CN102071423A - Plastic product and preparation method thereof - Google Patents
Plastic product and preparation method thereof Download PDFInfo
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- CN102071423A CN102071423A CN2009102389579A CN200910238957A CN102071423A CN 102071423 A CN102071423 A CN 102071423A CN 2009102389579 A CN2009102389579 A CN 2009102389579A CN 200910238957 A CN200910238957 A CN 200910238957A CN 102071423 A CN102071423 A CN 102071423A
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- electroless plating
- layer
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Abstract
The invention provides a plastic product and a preparation method thereof. The method comprises the following steps: 1) forming a plastic base, wherein the plastic base contains chemically plated accelerators which are one or more of Ni2O3, Co2O3, CuSiO3, CuC2O4, Cu/Fe/Mn or Cu/Fe/Al ternary co-sintered oxides and Cu/Fe/Al/Mn quaternary co-sintered oxides; 2) gasifying the surface of the plastic base with laser to expose the chemically plated accelerators; and 3) chemically plating copper or nickel and continuing chemical plating and/or electroplating at least once to form a metal layer on the surface of the plastic base. The preparation method provided by the invention has the advantages of simple process, low requirement for energy and low cost. In addition, the chemically plated accelerator is distributed in the plastic base, so the plating layer formed after chemical plating and the plastic base have very high adhesion.
Description
Technical field
The invention belongs to non-metal material surface metallization field, relate in particular to a kind of preparation method and a kind of plastics of plastics.
Background technology
Form metal level at frosting, the path as the electromagnetic signal conduction is widely used in fields such as automobile, industry, computer, communication.It is the core link that such plastics are made that frosting optionally forms metal level.Metallization of plastic surface is produced circuit a lot of methods, all adopts earlier in the prior art to form metal core as the electroless plating catalytic active center on the plastic basis material surface, carries out electroless plating then.
For example, US2003031803A1 discloses employing metal oxide particle such as ZnO, TiO
2, ZrO
2, Al
2O
3, CeO
2Deng being coated on surface of plastic matrix, be reduced into metal simple-substance with Ultra-Violet Laser then, as the catalyzer of electroless copper, then carry out copper-plating technique again.Wherein the top speed that moves of Ultra-Violet Laser is 100mm/s, and the generation of pattern there is not selectivity, and metal oxide particle is coated surface of plastic matrix, and is therefore relatively poor with plastic substrate sticking power, makes that last coating and the plastic substrate sticking power that forms is relatively poor.
US7060421 discloses a kind of method of metallization of plastic surface, by in plastic substrate, adding the metal oxide of spinel structure, wherein metallic element can be selected from copper, nickel, cobalt, chromium, iron etc., use Ultra-Violet Laser (wavelength is 248nm, 308nm, 355nm, 532nm) and infrared laser (wavelength is 1064nm and 10600nm) to activate then, metal oxide is decomposed discharge metal simple-substance, the catalyzer that these metal simple-substances plate as subsequent chemistry, thus can carry out electroless plating.Adopt the metal oxide of spinel structure in this method, induce the electroless plating metal level after restoring metal simple-substance under the lasing, complex process, energy requirement is high and to the requirement of equipment and technology all than higher.
Summary of the invention
The present invention is for solving the technical problem of the metallization of plastic surface complex process, energy requirement height, coating and the plastic basis material poor adhesive force that exist in the prior art.
The invention provides a kind of preparation method of plastics, may further comprise the steps:
1) moulding plastics matrix; Described plastic substrate is thermoplasticity or the thermosetting resin that contains electroless plating promotor, and electroless plating promotor is uniformly distributed in thermoplasticity or the thermosetting resin; Described electroless plating promotor is Ni
2O
3, Co
2O
3, CuSiO
3, CuC
2O
4, Cu/Fe/Mn or Cu/Fe/Al ternary co-sintering oxide compound, Cu/Fe/Al/Mn quaternary co-sintering oxide compound one or more;
2) laser gasification surface of plastic matrix exposes electroless plating promotor;
3) in step 2) electroless plating promotor Electroless copper or chemical nickel plating, proceed at least electroless plating and/or plating, form metal level at surface of plastic matrix.
The present invention also provides a kind of plastics, and described plastics comprise plastic substrate and are positioned at the metal level of surface of plastic matrix; Described plastics are prepared by method provided by the invention.
