CN102391633B - Plastic composition and application thereof, and plastic surface selective metallization method - Google Patents
Plastic composition and application thereof, and plastic surface selective metallization method Download PDFInfo
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- CN102391633B CN102391633B CN2011102020928A CN201110202092A CN102391633B CN 102391633 B CN102391633 B CN 102391633B CN 2011102020928 A CN2011102020928 A CN 2011102020928A CN 201110202092 A CN201110202092 A CN 201110202092A CN 102391633 B CN102391633 B CN 102391633B
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Abstract
The invention provides a plastic composition which comprises a plastic substrate component and a catalyst component, wherein the catalyst component is selected from one or more of oxides of metal elements in the 9th, 10th and 11th rows of the periodic table except copper, silicates, borate and oxalates of metal elements of the 9th, 10th and 11th rows in the periodic table, hydrogenation catalysts containing metal elements of the 9th, 10th and 11th rows in the periodic table, and ABO2 type composite oxides with delafossite structure; and A is selected from one of metal elements in the 9th, 10th and 11th rows of the periodic table, B is Ni, Mn, Cr, Al or Fe, and A is different from B. The invention also provides application of the plastic composition in plastic surface selective metallization. The invention also provides a plastic surface selective metallization method. By using the method, a circuit can be further formed easily.
Description
Related application
The application is dividing an application of application number is 200910261216.2, the applying date is on December 17th, 2009, denomination of invention is " method of plastics composite and application thereof and selective metallization of plastic surface " Chinese invention patent application.
Technical field
The present invention relates to a kind of method of plastics composite and the application in selective metallization of plastic surface and selective metallization of plastic surface.
Background technology
Directly form the technology of stereo circuit on the moulding surface, the functions such as the support of the function of the electric interconnection function of common circuit card, supporting components and parts and plastic component, protection can be implemented on a device, form circuit carrier three-dimensional, that integrate dynamo-electric function.This class technology is the applicable shape of design alternative as required, can realize multi-functionally, can reduce and level is installed, is reduced component number, in fields such as automobile, industry, computer, communications, is applied at present.
It is an important link of stereo circuit technology that frosting optionally metallizes.Metallization of plastic surface is produced circuit a lot of methods, US5599592A adds a kind of metal oxide in polymer materials, then the pattern needed with the infrared laser activation, will produce metal core at the position be activated, and these metal core are as the catalyzer of subsequent chemistry plating.But also there are some problems in the method, the metal oxide Sb added in the one, embodiment
2O
3A kind of carcinogenic substance and being prohibited from using, except Sb
2O
3In addition, can be considerably less by the metal oxide of infrared reduction; In addition, the document is also mentioned after metallization, need thermal treatment that metal level is diffused in plastics and could improve better the bonding force between metal level and plastic substrate, but metal level can the ground diffusion of much degree be a problem.
US2003031803A1 has also reported with metal oxide particle as ZnO, TiO
2, ZrO
2, Al
2O
3, CeO
2On the surface that is coated on matrix, then use the UV laser radiation, follow copper-plated technique again.The top speed that wherein UV moves is 100mm/s, and the generation of pattern is not had to selectivity.
US2004/0241422A1 and US7060421 have also reported the inorganic powder that adds spinel structure in plastic substrate, these mineral compound contain the elements such as copper, nickel, cobalt, chromium, iron, then use Ultra-Violet Laser (wavelength is 248nm, 308nm, 355nm, 532nm) and infrared laser (wavelength is 1064nm and 10600nm) to be activated.Mention especially the oxide compound with spinel structure in above-mentioned document and can under lasing, restore metal simple-substance, using metal simple-substance as nucleus, induce the electroless plating metal, form metal level.The realization of this process needs strict technology controlling and process, and needing to irradiate higher laser energy to be metal simple-substance by the Reduction of Oxide of spinel structure, thereby obtains the effect of inducing the electroless plating metal of expection, all higher to the requirement of equipment and process.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new plastics composite and the method for selective metallization of plastic surface, after using the method, can further easily form circuit.
The invention provides a kind of plastics composite, this plastics composite contains plastic basis material component and catalyst component, wherein, described catalyst component is to be selected from the periodic table of elements the 9th, 10 beyond copper removal and the oxide compound of 11 row metallic elements, silicate, borate and the oxalate of the periodic table of elements the 9th, 10 and 11 row metallic elements, the hydrogenation catalyst that contains the periodic table of elements the 9th, 10 and 11 row metallic elements and the ABO with delafossite structure
2One or more in the type composite oxides, described hydrogenation catalyst becomes pure catalyzer for making containing aldehyde, ketone, lipid acid or the fatty acid ester hydrogenation of carbonyl; Described A is a kind of for being selected from the periodic table of elements the 9th, 10 and 11 row metallic elements, and B is Ni, Mn, Cr, Al or Fe, and A is different from B.
