CN105734539A - Method for chemically plating various kinds of patterned metal onto plastic surface repeatedly - Google Patents
Method for chemically plating various kinds of patterned metal onto plastic surface repeatedly Download PDFInfo
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- CN105734539A CN105734539A CN201410753153.3A CN201410753153A CN105734539A CN 105734539 A CN105734539 A CN 105734539A CN 201410753153 A CN201410753153 A CN 201410753153A CN 105734539 A CN105734539 A CN 105734539A
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Abstract
The invention discloses a method for chemically plating various kinds of patterned metal onto a plastic surface repeatedly. The method for chemically plating various kinds of patterned metal onto the plastic surface repeatedly comprises the steps that firstly, initiator monomer containing bromine is synthesized, a small amount of initiator monomer is added into vinyl benzene or methyl methacrylate, and plastic modified through an initiator is obtained through a traditional continuous body polymerization technique; secondly, treatment is conducted through a plasma surface cleaner, so that the plastic surface is deactivated; thirdly, pattern processing is conducted on the plastic surface through a mechanical micromachining technique, so that patterned grooves are formed; and fourthly, the metalized patterns consistent with mechanical micromachining are obtained through chemical plating. According to the plastic prepared through the method, various kinds of metal can be repeatedly deposited on the plastic through polishing and grinding methods. By the adoption of the method, the surface metallization techniques for plastic are enriched, and the method is expected to have important application value in the fields such as the printed circuit board field, the electric component field and the optical instrument field.
Description
Technical field
The invention discloses a kind of method that can repeatedly repeat chemical plating multiple patterns metal at frosting.
Background technology
There is the feature such as non-flanged effect specific to good ductility, heat conductivity and electric conductivity and chemical plating due to chemical deposit, in recent decades, this technique is continuously available development in practice, it is widely used in the surface treatment (Electrolessplating:fundamentalsandapplications [M] .WilliamAndrew, 1990) of printed circuit board (PCB), household electrical appliance and ceramic component.Research worker develops various technology for expanding electroless plating technology, such as (AdvancedMaterials, 2013,25 (24): 3343-3350) such as micro-contact printing, nano impression, intaglio printing, silk screen printing, inkjet printings.
The thermoplastic being representative with polystyrene, has good machinability, with low cost, is widely used in optics industry due to its good light transmission again, and polystyrene also can make many electric components worked in high frequency environment and instrument etc..Metallization can give the physical property that frosting has institute's plating, and therefore the metallization of plastics is widely used in the fields such as electronic device, aircraft industry, building decoration.The method of metallization of plastic surface is divided into dry and wet two kinds.Dry method mainly includes vacuum evaporation, gas phase spraying, coated conductive layer etc.；Wet method mainly includes liquid phase spraying and chemical plating etc..With other metallization process the difference is that, chemical plating surface metal metallization processes can carry out at low temperatures, it is to avoid high-temperature operation, not easily makes plastic deformation, and equipment is simple, lower cost.
Summary of the invention
It is desirable to provide a kind of method that can repeatedly repeat chemical plating multiple patterns metal at frosting, the best advantage is that and remove original coating by frosting of polishing, can chemical gilding metal patterns over and over again.
First the present invention has synthesized a kind of brominated initiator monomer, adds this monomer a small amount of, utilizes traditional technique of continuous bulk polymerization, obtain the plastics modifiied through initiator in styrene or methyl methacrylate.Processing with plasma surface washer makes surface deactivate again.Utilize mechanical microfabrication techniques, frosting is carried out pattern processing, define the patterned groove that precision is 1～50 μm.The metallization pattern consistent with machinery micro Process is obtained followed by chemical plating.Utilize plastics prepared by the method can pass through the method repeatedly repeated deposition various metals of polishing, polishing.