The present inventor finds Ni by a large amount of experiments
2O
3, Co
2O
3, CuSiO
3, CuC
2O
4, Cu/Fe/Mn or Cu/Fe/Al ternary co-sintering oxide compound, Cu/Fe/Al/Mn quaternary co-sintering oxide compound need not to restore metal simple-substance, can be directly as electroless plating promotor, can directly carry out selective chemical plating on this electroless plating promotor surface, and this electroless plating promotor can not cause plastic degradation.Among the preparation method of plastics provided by the invention, described electroless plating promotor is uniformly distributed in the plastic substrate, laser selective irradiated plastics matrix surface, need not too high energy electroless plating promotor is reduced into metal simple-substance, and only need make the plastics gasification expose electroless plating promotor, can directly carry out electroless copper or chemical nickel plating, realize selective metallization of plastic surface, technology is simple, and is low to energy requirement, with low cost; In addition, electroless plating promotor is distributed in the plastic substrate, so coating that forms after the electroless plating and the bonding force in the plastic substrate are very high.
Embodiment
The invention provides a kind of preparation method of plastics, may further comprise the steps:
1) moulding plastics matrix; Described plastic substrate is thermoplasticity or the thermosetting resin that contains electroless plating promotor, and electroless plating promotor is uniformly distributed in thermoplasticity or the thermosetting resin; Described electroless plating promotor is Ni
2O
3, Co
2O
3, CuSiO
3, CuC
2O
4, Cu/Fe/Mn or Cu/Fe/Al ternary co-sintering oxide compound, Cu/Fe/Al/Mn quaternary co-sintering oxide compound one or more;
2) laser gasification surface of plastic matrix exposes electroless plating promotor;
3) in step 2) electroless plating promotor Electroless copper or chemical nickel plating, proceed at least electroless plating and/or plating, form metal level at surface of plastic matrix.
The present inventor finds, except metal simple-substance such as elemental copper and palladium can be used as the nucleus of electroless plating, nano cupric oxide can improve in the chemical plating fluid atoms metal widely in the sedimentary speed of carrier surface.The present inventor is by following experiment: the nano cupric oxide (particle diameter 40nm) of Aladdin reagent company is directly placed common chemical bronze plating liquid, and a large amount of copper simple substance fast deposition are in the nano cupric oxide surface, with its coating.So the certain granules size especially cupric oxide of nanometer particle size can promote electroless copper.But nano cupric oxide causes the degraded of plastics easily in the plastics the inside.The contriver finds Ni by a large amount of experiments
2O
3, Co
2O
3, CuSiO
3, CuC
2O
4, Cu/Fe/Mn or Cu/Fe/Al ternary co-sintering oxide compound, Cu/Fe/Al/Mn quaternary co-sintering oxide compound one or more can be used as electroless plating promotor, can directly carry out electroless copper/nickel on its surface, these materials are stored in the degraded that can not cause plastics in the plastics for a long time simultaneously.
Among the present invention, first moulding plastics matrix.Described plastic substrate is thermoplasticity or the thermosetting resin that contains electroless plating promotor, and wherein electroless plating promotor is uniformly distributed in thermoplasticity or the thermosetting resin.Described electroless plating promotor is Ni
2O
3, Co
2O
3, CuSiO
3, CuC
2O
4, Cu/Fe/Mn or Cu/Fe/Al ternary co-sintering oxide compound, Cu/Fe/Al/Mn quaternary co-sintering oxide compound one or more.
The electroless plating promotor of being adopted among the present invention, particle diameter are 20nm-100 μ m, are preferably 50nm-10 μ m, more preferably 200nm-4 μ m.In the electroless plating promotor of being adopted, Ni
2O
3, Co
2O
3, CuSiO
3, CuC
2O
4Can adopt to be purchased product, ball milling is to suitable particle diameter then; And Cu/Fe/Mn or Cu/Fe/Al ternary co-sintering oxide compound, Cu/Fe/Al/Mn quaternary co-sintering oxide compound can adopt following method preparation: buy corresponding metal oxide, mix back sintering between the 700-1500 degree in vacuum atmosphere oven through ball milling, then ball milling suitable particle diameter extremely.The molecular formula of described Cu/Fe/Mn ternary co-sintering oxide compound is CuFe
xMn
yO
z, x=0.01-2 wherein, y=0.01-2, z=2-4; The molecular formula of described Cu/Fe/Al ternary co-sintering oxide compound is CuFe
mAl
nO
1, m=0.01-2 wherein, n=0.01-2, l=2-4; The molecular formula of described Cu/Fe/Al/Mn quaternary co-sintering oxide compound is CuFe
aAl
bMn
cO
d, a=0.01-2 wherein, b=0.01-2, c=0.01-2, d=2-4.