The invention still further relates to the application of plastics composite provided by the invention in selective metallization of plastic surface.
The present invention also provides a kind of method of selective metallization of plastic surface, and the method comprises: plastics composite provided by the invention is mixed and injection moulding, obtain plastic sample; By the irradiation energy line, described plastic sample is carried out to etching, expose the catalyst component particle so that the partly plastic gasification is peeled off; The plastic sample that exposes the catalyst component particle is carried out to electroless copper.
The present invention is owing to having selected the component that is different from prior art, use catalyst component of the present invention can directly promote electroless copper, do not need, by induced with laser, the metallic element in catalyst component is reduced to this complicated and uppity process of simple substance, thereby widened the scope of operable energy line, more easily controlled the stability of technique.And easily obtain the shape of the chemical plating metal wanted on the plastic sample surface by the shape of controlling the irradiation energy line, can easily obtain on the plastic sample surface circuit needed.
In addition, from the data of table 1 of the present invention and table 2, can find out, utilize the method for selective metallization of plastic surface of the present invention, under the promotion of the catalyst component particle that used in the present invention, the electroless copper speed on the plastic sample surface of irradiating energy line up to the 1-9 micron/hour, chemical nickel plating speed up to the 1-8 micron/hour.
Embodiment
The invention provides a kind of plastics composite, this plastics composite contains plastic basis material component and catalyst component, wherein, described catalyst component is to be selected from the periodic table of elements the 9th, 10 beyond copper removal and the oxide compound of 11 row metallic elements, silicate, borate and the oxalate of the periodic table of elements the 9th, 10 and 11 row metallic elements, the hydrogenation catalyst that contains the periodic table of elements the 9th, 10 and 11 row metallic elements and the ABO with delafossite structure
2One or more in the type composite oxides, described hydrogenation catalyst becomes pure catalyzer for making containing aldehyde, ketone, lipid acid or the fatty acid ester hydrogenation of carbonyl; Described A is a kind of for being selected from the periodic table of elements the 9th, 10 and 11 row metallic elements, and B is Ni, Mn, Cr, Al or Fe, and A is different from B.
From promoting electroless copper and nickel plating effect aspect, consider, under preferable case, described catalyst component is to be selected from the periodic table of elements the 10th beyond copper removal and the oxide compound of 11 row metallic elements, silicate, borate and the oxalate of the periodic table of elements the 10th and 11 row metallic elements, the hydrogenation catalyst that contains the periodic table of elements the 10th and 11 row metallic elements and the ABO with delafossite structure
2One or more in the type composite oxides, described A is a kind of for being selected from the periodic table of elements the 10th and 11 row metallic elements, and B is Ni, Mn, Al or Fe, and A is different from B.
Wherein, in the periodic table of elements the 9th, 10 beyond described copper removal and the oxide compound of 11 row metallic elements, the metallic element of the periodic table of elements the 9th, 10 and 11 row can be Co, Rh, Pt, Ni, Pd, Pt, Ag or Au; As mentioned above, from the catalytic effect aspect, consider, be preferably the copper removal periodic table of elements the 10th in addition and the oxide compound of 11 metallic elements that are listed as, be preferably the oxide compound of Ni, Pd, Pt, Ag or Au; Because Pd, Pt, Ag and Au are precious metal, be of little use, therefore the more preferably oxide compound of more cheap Ni, that is to say, commonly used is the oxide compound of Ni or Co, wherein the preferred oxide compound of Ni.Therefore, specifically, the periodic table of elements the 9th, 10 beyond common described copper removal and the oxide compound of 11 row metallic elements can comprise Ni
2O
3, Co
2O
3And CoO, be preferably Ni
2O
3.
