CN113684473B - Electroless copper plating solution for plastics and preparation method thereof - Google Patents
Electroless copper plating solution for plastics and preparation method thereof Download PDFInfo
- Publication number
- CN113684473B CN113684473B CN202110846684.7A CN202110846684A CN113684473B CN 113684473 B CN113684473 B CN 113684473B CN 202110846684 A CN202110846684 A CN 202110846684A CN 113684473 B CN113684473 B CN 113684473B
- Authority
- CN
- China
- Prior art keywords
- copper plating
- chitosan oligosaccharide
- solution
- electroless copper
- stirring
- 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.)
- Active
Links
- 238000007747 plating Methods 0.000 title claims abstract description 80
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 79
- 239000010949 copper Substances 0.000 title claims abstract description 79
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000004033 plastic Substances 0.000 title claims abstract description 43
- 229920003023 plastic Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 claims abstract description 49
- 239000003607 modifier Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004475 Arginine Substances 0.000 claims abstract description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 14
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 61
- 238000003756 stirring Methods 0.000 claims description 42
- 229960003121 arginine Drugs 0.000 claims description 25
- 235000009697 arginine Nutrition 0.000 claims description 25
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 22
- JVTZFYYHCGSXJV-UHFFFAOYSA-N isovanillin Chemical compound COC1=CC=C(C=O)C=C1O JVTZFYYHCGSXJV-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 17
- KWTQSFXGGICVPE-UHFFFAOYSA-N 2-amino-5-(diaminomethylideneamino)pentanoic acid;hydron;chloride Chemical compound Cl.OC(=O)C(N)CCCN=C(N)N KWTQSFXGGICVPE-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical group NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical group CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000005187 foaming Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- -1 polypropylene Polymers 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The invention provides an electroless copper plating solution for plastics, which comprises the following components: 10-16 g/L of copper sulfate, 8-12 g/L of dimethylamino borane, 60-70 g/L of complexing agent, 40-50 mg/L of stabilizer, 50-70 mg/L of accelerator, 0.5-1 g/L of chitosan oligosaccharide modifier, 0.2-0.4 g/L of arginine modifier, 70-90 mg/L of surfactant, 5-8 g/L of sodium carbonate and the balance of deionized water, wherein the pH value of the electroless copper plating solution for plastics is 11-13. The invention also provides a preparation method of the electroless copper plating solution for plastics. The electroless copper plating solution for plastic provided by the invention has a good copper plating effect.
Description
Technical Field
The invention relates to an electroless copper plating solution, in particular to an electroless copper plating solution for plastics and a preparation method thereof.
Background
It is known that most plastics are insulators, so that it is not feasible to directly plate the surface of the plastics, for example, the surface of the plastics needs to be metallized first, i.e. a conductive metal film is coated on the surface of the plastics under the condition of no power supply, so that the surface of the plastics has a certain conductivity, and then the plating can be performed. The plastic surface metallization treatment methods include vacuum plating, metal plating, cathode sputtering, electroless plating and the like, and the electroless plating is more effective in the methods, so that the plastic surface metallization treatment method is widely applied to chemical production.
Electroless plating is to deposit a metal layer on the surface of a workpiece by chemical reduction to deposit a conductive copper or nickel layer on the surface of the original non-conductive plastic, and electroless copper plating is currently used in many cases. Not all plastics can be electroless plated, and ABS, polypropylene, polyoxymethylene, polyethylene, polystyrene, polyamide, etc. are currently available, with ABS being the most common. Electroless copper plating is used as the electroless copper plating solution, and the composition of the electroless copper plating solution has a great influence on the copper plating effect, i.e., the quality of the copper plating layer.