Described thermoplasticity/thermosetting resin is as well known to those skilled in the art, and for example thermoplastics can be for being selected from polyolefine, polyester, polymeric amide, polyarylether, polyester-imide, polycarbonate (PC), polycarbonate/(acrylonitrile-butadiene-styrene (ABS)) alloy (PC/ABS), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyimide (PI), polysulfones (PSU), polyether-ether-ketone (PEEK), polybenzimidazole (PBI) or the liquid crystalline polymers (LCP) one or more.Wherein, polyolefine can or gather (acrylonitrile-butadiene-styrene (ABS)) for polystyrene (PS), polypropylene (PP), polymethylmethacrylate.Polyester can for the poly terephthalic acid hexanaphthene to diformazan alcohol ester (PCT), PDAIP (PDAIP), poly terephthalic acid diallyl (PDAP), PBN (PBN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT).Polymeric amide can be 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), poly-hexamethylene terephthalamide (PA6T) or poly-paraphenylene terephthalamide's nonamethylene diamine (PA9T).Liquid crystalline polymers be well known to a person skilled in the art a kind of that constitute by the stiff molecule chain, existing liquid fluidity has the polymer substance of crystallophy performance anisotropic states (being liquid crystal state) again under certain physical condition.Described thermosetting resin can be selected from one or more of resol, urea-formaldehyde resin, melamine formaldehyde resin, Resins, epoxy, Synolac, urethane.
The method of moulding can adopt various forming method of the prior art, earlier electroless plating promotor, thermoplasticity/thermosetting resin fluoropolymer resin are mixed, adopt Banbury mixer, single screw rod or common plasticses such as twin screw extruder, the mixer mechanical preparation plastics composite that is mixed, pass through injection moulding, blowing then, extrude or the hot pressing extrusion equipment, make the plastic substrate of various desired shapes.
Among the present invention, because CuC
2O
4Easily decompose, can make the plastic substrate degraded, thereby reduce the mechanical property of plastic substrate.Therefore, as those skilled in the art's common practise, the temperature of moulding plastics matrix generally is lower than 300 ℃, so contains CuC as if in the described electroless plating promotor among the present invention
2O
4, CuC during moulding
2O
4Can not decompose yet.
Quality with plastic substrate is a benchmark, and the content of electroless plating promotor is 1-40%, is preferably 1-30%, more preferably 2-15%.
For improving the various performances of plastic substrate of the present invention, can also contain antioxidant, photostabilizer, lubricant, mineral filler in the described plastic substrate.It is known altogether that described antioxidant, photostabilizer, lubricant, mineral filler are those skilled in the art, can directly adopt and be purchased product.Among the present invention, with described antioxidant, photostabilizer, lubricant, mineral filler and electroless plating promotor, after thermoplasticity/the thermosetting resin fluoropolymer resin mixes, moulding obtains plastic substrate in the lump.
Quality with plastic substrate is a benchmark, and the content of oxidation inhibitor can be 0.01-2%, and the content of described photostabilizer can be 0.01-2%, and the content of lubricant can be 0.01-2%, and the content of mineral filler is 1-70%.
Oxidation inhibitor can improve the antioxidant property of plastic substrate.Described oxidation inhibitor is conventionally known to one of skill in the art, for example can be selected from the oxidation inhibitor 1098,1076,1010,168 of Ciba company.Photostabilizer can improve the light stability of plastic substrate.Described photostabilizer can be preferably hindered amine light stabilizer for various known photostabilizers, for example can be selected from the photostabilizer 944 of Ciba company.
Described lubricant can improve the flowability of plastics, thereby makes plastic substrate mix more evenly.Described lubricant can be selected from one or more in copolymerization wax (EVA wax), polyethylene wax and the stearate of methyl polysiloxane, ethylene/vinyl acetate.