Silicate, borate and the oxalate of the described periodic table of elements the 9th, 10 and 11 row metallic elements is the salt of the metal ion that can not dissociate in the process of processing plastic, in silicate, borate and the oxalate of the described periodic table of elements the 9th, 10 and 11 row metallic elements, the metallic element of the periodic table of elements the 9th, 10 and 11 row can be Co, Rh, Pt, Ni, Pd, Pt, Cu, Ag or Au; As mentioned above, from the catalytic effect aspect, consider, be preferably silicate, borate and the oxalate of the metallic element of the periodic table of elements the 10th and 11 row, be preferably silicate, borate and the oxalate of Ni, Pd, Pt, Cu, Ag or Au; Because Pd, Pt, Ag and Au are precious metal, therefore be of little use, more preferably more cheap Ni and silicate, borate and the oxalate of Cu, that is to say, commonly used is silicate, borate and the oxalate of Co, Ni and Cu, wherein silicate, borate and the oxalate of preferred Ni and Cu.Therefore, specifically, the common described periodic table of elements the 9th, 10 and silicate, borate and the oxalate of 11 row metallic elements can comprise CuSiO
3, NiSiO
3, CoSiO
3CuB
2O
4, Cu
3B
2O
6, NiB
2O
4, Ni
3B
2O
6NiC
2O
4, CuC
2O
4, CoC
2O
4.
As mentioned above, described hydrogenation catalyst becomes pure catalyzer for making containing aldehyde, ketone, lipid acid or the fatty acid ester hydrogenation of carbonyl, the object lesson of the such hydrogenation catalyst in the present invention has: Cu-Zn, Cu-Zn-Ni, Cu-Zn-Co, Cu-Zn-Ga, Co-La, Cu-Cd and Cu-Zn-Si series hydrocatalyst, these hydrogenation catalysts can be commercially available.Wherein, in Cu-Zn, in oxide compound, the ratio of the amount of substance of Cu and Zn can be 8: 1～4: 1; In Cu-Zn-Ni, in oxide compound, the ratio of the amount of substance of Cu, Zn and Ni can be (8-20): 1: (1-2); In Cu-Zn-Co, in oxide compound, the ratio of the amount of substance of Cu, Zn and Co can be (4-8): 1: (1-2); In Cu-Zn-Ga, in oxide compound, the ratio of the amount of substance of Cu, Zn and Ga can be (4-8): 1: (1-2); In Co-La, in oxide compound, the ratio of the amount of substance of Co and La can be 8: 1～4: 1; In Cu-Cd, in oxide compound, the ratio of the amount of substance of Cu and Cd can be 8: 1～4: 1; In Cu-Zn-Si, in oxide compound, the ratio of the amount of substance of Cu, Zn and Si can be (4-8): 1: 1.
The described ABO with delafossite structure
2In the type composite oxides, A, for being selected from the periodic table of elements the 9th, 10 and 11 row metallic elements, can think Co, Rh, Pt, Ni, Pd, Pt, Cu, Ag or Au; Consider from the catalytic effect aspect, be preferably the metallic element that is selected from the periodic table of elements the 10th and 11 row, be preferably Ni, Pd, Pt, Cu, Ag or Au; Because Pd, Pt, Ag and Au are precious metal, be of little use, therefore more preferably more cheap Ni and Cu, that is to say, as A, that commonly used is Ni, Cu or Co, wherein preferably Ni and Cu; B can be Ni, Mn, Cr, Al or Fe, and A is different from B, and the present invention is preferably containing environment being had to the catalyzer of the Cr element of pollution.Therefore, specifically, the described ABO with delafossite structure commonly used
2The type composite oxides can comprise MNiO
2, MMnO
2, MCrO
2, MAlO
2And MFeO
2, M can be Cu, Ni or Co.
The present invention has no particular limits plastic basis material component contained in described plastics composite and the content of catalyst component, as long as can realize goal of the invention, as long as that is to say that the content of catalyst component can make acquisition promote preferably the effect of electroless copper and nickel plating, but consider from the effect that obtains good promotion electroless copper and the aspect of saving catalyst levels, preferably in described plastics composite, with respect to the catalyst component of 100 weight parts, the content of described plastic basis material component is the 1000-10000 weight part.
In the present invention, described catalyst component can be particulate state, the present invention has no particular limits the size of granules of catalyst, but, from principle, in certain scope, particle is less, catalytic effect is better, therefore the average particle diameter of this particle is preferably and is not more than 100 microns, and more preferably 10 nanometers to 1 micron, be further 10 nanometer to 100 nanometers.
Described plastic basis material component can be known plastic basis material component, can be for example thermoplastic resin or thermosetting resin.
