CN105734539B - In the method that chemical plating multiple patterns metal can be repeated several times in frosting - Google Patents
In the method that chemical plating multiple patterns metal can be repeated several times in frosting Download PDFInfo
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- CN105734539B CN105734539B CN201410753153.3A CN201410753153A CN105734539B CN 105734539 B CN105734539 B CN 105734539B CN 201410753153 A CN201410753153 A CN 201410753153A CN 105734539 B CN105734539 B CN 105734539B
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Abstract
The invention discloses a kind of method that chemical plating multiple patterns metal can be repeated several times in frosting.The present invention has synthesized a kind of brominated initiator monomer first, and a small amount of monomer is added in styrene or methyl methacrylate, using traditional technique of continuous bulk polymerization, has obtained the plastics being modified by initiator.Being handled again with plasma surface washer makes surface deactivate.Using mechanical microfabrication techniques, pattern processing is carried out to frosting, forms patterned groove.The metallization pattern consistent with mechanical micro Process has been obtained followed by chemical plating.The plastics prepared using this method can pass through polishing, deposition various metals are repeated several times in the method for polishing.This method enriches the surface metalation technique of plastics, is expected to obtain important application in fields such as printed circuit board (PCB), electric components, optical instruments.
Description
Technical field
The invention discloses a kind of method that chemical plating multiple patterns metal can be repeated several times in frosting.
Background technology
Because there is chemical deposit non-flanged specific to good ductility, thermal conductivity and electric conductivity and chemical plating to imitate
The features such as answering, in recent decades, this technique are continuously available development in practice, have been widely used in printed circuit board (PCB), family
The surface treatment of electrical appliance and ceramic component（Electroless plating: fundamentals and
applications[M]. William Andrew, 1990）.Researcher develops various technologies and is used to expand chemical plating skill
Art, such as micro-contact printing, nano impression, intaglio printing, silk-screen printing, inkjet printing（Advanced Materials,
2013, 25(24): 3343-3350）.
Thermoplastic using polystyrene as representative, it is cheap with good machinability, cost, and because it is good
Translucency and be widely used in optics industry, polystyrene can also make many electric members to be worked in high frequency environment
Device and instrument etc..Metallization, which can assign frosting, has the physical property for plating metal, therefore the metallization of plastics is wide
It is general to be applied to the fields such as electronic device, aircraft industry, building decoration.The method of metallization of plastic surface is divided into dry and wet two
Kind.Dry method mainly includes vacuum evaporation, gas phase spraying, coated conductive layer etc.；Wet method mainly includes liquid phase spraying and chemical plating etc..
Unlike other metallization process, chemical plating surface metalation technique can be carried out at low temperature, avoid high-temperature operation, no
Easily make plastic deformation, and equipment is simple, lower cost.
The content of the invention
The present invention is intended to provide a kind of method that chemical plating multiple patterns metal can be repeated several times in frosting, this hair
Bright maximum advantage is to remove original coating by frosting of polishing, can chemical gilding metal patterns over and over again.
The present invention has synthesized a kind of brominated initiator monomer first, is added in styrene or methyl methacrylate a small amount of
The monomer, using traditional technique of continuous bulk polymerization, the plastics being modified by initiator are obtained.It is clear with plasma surface again
Washing device processing makes surface deactivate.Using mechanical microfabrication techniques, pattern processing is carried out to frosting, forms precision as 1
~50 μm of patterned groove.The metallization pattern consistent with mechanical micro Process has been obtained followed by chemical plating.Utilize the party
Plastics prepared by method can pass through polishing, deposition various metals are repeated several times in the method for polishing.
