1g/L.
10. according to the chemical bronze plating liquid described in any one of claim 1-3, it is characterised in that described pH adjusting agent is sodium hydroxide.
11. 1 kinds of electroless copper plating methods, directly contact with chemical bronze plating liquid including by workpiece to be plated, obtain plating piece after cleaning-drying；It is characterized in that, described chemical bronze plating liquid is the chemical bronze plating liquid described in any one of 1-10.
12. methods according to claim 11, it is characterised in that the temperature of described chemical bronze plating liquid is 45-55 DEG C, described time of contact is 60-300 minute.
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| CN108468039A (en) * | 2018-05-24 | 2018-08-31 | 江苏时瑞电子科技有限公司 | A kind of chemical bronze plating liquid and its copper-plating technique applied in zinc oxide varistor copper electrode |
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| CN101684554A (en) * | 2008-09-23 | 2010-03-31 | 比亚迪股份有限公司 | Chemical copper plating solution for polyimide film and surface chemical copper plating method thereof |
| CN102051607A (en) * | 2009-10-29 | 2011-05-11 | 比亚迪股份有限公司 | Electroless copper plating solution |
| CN102191491A (en) * | 2010-03-10 | 2011-09-21 | 比亚迪股份有限公司 | Chemical copper-plating solution and chemical copper-plating method |
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| CN101684554A (en) * | 2008-09-23 | 2010-03-31 | 比亚迪股份有限公司 | Chemical copper plating solution for polyimide film and surface chemical copper plating method thereof |
| CN102051607A (en) * | 2009-10-29 | 2011-05-11 | 比亚迪股份有限公司 | Electroless copper plating solution |
| CN102191491A (en) * | 2010-03-10 | 2011-09-21 | 比亚迪股份有限公司 | Chemical copper-plating solution and chemical copper-plating method |
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