Wherein, described thermoplastics can be for being selected from one or more in polyolefine, polycarbonate (PC), polyester, polymeric amide, polyarylether, polyester-imide, polycarbonate/(acrylonitrile-butadiene-styrene (ABS)) alloy (PC/ABS), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyimide (PI), polysulfones (PSU), polyether-ether-ketone (PEEK), polybenzimidazole (PBI) and liquid crystalline polymers (LCP).Wherein, " alloy " in described polycarbonate/(acrylonitrile-butadiene-styrene (ABS)) alloy is not general metal alloy but polymer alloy, polymer alloy generally refers to after polymkeric substance is processed by physical methods such as blend the mixture of two or more polymkeric substance obtained, and described polycarbonate/(acrylonitrile-butadiene-styrene (ABS)) alloy refers to the mixture of polycarbonate and acrylonitrile-butadiene-styrene (ABS).Described liquid crystalline polymers is a kind ofly the stiff molecule chain, to consist of, and the mobility that can occur existing liquid under certain physical condition has again the polymer substance of the physicals anisotropic states (this state is called liquid crystal state) of crystal.Particularly, described polyolefine can be for being selected from one or more in polystyrene (PS), polypropylene (PP), polymethylmethacrylate and poly-(acrylonitrile-butadiene-styrene (ABS)), described polyester can be for being selected from the poly terephthalic acid hexanaphthene to one or more in diformazan alcohol ester (PCT), PDAIP (PDAIP), poly terephthalic acid diallyl (PDAP), PBN (PBN), polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), described polymeric amide can be for being selected from polyhexamethylene adipamide (PA-66), poly-azelaoyl hexanediamine (PA-69), poly-succinyl hexanediamine (PA-64), nylon 612 (PA-612), polyhexamethylene sebacamide (PA-610), nylon 1010 (PA-1010), nylon 11 (PA-11), poly-lauramide (PA-12), poly-decoylamide (PA-8), poly-9 aminononanoic acid (PA-9), polycaprolactam (PA-6), poly-paraphenylene terephthalamide's phenylenediamine (PPTA), poly-6I hexamethylene isoterephalamide (MXD6), one or more in poly-hexamethylene terephthalamide (PA6T) and poly-paraphenylene terephthalamide's nonamethylene diamine (PA9T).
Described thermosetting resin can be for selecting one or more in resol, urea-formaldehyde resin, melamine formaldehyde resin, epoxy resin, Synolac and urethane.
In addition, plastic polymer of the present invention can also contain one or more in mineral filler, oxidation inhibitor, photostabilizer and lubricant.
In described plastics composite, with respect to the catalyst component of 100 weight parts, the content of described mineral filler can be the 10-70 weight part.The gross weight of plastics composite of take is benchmark, and the content of described oxidation inhibitor can be the 0.01-1 % by weight, and the content of described photostabilizer can be the 0.01-1 % by weight, and the content of described lubricant can be the 0.01-1 % by weight.
Wherein, described mineral filler can be laser not to be played to the physics filler of any physics or chemical action, for example, and talcum powder and calcium carbonate; Although glass fibre is insensitive to laser, add glass fibre can greatly deepen the degree of depth of plastic substrate depression after laser activation, be conducive to the adhesion of copper in electroless copper.Described mineral filler can also be the mineral filler that laser is played a role, and for example, stannic oxide especially nano tin dioxide can increase the capacity usage ratio of infrared laser when peeling off frosting; Functional filler also has carbon black, and it also can increase plastics to infrared absorption, increases the extent of exfoliation of plastics.Preferably do not contain Cr etc. in described mineral filler to environment and the harmful element of human body.Described mineral filler can also be glass microballon, calcium sulfate, barium sulfate, titanium dioxide, pearlescence, wollastonite, diatomite, kaolin, coal dust, potter's clay, mica, kerosene shale ash, pure aluminium silicate, aluminum oxide, carbon fiber, silicon-dioxide or zinc oxide.
Described oxidation inhibitor can improve the antioxidant property of resin combination of the present invention, thereby improves the work-ing life of the product finally obtained.Described oxidation inhibitor has been conventionally known to one of skill in the art, for example can contain primary antioxidant and auxiliary antioxidant, and the weight ratio of described primary antioxidant and described auxiliary antioxidant can be 1: 1-4.Described primary antioxidant can be hindered phenol type antioxidant, the example of this hindered phenol type antioxidant comprises oxidation inhibitor 1098 and 1010 (oxidation inhibitor that Ciba company produces), wherein the main component of oxidation inhibitor 1098 is N, N '-bis--(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, the main component of antioxidant 1010 is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane; Described auxiliary antioxidant can be phosphite type oxidation inhibitor, and the example of this phosphite type oxidation inhibitor has irgasfos 168 (oxidation inhibitor that Ciba company produces), and its main component is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester.The oxidation inhibitor that the present invention preferably adopts is for as the antioxidant 1010 of primary antioxidant with as the mixture of the irgasfos 168 of auxiliary antioxidant.