Mineral filler can be talcum powder, lime carbonate, glass fibre, ca silicate fibre, stannic oxide or carbon black.Wherein, glass fibre can be deepened the degree of depth of plastic substrate depression after the laser gasification, helps the adhesion of copper in the electroless copper; Stannic oxide especially nano tin dioxide or carbon black can increase the capacity usage ratio of laser.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.Preferably do not contain the element to environment and human body harmful such as Cr in the described mineral filler.
Among the present invention, electroless plating promotor is uniformly distributed in the plastic substrate, so the sticking power of electroless plating promotor and plastic substrate is very high, and follow-up electroless plating is directly carried out on described electroless plating promotor surface, therefore, make that the sticking power of last metal plating that forms and plastic substrate is also very high.
According to preparation method provided by the invention, the laser gasification surface of plastic matrix by laser gasification, forms figure at surface of plastic matrix.The laser radiation zone, the fluoropolymer resin gasification in the plastic substrate, thus electroless plating promotor is come out.Institute's employing laser equipment can be general infrared laser, for example CO
2Laser marking machine.Described Wavelength of Laser is 157nm-10.6 μ m, and sweep velocity is 500-8000mm/s, and step-length is 3-9 μ m, delays time to be 30-100 μ s, and frequency is 30-40KHz, and power is 3-4W, and filling spacing is 10-50 μ m.Among the present invention, lower to the energy requirement of laser, the surface of plastic matrix that only need gasify exposes electroless plating promotor and gets final product, and is metal simple-substance and need not to reduce electroless plating promotor.
The thickness of the plastic substrate after the general moulding is more than the 500 μ m, the plastic substrate thickness that generally etches away during laser gasification is several microns to tens microns, thereby make the electroless plating promotor in the plastic substrate come out, surface of plastic matrix forms on the microcosmic to having the rough surface structure in rugged space.When follow-up electroless copper/nickel, copper/nickel just is embedded in the hole of uneven surface, thereby and forms very strong bonding force between the plastic sample.
Among the present invention, the laser radiation zone of plastic substrate, smog is produced in the plastics gasification.Cover in chemical plating catalyst for preventing that smog from falling, can be the laser configurations extractor fan, smog is taken away as far as possible, also can be after laser gasification be finished the ultrasonic cleaning plastic substrate.
According to preparation method provided by the invention, after the laser gasification, the plastic substrate in laser radiation zone exposes electroless plating promotor, and electroless copper or chemical nickel plating are carried out in this electroless plating promotor surface then.Described method of carrying out electroless copper or chemical nickel plating is those skilled in the art's common chemical electroplating method, for example the plastic substrate through laser gasification can be contacted with chemical bronze plating liquid or chemical nickel-plating liquid.
The electroless plating promotor that exposes in the plastic substrate, after chemical bronze plating liquid or chemical nickel-plating liquid contact, electroless plating promotor can promote cupric ion or the nickel ion generation reduction reaction in the chemical plating fluid, generate metallic copper or nickel particle, be wrapped in electroless plating promotor surface, and the copper coating or the nickel coating of the densification of interconnection formation one deck, thereby form the first layer coating fast in the laser radiation zone.
For decorative surface, practicality and the erosion resistance that improves coating, can also proceed at least electroless plating and/or plating on copper coating or nickel coating surface, obtain described metal level at last.
For example, carry out chemical nickel plating, after plastic substrate laser gasification zone forms nickel coating, can also continue on nickel coating, to continue to form other metal plating by the method for prior art routine on electroless plating promotor surface.The method of described prior art routine comprises electroless plating, plating.Under the preferable case, can proceed one time electroless copper on the nickel coating surface, form copper coating on the nickel coating surface; Carry out chemical nickel plating again one time, obtain complex metal layer, this complex metal layer has the Ni-Cu-Ni structure outside the lining.More preferably under the situation, by dodging Gold plated Layer, make the metal level of surface of plastic matrix outside the lining, have the Ni-Cu-Ni-Au structure at the composition metal laminar surface.