Chinese patent application CN201310191861.8 discloses a plastic copper plating solution, which comprises the following components in parts by weight: 1-9 parts of sodium hydroxide, 9-16 parts of trisodium phosphate, 2-6 parts of chromium oxide, 6-17 parts of hydrochloric acid, 3-11 parts of silver nitrate, 6-22 parts of copper sulfate, 5-8 parts of copper alkenylene acid, 2-7 parts of ammonium nitrate and 3-13 parts of potassium pyrophosphate. The invention has the following problems: the copper plating effect of the plastic copper plating solution is not ideal.
Disclosure of Invention
The invention aims to solve the technical problem of providing an electroless copper plating solution for plastics, which has a good copper plating effect.
In order to solve the technical problems, the technical scheme of the invention is as follows:
an electroless copper plating solution for plastics comprises the following components: 10-16 g/L of copper sulfate, 8-10 g/L of dimethylamino borane, 60-70 g/L of complexing agent, 40-50 mg/L of stabilizer, 50-70 mg/L of accelerator, 0.5-1 g/L of chitosan oligosaccharide modifier, 0.2-0.4 g/L of arginine modifier, 70-90 mg/L of surfactant, 5-8 g/L of sodium carbonate and the balance of deionized water, wherein the pH value of the electroless copper plating solution for plastics is 11-13.
Further, the complexing agent is EDTA.
Further, the stabilizer of the invention is thiourea.
Further, the accelerator of the invention is 2, 6-diaminopyridine.
Further, the chitosan oligosaccharide modifier provided by the invention is prepared by the following steps:
adding chitosan oligosaccharide into absolute ethyl alcohol, stirring for 30-40 minutes at 55-65 ℃ to obtain chitosan oligosaccharide solution, adjusting the pH value to 6, then adding isovanillin into the chitosan oligosaccharide solution dropwise, stirring for 4-5 hours at 70-80 ℃ and standing overnight to obtain reaction solution, carrying out suction filtration on the reaction solution to obtain a filter cake, washing the filter cake with absolute ethyl alcohol for 3 times, and drying the filter cake to constant weight to obtain a chitosan oligosaccharide modified substance.
Further, in the preparation step of the chitosan oligosaccharide modified product, the concentration of the chitosan oligosaccharide solution is 0.5g/mL, and the ratio of the chitosan oligosaccharide solution to the isovanillin is (7-8) mL to 1g.
Further, the arginine modifier of the invention is prepared by the following steps:
mixing L-arginine hydrochloride, sodium bicarbonate and distilled water, cooling to 5 ℃, dropwise adding methacrylic anhydride, maintaining the temperature and stirring for 30-40 minutes to obtain a mixed solution, filtering the mixed solution to obtain filter residues, washing the filter residues with dichloromethane for 3 times, and freeze-drying the filter residues to constant weight to obtain the arginine modified substance.
Further, in the preparation step of the arginine modifier, the proportion of L-arginine hydrochloride, sodium bicarbonate, distilled water and methacrylic anhydride is 1g (0.7-0.9 g) (5-6 mL) and 0.6mL.
Further, the surfactant is octyl phenol polyoxyethylene ether.
Another technical problem to be solved by the invention is to provide a preparation method of the electroless copper plating solution for plastics.
In order to solve the technical problems, the technical scheme is as follows:
the preparation method of the electroless copper plating solution for the plastic comprises the following steps:
weighing the components according to the formula, adding copper sulfate into deionized water, stirring for 10-15 minutes, adding a complexing agent, stirring for 10-15 minutes, adding sodium carbonate to adjust the pH value to 11-13, adding other components, and stirring for 2-3 hours to obtain the electroless copper plating solution for plastics.
Compared with the prior art, the invention has the following beneficial effects:
1) According to the invention, the chitosan oligosaccharide and the isovanillin are subjected to condensation reaction to prepare the chitosan oligosaccharide modified substance, which can refine the crystallization of the copper plating layer, reduce the porosity of the copper plating layer, improve the compactness of the copper plating layer and improve the ductility of the copper plating layer.