Described photostabilizer can make to provide the light stability of resin combination of the present invention, thereby improves the work-ing life of the product finally obtained.Described photostabilizer can be various known photostabilizers, hindered amine type light stabilizer for example, and the example of hindered amine type light stabilizer has two (2,2,6,6-tetramethyl--4-piperidyl) sebates.
Thereby described lubricant can make resin combination have better mobility, that resin combination is mixed to get is more even.Described lubricant can be various known lubricants, can be for example one or more in the copolymerization wax (EVA wax), polyethylene wax (PE wax) and the stearate that are selected from ethylene/vinyl acetate.
The invention still further relates to the application of plastics composite provided by the invention in selective metallization of plastic surface.Easily obtain the shape of the chemical plating metal wanted by the shape of controlling the irradiation energy line on the plastic sample surface, can easily obtain on the plastic sample surface circuit needed.
The present invention also provides a kind of method of selective metallization of plastic surface, and the method comprises: plastics composite provided by the invention is mixed and injection moulding, obtain plastic sample; By the irradiation energy line, described plastic sample is carried out to etching, expose the catalyst component particle so that the partly plastic gasification is peeled off; The plastic sample that exposes the catalyst component particle is carried out to electroless copper.
The present invention has no particular limits the method for injection moulding, can use the method for conventional injection moulding, for example can first will put into the forcing machine extruding pelletization in described plastics composite, and then put into the plastic sample that injection moulding machine is injection molded into the shape needed and get final product.
In the present invention, to by the irradiation energy line, described plastic sample being carried out to etched degree, have no particular limits, only otherwise plastic sample is punctured and can expose the catalyst component particle and get final product, if the plastics that etch away are thicker, there is partially catalyzed agent component particles to fall down also not affect and realize purpose of the present invention, will fall at the lip-deep particle of plastic sample and clean out and get final product.
Described energy line can obtain by various known approach, preferably by laser apparatus, obtain laser, thereby pass through irradiating laser and obtain energy line, the wavelength of described laser is 157 nanometers to 10.6 micron, and sweep velocity is the 500-8000 mm/second, and step-length is the 3-9 micron, time delay is the 30-100 microsecond, frequency is the 30-40 kilohertz, and power is 3-4 watt, and filling spacing is the 10-50 micron.The thickness of general plastic sample is at least 1 micron, by irradiating such laser, the thickness of the plastics that generally etch away is several microns to tens microns, thereby make the catalyst component particle in plastic sample come out, plastic sample forms on microcosmic as having the rough surface structure in rugged space.When follow-up electroless copper, copper just is embedded in the hole of uneven surface, thereby and forms very strong bonding force between plastic sample.
The plastics that expose the catalyst component particle are carried out to the method for electroless copper also for conventionally known to one of skill in the art, for example the method can comprise the plastic sample after etching is contacted with copper electrolyte, described copper electrolyte contains mantoquita and reductive agent, the pH value is 12-13, described reductive agent can be reduced to copper simple substance by cupric ion in mantoquita, and for example described reductive agent can be one or more in oxoethanoic acid, hydrazine and inferior sodium phosphate.For example, " sufacing " in December, 2002, interim basic composition is of disclosing a typical plating solution of the 31st volume the 6th: CuSO
45H
2O:0.12mol/L, Na
2EDTA2H
2O:0.14mol/L, yellow prussiate of potash: 10mg/L, 2,2 '-dipyridyl: 10mg/L, oxoethanoic acid (HOCCOOH): 0.10mol/L, and with NaOH and H
2SO
4The pH value of regulating plating solution is 12.5-13.In addition, if feel the copper thickness deficiency after electroless copper, can also carry out electro-coppering.
Under preferable case, after method of the present invention also is included in copper facing and finishes again electroless plating one deck nickel prevent that the copper coating surface is oxidized.
Method of the present invention is first electroless plating one deck nickel before electroless copper more preferably, to prevent plastics, is placed on water suction post-etching copper coating in air.
The method of chemical nickel plating has been conventionally known to one of skill in the art, for example the method can comprise plastic sample is contacted with nickel-plating liquid, for example, consisting of of a typical nickel plating solution: single nickel salt: 23g/l, inferior sodium phosphate: 18g/l, lactic acid: 20g/l, oxysuccinic acid: 15g/l, PH:5.2 (regulating with NaOH) temperature: 85-90 ℃.Thickness to chemical Ni-plating layer has no particular limits, as long as plastic substrate can be completed to covering, so the thickness of nickel coating is preferably 0.5-1 μ m, need not make nickel coating too thick.
Below with reference to embodiment, the present invention will be described in more detail.
