CN1044670A - Nitrogen heterocyclic ring and metallic copper polycoordination prepare the technology of surfacecti proteon film - Google Patents
Nitrogen heterocyclic ring and metallic copper polycoordination prepare the technology of surfacecti proteon film Download PDFInfo
- Publication number
- CN1044670A CN1044670A CN89105394.8A CN89105394A CN1044670A CN 1044670 A CN1044670 A CN 1044670A CN 89105394 A CN89105394 A CN 89105394A CN 1044670 A CN1044670 A CN 1044670A
- Authority
- CN
- China
- Prior art keywords
- copper
- technology
- treatment solution
- polycoordination
- heterocyclic ring
- 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
- 239000010949 copper Substances 0.000 title claims abstract description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 60
- 238000005516 engineering process Methods 0.000 title claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- -1 nitrogen-containing heterocycle compound Chemical class 0.000 claims abstract description 7
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 229910001369 Brass Inorganic materials 0.000 claims description 3
- 239000010951 brass Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005530 etching Methods 0.000 abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000012528 membrane Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000000280 densification Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- GJYZJBJNBLCCQO-UHFFFAOYSA-N 2-(2h-benzotriazol-4-yl)ethanol Chemical compound OCCC1=CC=CC2=NNN=C12 GJYZJBJNBLCCQO-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Nitrogen heterocyclic ring and metallic copper polycoordination prepare the technology of surfacecti proteon film, belong to the anti-corrosion of metal field.With nitrogen-containing heterocycle compound and aqueous ethanol preparation copper treatment solution, add promotor, generate the polymerization protective film at copper surface, membrane structure densification, firm, can be alkaline-resisting, the alkaline ammonia etching liquid corrosion of acid and copper, weldability is unaffected, and this technology is used for the manufacturing and the protection of anticorrosion, the printed-wiring board (PWB) of copper and copper alloy.
Description
The invention belongs to the anti-corrosion of metal technical field.
Existing copper anti-corrosion method has several, a kind of be nitrogen-containing heterocycle compound be dissolved in the contacted medium of copper in, slow down the action of rust of medium to copper; Another kind is with nitrogen-containing heterocycle compound, as benzotriazole, directly is coated in the copper surface, with the oxide compound react with on copper surface, generates the protective film with polymer architecture.The surfacecti proteon film of Zhi Bei the copper corrosion that can slow down atmosphere, water, weak acid, diluted alkaline like this, but the not corrosion of the alkaline ammonia etching liquid of ability highly basic, strong acid or copper.(reference: 1.Patel, N.K.; Franco, J.and Patel, I.S., J.Indian Chem.Soc., LIV, 1977,315.2.Fox, G.P.; Lewis, G.and Boden, P.J., Corrosion Science, 19,1979,457.3.Bakszt, M., Gircuit Word, 11,1985,14.4.Xue, G.; Jiang, S.; Huang, X.and Shi, G., J.Chem.Soc.Dalton Trans., 1988,1487.)
The present invention seeks to adopt the chemical polymerization method, under the promotor effect, make nitrogen-containing heterocycle compound (imidazoles, benzimidazolyl, benzotriazole etc.) generate the chemical protection film of compact and firm on metallic copper (or copper alloy) surface, the alkaline ammonia etching agent of protection highly basic, strong acid and copper is to the corrosion of metallic copper (or copper alloy), is used for the manufacturing and the corrosion protection of anticorrosion, the printed circuit board (PCB) of copper.
Content of the present invention is made up of following steps:
1, the preparation of anti-etching treatment fluid with nitrogen-containing heterocycle compound (as in imidazoles, benzimidazolyl, benzotriazole and the derivative any) be dissolved in the aqueous ethanol, nitrogen-containing heterocycle compound is 1: 30～1 with the ratio of aqueous ethanol: the 200(weight ratio).Be made into the copper treatment solution.Water and alcoholic acid weight ratio are 1: 1～1: 10 in the used aqueous ethanol.