2) According to the invention, L-arginine hydrochloride and methacrylic anhydride are subjected to grafting reaction under the help of sodium bicarbonate to prepare an arginine modified product, so that the ductility of a copper plating layer can be further improved, and the binding force of the copper plating layer can be improved.
Detailed Description
The present invention will be described in detail with reference to specific examples, wherein the exemplary embodiments of the present invention and the descriptions thereof are provided for the purpose of illustrating the present invention, but are not to be construed as limiting the present invention.
Example 1
The electroless copper plating solution for plastics comprises the following components: 15g/L of copper sulfate, 9g/L of dimethylaminoborane, 66g/L of EDTA, 45mg/L of thiourea, 60mg/L of 2, 6-diaminopyridine, 0.8g/L of chitosan oligosaccharide modifier, 0.3g/L of arginine modifier, 80mg/L of octyl phenol polyoxyethylene ether, 7g/L of sodium carbonate and the balance of deionized water, wherein the pH value of the electroless copper plating solution for plastics is 12.
The chitosan oligosaccharide modifier is prepared by the following steps:
adding chitosan oligosaccharide into absolute ethyl alcohol, stirring for 35 minutes at 60 ℃ to obtain a chitosan oligosaccharide solution with the concentration of 0.5g/mL, adjusting the pH value to 6, then adding isovanillin into the chitosan oligosaccharide solution dropwise, wherein the ratio of the chitosan oligosaccharide solution to the isovanillin is 7.5mL to 1g, stirring for 4.5 hours at 75 ℃ and then standing overnight to obtain a reaction solution, filtering the reaction solution to obtain a filter cake, washing the filter cake with absolute ethyl alcohol for 3 times, and drying the filter cake to constant weight to obtain a chitosan oligosaccharide modified substance.
The arginine modifier is prepared by the following steps:
mixing L-arginine hydrochloride, sodium bicarbonate and distilled water, cooling to 5 ℃, dropwise adding methacrylic anhydride, wherein the ratio of the L-arginine hydrochloride to the sodium bicarbonate to the distilled water to the methacrylic anhydride is 1g to 0.8g to 5.5mL to 0.6mL, carrying out heat preservation and stirring for 35 minutes to obtain a mixed solution, filtering the mixed solution to obtain filter residues, washing the filter residues with dichloromethane for 3 times, and then freeze-drying the filter residues to constant weight to obtain the arginine modified substance.
The preparation method of example 1 comprises the following steps:
weighing the components according to the formula, adding copper sulfate into deionized water, stirring for 12 minutes, adding EDTA, stirring for 12 minutes, adding sodium carbonate to adjust the pH value to 12, adding other components, and stirring for 2.5 hours to obtain the electroless copper plating solution for plastics.
Example 2
The electroless copper plating solution for plastics comprises the following components: 12g/L of copper sulfate, 10g/L of dimethylaminoborane, 70g/L of EDTA, 40mg/L of thiourea, 66mg/L of 2, 6-diaminopyridine, 0.7g/L of chitosan oligosaccharide modifier, 0.2g/L of arginine modifier, 90mg/L of octylphenol polyoxyethylene ether, 5g/L of sodium carbonate and the balance of deionized water, wherein the pH value of the electroless copper plating solution for plastics is 11.5.
The chitosan oligosaccharide modifier is prepared by the following steps:
adding chitosan oligosaccharide into absolute ethyl alcohol, stirring for 40 minutes at 57 ℃ to obtain a chitosan oligosaccharide solution with the concentration of 0.5g/mL, adjusting the pH value to 6, then adding isovanillin into the chitosan oligosaccharide solution dropwise, stirring for 4.5 hours at 72 ℃ for standing overnight to obtain a reaction solution, filtering the reaction solution to obtain a filter cake, washing the filter cake with absolute ethyl alcohol for 3 times, and drying the filter cake to constant weight to obtain a chitosan oligosaccharide modified substance.