A kind of method that chemical plating multiple patterns metal can be repeated several times in frosting, it is characterised in that this method bag
Include following steps：
A, load propenyl or propylene 01 derivatives and triethylamine in the reactor, 2- bromo isobutyls are added into reactor
Acylbromide and dichloromethane, are reacted at room temperature, and reaction is filtered after terminating, then are eaten respectively with hydrochloric acid, saturated sodium carbonate, saturation
Salt solution cleans repeatedly, obtains the light yellow oily liquids for having fragranced, with the isolated brominated initiator monomer of silicagel column；To modeling
The brominated initiator monomer is added in material list body, by polymerisation, is obtained by modified plastics；
B, the plastics obtained by step A are put into the processing of plasma surface washer, make surfaces nonreactive, recycle machinery micro-
Process technology carries out pattern processing in frosting；
C, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and solvent are added in the reactor, add 2,2- connection pyrroles
Pyridine and cuprous bromide, the plastics that will be patterned under argon gas protection are put into reactor；
D, the plastics obtained by step C are put into tetrachloro-palladium acid ammonium salt solution and stood, be subsequently placed in the chemical plating of metal ion
In solution, the metal pattern consistent with mechanical micro Process in step B is obtained；
E, repeatedly weighed according to step described in B~D again by polishing by the metal pattern plastics that above-mentioned steps obtain
Multiple chemical plating different metal.
In step, brominated initiator monomer has below formula：
N numerical value is 1~6 in formula.
In step, plastic monomer is selected from styrene or methyl methacrylate.
In step, polymerisation refers under the conditions of 50~90 DEG C first pre-polymerization 1~5 hour in the reactor, then will
The performed polymer of clear viscous continuous bulk polymerization 1~6 hour under the conditions of 100~200 DEG C.
In stepb, the time handled with plasma surface washer is 1~10 minute.
In step C, reaction temperature is 30~60 DEG C, and the reaction 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 1~5 mmol/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 be more by polishing multiplicating deposition
Kind metal pattern.
Advantages of the present invention：
（1）Mechanical microfabrication techniques are utilized in the present invention, the high metallization pattern of precision, and use can be prepared
It is simple to operate to learn coating technology, without copper clad laminate, and does not produce a large amount of etching waste liquors, it is low to prepare cost.
（2）The plastics prepared in the present invention can be repeated several times carries out chemical plating on surface, makes plastics traditional " one
Secondary property " use is changed into " muptiple-use " the surface metalation plastics for using, can preparing different performance.
The present invention, with reference to chemical plating and mechanical microfabrication techniques, is realized in plastics by being modified to conventional plastic
The metal pattern on surface, and can various metals of chemical plating over and over again by frosting of polishing.The present invention is abundant
The surface metalation technique of plastics, be expected to obtain in fields such as printed circuit board (PCB), electric components, optical instruments it is important should
With.
Embodiment
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, 24.4mL propenyl and 87.7mL triethylamine are loaded into round-bottomed flask, is added dropwise 29.6mL's with dropping funel
2- bromo isobutyl acylbromides and 100mL dichloromethane mixed liquors, react at room temperature.Reaction is filtered after terminating, then is used respectively
Hydrochloric acid, saturated sodium carbonate, saturated aqueous common salt clean repeatedly, obtain the light yellow oily liquids for having fragranced, with silica gel post separation
Obtain brominated initiator monomer.Brominated initiator monomer is added in styrene according to 1% ratio, adds a small amount of azo
Initiator of the bis-isobutyronitrile as continuous bulk polymerization, is stirred.First pre-polymerization 1 hour at 90 DEG C, then will be transparent
Sticky performed polymer pours in a mold, continuous bulk polymerization 6 hours under the conditions of 200 DEG C, obtains by modified polyphenyl second
Alkene transparent plastic；
B, the plastics obtained by step A are put into plasma surface washer to handle 1 minute, make surfaces nonreactive, recycled
Mechanical microfabrication techniques carry out pattern processing in frosting；
C, add in the reactor 4.6g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 240mg 2,2- bipyridyls,
60mg cuprous bromides, 4mL deionized waters, 2mL methanol, stirred under argon gas protection.Added into reactor in B
Plastics, reacted 2 hours at 30 DEG C.The plastics of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride film are modified；
D, above-mentioned plastics are placed in tetrachloro-palladium acid ammonium salt solution and stand 15 minutes.The concentration of tetrachloro-palladium acid ammonium salt solution is 1
mmol/L；It is subsequently placed in chemical bronze plating liquid, obtains deposited a layer thickness on surface for 5 μm and with pattern described in B
Change the plastics of copper coating.Chemical bronze plating liquid used is configured by document report（Electroless plating: fundamentals
and applications[M]. William Andrew, 1990）.
Embodiment 2：
The gold of frosting chemical plating patterning
A, the synthesis of brominated initiator is the same as described in embodiment 1.Brominated initiator monomer is added to according to 5% ratio
In methyl methacrylate, initiator of a small amount of azodiisobutyronitrile as continuous bulk polymerization is added, is stirred.
First pre-polymerization 5 hours at 50 DEG C, then pour the performed polymer of clear viscous in a mold, the continuous bulk under the conditions of 100 DEG C
Polymerization 1 hour, is obtained by modified polymethyl methacrylate transparent plastic；
B, the plastics obtained by step A are put into plasma surface washer to handle 10 minutes, make surfaces nonreactive, recycled
Mechanical microfabrication techniques carry out pattern processing in frosting；
C, add in the reactor 8.9g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 220mg 2,2- bipyridyls,
39mg cuprous bromides, 8mL deionized waters, 4mL methanol, stirred under argon gas protection.Added into reactor in B
Plastics, reacted 12 hours at 60 DEG C.The plastics of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride film are modified；
D, above-mentioned plastics are placed in tetrachloro-palladium acid ammonium salt solution and stand 60 minutes.The concentration of tetrachloro-palladium acid ammonium salt solution is 5
mmol/L；It is subsequently placed in chemical bronze plating liquid several seconds, the very thin copper of a layer thickness is deposited on the surface of patterning, is then put
In chemical gold plating liquid.Obtain deposited a layer thickness on surface for 4 μm and with the modeling of patterned gold coating described in B
Material.Chemical gold plating liquid used is configured by document report（Electroless plating: fundamentals and
applications[M]. William Andrew, 1990）.
Embodiment 3：
The silver and nickel of frosting chemical plating patterning
A, the synthesis of brominated initiator is the same as described in embodiment 1.Brominated initiator monomer is added to according to 15% ratio
In styrene, initiator of a small amount of azodiisobutyronitrile as continuous bulk polymerization is added, is stirred.First at 70 DEG C
Lower pre-polymerization 2 hours, then the performed polymer of clear viscous is poured in a mold, continuous bulk polymerization 4 is small under the conditions of 150 DEG C
When, obtain by modified polystyrene transparent plastic；
B, the plastics obtained by step A are put into plasma surface washer to handle 5 minutes, make surfaces nonreactive, recycled
Mechanical microfabrication techniques carry out pattern processing in frosting；
C, add in the reactor 12.4g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 189mg 2,2- bipyridyls,
72mg cuprous bromides, 16mL deionized waters, 8mL methanol, stirred under argon gas protection.Added into reactor in B
Plastics, reacted 6 hours at 50 DEG C.The plastics of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride film are modified；
D, above-mentioned plastics are placed in tetrachloro-palladium acid ammonium salt solution and stand 30 minutes.The concentration of tetrachloro-palladium acid ammonium salt solution is 3
mmol/L；It is subsequently placed in chemical nickel-plating liquid, obtains deposited a layer thickness on surface for 9 μm and with pattern described in B
Change the plastics of nickel coating.Chemical nickel-plating liquid used is configured by document report（Electroless plating: fundamentals
and applications[M]. William Andrew, 1990）.
E, the nickel patterning plastics obtained by above-mentioned steps are handled according to step described in B~C again, then are placed in four
60 minutes are stood in ammonium chloropalladate solution.The concentration of tetrachloro-palladium acid ammonium salt solution is 3 mmol/L；It is subsequently placed in chemical plating liquid,
Obtain on surface while there are the plastics that nickel coating and silvering are patterned described in B.Chemical plating liquid used presses document report
Configuration（Electroless plating: fundamentals and applications[M]. William Andrew,
1990）.
Claims (9)
- A kind of 1. method that chemical plating multiple patterns metal can be repeated several times in frosting, it is characterised in that this method includes Following steps：A, load propenyl or propylene 01 derivatives and triethylamine in the reactor, 2- bromo isobutyl acylbromides are added into reactor And dichloromethane, to react at room temperature, reaction is filtered after terminating, then respectively with hydrochloric acid, saturated sodium carbonate, saturated aqueous common salt Clean repeatedly, obtain the light yellow oily liquids for having fragranced, with the isolated brominated initiator monomer of silicagel column；To plastics list The brominated initiator monomer is added in body, by polymerisation, is obtained by modified plastics；Brominated initiator monomer has such as Lower formula：N numerical value is 1~6 in formula；B, the plastics obtained by step A are put into the processing of plasma surface washer, make surfaces nonreactive, recycle mechanical micro Process Technology carries out pattern processing in frosting；C, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and solvent are added in the reactor, add 2,2- bipyridyls and Cuprous bromide, the plastics that will be patterned under argon gas protection are put into reactor；D, the plastics obtained by step C are put into tetrachloro-palladium acid ammonium salt solution and stood, be subsequently placed in the chemical plating solution of metal ion In, obtain the metal pattern consistent with mechanical micro Process in step B；E, by the metal pattern plastics that above-mentioned steps obtain by polishing, again according to step multiplicatingization described in B~D Learn plating different metal.
- 2. the method as described in claim 1, it is characterised in that in step A, plastic monomer is selected from styrene or methacrylic acid Methyl esters.
- 3. the method as described in claim 1, it is characterised in that in step A, polymerisation refer under the conditions of 50~90 DEG C First pre-polymerization 1~5 hour in reactor, then by the performed polymer of clear viscous under the conditions of 100~200 DEG C continuous bulk polymerization 1 ~6 hours.
- 4. the method as described in claim 1, it is characterised in that in step B, with the time of plasma surface washer processing For 1~10 minute.
- 5. the method as described in claim 1, it is characterised in that in step C, reaction temperature is 30~60 DEG C, the reaction time 1 ~12 hours.
- 6. the method as described in claim 1, it is characterised in that in step C, reaction dissolvent is first alcohol and water.
- 7. the method as described in claim 1, it is characterised in that in step D, the concentration of tetrachloro-palladium acid ammonium salt solution is 1~5 mmol/L。
- 8. the method as described in claim 1, it is characterised in that in step D, metal ion chemistry plating liquor be selected from containing gold, The chemical plating solution of silver, copper or nickel.
- 9. method as claimed in claim 1, it is characterised in that in step E, the metal pattern that is obtained by above-mentioned steps Deposition various metals pattern is repeated several times by polishing in plastics.
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| CN113981421B (en) * | 2021-07-09 | 2022-07-01 | 西安电子科技大学 | Method for preparing erasable metal electrode on plastic surface |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102786645A (en) * | 2012-08-08 | 2012-11-21 | 东华大学 | Preparation method of crystalline/amorphous triblock copolymer |
| CN103421204A (en) * | 2013-08-20 | 2013-12-04 | 常州大学 | Surface-amphiphilic polyester film and preparation method thereof |
-
2014
- 2014-12-11 CN CN201410753153.3A patent/CN105734539B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102786645A (en) * | 2012-08-08 | 2012-11-21 | 东华大学 | Preparation method of crystalline/amorphous triblock copolymer |
| CN103421204A (en) * | 2013-08-20 | 2013-12-04 | 常州大学 | Surface-amphiphilic polyester film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Electrochemically Induced Surface-Initiated Atom-Transfer Radical Polymerization;Bin Li等;《Angewandte Chemie International Edition》;20120531;第5092-5095页 * |
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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 |