Embodiment 1
The present embodiment is for illustrating the method for plastics composite of the present invention and selective metallization of plastic surface.
The Ni that is 50 nanometers by the average particle diameter of 100g
2O
3With the talcum powder of 10g, join in the polycarbonate of 1000g, high-speed mixing is even, obtains plastics composite of the present invention, then it is proceeded to extruding pelletization in forcing machine, and then it is proceeded in injection moulding machine to the plastic sample that is injection molded into 2 mm thick.Plastic sample is placed on the laser apparatus sample table, by laser focusing, computer program is controlled the movement of light beam or sample table, and laser apparatus used is the YLP-20 of big nation type laser apparatus, and laser parameter is: wavelength 1064nm, sweep velocity 1000mm/s, step-length 9 μ m, time delay 30 μ s, frequency 40KHz, power 3W, fill spacing 50 μ m.After laser ablation, plastic sample is carried out to abatement processes, then be placed in and consist of CuSO
45H
2O:0.12mol/L, Na
2EDTA2H
2O:0.14mol/L, yellow prussiate of potash: 10mg/L, 2,2 '-dipyridyl: 10mg/L, oxoethanoic acid (HOCCOOH): in the plating solution of 0.10mol/L, and with NaOH and H
2SO
4The pH value of regulating plating solution is 12.5 to carry out electroless copper, and after tested, copper facing speed is 4 μ m/h.
Embodiment 2
The present embodiment is for illustrating the method for plastics composite of the present invention and selective metallization of plastic surface.
The Co that is 100 nanometers by the average particle diameter of 100g
2O
3With the glass fibre of 30g, join in the PC of 5000g, high-speed mixing is even, obtains plastics composite of the present invention, then it is proceeded to extruding pelletization in forcing machine, and then it is proceeded in injection moulding machine to the plastic sample that is injection molded into 2 mm thick.Plastic sample is placed on the laser apparatus sample table, by laser focusing, computer program is controlled the movement of light beam or sample table, and laser apparatus used is the YLP-20 of big nation type laser apparatus, and laser parameter is: wavelength 300nm, sweep velocity 5000mm/s, step-length 3 μ m, time delay 60 μ s, frequency 40KHz, power 3W, fill spacing 30 μ m.After laser ablation, plastic sample is carried out to abatement processes, then be placed in and consist of CuSO
45H
2O:0.12mol/L, Na
2EDTA2H
2O:0.14mol/L, yellow prussiate of potash: 10mg/L, 2,2 '-dipyridyl: 10mg/L, oxoethanoic acid (HOCCOOH): in the plating solution of 0.10mol/L, and with NaOH and H
2SO
4The pH value of regulating plating solution is 13 to carry out electroless copper, and after tested, copper facing speed is 2 μ m/h.
Embodiment 3
The present embodiment is for illustrating the method for plastics composite of the present invention and selective metallization of plastic surface.
The CuSiO that is 500 nanometers by the average particle diameter of 100g
3With the kaolin of 70g, join in the 10000g polyethylene terephthalate, high-speed mixing is even, obtain plastics composite of the present invention, then it is proceeded to extruding pelletization in forcing machine, and then it is proceeded in injection moulding machine to the plastic sample that is injection molded into 2 mm thick.Plastic sample is placed on the laser apparatus sample table, by laser focusing, computer program is controlled the movement of light beam or sample table, and laser apparatus used is the YLP-20 of big nation type laser apparatus, and laser parameter is: wavelength 10600nm, sweep velocity 8000mm/s, step-length 6 μ m, time delay 100 μ s, frequency 30KHz, power 4W, fill spacing 40 μ m.After laser ablation, plastic sample is carried out to abatement processes, then be placed in and consist of CuSO
45H
2O:0.12mol/L, Na
2EDTA2H
2O:0.14mol/L, yellow prussiate of potash: 10mg/L, 2,2 '-dipyridyl: 10mg/L, oxoethanoic acid (HOCCOOH): in the plating solution of 0.10mol/L, and with NaOH and H
2SO
4The pH value of regulating plating solution is 12.5 to carry out electroless copper, and after tested, copper facing speed is 5 μ m/h.
Embodiment 4-19
The present embodiment is for illustrating the method for plastics composite of the present invention and selective metallization of plastic surface.
Adopt the described method of embodiment 1 to prepare plastics composite and make selective metallization of plastic surface, different, adopt respectively the catalyst component shown in table 1, and measure respectively the copper facing speed of embodiment 4-19, result is as shown in table 1.
Wherein, the hydrogenation catalyst used in embodiment is self-control and obtains, and the self-control method is according to document: Acta PhySico-Chimica Sinica, 2004,20 (5): 524-528 and Angew.Chem.Int.Ed.2003, the described method of 42,3815-3817 is carried out.
For example prepared according to the method for being prepared as follows by the Cu-Zn hydrogenation catalyst: by Cu: the mixed nitrate solution that the Zn mol ratio is 8: 1 preparation Cu and Zn, making the total concn of metal ion in mixed solution is that the total concn of cupric ion and zine ion is 0.25mol/L, with Na
2CO
3For precipitation agent, Na
2CO
3Concentration be 0.5mol/L, under 85 ℃ and rapid stirring, and drip adds above-mentioned mixed nitrate solution and Na
2CO
3Solution is in reactor, control the pH=6.8 of solution～7.0 with the rate of addition of two kinds of solution simultaneously, when reaction finishes, the pH value of solution is then aging 1h at this temperature of 7.0., and cooled and filtered, use deionized water wash, drain, and, 110 ℃ of oven dry, then at 350 ℃ of roasting 4h, just can obtain required Cu-Zn hydrogenation catalyst, in the Cu-Zn hydrogenation catalyst made after testing, in oxide compound, the ratio of the amount of substance of Cu and Zn is 8.1: 1.
Comparative Examples 1
This Comparative Examples is for illustrating the method for existing plastics composite and selective metallization of plastic surface.
Adopt the described method of embodiment 1 to prepare plastics composite and make selective metallization of plastic surface, different, adopt respectively the catalyst component shown in table 1, and measure the copper facing speed of Comparative Examples 1, result is as shown in table 1.
Table 1
Comparing embodiment 1 and Comparative Examples 1 can find out, in other condition, under identical condition, adopts existing catalyst component ZnO, and electroless copper speed is only 0.05 μ m/h, and uses the preferred Ni of the present invention
2O
3As catalyst component, electroless copper speed is up to 4 μ m/h.
Embodiment 20-38
The present embodiment is for illustrating the method for plastics composite of the present invention and selective metallization of plastic surface.
Embodiment 20-38 adopts respectively the described method of embodiment 1-19 to prepare plastics composite and make selective metallization of plastic surface, different is, to irradiating the plastic sample of too drastic light, first chemical nickel plating before electroless copper, and measure respectively the nickel plating speed of embodiment 20-38, result is as shown in table 2.The method of chemical nickel plating is as described below:
After laser ablation, plastic sample is carried out to abatement processes, then be placed in and consist of single nickel salt: 23g/l, inferior sodium phosphate: 18g/l, lactic acid: 20g/l, in the plating solution of oxysuccinic acid: 15g/l, regulating pH with NaOH is 5.2, and bath temperature is 90 ℃, carries out chemical nickel plating.
Comparative Examples 2
This Comparative Examples is for illustrating the method for existing plastics composite and selective metallization of plastic surface.
Adopt the described method of Comparative Examples 1 to prepare plastics composite and make selective metallization of plastic surface, different, to irradiating the plastic sample of too drastic light, first chemical nickel plating before electroless copper, and the nickel plating speed of mensuration Comparative Examples 2, result is as shown in table 2.Chemical nickel plating method adopts the method described in embodiment 20-38 to carry out.
Table 2
Comparing embodiment 20 and Comparative Examples 2 can find out, in other condition, under identical condition, adopts existing catalyst component ZnO, and chemical nickel plating speed is only 0.05 μ m/h, and uses the preferred Ni of the present invention
2O
3As catalyst component, chemical nickel plating speed is up to 3 μ m/h.
Claims (10)
1. the method for a selective metallization of plastic surface, the method comprises:
Plastics composite is mixed and injection moulding, obtain plastic sample;
By the irradiation energy line, described plastic sample is carried out to etching, expose the catalyst component particle so that the partly plastic gasification is peeled off;
The plastic sample that exposes the catalyst component particle is carried out to electroless copper;
Wherein, described plastics composite contains plastic basis material component and catalyst component, described catalyst component is to be selected from one or more in Cu-Zn-Ni, Cu-Zn-Co, Cu-Zn-Ga, Co-La, Cu-Cd and Cu-Zn-Si series hydrocatalyst, and described hydrogenation catalyst becomes pure catalyzer for making containing aldehyde, ketone, lipid acid or the fatty acid ester hydrogenation of carbonyl;
Described energy line obtains by irradiating laser, and the wavelength of described laser is 157 nanometers to 10.6 micron, and sweep velocity is the 500-8000 mm/second, step-length is the 3-9 micron, and time delay is the 30-100 microsecond, and frequency is the 30-40 kilohertz, power is 3-4 watt, and filling spacing is the 10-50 micron.
2. method according to claim 1, wherein, in described plastics composite, with respect to the catalyst component of 100 weight parts, the content of described plastic basis material component is the 1000-10000 weight part.
3. method according to claim 1 and 2, wherein, described catalyst component is particulate state, the average particle diameter of this particle is not more than 100 microns.
4. method according to claim 3, wherein, the average particle diameter of described particle is 10 nanometers to 1 micron.
5. method according to claim 4, wherein, the average particle diameter of described particle is 10 nanometer to 100 nanometers.
6. method according to claim 1 and 2, wherein, described plastic basis material component is thermoplastic resin or thermosetting resin.
7. method according to claim 6, wherein, described thermoplastic resin is for being selected from one or more in polyolefine, polycarbonate, polyester, polymeric amide, polyarylether, polyester-imide, polycarbonate/(acrylonitrile-butadiene-styrene (ABS)) alloy, polyphenylene sulfide, polyimide, polysulfones, polyether-ether-ketone, polybenzimidazole and liquid crystalline polymers, and described thermosetting resin is to be selected from one or more in resol, urea-formaldehyde resin, melamine formaldehyde resin, epoxy resin, Synolac and urethane.
8. method according to claim 1, wherein, described plastics composite also contains one or more in mineral filler, oxidation inhibitor, photostabilizer and lubricant;
In described plastics composite, with respect to the catalyst component of 100 weight parts, the content of described mineral filler is the 10-70 weight part; The gross weight of plastics composite of take is benchmark, and the content of described oxidation inhibitor is the 0.01-1 % by weight, and the content of described photostabilizer is the 0.01-1 % by weight, and the content of described lubricant is the 0.01-1 % by weight;
Described mineral filler is one or more that are selected from glass fibre, stannic oxide, glass microballon, calcium carbonate, calcium sulfate, barium sulfate, talcum powder, titanium dioxide, pearlescence, wollastonite, diatomite, kaolin, coal dust, potter's clay, mica, kerosene shale ash, pure aluminium silicate, aluminum oxide, carbon black, carbon fiber, silicon-dioxide and zinc oxide;
Described oxidation inhibitor contains primary antioxidant and auxiliary antioxidant, and the weight ratio of described primary antioxidant and described auxiliary antioxidant is 1:1-4, and described primary antioxidant is hindered phenol type antioxidant, and described auxiliary antioxidant is phosphite type oxidation inhibitor;
Described photostabilizer is hindered amine type light stabilizer;
Described lubricant is to be selected from one or more in copolymerization wax, polyethylene wax and the stearate of ethylene/vinyl acetate.
9. according to the method for claim 1 or 8 described selective metallization of plastic surface, wherein, the method also is included in chemical nickel plating after electroless copper.
10. according to the method for claim 1 or 8 described selective metallization of plastic surface, wherein, the method also is included in the front chemical nickel plating of electroless copper.
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| KR101610346B1 (en) | 2013-04-26 | 2016-04-07 | 주식회사 엘지화학 | Composition and method for forming conductive pattern, and resin structure having conductive pattern thereon |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1395462A (en) * | 2002-06-06 | 2003-02-05 | 华中科技大学 | Electric circuit board production and its repairing method |
| CN1518850A (en) * | 2001-07-05 | 2004-08-04 | Lpkf激光和电子股份公司 | Conductor track structures and method for production thereof |
| CN101268134A (en) * | 2005-04-27 | 2008-09-17 | 巴斯福股份公司 | Plastic objects for metallizing having improved shaping properties |
| CN101283414A (en) * | 2005-09-09 | 2008-10-08 | 巴斯夫欧洲公司 | Dispersion containing two different metals for applying a metal layer |
-
2009
- 2009-12-17 CN CN2011102020928A patent/CN102391633B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1518850A (en) * | 2001-07-05 | 2004-08-04 | Lpkf激光和电子股份公司 | Conductor track structures and method for production thereof |
| CN1395462A (en) * | 2002-06-06 | 2003-02-05 | 华中科技大学 | Electric circuit board production and its repairing method |
| CN101268134A (en) * | 2005-04-27 | 2008-09-17 | 巴斯福股份公司 | Plastic objects for metallizing having improved shaping properties |
| CN101283414A (en) * | 2005-09-09 | 2008-10-08 | 巴斯夫欧洲公司 | Dispersion containing two different metals for applying a metal layer |
Non-Patent Citations (2)
| Title |
|---|
| 第10页第1段至第13页第7段. |
| 第28页倒数第1段-29页第7段. |
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