A kind of method that can repeatedly repeat chemical plating multiple patterns metal at frosting, it is characterised in that the method includes following step:
A, load propenyl or propenyl derivant and triethylamine in the reactor, 2-bromo isobutyl acylbromide and dichloromethane is added in reactor, at room temperature react, reaction is filtered after terminating, repeatedly clean with hydrochloric acid, saturated sodium carbonate, saturated aqueous common salt respectively again, obtain the light yellow oily liquids having fragranced, separate with silicagel column and obtain brominated initiator monomer；In plastic monomer, add this brominated initiator monomer, by polyreaction, obtain through modified plastics；
B, the plastics of step A gained are put into plasma surface washer processing, make surfaces nonreactive, recycling mechanical microfabrication techniques carries out pattern processing at frosting；
C, in the reactor addition MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and solvent, add 2,2-bipyridyls and cuprous bromide, and the plastics that will be patterned under argon shield are put in reactor；
D, the plastics of step C gained are put in tetrachloro-palladium acid ammonium salt solution and stand, be subsequently placed in the chemical plating solution of metal ion, obtain and the machinery consistent metal pattern of micro Process in step B；
E, the metal pattern plastics process polishing obtained by above-mentioned steps, described in B～D, step repeatedly repeats chemical plating different metal again.
In step, brominated initiator monomer has below formula:
In formula, the numerical value of n is 1～6.
In step, plastic monomer is selected from styrene or methyl methacrylate.
In step, polyreaction refers under 50～90 DEG C of conditions first pre-polymerization 1～5 hour in the reactor, subsequently by the performed polymer of clear viscous continuous bulk polymerization 1～6 hour under 100～200 DEG C of conditions.
In stepb, the time processed with plasma surface washer is 1～10 minute.
In step C, reaction temperature is 30～60 DEG C, and the response time is 1～12 hour.
In step C, reaction dissolvent is first alcohol and water.
In step D, the concentration of tetrachloro-palladium acid ammonium salt solution is 1～5mmol/L.
In step D, metal ion chemistry plating liquor is selected from the chemical plating solution containing gold, silver, copper or nickel.
In step E, the metal pattern plastics obtained by above-mentioned steps can pass through repeatedly repeated deposition various metals pattern of polishing.
Advantages of the present invention:
(1) utilizing mechanical microfabrication techniques in the present invention, can prepare the metallization pattern that precision is high, and adopted electroless plating technology is simple to operate, it is not necessary to copper clad laminate, and not produce a large amount of etching waste liquor, preparation cost is low.
(2) in the present invention, the plastics of preparation can repeatedly repeat to carry out chemical plating on surface, makes plastics traditional " disposable " use and becomes " muptiple-use " use, it is possible to prepares the surface metalation plastics of different performance.
The present invention is by being modified conventional plastic, in conjunction with chemical plating and mechanical microfabrication techniques, it is achieved that at the metal pattern of frosting, and can the various metal of chemical plating over and over again by frosting of polishing.The present invention enriches the surface metal metallization processes of plastics, is expected to obtain important application in fields such as printed circuit board (PCB), electric components, optical instruments.
Detailed description of the invention
In order to be better understood from the present invention, it is illustrated with the following examples:
Embodiment 1:
The copper of frosting chemical plating patterning
A, the triethylamine of the propenyl of 24.4mL and 87.7mL is loaded round-bottomed flask, drip 2-bromo isobutyl acylbromide and the 100mL dichloromethane mixed liquor of 29.6mL with Dropping funnel, at room temperature react.Reaction is filtered after terminating, more repeatedly cleans with hydrochloric acid, saturated sodium carbonate, saturated aqueous common salt respectively, obtains the light yellow oily liquids having fragranced, separates with silicagel column and obtains brominated initiator monomer.Brominated initiator monomer is joined in styrene according to the ratio of 1%, adds a small amount of azodiisobutyronitrile initiator as continuous bulk polymerization, stir.First pre-polymerization 1 hour at 90 DEG C, builds in a mold by the performed polymer of clear viscous subsequently, and continuous bulk polymerization 6 hours under 200 DEG C of conditions obtain through modified polystyrene transparent plastic；
B, the plastics of step A gained are put into plasma surface washer processing 1 minute, make surfaces nonreactive, recycling mechanical microfabrication techniques carries out pattern processing at frosting；
C, in the reactor addition 4.6g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 2, the 2-bipyridyls of 240mg, 60mg cuprous bromide, 4mL deionized water, 2mL methanol, stir under argon shield.In reactor, add the plastics in B, react 2 hours at 30 DEG C.Obtain having modified the plastics of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride thin film；
D, above-mentioned plastics are placed in tetrachloro-palladium acid ammonium salt solution stand 15 minutes.The concentration of tetrachloro-palladium acid ammonium salt solution is 1mmol/L；It is subsequently placed in chemical bronze plating liquid, obtains deposited on surface a layer thickness and be 5 μm and there are the plastics of patterned copper coating described in B.Chemical bronze plating liquid used presses bibliographical information configuration (Electrolessplating:fundamentalsandapplications [M] .WilliamAndrew, 1990).
Embodiment 2:
The gold of frosting chemical plating patterning
A, brominated initiator synthesis with described in embodiment 1.Brominated initiator monomer is joined in methyl methacrylate according to the ratio of 5%, adds a small amount of azodiisobutyronitrile initiator as continuous bulk polymerization, stir.First pre-polymerization 5 hours at 50 DEG C, build in a mold by the performed polymer of clear viscous subsequently, and continuous bulk polymerization 1 hour under 100 DEG C of conditions obtains through modified polymethyl methacrylate transparent plastic；
B, the plastics of step A gained are put into plasma surface washer processing 10 minutes, make surfaces nonreactive, recycling mechanical microfabrication techniques carries out pattern processing at frosting；
C, in the reactor addition 8.9g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 2, the 2-bipyridyls of 220mg, 39mg cuprous bromide, 8mL deionized water, 4mL methanol, stir under argon shield.In reactor, add the plastics in B, react 12 hours at 60 DEG C.Obtain having modified the plastics of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride thin film；
D, above-mentioned plastics are placed in tetrachloro-palladium acid ammonium salt solution stand 60 minutes.The concentration of tetrachloro-palladium acid ammonium salt solution is 5mmol/L；It is subsequently placed in chemical bronze plating liquid several seconds, deposited, on the surface of patterning, the copper that a layer thickness is very thin, be then placed in chemical gold plating liquid.Obtain deposited a layer thickness on surface to be 4 μm and there are the plastics of patterned gold coating described in B.Chemical gold plating liquid used presses bibliographical information configuration (Electrolessplating:fundamentalsandapplications [M] .WilliamAndrew, 1990).
Embodiment 3:
The silver of frosting chemical plating patterning and nickel
A, brominated initiator synthesis with described in embodiment 1.Brominated initiator monomer is joined in styrene according to the ratio of 15%, adds a small amount of azodiisobutyronitrile initiator as continuous bulk polymerization, stir.First pre-polymerization 2 hours at 70 DEG C, build in a mold by the performed polymer of clear viscous subsequently, and continuous bulk polymerization 4 hours under 150 DEG C of conditions obtain through modified polystyrene transparent plastic；
B, the plastics of step A gained are put into plasma surface washer processing 5 minutes, make surfaces nonreactive, recycling mechanical microfabrication techniques carries out pattern processing at frosting；
C, in the reactor addition 12.4g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 2, the 2-bipyridyls of 189mg, 72mg cuprous bromide, 16mL deionized water, 8mL methanol, stir under argon shield.In reactor, add the plastics in B, react 6 hours at 50 DEG C.Obtain having modified the plastics of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride thin film；
D, above-mentioned plastics are placed in tetrachloro-palladium acid ammonium salt solution stand 30 minutes.The concentration of tetrachloro-palladium acid ammonium salt solution is 3mmol/L；It is subsequently placed in chemical nickel-plating liquid, obtains deposited on surface a layer thickness and be 9 μm and there are described in B to pattern the plastics of nickel coating.Chemical nickel-plating liquid used presses bibliographical information configuration (Electrolessplating:fundamentalsandapplications [M] .WilliamAndrew, 1990).
E, the nickel patterning plastics step described in B～C again obtained by above-mentioned steps are processed, then are placed in tetrachloro-palladium acid ammonium salt solution and stand 60 minutes.The concentration of tetrachloro-palladium acid ammonium salt solution is 3mmol/L；It is subsequently placed in chemical plating liquid, obtains that there are on surface the plastics patterning nickel coating and silvering described in B simultaneously.Chemical plating liquid used presses bibliographical information configuration (Electrolessplating:fundamentalsandapplications [M] .WilliamAndrew, 1990).
Claims (10)
1. the method that can repeatedly repeat chemical plating multiple patterns metal at frosting, it is characterised in that the method includes following step:
A, load propenyl or propenyl derivant and triethylamine in the reactor, 2-bromo isobutyl acylbromide and dichloromethane is added in reactor, at room temperature react, reaction is filtered after terminating, repeatedly clean with hydrochloric acid, saturated sodium carbonate, saturated aqueous common salt respectively again, obtain the light yellow oily liquids having fragranced, separate with silicagel column and obtain brominated initiator monomer；In plastic monomer, add this brominated initiator monomer, by polyreaction, obtain through modified plastics；
B, the plastics of step A gained are put into plasma surface washer processing, make surfaces nonreactive, recycling mechanical microfabrication techniques carries out pattern processing at frosting；
C, in the reactor addition MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and solvent, add 2,2-bipyridyls and cuprous bromide, and the plastics that will be patterned under argon shield are put in reactor；
D, the plastics of step C gained are put in tetrachloro-palladium acid ammonium salt solution and stand, be subsequently placed in the chemical plating solution of metal ion, obtain and the machinery consistent metal pattern of micro Process in step B；
E, the metal pattern plastics process polishing obtained by above-mentioned steps, described in B～D, step repeatedly repeats chemical plating different metal again.
2. the method for claim 1, it is characterised in that in step A, brominated initiator monomer has below formula:
In formula, the numerical value of n is 1～6.
3. the method for claim 1, it is characterised in that in step A, plastic monomer is selected from styrene or methyl methacrylate.
4. the method for claim 1, it is characterised in that in step A, polyreaction refers under 50～90 DEG C of conditions first pre-polymerization 1～5 hour in the reactor, subsequently by the performed polymer of clear viscous continuous bulk polymerization 1～6 hour under 100～200 DEG C of conditions.
5. the method for claim 1, it is characterised in that in step B, the time processed with plasma surface washer is 1～10 minute.
6. the method for claim 1, it is characterised in that in step C, reaction temperature is 30～60 DEG C, and the response time is 1～12 hour.
7. the method for claim 1, it is characterised in that in step C, reaction dissolvent is first alcohol and water.
8. the method for claim 1, it is characterised in that in step D, the concentration of tetrachloro-palladium acid ammonium salt solution is 1～5mmol/L.
9. the method for claim 1, it is characterised in that in step D, metal ion chemistry plating liquor is selected from the chemical plating solution containing gold, silver, copper or nickel.
10. method as claimed in claim 1, it is characterised in that in step E, the metal pattern plastics obtained by above-mentioned steps pass through repeatedly repeated deposition various metals pattern of polishing.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112501535A (en) * | 2020-12-15 | 2021-03-16 | 安徽恒茂宜高电镀科技有限公司 | Method and device for enhancing binding force of new energy automobile plastic accessory coating |
| CN113981421A (en) * | 2021-07-09 | 2022-01-28 | 西安电子科技大学 | Method for preparing erasable metal electrode on plastic surface |
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| CN1324412A (en) * | 1998-10-02 | 2001-11-28 | Nkt研究中心有限公司 | Method for metallizing surface of a solid polymer substrate and the product obtd. |
| CN102030482A (en) * | 2010-10-13 | 2011-04-27 | 中国科学院化学研究所 | Method for preparing nanometer patterning bipolymer brush |
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| CN1324412A (en) * | 1998-10-02 | 2001-11-28 | Nkt研究中心有限公司 | Method for metallizing surface of a solid polymer substrate and the product obtd. |
| CN102030482A (en) * | 2010-10-13 | 2011-04-27 | 中国科学院化学研究所 | Method for preparing nanometer patterning bipolymer brush |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112501535A (en) * | 2020-12-15 | 2021-03-16 | 安徽恒茂宜高电镀科技有限公司 | Method and device for enhancing binding force of new energy automobile plastic accessory coating |
| CN112501535B (en) * | 2020-12-15 | 2023-01-13 | 安徽恒茂宜高电镀科技有限公司 | Method and device for enhancing binding force of new energy automobile plastic accessory coating |
| CN113981421A (en) * | 2021-07-09 | 2022-01-28 | 西安电子科技大学 | Method for preparing erasable metal electrode on plastic surface |
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Effective date of registration: 20220413 Address after: 264006 5, R & D building, Yeda Science Park, No. 300, Changjiang Road, Yantai Economic and Technological Development Zone, Shandong Province Patentee after: Yantai Zhongke advanced materials and green chemical industry technology Research Institute Address before: 730000 No. 18 Tianshui Middle Road, Chengguan District, Gansu, Lanzhou Patentee before: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences |
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