CN102345123A - Method for producing plastic product and plastic product - Google Patents
Method for producing plastic product and plastic product Download PDFInfo
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- CN102345123A CN102345123A CN201110237586XA CN201110237586A CN102345123A CN 102345123 A CN102345123 A CN 102345123A CN 201110237586X A CN201110237586X A CN 201110237586XA CN 201110237586 A CN201110237586 A CN 201110237586A CN 102345123 A CN102345123 A CN 102345123A
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- electroless plating
- layer
- plating
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Abstract
The invention provides a method for producing a plastic product and the plastic product. The production method comprises the following steps: 1) forming a plastic substrate, wherein the plastic substrate comprises a chemical plating enhancer which is one or more selected from Ni2O3, Co2O3, CuSiO3, CuC2O4, Cu/Fe/Mn or Cu/Fe/Al ternary co-sintering oxide, Cu/Fe/Al/Mn quaternary co-sintering oxide; 2) laser gasificating the surface of the plastic substrate, exposing the chemical plating enhancer; 3) performing chemical copper plating or chemical nickel plating, continuously carrying out a chemical plating and/or electroplating, forming a metal layer on the surface of the plastic substrate. The method of the invention has the advantages of simple process, low energy requirement and low cost; in addition, the chemical plating enhancer is distributed in the plastic substrate, thereby a plating layer formed by chemical plating has high binding force with the plastic substrate.
Description
Related application
The application is that application number is 200910238957.9, the applying date is on December 30th, 2009, denomination of invention is divided an application for the Chinese invention patent application of " a kind of preparation method of plastics and a kind of plastics ".
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 has 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 100 mm/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; Through 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; Said 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; Said 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 said plastics comprise plastic substrate and the metal level that is positioned at surface of plastic matrix; Said plastics are prepared by method provided by the invention.
The present inventor finds Ni through 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; Said 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; Said 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; Said 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 tests through following: 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 is 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 through 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.Said 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.Said 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, then ball milling to suitable particle diameter; 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; Through after the ball mill mixing in vacuum atmosphere oven sintering between the 700-1500 degree, ball milling to suitable particle diameter then.The molecular formula of said 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 said 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 said 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.
Said 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); Gather azelaoyl hexanediamine (PA-69); Gather succinyl hexanediamine (PA-64); Nylon 612 (PA-612); Polyhexamethylene sebacamide (PA-610); Nylon 1010 (PA-1010); Nylon 11 (PA-11); Gather lauramide (PA-12); Gather decoylamide (PA-8); Gather 9 aminononanoic acid (PA-9); Polycaprolactam (PA-6); Gather paraphenylene terephthalamide's phenylenediamine (PPTA); Gather 6I hexamethylene isoterephalamide (MXD6); Gather hexamethylene terephthalamide (PA6T) or gather 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.Said 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
4Be prone to 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 said 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 the plastic substrate that the present invention adopted, can also contain antioxidant, photostabilizer, lubricant, mineral filler in the said plastic substrate.It is known altogether that said antioxidant, photostabilizer, lubricant, mineral filler are those skilled in the art, can directly adopt and be purchased product.Among the present invention, with said 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 said 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.Said 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.Said photostabilizer can be preferably hindered amine light stabilizer for various known photostabilizers, for example can be selected from the photostabilizer 944 of Ciba company.
Said lubricant can improve the flowability of plastics, thereby makes plastic substrate mix more evenly.Said 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.Said 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 said 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 said 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 through 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.Said 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 30-40 KHz, and power is 3-4 W, 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 of plastic substrate zone, 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 accomplished 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.Said 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 that passes 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 fine and close copper coating or the nickel coating 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 said 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 through the conventional method of prior art on electroless plating promotor surface.The conventional method of said prior art 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, through 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 conventional method of prior art 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, through 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, said chemical bronze plating liquid contains mantoquita and reductive agent, and the pH value is 12-13, and said 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.Said 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
2O 0.12mol/L, Na
2EDTA2H
2O 0.14mol/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 think behind the electroless copper that copper coating thickness is not enough, 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, using NaOH to regulate pH is 5.2, temperature: 85-90 ℃.
Among the present invention, carry out the not restriction of time of electroless copper or chemical nickel plating on electroless plating promotor surface.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 on nickel coating, dodging Gold plated Layer 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 area surfaces; So the sedimentary speed of its metallochemistry is very slow and sticking power is very low; Basically there is not metal deposition during electroless plating; If few 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.
Said plastics comprise plastic substrate and are positioned at the metal level that surface of plastic matrix forms pattern.Said 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 will to combine 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 that (Nanjing Rubber-Plastic Machinery Plant) was extruded into tubing with single screw extrusion machine after 100:15:10:0.2 adopted high mixer to mix by mass ratio, 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
2O 0.12mol/L, Na
2EDTA2H
2O 0.14mol/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, using NaOH to regulate pH is 5.2.
Through above-mentioned steps, obtain the plastics as tubing of present embodiment.
Embodiment 2
Adopt the plastics that prepare present embodiment with embodiment 1 identical method, 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 that extruding pelletization injection moulding again was an electric appliance casing after 100:20:0.2:0.1 mixed by mass ratio;
Adopt infrared laser on electric appliance casing, to print the metallic circuit figure in the step (2); After laser gasification is accomplished, 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.
Through above-mentioned steps, obtain the plastics as electric appliance casing of present embodiment.
Embodiment 3
Adopt the plastics that prepare present embodiment with embodiment 2 identical methods, 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 that 100:15:35:0.2 directly uses twin screw extruder (Nanjing Rubber-Plastic Machinery Plant) compounding by mass ratio, 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 thick dodges the neutral gold plating liquid of BG-24 that gold plating liquid adopts Shenzhen company of lappingout wound chemical company.
Through above-mentioned steps, obtain the plastics as the automotive connector shell of present embodiment.
Embodiment 4
Adopt the plastics that prepare present embodiment with embodiment 2 identical methods, 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 after 100:10:0.2:0.1 mixes by mass ratio, 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.
Through 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 that 100:10:10:0.2:0.1 adopts high mixer to mix by mass ratio, uses the twin screw extruder granulation then, again through injection moulding, manufacturing solar cells open air connector shell.
(3) adopt with embodiment 2 in the identical method of step (2) on the connector shell of solar cell open air, print the metallic circuit figure.
(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.
Through above-mentioned steps, obtain the plastics as the outdoor connector shell of solar cell of present embodiment.
Embodiment 6
Adopt the plastics that prepare present embodiment with embodiment 5 identical methods, 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 after 100:10:0.2:0.1 mixes by mass ratio, extruding pelletization through 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.
Through 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), 8.67g Al
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 after 100:10:0.2:0.1 mixes by mass ratio, extruding pelletization through 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.
Through 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; Said 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; Said 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 30-40 KHz; Power is 3-4 W, 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 said 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 said electroless plating promotor is 20nm-100 μ m.
7. according to claim 1 or 6 described preparing methods, it is characterized in that the molecular formula of said 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 said 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 said 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 said 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; Said 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 said plastic substrate.
11. plastics, said plastics comprise plastic substrate and the metal level that is positioned at surface of plastic matrix; Said plastics are prepared by the described method of claim 1.
12. plastics according to claim 11 is characterized in that, said 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643535A (en) * | 2012-05-04 | 2012-08-22 | 金发科技股份有限公司 | Modified resin composition and preparation method and application thereof |
| CN103540151A (en) * | 2012-07-13 | 2014-01-29 | 金发科技股份有限公司 | Modified resin composition for depositing metal film as well as preparation method and application of modified resin composition |
| CN105755514A (en) * | 2014-12-17 | 2016-07-13 | 比亚迪股份有限公司 | Chemical plating catalyst and preparation method thereof, plastic base material composition, and plastic product and preparation method thereof |
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| US6194032B1 (en) * | 1997-10-03 | 2001-02-27 | Massachusetts Institute Of Technology | Selective substrate metallization |
| DE10132092A1 (en) * | 2001-07-05 | 2003-01-23 | Lpkf Laser & Electronics Ag | Track structures and processes for their manufacture |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643535A (en) * | 2012-05-04 | 2012-08-22 | 金发科技股份有限公司 | Modified resin composition and preparation method and application thereof |
| CN103540151A (en) * | 2012-07-13 | 2014-01-29 | 金发科技股份有限公司 | Modified resin composition for depositing metal film as well as preparation method and application of modified resin composition |
| CN103540151B (en) * | 2012-07-13 | 2016-05-25 | 金发科技股份有限公司 | For the modified resin composition of depositing metal films, its preparation method with and application |
| CN105755514A (en) * | 2014-12-17 | 2016-07-13 | 比亚迪股份有限公司 | Chemical plating catalyst and preparation method thereof, plastic base material composition, and plastic product and preparation method thereof |
| CN105755514B (en) * | 2014-12-17 | 2018-02-09 | 比亚迪股份有限公司 | Chemical plating catalyst and preparation method thereof and plastic basis material composition and plastic products and preparation method thereof |
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