Carry out electroless copper on electroless plating promotor surface, after plastic substrate laser gasification zone forms copper coating, also can adopt the method for prior art routine to continue on copper coating, to continue to form other metal plating.Under the preferable case, oxidized for the copper coating that prevents surface of plastic matrix, can proceed chemical nickel plating one time, form one deck nickel coating on the copper coating surface, the metal level of the surface of plastic matrix that obtains outwards has the Cu-Ni structure from the lining.More preferably under the situation, by dodging Gold plated Layer, make the metal level of surface of plastic matrix outwards have the Cu-Ni-Au structure from the lining at the Cu-Ni layer on surface of metal.
Among the present invention, have in the metal level of Ni-Cu-Ni, Ni-Cu-Ni-Au, Cu-Ni or Cu-Ni-Au structure, the thickness of various Ni layers is 0.1-50 μ m, is preferably 1-10 μ m, more preferably 2-3 μ m; Copper layer thickness is 0.1-100 μ m, is preferably 1-50 μ m, more preferably 5-30 μ m; The thickness of Au layer is 0.01-10 μ m, is preferably 0.01-2 μ m, more preferably 0.1-1 μ m.
Wherein, the chemical bronze plating liquid that is adopted, chemical nickel-plating liquid, electroplate liquid copper liquid or electronickelling liquid, dodge the various plating baths that gold plating liquid that Gold plated Layer adopts all adopts those skilled in the art to use always.For example, described chemical bronze plating liquid contains mantoquita and reductive agent, and the pH value is 12-13, and described reductive agent can be reduced to copper simple substance with cupric ion in the mantoquita, and reductive agent can be in oxoethanoic acid, hydrazine and the inferior sodium phosphate one or more.Described electroless copper yet can directly adopt disclosed copper plating bath in the prior art, and for example " sufacing " in December, 2002, the 31st rolls up the 6th interim disclosed a kind of plating bath: CuSO
45H
2O0.12mol/L, Na
2EDTA2H
2O0.14mol/L, yellow prussiate of potash 10mg/L, 2,2 '-dipyridyl 10mg/L, oxoethanoic acid (HCOCOOH) 0.10mol/L, and with NaOH and H
2SO
4The pH value of regulating plating bath is 12.5-13.In addition, if feel copper coating thickness deficiency behind the electroless copper, also can carry out electro-coppering.Chemical nickel plating also can adopt nickel-plating liquid of the prior art, and for example it consists of: single nickel salt: 23g/l, and inferior sodium phosphate: 18g/l, lactic acid: 20g/l, oxysuccinic acid: 15g/l, regulating pH with NaOH is 5.2, temperature: 85-90 ℃.
Among the present invention, the time of carrying out electroless copper or chemical nickel plating on electroless plating promotor surface without limits.Under the preferable case, it is 10-240 minute in the time of electroless plating promotor Electroless copper; In the time of electroless plating promotor chemical nickel plating on surface is 8-15 minute.
The method of dodging Gold plated Layer on nickel coating also is conventionally known to one of skill in the art, repeats no more among the present invention.The gold plating liquid that adopts when wherein dodging Gold plated Layer can directly adopt the neutral gold plating liquid of BG-24 of Shenzhen lappingout wound chemical company.
Surface of plastic matrix is not by the zone of laser radiation, non-chemical plating promotor exists, and it is coarse that its surface can not show a candle to the laser radiation region surface, so the sedimentary speed of its metallochemistry is very slow and sticking power is very low, substantially there is not metal deposition during electroless plating, if small part deposition is arranged but can wipe out easily, thereby realize of the present inventionly, and obtain plastics provided by the invention directly in the purpose of selective metallization of plastic surface.
Described plastics comprise plastic substrate and are positioned at the metal level that surface of plastic matrix forms pattern.Described metal level is Ni-Cu-Ni layer, Ni-Cu-Ni-Au layer, Cu-Ni layer or Cu-Ni-Au layer from the inside to surface.
The present invention will be described in more detail below with reference to embodiment.Raw materials usedly in embodiment and the Comparative Examples all be available commercially.
Embodiment 1
(1) with CuC
2O
42H
2O, crystal water is taken off in vacuum-drying, and ball milling is below the 1 μ m to D50, drying; With PP resin, CuC
2O
4, talcum powder and antioxidant 1010 be 100: 15: 10 by mass ratio: 0.2 adopt high mixer to mix after, (Nanjing Rubber-Plastic Machinery Plant) is extruded into tubing with single screw extrusion machine, extrusion temperature is 180 ℃.