2, the pre-treatment of metallic copper (or copper alloy) is that the matrix material of copper is (as printing with copper sheet or brass work (external form is not limit) or top layer
Give making sheet) with diluted alkaline flush away surface and oil contaminant, under room temperature, put in the dilute hydrochloric acid and soaked 1-5 minute, the flush away copper surface oxide again.Take out, to neutral, immediately be dipped in the copper treatment solution by step 1 preparation with water rinse.
3, the preparation of copper surface nitrogen heterocyclic ring polymeric membrane connects step 2, adds promotor-mercaptobenzoimidazole salt
(M can be Cu
+, Cu
++, Zn
++, H
+).Generally, the promotor input amount accounts for 0.1～1% of treatment solution gross weight, under 40 ℃ of-60 ℃ of temperature, stirs 30～60 minutes.Take out copper sheet, after the aqueous ethanol washing, under 50 ℃ of-70 ℃ of temperature, dried by the fire 30～60 minutes, promptly generate the polymerization protective film of compact and firm on the copper surface.Thicknesses of layers is 3～15 microns.
The advantage that the present invention compared with prior art has is, adopt the technology of the present invention in the surperficial protective film densification that generates of copper, firm, not only can prevent the corrosion of copper in air, water or weak acid, diluted alkaline, and can prevent the corrosion of copper in the media such as alkaline ammonia etching liquid of highly basic, strong acid and copper.Keep copper complete incorrosive time in the alkaline ammonia etching liquid of highly basic, strong acid and copper to reach several ten minutes, even more than number picks up hour, and weldability is unaffected.
The time that the protective film of the present invention's preparation and the benzotriazole protective film for preparing by document (2) are kept perfectly in media such as strong acid, highly basic contrasts as following table:
| Medium | The protective membrane of the present invention's preparation is pressed the protective membrane of document (2) preparation |
| NaOH?10%?20℃ NaOH?10%?50℃ | 48 hours 4 hours 20 hours 1 hour |
| H?Cl?5%?20℃ H?Cl?5%?50℃ | 48 hours 1 minute 15 hours 0.5 minute |
| 50 ℃ of the alkaline ammonia etching liquids of 20 ℃ of copper of alkaline ammonia etching liquid of copper | 40 minutes 1 minute 10 minutes 0.5 minute |
The time that the chemical protection film of copper surface is kept perfectly after soaking in medium can be used cyclic voltammetry.Be about to the metallic copper that adopts the technology of the present invention to handle, and the metallic copper of handling by document soaks the some time in highly basic, strong acid or other etch medium, taking-up is washed till neutrality, as the working electrode of cyclic voltammetric, makes reference electrode with saturated calomel electrode, platinum is made counter electrode, the hac buffer of PH=6 is made dielectric medium, makes electrolyzer with 100 milliliters little burning bosoms, uses voltammetric analyzer scan round, record volt-ampere curve, i.e. voltage-to-current curve.If it still is complete soaking the protective film on the copper surface of some time in medium, then the resistance on copper surface is very big, and the electric current of volt-ampere curve is very little, levels off to zero.If the protective film on copper surface crack or perforation occur after soaking in medium, then electric current can pass through from crack or perforation, and the scanning first time of volt-ampere curve shows that promptly electric current enlarges markedly, and the redox absorption peak of copper occurs.
The alkaline ammonia etching liquid of copper has the intensive erosion to metallic copper.The technology of the present invention has tangible corrosion protection result to this medium.Following table has contrasted the copper sheet of the technology of the present invention protection and the copper sheet of the technical protection that document (1) is reported soaks the variation of thickness afterwards in this medium.Metal copper sheet thickness is 0.100mm before handling, and adopts the technology of the present invention to handle the back and respectively forms the thick protective membrane of 0.005mm two of copper sheets.The technology of document (1) report is that mercapto benzothiazole is dissolved among the medium, to slow down the corrosion of medium to copper.
| The temperature of medium, time | The copper sheet of pressing document (1) protection of the technology of the present invention protection soaks back thickness copper sheet and soaks back thickness |
| 20 ℃ 40 minutes 50 ℃ 10 minutes | 0.106mm 0.045mm 0.105mm 0mm |
The best way that realizes the technology of the present invention is exemplified below:
(30 * 10 * 0.10mm) with being immersed in taking-up in 1 minute in 3% hydrochloric acid after the diluted alkaline washing with copper sheet for example, be washed till neutrality with ethanol, immediately immerse (concentration is 1.5%) in 100ml benzotriazole-Ethanol Treatment liquid, adding 0.5 gram mercaptobenzoimidazole cuprous salt in solution (
) do promotor, be warming up to 50 ℃, kept 1 hour, take out, be immersed in the 50ml ethanol and took out in 5 minutes, 60 ℃ of bakings 30 minutes down respectively are 5 microns polymerization protective film at the two-sided formation thickness of copper sheet.This surface has the copper sheet of protective film to immerse 10%NaOH(50 ℃) in 10 minutes, immerse again in the alkaline ammonia etching liquid (50 ℃) of copper and to take out in 5 minutes, detect with cyclic voltammetry, copper surfacecti proteon film is firmly harmless.Complete appearance, smooth.
Sample behind above-mentioned usefulness alkali, the ammonia solution successive soaking still can be used for spot welding, and solder joint is not peeled off by brute force, and weldability is good.
Claims (2)
1, nitrogen-containing heterocycle compound and metallic copper polycoordination prepare the technology of surfacecti proteon film, it is characterized in that being mixed with the copper treatment solution in 1: 30～1: 200 ratio with nitrogen heterocyclic ring and aqueous ethanol, the brass work surface is cleaned up with diluted alkaline, diluted acid, remove degreasing, oxide compound, immerse in the copper treatment solution rapidly, add promotor mercaptobenzoimidazole salt:
(M=Cu
++, Cu
+, Zn
++, or H
+).Promote that dosage accounts for 0.1～1% of treatment solution gross weight, under 40 ℃～60 ℃, stirred 30～60 minutes, after the taking-up washing, dried by the fire 30～60 minutes down in 50 ℃～70 ℃.Generating thickness on brass work surface is the polymerization protective film of 3～15 microns compact and firm, is used for the manufacturing and the protection of anticorrosion, the printed-wiring board (PWB) of copper and copper alloy.
2, technology according to claim 1 is characterized in that promotor preferably adopts
, consumption accounts for 0.1～1% of treatment solution gross weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89105394.8A CN1044670A (en) | 1989-02-01 | 1989-02-01 | Nitrogen heterocyclic ring and metallic copper polycoordination prepare the technology of surfacecti proteon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89105394.8A CN1044670A (en) | 1989-02-01 | 1989-02-01 | Nitrogen heterocyclic ring and metallic copper polycoordination prepare the technology of surfacecti proteon film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1044670A true CN1044670A (en) | 1990-08-15 |
Family
ID=4856156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89105394.8A Pending CN1044670A (en) | 1989-02-01 | 1989-02-01 | Nitrogen heterocyclic ring and metallic copper polycoordination prepare the technology of surfacecti proteon film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1044670A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690957A (en) * | 2012-06-15 | 2012-09-26 | 紫金矿业集团股份有限公司 | Method for extracting gold from copper-containing gold oxide ore |
| CN103425001A (en) * | 2013-07-19 | 2013-12-04 | 杨桂望 | Resist membrane cleaning composition |
| CN104775126A (en) * | 2014-12-24 | 2015-07-15 | 四川理工学院 | Application of 1, 2-di (benzimidazole-2-sulfenyl) ethane in preparation of metal pickling solution |
| CN105568293A (en) * | 2015-12-15 | 2016-05-11 | 铜陵铜官府文化创意股份公司 | Storage method of copper artware |
| CN113737167A (en) * | 2021-09-22 | 2021-12-03 | 东莞市四辉表面处理科技有限公司 | Copper material antioxidant and preparation method thereof |
-
1989
- 1989-02-01 CN CN89105394.8A patent/CN1044670A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690957A (en) * | 2012-06-15 | 2012-09-26 | 紫金矿业集团股份有限公司 | Method for extracting gold from copper-containing gold oxide ore |
| CN102690957B (en) * | 2012-06-15 | 2014-07-16 | 紫金矿业集团股份有限公司 | Method for extracting gold from copper-containing gold oxide ore |
| CN103425001A (en) * | 2013-07-19 | 2013-12-04 | 杨桂望 | Resist membrane cleaning composition |
| CN104775126A (en) * | 2014-12-24 | 2015-07-15 | 四川理工学院 | Application of 1, 2-di (benzimidazole-2-sulfenyl) ethane in preparation of metal pickling solution |
| CN104775126B (en) * | 2014-12-24 | 2017-10-27 | 四川理工学院 | A kind of 1,2 2 (sulfenyl of the benzimidazole 2) applications of ethane in metal pickle liquor is prepared |
| CN105568293A (en) * | 2015-12-15 | 2016-05-11 | 铜陵铜官府文化创意股份公司 | Storage method of copper artware |
| CN105568293B (en) * | 2015-12-15 | 2018-08-07 | 铜陵铜官府文化创意股份公司 | The store method of copper artware |
| CN113737167A (en) * | 2021-09-22 | 2021-12-03 | 东莞市四辉表面处理科技有限公司 | Copper material antioxidant and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1172525A (en) | Copper-containing articles with a corrosion inhibitor coating and method of producing the coating | |
| US7396596B2 (en) | Article with a coating of electrically conductive polymer | |
| ES2219730T3 (en) | PROCEDURE TO IMPROVE THE SOLUBILITY OF A SURFACE. | |
| EP0797690B1 (en) | Printed circuit board manufacture | |
| CN1292896C (en) | Laminate and its production method | |
| TWI420994B (en) | Article with a coating of electrically conductive polymer and precious/semiprecious metal and process for production thereof | |
| CN111360450B (en) | Organic solderability preservative and preparation method of organic copper coordination polymer film | |
| EP0710522A1 (en) | Flux formulation | |
| Lee et al. | Electrochemical migration in electronic materials: factors affecting the mechanism and recent strategies for inhibition | |
| CN1044670A (en) | Nitrogen heterocyclic ring and metallic copper polycoordination prepare the technology of surfacecti proteon film | |
| JP3395854B2 (en) | Chemical reduction solution of copper oxide and method for producing multilayer printed wiring board using the same | |
| EP2411559B1 (en) | Organic polymer coatings for protection against creep corrosion | |
| CN103388152B (en) | A kind of Copper base material pickle solution with corrosion mitigating effect | |
| CN105002528A (en) | Cyanide-free silver electroplating solution and electroplating method thereof | |
| CN101487124A (en) | Method for forming arginine self-assembly corrosion inhibition film on copper surface | |
| JP5740727B2 (en) | Sealing treatment agent and sealing treatment method | |
| Oh et al. | Galvanic corrosion of Cu coupled to Au on a print circuit board; effects of pretreatment solution and etchant concentration in organic solderability preservatives soft etching solution | |
| Milić et al. | Influence of benzotriazole on corrosion behaviour of CuAlNiSi alloy in alkaline medium | |
| JP3668767B2 (en) | Surface treatment method for metals such as solder, electroless solder, silver, nickel and zinc | |
| JPH07330738A (en) | Protecting agent for metal surface and production using the same | |
| CN106917078A (en) | Palladium method is plated in a kind of displacement for copper surface | |
| CN105101645A (en) | OSP (Organic Solderability Preservatives) surface treatment method of metal substrate | |
| Yoshihara | Newly Developed Real Time Monitoring System for Ionic Migration by Means of Quartz Crystal Microbalance (QCM) and Electrochemical Impedance Spectroscopy (EIS) | |
| CN112694811A (en) | Water-based copper workpiece anticorrosion treating agent and application thereof | |
| Ameer et al. | Interface analysis of pure Sn, pure Ag and Sn Ag binary alloys in H2SO4 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |