CN102191501A - Palladium remover and preparation method thereof, and plastic surface activation method - Google Patents
Palladium remover and preparation method thereof, and plastic surface activation method Download PDFInfo
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- CN102191501A CN102191501A CN2010101222735A CN201010122273A CN102191501A CN 102191501 A CN102191501 A CN 102191501A CN 2010101222735 A CN2010101222735 A CN 2010101222735A CN 201010122273 A CN201010122273 A CN 201010122273A CN 102191501 A CN102191501 A CN 102191501A
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- Prior art keywords
- palladium
- liquid
- nickel
- complexing agent
- plating
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 283
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 141
- 229920003023 plastic Polymers 0.000 title claims abstract description 49
- 239000004033 plastic Substances 0.000 title claims abstract description 49
- 230000004913 activation Effects 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 36
- 238000007747 plating Methods 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008139 complexing agent Substances 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 91
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- -1 polymeric flocculant Substances 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 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 description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 35
- 239000002184 metal Substances 0.000 abstract description 35
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 238000001994 activation Methods 0.000 description 25
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical class [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 17
- 238000007772 electroless plating Methods 0.000 description 9
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910000906 Bronze Inorganic materials 0.000 description 5
- 239000010974 bronze Substances 0.000 description 5
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000003245 working effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 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 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Chemically Coating (AREA)
Abstract
The invention provides a palladium remover, a preparation method thereof, and a plastic surface activation method. The palladium remover comprises sulfuric acid, a fluorine-free palladium complexing agent, a polymeric flocculant and water. The plastic surface activation method comprises the following steps: (1) submerging a plastic base material plated with copper layer locally into ion palladium activating solution to start activation, and contacting the plastic base material with the palladium remover to obtain a member to be nickeled; (2) carrying out chemical nickel plating on the member to obtain plastic whose local surface is plated with a copper layer and a nickel layer in order. The palladium remover in the invention is nontoxic and environment-friendly, has a long service life, and produces no corrosion to other metal in the process of removing metal palladium. Simultaneously, according to the plastic surface activation method in the invention, a plastic base material plated with copper layer locally is activated and then is subjected to chemical nickel-plating. The method is suitable for the common plastic which needs to be plated with the copper layer and the nickel layer locally in order, and solves the problem that present palladium remover can not remove palladium thoroughly.
Description
Technical field
The present invention relates to this palladium ion removal liquid of a kind of palladium removal liquid and preparation method thereof and a kind of employing and carry out the frosting activation method.
Background technology
Need metallize and all the other zones do not need metallized plastics for regional area, after the ionic palladium activation treatment, the ionic palladium of non-metallic region surface is not easy to remove, and following side reaction takes place for palladium ion and water:
2H
2O→H
3O
++OH-
Pd
2++2OH
-→Pd(OH)
2
The by product palladium hydroxide that generates can be difficult to wash off attached to non-metallic region surface, carry out second kind of metal of electroless plating the time, palladium ion or palladium hydroxide attached to non-metallic region surface can play catalytic activity, cause non-metallic region surface plating little metal, cause the product yield to descend.
Particularly in circuit card electroless plating field, if, can cause short circuit phenomenon not needing the electroless plating zone metal-coated.
The metallized a lot of methods of frosting regional area, for example, disclose a kind of in the prior art, at the metal oxide that in plastic substrate, adds spinel structure, laser activates the frosting regional area, the metal oxide of regional area is decomposed discharge metal simple-substance, these metal simple-substances are as the electroless plating catalytic active center, thereby can carry out electroless plating.When needs plate two or more metal, behind first kind of metal of regional area plating, also need under the situation of second kind of metal of electroless plating, sometimes need base material is carried out surface activation process, the purpose of activation treatment is a certain amount of fine particle of noble metal with catalytic activity of absorption on non metallic substrate, so that bring out electroless plating subsequently.Activating treatment process commonly used has colloidal palladium activation method and ionic palladium activation method.Frosting adopts the colloidal palladium activation, and can cause non-metallic zone to be sticked has colloidal palladium, and then causes non-metallic zone after carrying out electroless plating, forms metal level in non-metallic region surface, causes product defective.And the ionic palladium activation can produce the palladium ion of above-mentioned non-metallic region surface or the problem that palladium hydroxide is difficult to wash-out.
The composition fluorochemical commonly used that palladium of the prior art is removed liquid removes palladium hydroxide and palladium ion, and fluorochemical and palladium complexing form easy eluted palladium complex, but fluorochemical toxicity is stronger.Or remove palladium hydroxide and palladium ion with some diluted acid, and very short but this palladium is removed the life-span of liquid, often can only be with once, because the palladium behind the wash-out palladium is removed palladium content concn in the liquid when big, the part palladium ion still can be attached on the base material.
Disclose a kind of palladium among the CN100543187C and removed liquid, strong volatility pungency acid such as employing nitric acid are main component, and the corrodibility of nitric acid is more intense.If on the base material plating first kind of metal level arranged, need to carry out second kind of metal level of plating after the palladium activation, palladium is removed liquid can corrode first kind of metal level, so palladium is removed in the liquid and added the anticorrosive metal agent among the CN100543187C.
Have two pieces of Japanese Patent spies to open clear 63-72198 in addition, the spy opens flat 7-207466 and also proposes to use fluoroboric acid respectively, and toxic substances such as prussiate are removed the main ingredient of liquid as palladium.Because of the content of above-mentioned fluoroboric acid, prussiate higher, health to environment and people has a significant impact, and the work-ing life of the liquid of palladium removal simultaneously is shorter, repeatedly after the use several times, along with increasing of the palladium ion concentration in the palladium removal liquid, the activity that palladium removal liquid removes palladium descends very fast.
Summary of the invention
The present invention solves the palladium that exists in the prior art to remove liquid when removing palladium metal, to the problem that other metal can produce corrosion or the work-ing life of or removal liquid unfavorable to environment is short.
The invention provides a kind of palladium and remove liquid, described palladium is removed liquid and is contained sulfuric acid, floride-free type palladium complexing agent, polymeric flocculant, water.
The present invention also provides above-mentioned palladium to remove the preparation method of liquid, and floride-free type palladium complexing agent, polymeric flocculant are dispersed in the water, obtains mixed solution; Sulfuric acid is joined in the mixed solution, obtain palladium and remove liquid.
The present invention also provides a kind of frosting activation method, comprises following steps:
1) plastic basis material that the part is coated with the copper layer immerses in the ionic palladium activation solution after the activation, removes liquid with palladium again and contacts; Obtain the nickel unplated piece;
2) the nickel unplated piece is carried out chemical nickel plating; Obtain local surfaces successively plating the plastics of copper layer, nickel dam are arranged; It is that above-mentioned palladium is removed liquid that described palladium is removed liquid.
The present inventor is through a large amount of experiments, be surprised to find that, adopt floride-free type palladium complexing agent with polymeric flocculant, the concentration that palladium ion is removed in the liquid at palladium maintains a more suitable concentration, most of palladium ion and floride-free type palladium complexing agent carry out complexing, make palladium ion can not generate the palladium hydroxide that is easy to attached to workpiece surface; Simultaneously, in case the palladium ion concentration that palladium is removed in the liquid is too high, the flocculating settling reaction can take place with polymeric flocculant in excessive palladium ion, excessive palladium ion is deposited in the bottom that palladium is removed liquid, the palladium ion that palladium is removed in the liquid maintains a preferable scope all the time, simultaneously, reduced the usage quantity of complexing agent.Because of the solubility limit of complexing agent in palladium removal liquid, therefore, the content of the complexing agent in the palladium removal liquid can not be very high, adds polymeric flocculant and guaranteed that the palladium content in the liquid is always in low scope, so reduced the usage quantity of complexing agent than prior art.And the existence of polymeric flocculant, can make palladium remove liquid and use repeatedly repeatedly, and need not it be upgraded, only need to be deposited in palladium and remove the sedimentation and filtration of liquid bottom and remove and get final product.Therefore, palladium of the present invention is removed will grow than prior art in work-ing life of liquid.And sulfuric acid is when making palladium of the present invention remove liquid to maintain a sour environment, and general palladium remove liquid need be better in result of use under the hot environment, the vitriolic high-temperature volatile is less, can reduce under the high temperature acid mist to the influence of environment.And the toxicity of common fluorine-containing type palladium complexing agent is stronger, is unfavorable for environment.Palladium of the present invention is removed the liquid asepsis environment-protecting, long service life, and other metal to substrate surface can not produce corrosion simultaneously.
Simultaneously, frosting activation method provided by the invention, chemical nickel plating again after the plastic basis material that the part is coated with the copper layer activates, be applicable to now common need regional area successively plating the plastics of copper layer, nickel dam are arranged; It is unclean to have solved existing palladium remover removal palladium, and the non-metallic zone that causes is coated with the problem of minor amount of nickel.
Embodiment
The invention provides a kind of palladium and remove liquid, described palladium is removed liquid and is contained sulfuric acid, floride-free type palladium complexing agent, polymeric flocculant, water.
Described palladium is removed in the liquid, and vitriolic content is 0.1-2mol/L, and the content of floride-free type palladium complexing agent is 0.01-2mol/L, and the content of polymeric flocculant is 0.0005-0.05g/L.
Described floride-free type palladium complexing agent is not fluorine-containing palladium complexing agent, and the toxicity of common fluorine-containing type palladium complexing agent is stronger, is unfavorable for environment.The present inventor finds that through experiment floride-free type palladium complexing agent is preferably tetrasodium ethylenediamine tetraacetate, ammonium citrate, acetic acid, one or more in the trolamine.
Described polymeric flocculant is one or more in polyacrylamide, sodium polyacrylate, the polyvinyl alcohol.The molecular weight of described polymeric flocculant is 0.0005-0.05g/L.The molecular weight of described polymeric flocculant is preferably 1000000-100000000.
The present invention also provides above-mentioned palladium to remove the preparation method of liquid, and floride-free type palladium complexing agent, polymeric flocculant are dispersed in the water, obtains mixed solution; Sulfuric acid is joined in the mixed solution, obtain palladium and remove liquid.
The present invention also provides a kind of frosting activation method, comprises following steps:
1) plastic basis material that the part is coated with the copper layer immerses in the ionic palladium activation solution after the activation, removes liquid with palladium again and contacts; Obtain the nickel unplated piece;
2) the nickel unplated piece is carried out chemical nickel plating; Obtain local surfaces successively plating the plastics of copper layer, nickel dam are arranged; It is that above-mentioned palladium is removed liquid that described palladium is removed liquid.
The preparation method that above-mentioned part is coated with the plastic basis material of copper layer is one of method of the common frosting localized metallicization of those skilled in the art, concrete, to carry out through the base material that contains metal oxide of oil removal treatment, laser obtains the base material that local surfaces has the metal active center for three-dimensional laser device or two-dimensional laser device (for example laser apparatus of Le Puke company production) that those skilled in the art use always behind the laser activation.Described metal oxide, optional autoxidation copper, nickel oxide, cobalt oxide, chromic oxide, ferric oxide.Selective oxidation copper of the present invention behind the local laser activation, obtains the plastic basis material that local surfaces has the copper activity center.Be placed on and carry out electroless copper in the chemical bronze plating liquid, obtain the plastic basis material that the part is coated with the copper layer.Described chemical bronze plating liquid is a kind of of the known chemical bronze plating liquid of those skilled in the art, the content of concrete electroless copper is cupric sulfate pentahydrate 8-12g/L, EDTA disodium salt 40-50g/L, sodium hydroxide 12-15g/L, methyl alcohol 10-40g/L, yellow prussiate of potash 20-40mg/L, dipyridyl 20-40g/L, formaldehyde 2-5g/L.Wherein temperature of reaction is 70 degrees centigrade.
Above-mentioned chemical nickel-plating liquid is a kind of of the known chemical nickel-plating liquid of those skilled in the art, and is commercially available, as the bright acidic nickel plating solution of middle phosphorescence of Atotech company production.
Described ionic palladium activation solution is a kind of of the common ionic palladium activation solution of those skilled in the art, and described ionic palladium activation solution contains Palladous chloride, hydrochloric acid and water, wherein Palladous chloride 0.00005-0.0005mol/L, hydrochloric acid 0.1-0.5mol/L.
Above-mentioned plastic basis material comprises that with the condition that palladium removal liquid contacts temperature is 40-50 ℃, and the time is 1-5 minute.
Not all local electroplating has the plastic basis material of first kind of metal level all to need to activate just can second kind of metal level of chemical plating, and the metal level that copper facing successively provided by the invention, nickel plating form belongs to the complex metal layer that one kind of multiple more common metals constitute.If nickel plating successively, copper facing, then nickel dam can directly carry out electroless copper, and does not need to activate, because nickel dam can be used as the active centre of electroless copper.As for when needing first kind of metal level activated, could carry out second kind of metal level of plating with the form of electroless plating, those skilled in the art can judge according to the character of different metal, and these belong to the common practise of this area, do not repeat them here.
The present invention will be described in more detail below with reference to embodiment.Raw materials usedly among the embodiment all be available commercially.
Embodiment 1
Palladium is removed liquid:
Sulfuric acid 1mol/L
Acetic acid 0.5mol/L,
Polyacrylamide 0.001g/L.
At first, acetic acid, polyacrylamide are dispersed in the water, obtain mixed solution; Sulfuric acid is joined in the mixed solution, obtain palladium and remove liquid.
Will be through the plastic basis material that contains cupric oxide of oil removal treatment, the plastic basis material area is 1 square decimeter, the laser apparatus that adopts Le Puke company to produce obtains the base material that local surfaces has the copper activity center behind the laser activation.Be placed in 70 ℃ the chemical bronze plating liquid and carry out electroless copper, obtain the plastic basis material that the part is coated with the copper layer.Wherein, the localized metallic region area is 0.25 square decimeter.
The content of chemical bronze plating liquid is cupric sulfate pentahydrate 12g/L, EDTA disodium salt 50g/L, sodium hydroxide 15g/L, methyl alcohol 40g/L, yellow prussiate of potash 40mg/L, dipyridyl 40g/L, formaldehyde 5g/L.
The plastic basis material that the part is coated with the copper layer immerses priming reaction 1h in the ionic palladium activation solution, and the ionic palladium activation solution contains Palladous chloride 0.0001mol/L, hydrochloric acid 0.2mol/L.
Be that 45 ℃ above-mentioned palladium is removed liquid and contacted 5 minutes with temperature again; Obtain the nickel unplated piece;
The bright acidic nickel plating solution of phosphorescence of the nickel unplated piece being put into 90 ℃ Atotech company production carries out chemical nickel plating; Obtain local surfaces successively plating the plastics X1 of copper layer, nickel dam is arranged.
Embodiment 2
Be that with the difference of embodiment 1 palladium removes liquid, obtain local surfaces successively plating the plastics X2 of copper layer, nickel dam is arranged.
Palladium is removed liquid:
Sulfuric acid 1.5mol/L
Tetrasodium ethylenediamine tetraacetate 0.05mol/L,
Polyvinyl alcohol 0.015g/L.
Embodiment 3
Be that with the difference of embodiment 1 palladium is removed liquid, obtain local surfaces successively plating the plastics X3 of copper layer, nickel dam is arranged.
Palladium is removed liquid:
Sulfuric acid 1mol/L
Ammonium citrate 0.1mol/L,
Sodium polyacrylate 0.001g/L.
Embodiment 4
Be that with the difference of embodiment 1 palladium is removed liquid, obtain local surfaces successively plating the plastics X4 of copper layer, nickel dam is arranged.
Palladium is removed liquid:
Sulfuric acid 2mol/L
Ammonium citrate 0.15mol/L,
Polyvinyl alcohol 0.001g/L.
Comparative Examples 1
Be that with the difference of embodiment 1 palladium is removed liquid, obtain local surfaces successively plating the plastics D1 of copper layer, nickel dam is arranged.
Palladium is removed the recipe configuration of the embodiment 1 in the table 1 that liquid is CN100543187C.
Comparative Examples 2
Be that with the difference of embodiment 1 palladium is removed liquid, obtain local surfaces successively plating the plastics D2 of copper layer, nickel dam is arranged.
The difference of removing liquid with the palladium of embodiment 1 is not contain the polymeric flocculant polyacrylamide, and the concentration with complexing agent acetic acid changes to 0.8mol/L simultaneously.
Performance test
Palladium is removed the life test of liquid: palladium is removed liquid and is used the number of times that occurs nickel point or nickel bar to the non-metallic zone of plastic basis material to reflect the life-span of palladium removal liquid repeatedly, for example, same palladium is removed on the plastic basis material that liquid is used in a plurality of method preparations according to embodiment 1 repeatedly, obtain a plurality of identical X1, nickel point or nickel bar appear until the surface of plastic basis material, explanation this moment, palladium is removed liquid and can not have been used repeatedly again.If the number of times that palladium removal liquid is used repeatedly is many more, so just illustrate that the life-span of palladium removal liquid is long more, help suitability for industrialized production more.
Table 1
| The visual inspection outward appearance | Palladium is removed liquid and is used the number of times that occurs nickel point or nickel bar to the non-metallic zone of plastic basis material repeatedly | |
| X1 | Plastic basis material localized metallic region surface is smooth, and the no any metal in non-metallic zone occurs | 102 times |
| X2 | Plastic basis material localized metallic region surface is smooth, and the no any metal in non-metallic zone occurs | 109 times |
| X3 | Plastic basis material localized metallic region surface is smooth, and the no any metal in non-metallic zone occurs | 103 times |
| X4 | Plastic basis material localized metallic region surface is smooth, and the no any metal in non-metallic zone occurs | 105 times |
| D1 | Coarse, the blackout of plastic basis material localized metallic region surface, non-metallic zone occurs having metalluster on a small quantity, white shows slightly gray nickel point. | 9 times |
| D2 | Plastic basis material localized metallic region surface is smooth, and big variation does not take place metallized area metal level color, and non-metallic zone occurs having metalluster on a small quantity, white shows slightly gray nickel point | 11 times |
As can be seen from Table 1, embodiments of the invention 1-4 compares as can be seen with Comparative Examples 1-2, and the work-ing life of palladium removal liquid of the present invention is obviously better than Comparative Examples.It is obvious to adopt palladium of the present invention to remove liquid removal palladium effect simultaneously, can find out from the outward appearance in plastic basis material localized metallic zone, if the localized metallic region surface is smooth, the no any macroscopic metal in non-metallic zone occurs, the effect that palladium removal liquid wash-out palladium ion or palladium hydroxide are described is better, does not cause a large amount of appearance in non-metallic zone of palladium ion or palladium hydroxide.Coarse, the blackout of the plastic basis material localized metallic region surface of Comparative Examples 1, illustrate palladium remove corrosion first kind of metal level be the copper layer, cause the copper layer that plating successively obtains, the surface irregularity of nickel dam, a large amount of copper layers is dissolved in palladium and removes in the liquid, and then causes the metallized area surface irregularity of the plastic basis material that finally obtains.The plastic basis material localized metallic region surface of Comparative Examples 2 is smooth, big variation does not take place in metallized area metal level color, non-metallic zone occurs having metalluster on a small quantity, white shows slightly gray nickel point, explanation, only adopt the palladium complexing agent, even the concentration of the palladium complexing agent that adopts is bigger, still having a small amount of macroscopic nickel point occurs, illustrate that polymeric flocculant can reduce the drag-out of palladium, and keep taking off palladium agent palladium content all the time in low scope, be beneficial to and improve complexing agent and the efficient of acid, therefore can increase the effect of washing with the palladium hydroxide reaction.
Claims (10)
1. a palladium is removed liquid, and described palladium is removed liquid and contained sulfuric acid, floride-free type palladium complexing agent, polymeric flocculant, water.
2. palladium according to claim 1 is removed liquid, it is characterized in that, described palladium is removed in the liquid, and vitriolic content is 0.1-2mol/L, and the content of floride-free type palladium complexing agent is 0.01-2mol/L, and the content of polymeric flocculant is 0.0005-0.05g/L.
3. palladium according to claim 1 is removed liquid, it is characterized in that described floride-free type palladium complexing agent is one or more in tetrasodium ethylenediamine tetraacetate, ammonium citrate, the acetic acid.
4. palladium according to claim 1 is removed liquid, it is characterized in that described polymeric flocculant is one or more in polyacrylamide, sodium polyacrylate, the polyvinyl alcohol.
5. palladium according to claim 1 is removed liquid, it is characterized in that the molecular weight of described polymeric flocculant is 1000000-100000000.
6. the preparation method of a palladium removal liquid is dispersed in floride-free type palladium complexing agent, polymeric flocculant in the water, obtains mixed solution; Sulfuric acid is joined in the mixed solution, obtain palladium and remove liquid.
7. palladium according to claim 6 is removed liquid, it is characterized in that, described palladium is removed in the liquid, and vitriolic content is 0.1-2mol/L, and the content of floride-free type palladium complexing agent is 0.01-2mol/L, and the content of polymeric flocculant is 0.0005-0.05g/L.
8. frosting activation method comprises following steps:
1) plastic basis material that the part is coated with the copper layer immerses in the ionic palladium activation solution after the activation, removes liquid with palladium again and contacts; Obtain the nickel unplated piece;
2) the nickel unplated piece is carried out chemical nickel plating; Obtain local surfaces successively plating the plastics of copper layer, nickel dam are arranged;
It is that each described palladium of claim 1-5 is removed liquid that described palladium is removed liquid.
9. method according to claim 8, wherein, described ionic palladium activation solution contains Palladous chloride, hydrochloric acid, water.
10. method according to claim 8, wherein, plastic basis material comprises that with the condition that palladium removal liquid contacts temperature is 40-50 ℃, the time is 1-5 minute.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103280567A (en) * | 2013-03-06 | 2013-09-04 | 广州市东力电池实业有限公司 | Li4Ti5O12 having surface chemically plated by metal, and preparation method thereof |
| CN104470236A (en) * | 2013-09-16 | 2015-03-25 | 深圳市兴经纬科技开发有限公司 | Post-immersing liquid of circuit board electroless nickel immersion gold and post-immersing method |
| CN112981402A (en) * | 2020-10-21 | 2021-06-18 | 东莞小禹科技有限公司 | Processing method of metal alloy |
| CN114345325A (en) * | 2021-12-31 | 2022-04-15 | 河北海力香料股份有限公司 | Reactivation method of palladium/carbon catalyst |
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| DE4239852A1 (en) * | 1992-11-27 | 1994-06-01 | Saxonia Metallhuetten Verarb | Refining palladium-contg. crude silver by electrolysis - involves removing palladium from electrolyte with ion-exchange resin contg. chelating anchor gps. and recycling electrolyte. |
| WO2002008491A1 (en) * | 2000-07-26 | 2002-01-31 | Mitsubishi Gas Chemical Company, Inc. | Palladium removing solution and method for removing palladium |
| CN1995459A (en) * | 2006-11-24 | 2007-07-11 | 江苏工业学院 | Solution for removing printing board surface adhesion palladium and removing method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103280567A (en) * | 2013-03-06 | 2013-09-04 | 广州市东力电池实业有限公司 | Li4Ti5O12 having surface chemically plated by metal, and preparation method thereof |
| CN103280567B (en) * | 2013-03-06 | 2016-11-23 | 广东工业大学 | A kind of surface chemical metal plating modifies Li4ti5o12and preparation method thereof |
| CN104470236A (en) * | 2013-09-16 | 2015-03-25 | 深圳市兴经纬科技开发有限公司 | Post-immersing liquid of circuit board electroless nickel immersion gold and post-immersing method |
| CN112981402A (en) * | 2020-10-21 | 2021-06-18 | 东莞小禹科技有限公司 | Processing method of metal alloy |
| CN114345325A (en) * | 2021-12-31 | 2022-04-15 | 河北海力香料股份有限公司 | Reactivation method of palladium/carbon catalyst |
| CN114345325B (en) * | 2021-12-31 | 2022-11-22 | 河北海力香料股份有限公司 | Reactivation method of palladium/carbon catalyst |
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