(2) (laser parameter is for Taide, the DPF-M12) outside surface of the whole tubing of irradiation: wavelength 1064nm, sweep velocity 1000mm/s, step-length 9 μ m, the 30 μ s that delay time, frequency 40KHz, power 3W, filling spacing 50 μ m to adopt infrared laser; Clean tube surfaces.
(3) immerse in the chemical bronze plating liquid 3 hours, forming thickness is the copper layer of 10 μ m, immerses chemical nickel-plating liquid 10 minutes, and it is the nickel dam of 3 μ m that copper layer outside forms thickness; Chemical bronze plating liquid: CuSO
45H
2O0.12mol/L, Na
2EDTA2H
2O0.14mol/L, yellow prussiate of potash 10mg/L, 2,2 '-dipyridyl 10mg/L, oxoethanoic acid (HCOCOOH) 0.10mol/L, and with NaOH and H
2SO
4The pH value of regulating plating bath is 12.5-13; Chemical nickel-plating liquid: single nickel salt: 23g/l, inferior sodium phosphate: 18g/l, lactic acid: 20g/l, oxysuccinic acid: 15g/l, regulating pH with NaOH is 5.2.
By above-mentioned steps, obtain the plastics as tubing of present embodiment.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare the plastics of present embodiment, difference is:
In the step (1), with CuSiO
3Ball milling is below the 2 μ m to D50, drying; With PC resin, CuSiO
3, antioxidant 168, EVA wax be 100: 20: 0.2 by mass ratio: 0.1 mix after, extruding pelletization injection moulding again is an electric appliance casing;
Adopt infrared laser on electric appliance casing, to print the metallic circuit figure in the step (2); After laser gasification is finished, the ultrasonic cleaning electric appliance casing;
In the step (3), the order of electroless plating is: first chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes, and electroless copper formed the thick copper layer of 11 μ m in 3 hours again, and last chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes.
By above-mentioned steps, obtain the plastics as electric appliance casing of present embodiment.
Embodiment 3
Adopt the method identical with embodiment 2 to prepare the plastics of present embodiment, difference is:
In the step (1), with Co
2O
3Ball milling is below the 5 μ m to D50, drying; With PBT resin, Co
2O
3, glass fibre and photostabilizer 944 be 100: 15: 35 by mass ratio: 0.2 directly with twin screw extruder (Nanjing Rubber-Plastic Machinery Plant) compounding, and granulation is injection molded into the automotive connector shell;
In the step (3), electroless plating is in proper order: first chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes, electroless copper formed the thick copper layer of 6 μ m in 2 hours again, last chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes, the gold layer of last flash 0.03 micron thickness dodges the neutral gold plating liquid of BG-24 that gold plating liquid adopts Shenzhen company of lappingout wound chemical company.
By above-mentioned steps, obtain the plastics as the automotive connector shell of present embodiment.
Embodiment 4
Adopt the method identical with embodiment 2 to prepare the plastics of present embodiment, difference is:
In the step (1), with Ni
2O
3Ball milling is below the 10 μ m to D50, drying; With PC resin, Ni
2O
3, antioxidant 1076 and polyethylene wax be 100: 10: 0.2 by mass ratio: 0.1 mix after, extruding pelletization, the shell of hollow blow molding automotive electronics component;
In the step (3), the order of electroless plating is: first chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes, and electroless copper formed the thick copper metal layer of 6 μ m in 2 hours again, and last chemical nickel plating formed the metal nickel dam of the thick protection usefulness of 4 μ m in 12 minutes.
By above-mentioned steps, obtain the plastics of the shell that is used as the automotive electronics component of present embodiment.
Embodiment 5
(1) with 54.1g CuO (0.68mol), 27.13g Fe
2O
3(0.17mol) with 26.87g Mn
2O
3(0.17mol) mix, roasting 2h in 1000 ℃ of following air, being milled to the powder median size through clipping the ball is 0.8 μ m, consists of CuFe with analysis means analysis products such as XPS
0.5Mn
0.5O
2.5
(2) with PPO resin, CuFe
0.5Mn
0.5O
2.5, ca silicate fibre, antioxidant 1076 and polyethylene wax be 100: 10: 10 by mass ratio: adopt high mixer mix at 0.2: 0.1, use the twin screw extruder granulation then,, make solar cell open air connector shell again by injection moulding.
(3) adopt the method identical on the outdoor connector shell of solar cell, to print the metallic circuit figure with step (2) among the embodiment 2.
(4) electroless plating order: first chemical nickel plating formed the thick nickel dam of 2 μ m in 8 minutes, and electroless copper formed the thick copper layer of 15 μ m in 4 hours again, and chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes then, the gold layer that last flash 0.03 μ m is thick.
By above-mentioned steps, obtain the plastics as the outdoor connector shell of solar cell of present embodiment.
Embodiment 6
Adopt the method identical with embodiment 5 to prepare the plastics of present embodiment, difference is:
In the step (1), with 54.1g CuO (0.68mol), 27.13g Fe
2O
3(0.17mol), 17.33g Al
2O
3(0.17mol) mix, roasting 2h in 1000 ℃ of following air, being milled to the powder median size through clipping the ball is 0.5 μ m, consists of CuFe with analysis means analysis products such as XPS
0.5Al
0.5O
2.5
In the step (2), with PA6T resin, CuFe
0.5Al
0.5O
2.5, antioxidant 1076 and polyethylene wax be 100: 10: 0.2 by mass ratio: 0.1 mix after, extruding pelletization by injection moulding, is made the electric power connector shell of motor car engine;
In the step (4), the electroless plating order: first chemical nickel plating formed the thick nickel dam of 2 μ m in 8 minutes, and electroless copper formed the thick copper metal layer of 15 μ m in 4 hours again, and chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes then, the gold layer that last flash 0.03 μ m is thick.
By above-mentioned steps, obtain the plastics as the car engine electronic connector shell of present embodiment.
Embodiment 7
This employing and embodiment 5 identical methods prepare the plastics of present embodiment, and difference is:
In the step (1), with 54.1g CuO (0.68mol), 13.56g Fe
2O
3(0.085mol), 8.67gAl
2O
3(0.085mol) with 26.87g Mn
2O
3(0.17mol) mix, roasting 2h in 1000 ℃ of following air, being milled to the powder median size through clipping the ball is 1.0 μ m, consists of CuFe with analysis means analysis products such as XPS
0.25Al
0.25Mn
0.5O
2.5
In the step (2), with PPS resin, CuFe
0.25Al
0.25Mn
0.5O
2.5, antioxidant 1076 and polyethylene wax be 100: 10: 0.2 by mass ratio: 0.1 mix after, extruding pelletization by injection moulding, is made the housing of electric power connector;
In the step (4), the electroless plating order: first electroless copper formed the thick copper layer of 12 μ m in 3 hours, and chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes then.
By above-mentioned steps, obtain the plastics of the electric power connector housing of present embodiment.
Claims (12)
1. the preparation method of plastics may further comprise the steps:
1) moulding plastics matrix; Described plastic substrate is thermoplasticity or the thermosetting resin that contains electroless plating promotor, and electroless plating promotor is uniformly distributed in thermoplasticity or the thermosetting resin; Described electroless plating promotor is Ni
2O
3, Co
2O
3, CuSiO
3, CuC
2O
4, Cu/Fe/Mn or Cu/Fe/Al ternary co-sintering oxide compound, Cu/Fe/Al/Mn quaternary co-sintering oxide compound one or more;
2) laser gasification surface of plastic matrix exposes electroless plating promotor;
3) in step 2) electroless plating promotor Electroless copper or chemical nickel plating, proceed at least electroless plating and/or plating, form metal level at surface of plastic matrix.
2. preparation method according to claim 1 is characterized in that, the mode of moulding is injection moulding, blowing, extrudes or hot pressing in the step 1).
3. preparation method according to claim 1, it is characterized in that, step 2) condition of laser gasification comprises in: Wavelength of Laser is 157nm-10.6 μ m, sweep velocity is 500-8000mm/s, step-length is 3-9 μ m, delays time to be 30-100 μ s, and frequency is 30-40KHz, power is 3-4W, and filling spacing is 10-50 μ m.
4. preparation method according to claim 1 is characterized in that, behind electroless plating promotor chemical nickel plating on surface, continues electroless plating or/and electroplate in the step 3), forms Ni-Cu-Ni layer, Ni-Cu-Ni-Au layer at surface of plastic matrix; Or after electroless plating promotor Electroless copper, continue electroless plating or/and electroplate, form Cu-Ni layer or Cu-Ni-Au layer at surface of plastic matrix.
5. preparation method according to claim 4, it is characterized in that, the thickness of various Ni layers is 0.1-50 μ m in described Ni-Cu-Ni layer, Ni-Cu-Ni-Au layer, Cu-Ni layer or the Cu-Ni-Au layer, and the thickness of Cu layer is 0.1-100 μ m, and the thickness of Au layer is 0.01-10 μ m.
6. preparation method according to claim 1 is characterized in that, the median size of described electroless plating promotor is 20nm-100 μ m.
7. according to claim 1 or 6 described preparation methods, it is characterized in that the molecular formula of described Cu/Fe/Mn ternary co-sintering oxide compound is CuFe
xMn
yO
z, x=0.01-2 wherein, y=0.01-2, z=2-4; The molecular formula of described Cu/Fe/Al ternary co-sintering oxide compound is CuFe
mAl
nO
l, m=0.01-2 wherein, n=0.01-2, l=2-4; The molecular formula of described Cu/Fe/Al/Mn quaternary co-sintering oxide compound is CuFe
aAl
bMn
cO
d, a=0.01-2 wherein, b=0.01-2, c=0.01-2, d=2-4.
8. preparation method according to claim 1, it is characterized in that described thermoplastics is selected from one or more of polyolefine, polyester, polymeric amide, polyarylether, polyester-imide, polycarbonate/(acrylonitrile-butadiene-styrene (ABS)) alloy, polyphenylene sulfide, polyimide, polysulfones, polyether-ether-ketone, polybenzimidazole, liquid crystalline polymers; Described thermosetting resin is selected from one or more of resol, urea-formaldehyde resin, melamine formaldehyde resin, Resins, epoxy, Synolac, urethane.
9. preparation method according to claim 1 is characterized in that, is benchmark with the quality of plastic substrate, and wherein the content of electroless plating promotor is 1-40%.
10. preparation method according to claim 1 is characterized in that, also contains antioxidant, photostabilizer, lubricant, mineral filler in the described plastic substrate.
11. plastics, described plastics comprise plastic substrate and are positioned at the metal level of surface of plastic matrix; Described plastics are prepared by the described method of claim 1.
12. plastics according to claim 11 is characterized in that, described metal level is Ni-Cu-Ni layer, Ni-Cu-Ni-Au layer, Cu-Ni layer or Cu-Ni-Au layer from the inside to surface.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102389579A CN102071423B (en) | 2009-12-30 | 2009-12-30 | Preparation method of plastic product and plastic product |
| KR1020147028811A KR101607045B1 (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| EP10827682.5A EP2379772B1 (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| PCT/CN2010/072055 WO2011072506A1 (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| EP13151236.0A EP2584066B1 (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| DK13151235.2T DK2584065T3 (en) | 2009-12-17 | 2010-04-22 | Surface metallization method, method of making plastic article and plastic article made thereby |
| KR1020137013358A KR20130064824A (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| US13/128,401 US20110281135A1 (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| DK13151236.0T DK2584066T3 (en) | 2009-12-17 | 2010-04-22 | Surface metallization method, method of making plastic articles and plastic article made therefrom |
| EP13151235.2A EP2584065B1 (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| KR1020137013356A KR20130064822A (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| JP2012506325A JP6082595B2 (en) | 2009-12-17 | 2010-04-22 | Method of surface metallization, method of preparing plastic products, and plastic products produced from such methods |
| KR1020147028810A KR101615846B1 (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| EP13151234.5A EP2584064B1 (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| KR1020147007686A KR101623664B1 (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| KR1020117020318A KR101313151B1 (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| KR1020137013357A KR20130064823A (en) | 2009-12-17 | 2010-04-22 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
| US14/836,750 US20160068963A1 (en) | 2009-12-17 | 2015-08-26 | Surface metallizing method, method for preparing plastic article and plastic article made therefrom |
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| CN 201110237586 Division CN102345123B (en) | 2009-12-30 | 2009-12-30 | Method for producing plastic product and plastic product |
| CN 201110268153 Division CN102409319B (en) | 2009-12-30 | 2009-12-30 | Preparation method of plastic product and plastic product |
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