The arginine modifier is prepared by the following steps:
mixing L-arginine hydrochloride, sodium bicarbonate and distilled water, cooling to 5 ℃, dropwise adding methacrylic anhydride, wherein the ratio of the L-arginine hydrochloride to the sodium bicarbonate to the distilled water to the methacrylic anhydride is 1g to 0.7g to 5mL to 0.6mL, carrying out heat preservation and stirring for 30 minutes to obtain a mixed solution, filtering the mixed solution to obtain filter residues, washing the filter residues with dichloromethane for 3 times, and then carrying out freeze drying to constant weight to obtain the arginine modified product.
The preparation method of example 2 comprises the following steps:
weighing the components according to the formula, adding copper sulfate into deionized water, stirring for 15 minutes, adding EDTA, stirring for 15 minutes, adding sodium carbonate to adjust the pH value to 11.5, adding other components, and stirring for 3 hours to obtain the electroless copper plating solution for plastics.
Example 3
The electroless copper plating solution for plastics comprises the following components: 10g/L of copper sulfate, 8g/L of dimethylaminoborane, 60g/L of EDTA, 50mg/L of thiourea, 70mg/L of 2, 6-diaminopyridine, 0.5g/L of chitosan oligosaccharide modifier, 0.2g/L of arginine modifier, 70mg/L of octylphenol polyoxyethylene ether, 8g/L of sodium carbonate and the balance of deionized water, wherein the pH value of the electroless copper plating solution for plastics is 11.
The chitosan oligosaccharide modifier is prepared by the following steps:
adding chitosan oligosaccharide into absolute ethyl alcohol, stirring for 36 minutes at 65 ℃ to obtain a chitosan oligosaccharide solution with the concentration of 0.5g/mL, adjusting the pH value to 6, then adding isovanillin into the chitosan oligosaccharide solution dropwise, stirring for 4 hours at 80 ℃ for standing overnight to obtain a reaction solution, filtering the reaction solution to obtain a filter cake, washing the filter cake with absolute ethyl alcohol for 3 times, and drying the filter cake to constant weight to obtain a chitosan oligosaccharide modified substance.
The arginine modifier is prepared by the following steps:
mixing L-arginine hydrochloride, sodium bicarbonate and distilled water, cooling to 5 ℃, dropwise adding methacrylic anhydride, wherein the ratio of the L-arginine hydrochloride to the sodium bicarbonate to the distilled water to the methacrylic anhydride is 1g to 0.8g to 5mL to 0.6mL, carrying out heat preservation and stirring for 32 minutes to obtain a mixed solution, filtering the mixed solution to obtain filter residues, washing the filter residues with dichloromethane for 3 times, and then carrying out freeze drying to constant weight to obtain the arginine modified product.
The preparation method of example 3 comprises the following steps:
weighing the components according to the formula, adding copper sulfate into deionized water, stirring for 10 minutes, adding EDTA, stirring for 10 minutes, adding sodium carbonate to adjust the pH value to 11, adding other components, and stirring for 2 hours to obtain the electroless copper plating solution for plastics.
Example 4
The electroless copper plating solution for plastics comprises the following components: 16g/L of copper sulfate, 8.5g/L of dimethylaminoborane, 68g/L of EDTA, 42mg/L of thiourea, 50mg/L of 2, 6-diaminopyridine, 1g/L of chitosan oligosaccharide modifier, 0.4g/L of arginine modifier, 75mg/L of octylphenol polyoxyethylene ether, 6g/L of sodium carbonate and the balance of deionized water, wherein the pH value of the electroless copper plating solution for plastics is 13.
The chitosan oligosaccharide modifier is prepared by the following steps:
adding chitosan oligosaccharide into absolute ethyl alcohol, stirring for 30 minutes at 55 ℃ to obtain a chitosan oligosaccharide solution with the concentration of 0.5g/mL, adjusting the pH value to 6, then adding isovanillin into the chitosan oligosaccharide solution dropwise, stirring for 5 hours at 70 ℃ for standing overnight to obtain a reaction solution, filtering the reaction solution to obtain a filter cake, washing the filter cake with absolute ethyl alcohol for 3 times, and drying the filter cake to constant weight to obtain a chitosan oligosaccharide modified substance.
The arginine modifier is prepared by the following steps:
mixing L-arginine hydrochloride, sodium bicarbonate and distilled water, cooling to 5 ℃, dropwise adding methacrylic anhydride, wherein the ratio of the L-arginine hydrochloride to the sodium bicarbonate to the distilled water to the methacrylic anhydride is 1g to 0.9g to 6mL to 0.6mL, carrying out heat preservation and stirring for 40 minutes to obtain a mixed solution, filtering the mixed solution to obtain filter residues, washing the filter residues with dichloromethane for 3 times, and then carrying out freeze drying to constant weight to obtain the arginine modified product.
The preparation method of example 4 comprises the following steps:
weighing the components according to the formula, adding copper sulfate into deionized water, stirring for 11 minutes, adding EDTA, stirring for 11 minutes, adding sodium carbonate to adjust the pH value to 13, adding other components, and stirring for 2.5 hours to obtain the electroless copper plating solution for plastics.
Reference example 1:
the difference from example 1 is that: the components do not comprise the chitosan oligosaccharide modifier, so that the preparation step of the chitosan oligosaccharide modifier is omitted.
Reference example 2:
the difference from example 1 is that: the components do not comprise arginine modifier, so that the preparation step of arginine modifier is omitted.
Comparative example: example 1 of chinese patent application No. CN 201310191861.8.
Test example 1: copper plating layer binding force test
The substrate to be tested was an ABS plate of 4cm X2.5 cm, which was immersed in a degreasing liquid at 60℃for 10 minutes with stirring, taken out, washed, coarsened with a coarsening system at 60℃for 10 minutes, taken out, washed, immersed in an activating liquid at 65℃for 1 minute with stirring, then neutralized with a neutralizing liquid at 60℃for 30 seconds, rinsed 3 times with distilled water, immersed in an electroless copper plating liquid at 35℃for 2 hours with stirring (examples 1 to 4, reference examples 1 to 2, comparative examples), and rinsed 3 times with distilled water after the completion of the above, to obtain a substrate on which a copper plating layer was deposited.
And testing the binding force of the copper plating layer by adopting a high-low temperature impact method: the substrates obtained in examples 1 to 4, reference example 2 and comparative example were placed in hot water at 80℃for 1 hour, immediately immersed in a low-temperature water bath at 5℃for 30 seconds after being taken out, and after repeating 3 times, the presence or absence of foaming and peeling on the surface of the copper plating layer was observed, and the test results are shown in Table 1:
TABLE 1
| Example 1 | No foaming and peeling phenomenon occurs on the surface of the copper plating layer |
| Example 2 | No foaming and peeling phenomenon occurs on the surface of the copper plating layer |
| Example 3 | No foaming and peeling phenomenon occurs on the surface of the copper plating layer |
| Example 4 | No foaming and peeling phenomenon occurs on the surface of the copper plating layer |
| Reference example 2 | Foaming and peeling of the copper plating layer surface |
| Comparative example | Foaming and peeling of the copper plating layer surface |
As can be seen from Table 1, the copper plating layers of examples 1 to 4 of the present invention all showed no foaming and peeling, indicating that the copper plating layers obtained by the present invention had a good bonding force. The composition of the comparative example 2 was different from that of example 1, and the copper plating layer surface of the comparative example 2 was foamed and peeled as compared with example 1, indicating that the arginine modified product used in the present invention can improve the binding force of the copper plating layer.
Test example 2: copper plating ductility test
The copper plating layers peeled off from the substrates obtained in examples 1 to 4, reference examples 1 to 2 and comparative example in test example 1 were respectively tested with an electronic universal tester with a pulling speed of 10mm/min and a pulling force of 50N/cm, and the higher the elongation, the better the ductility, and the test results are shown in Table 2:
TABLE 2
| Elongation (%) | |
| Example 1 | 24.87 |
| Example 2 | 24.26 |
| Example 3 | 23.64 |
| Example 4 | 25.75 |
| Reference example 1 | 21.93 |
| Reference example 2 | 22.08 |
| Comparative example | 18.52 |
As can be seen from Table 2, the elongation of examples 1-4 of the present invention is significantly higher than that of the comparative example, indicating that the ductility of the copper plating obtained by using the present invention is better. The partial components of reference examples 1-2 are different from those of example 1, and the elongation of each of reference example 1 and reference example 2 is reduced as compared with example 1, indicating that both the chitosan modified material and the arginine modified material used in the present invention can improve the ductility of the copper plating layer.
Test example 3: copper plating porosity test
The test substrate was an iron piece of 10cm×5cm, the substrate was immersed in a degreasing liquid at 60 ℃ for stirring treatment for 10 minutes, taken out, washed, immersed in an activating liquid at 65 ℃ for stirring treatment for 1 minute, then neutralized with a neutralizing liquid at 60 ℃ for 30 seconds, rinsed 3 times with distilled water, immersed in an electroless copper plating liquid at 35 ℃ for 2 hours under stirring, and rinsed 3 times with distilled water to obtain a substrate on which a copper plating layer was deposited.
The porosity of the copper plating layer is tested by adopting a filter paper pasting method, the test solution is 10g/L of potassium ferricyanide and 20g/L of sodium chloride, the filter paper is tightly pasted on the surface of the copper plating layer on the substrate obtained in examples 1-4, reference example 1 and comparative example after being soaked in the test solution, the filter paper is removed after 20 minutes, and is washed clean by distilled water and then dried, the number of blue spots on the filter paper is recorded, and the porosity is calculated:
porosity = number of blue spots/copper plating area (in/cm 2 )
The test results are shown in table 3:
TABLE 3 Table 3
| Porosity (units/cm) 2 ) | |
| Example 1 | 2 |
| Example 2 | 3 |
| Example 3 | 4 |
| Example 4 | 2 |
| Reference example 1 | 8 |
| Comparative example | 17 |
As can be seen from Table 3, the porosity of each of examples 1-4 of the present invention is significantly lower than that of the comparative example, indicating that the copper plating obtained using the present invention is lower in porosity. The partial composition of reference example 1 is different from that of example 1, and the porosity of reference example 1 is increased compared with that of example 1, indicating that the chitosan oligosaccharide modified material used in the present invention can reduce the porosity of the copper plating layer.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (5)
1. An electroless copper plating solution for plastics is characterized in that: the composition comprises the following components: 10-16 g/L of copper sulfate, 8-10 g/L of dimethylamino borane, 60-70 g/L of complexing agent, 40-50 mg/L of stabilizer, 50-70 mg/L of accelerator, 0.5-1 g/L of chitosan oligosaccharide modifier, 0.2-0.4 g/L of arginine modifier, 70-90 mg/L of surfactant, 5-8 g/L of sodium carbonate and the balance of deionized water, wherein the pH value of the electroless copper plating solution for plastics is 11-13; the complexing agent is EDTA; the stabilizer is thiourea; the accelerator is 2, 6-diaminopyridine;
the chitosan oligosaccharide modifier is prepared by the following steps:
adding chitosan oligosaccharide into absolute ethyl alcohol, stirring for 30-40 minutes at 55-65 ℃ to obtain chitosan oligosaccharide solution, adjusting the pH value to 6, then adding isovanillin into the chitosan oligosaccharide solution dropwise, stirring for 4-5 hours at 70-80 ℃ and standing overnight to obtain reaction solution, carrying out suction filtration on the reaction solution to obtain a filter cake, washing the filter cake with absolute ethyl alcohol for 3 times, and drying the filter cake to constant weight to obtain a chitosan oligosaccharide modified substance;
the arginine modifier is prepared by the following steps:
mixing L-arginine hydrochloride, sodium bicarbonate and distilled water, cooling to 5 ℃, dropwise adding methacrylic anhydride, maintaining the temperature and stirring for 30-40 minutes to obtain a mixed solution, filtering the mixed solution to obtain filter residues, washing the filter residues with dichloromethane for 3 times, and freeze-drying the filter residues to constant weight to obtain the arginine modified substance.
2. An electroless copper plating solution for plastic according to claim 1, wherein: in the preparation step of the chitosan oligosaccharide modifier, the concentration of the chitosan oligosaccharide solution is 0.5g/mL, and the ratio of the chitosan oligosaccharide solution to the isovanillin is (7-8) mL to 1g.
3. An electroless copper plating solution for plastic according to claim 1, wherein: in the preparation step of the arginine modifier, the proportion of L-arginine hydrochloride, sodium bicarbonate, distilled water and methacrylic anhydride is 1g (0.7-0.9 g) (5-6 mL) and 0.6mL.
4. An electroless copper plating solution for plastic according to claim 1, wherein: the surfactant is octyl phenol polyoxyethylene ether.
5. The method for producing an electroless copper plating solution for plastic according to any one of claims 1 to 4, characterized in that: the method comprises the following steps:
weighing the components according to the formula, adding copper sulfate into deionized water, stirring for 10-15 minutes, adding a complexing agent, stirring for 10-15 minutes, adding sodium carbonate to adjust the pH value to 11-13, adding other components, and stirring for 2-3 hours to obtain the electroless copper plating solution for plastics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110846684.7A CN113684473B (en) | 2021-07-26 | 2021-07-26 | Electroless copper plating solution for plastics and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110846684.7A CN113684473B (en) | 2021-07-26 | 2021-07-26 | Electroless copper plating solution for plastics and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113684473A CN113684473A (en) | 2021-11-23 |
| CN113684473B true CN113684473B (en) | 2023-04-25 |
Family
ID=78577915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110846684.7A Active CN113684473B (en) | 2021-07-26 | 2021-07-26 | Electroless copper plating solution for plastics and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113684473B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113089044B (en) * | 2021-04-07 | 2022-07-12 | 广东宇豪新材料科技有限公司 | Plastic shell metallization plating method, wear-resistant plastic |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103422078A (en) * | 2012-05-22 | 2013-12-04 | 比亚迪股份有限公司 | Chemical copper plating solution and preparation method thereof |
| CN103805971A (en) * | 2014-03-11 | 2014-05-21 | 东华大学 | Method for activating electroless copper-plated textile with nickel salt |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04176460A (en) * | 1990-11-13 | 1992-06-24 | Tomoji Tanaka | Paper cloth product for prevention of excessive rubbing on bed |
| JP2001187801A (en) * | 1999-12-28 | 2001-07-10 | Daishin Kagaku Kk | N-alkylchitosan derivative and its production method |
| WO2007066460A1 (en) * | 2005-12-06 | 2007-06-14 | Ebara-Udylite Co., Ltd. | Palladium complex and catalyst-imparting treatment solution using the same |
| JP5864161B2 (en) * | 2011-08-23 | 2016-02-17 | 石原ケミカル株式会社 | Copper filling method and electronic component manufacturing method using the method |
| JP6145681B2 (en) * | 2014-02-07 | 2017-06-14 | 石原ケミカル株式会社 | Aqueous copper colloid catalyst solution for electroless copper plating and electroless copper plating method |
| JP6209770B2 (en) * | 2015-02-19 | 2017-10-11 | 石原ケミカル株式会社 | Copper colloid catalyst solution for electroless copper plating and electroless copper plating method |
| CN104975311A (en) * | 2015-07-01 | 2015-10-14 | 张志梁 | Copper plating liquid and process for direct cyanide-free acid copper plating on steel substrate |
| CN108203484B (en) * | 2016-12-20 | 2022-03-01 | 罗门哈斯公司 | Latex functionalized with arginine-functionalized monomer building blocks |
| JP6343787B1 (en) * | 2017-06-01 | 2018-06-20 | 石原ケミカル株式会社 | Copper colloid catalyst solution for electroless copper plating and electroless copper plating method |
| CN107446523B (en) * | 2017-08-30 | 2018-08-21 | 阜南盛原木业有限公司 | A kind of glued board adhesive |
| CN107881539A (en) * | 2017-11-28 | 2018-04-06 | 江苏澳光电子有限公司 | A kind of rhotanium electroplate liquid and its application |
| CN110129839B (en) * | 2019-05-20 | 2021-05-14 | 江西鹏凯环保工程设备有限公司 | Preparation method of copper plating brightener |
| CN112618785B (en) * | 2020-12-15 | 2022-07-01 | 广东省微生物研究所（广东省微生物分析检测中心） | Porous antibacterial hydrogel dressing and preparation method thereof |
-
2021
- 2021-07-26 CN CN202110846684.7A patent/CN113684473B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103422078A (en) * | 2012-05-22 | 2013-12-04 | 比亚迪股份有限公司 | Chemical copper plating solution and preparation method thereof |
| CN103805971A (en) * | 2014-03-11 | 2014-05-21 | 东华大学 | Method for activating electroless copper-plated textile with nickel salt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113684473A (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3584352B1 (en) | Electroless plating method | |
| CN101298688B (en) | Tin or Tin Alloy Plating Solutions | |
| CN111962051B (en) | Chemical copper plating solution for heterojunction solar battery and preparation method thereof | |
| TW201127987A (en) | Pretreatment solution for non-electrolytic plating | |
| KR102474143B1 (en) | Method for forming metal film on polyimide resin | |
| TW201006966A (en) | Electrolytic tin plating solution and electrolytic tin plating method | |
| CN113684473B (en) | Electroless copper plating solution for plastics and preparation method thereof | |
| CN115558963A (en) | Tin electroplating process for electronic element | |
| EP3070185B1 (en) | Conductive film-forming bath | |
| JP3052515B2 (en) | Electroless copper plating bath and plating method | |
| JP7360155B2 (en) | Electroless nickel plating film and pretreatment method for forming the electroless nickel plating film | |
| RU2398049C2 (en) | Improved stabilisation and working characteristics of auto-catalyst procedures of coating application by method of chemical reduction | |
| JP3071286B2 (en) | Pretreatment agent for electroless plating of aluminum base material and electroless plating method thereof | |
| US4309462A (en) | Conditioning of caprolactam polymers for electroless plating | |
| CN101107388B (en) | Method for producing plated resin formed article | |
| CN118480772B (en) | Low-stress additive, low-stress chemical nickel plating liquid medicine and application thereof | |
| US20180179634A1 (en) | Method for electroless plating | |
| CN121344696A (en) | A cyanide-free cadmium plating bath solution, its preparation method and its application in cadmium plating. | |
| US12584225B1 (en) | Resin material treatment method, and compositions for the same | |
| EP3339472A2 (en) | Electroless plating method | |
| CN119061388B (en) | A high-stability chemical copper plating solution and preparation method thereof | |
| CN119615135B (en) | Electroless copper plating additive, electroless copper plating solution and electroless copper plating method for IC carrier plate | |
| JP7138880B1 (en) | Electroless plating method | |
| CN101107121A (en) | Method for metallizing polymeric foams to produce antimicrobial and filter materials | |
| KR101770687B1 (en) | The surface treatment agent for communication-connector and mobile communication-connector and Surface treatment method of connector using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |