CN102071423B - Preparation method of plastic product and plastic product - Google Patents

Preparation method of plastic product and plastic product Download PDF

Info

Publication number
CN102071423B
CN102071423B CN2009102389579A CN200910238957A CN102071423B CN 102071423 B CN102071423 B CN 102071423B CN 2009102389579 A CN2009102389579 A CN 2009102389579A CN 200910238957 A CN200910238957 A CN 200910238957A CN 102071423 B CN102071423 B CN 102071423B
Authority
CN
China
Prior art keywords
electroless plating
layer
preparation
promotor
plating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2009102389579A
Other languages
Chinese (zh)
Other versions
CN102071423A (en
Inventor
宫清
周良
苗伟峰
张�雄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BYD Co Ltd
Original Assignee
BYD Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to CN2009102389579A priority Critical patent/CN102071423B/en
Application filed by BYD Co Ltd filed Critical BYD Co Ltd
Priority to KR1020147028810A priority patent/KR101615846B1/en
Priority to DK13151235.2T priority patent/DK2584065T3/en
Priority to KR1020137013358A priority patent/KR20130064824A/en
Priority to US13/128,401 priority patent/US20110281135A1/en
Priority to KR1020137013356A priority patent/KR20130064822A/en
Priority to EP13151235.2A priority patent/EP2584065B1/en
Priority to PCT/CN2010/072055 priority patent/WO2011072506A1/en
Priority to EP13151236.0A priority patent/EP2584066B1/en
Priority to KR1020137013357A priority patent/KR20130064823A/en
Priority to JP2012506325A priority patent/JP6082595B2/en
Priority to KR1020147007686A priority patent/KR101623664B1/en
Priority to KR1020117020318A priority patent/KR101313151B1/en
Priority to EP10827682.5A priority patent/EP2379772B1/en
Priority to EP13151234.5A priority patent/EP2584064B1/en
Priority to KR1020147028811A priority patent/KR101607045B1/en
Priority to DK13151236.0T priority patent/DK2584066T3/en
Publication of CN102071423A publication Critical patent/CN102071423A/en
Publication of CN102071423B publication Critical patent/CN102071423B/en
Application granted granted Critical
Priority to US14/836,750 priority patent/US20160068963A1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Chemically Coating (AREA)

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

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, computingmachine, 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 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; Through in plastic substrate, adding the MOX of spinel structure; Wherein metallic element can be selected from copper, nickel, cobalt, chromium, iron etc., uses Ultra-Violet Laser (wavelength is 248nm, 308nm, 355nm, 532nm) and infrared laser (wavelength is 1064nm and 10600nm) to carry out activation then, MOX 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 MOX 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.
Contriver of the present invention 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.
Contriver of the present invention 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.Contriver of the present invention 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 MOX; 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 1, 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), ppe (PPO), polyphenylene sulfide (PPS), polyimide (PI), polysulfones (PSU), polyetheretherketone (PEEK), polybenzimidazole (PBI) or the liquid crystalline polymers (LCP) one or more.Wherein, polyolefine can or gather (acrylonitrile-butadiene-styrene (ABS)) for PS (PS), Vestolen PP 7052 (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 nonanedioyl 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 mesomorphism) again under certain physical condition.Said thermosetting resin can be selected from one or more of resol, urea-formaldehyde resin, melamine formaldehyde resin, epoxy resin, 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 mechanically pref 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 inhibitor, photostabilizer, lubricant, mineral filler in the said plastic substrate.It is known altogether that said inhibitor, photostabilizer, lubricant, mineral filler are those skilled in the art, can directly adopt and be purchased product.Among the present invention, with said inhibitor, 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, spun glass, ca silicate fibre, White tin oxide or carbon black.Wherein, spun glass can be deepened the degree of depth of plastic substrate depression after the laser gasification, helps the adhesion of copper in the electroless copper; White tin 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, permanent white, titanium oxide, pearlescence, wollastonite, zeyssatite, kaolin, coal dust, potter's clay, mica, kerosene shale ash, pure aluminium silicate, aluminum oxide, thomel, 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, makes 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 30-40KHz, 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 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 can the plastic substrate that pass through laser gasification 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, generates metallic copper or nickel particle, is wrapped in electroless plating promotor surface; And fine and close copper coating or the nickel coatings 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 coatings surface, obtain said metal level at last.
For example, carry out chemical nickel plating, after plastic substrate laser gasification zone forms nickel coatings, can also continue on nickel coatings, 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 coatings surface, form copper coating on the nickel coatings 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 coatings 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 various plating baths that the gold plating liquid that the chemical bronze plating liquid that is adopted, chemical nickel-plating liquid, electroplate liquid copper liquid or electronickelling liquid, sudden strain of a muscle Gold plated Layer adopt 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 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 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 coatings, 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 to can not show a candle to the laser radiation region surface coarse on its surface, 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 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, 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, inhibitor 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 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, spun glass 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, and 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, inhibitor 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.
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, inhibitor 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, 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, inhibitor 1076 and polyethylene wax be 100: 10: 0.2 by mass ratio: 0.1 mix after, 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), 8.67gAl 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, inhibitor 1076 and polyethylene wax be 100: 10: 0.2 by mass ratio: 0.1 mix after, 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 (1)

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 one or more of Cu/Fe/Mn or Cu/Fe/Al ternary co-sintering oxide compound, Cu/Fe/Al/Mn quaternary co-sintering oxide compound, and wherein, 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;
2) laser gasification surface of plastic matrix exposes electroless plating promotor, and the condition of wherein said laser gasification comprises: 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;
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 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.
4, preparation method according to claim 3; 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.
5, preparation method according to claim 1 is characterized in that, the median size of said electroless plating promotor is 20nm-100 μ m.
6, 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, polyphenylene sulfide, polyimide, polysulfones, polyetheretherketone, polybenzimidazole, liquid crystalline polymers; Said thermosetting resin is selected from one or more of resol, urea-formaldehyde resin, melamine formaldehyde resin, epoxy resin, Synolac, urethane.
7, 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%.
8, preparation method according to claim 1 is characterized in that, also contains inhibitor, photostabilizer, lubricant or mineral filler in the said plastic substrate.
CN2009102389579A 2009-12-17 2009-12-30 Preparation method of plastic product and plastic product Active CN102071423B (en)

Priority Applications (18)

Application Number Priority Date Filing Date Title
CN2009102389579A CN102071423B (en) 2009-12-30 2009-12-30 Preparation method of plastic product and plastic product
KR1020117020318A KR101313151B1 (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
US13/128,401 US20110281135A1 (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
EP13151235.2A EP2584065B1 (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
EP10827682.5A EP2379772B1 (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
KR1020137013358A KR20130064824A (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
EP13151234.5A EP2584064B1 (en) 2009-12-17 2010-04-22 Surface metallizing method, method for preparing plastic article and plastic article made therefrom
KR1020147028811A KR101607045B1 (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
KR1020147007686A KR101623664B1 (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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009102389579A CN102071423B (en) 2009-12-30 2009-12-30 Preparation method of plastic product and plastic product

Related Child Applications (2)

Application Number Title Priority Date Filing Date
CN 201110268153 Division CN102409319B (en) 2009-12-30 2009-12-30 Preparation method of plastic product and plastic product
CN 201110237586 Division CN102345123B (en) 2009-12-30 2009-12-30 Method for producing plastic product and plastic product

Publications (2)

Publication Number Publication Date
CN102071423A CN102071423A (en) 2011-05-25
CN102071423B true CN102071423B (en) 2012-01-04

Family

ID=44030176

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009102389579A Active CN102071423B (en) 2009-12-17 2009-12-30 Preparation method of plastic product and plastic product

Country Status (1)

Country Link
CN (1) CN102071423B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103088321A (en) * 2011-10-27 2013-05-08 深圳市微航磁电技术有限公司 Structure and manufacturing method for selectively forming metal on plastic substrate
EP2604648A1 (en) * 2011-12-12 2013-06-19 Mitsubishi Chemical Europe GmbH Thermoplastic composition
CN103517570B (en) * 2012-06-28 2018-09-25 广州光宝移动电子部件有限公司 The production method and shell of electronic circuit
CN102817018A (en) * 2012-09-13 2012-12-12 格林精密部件（惠州）有限公司 Machining method of decoration formed by laser on housing and manufacturing equipment
CN103022638B (en) * 2012-12-13 2015-07-29 深圳市维力谷无线技术有限公司 A kind of method adopting laser direct structuring technique to make embedded antenna for mobile terminal
CN103022664B (en) * 2012-12-19 2015-12-02 上海蓝沛新材料科技股份有限公司 Three-dimensional antenna manufacture method
US20140296411A1 (en) 2013-04-01 2014-10-02 Sabic Innovative Plastics Ip B.V. High modulus laser direct structuring composites
US9668342B2 (en) 2013-09-27 2017-05-30 Lg Chem, Ltd. Composition and method for forming conductive pattern, and resin structure having conductive pattern thereon
CN105803432B (en) * 2016-03-15 2018-04-06 国网安徽省电力公司电力科学研究院 A kind of preparation method using Ni P alloy-layers as the Cu/Al composite plates of interface barrier
CN111218703A (en) * 2018-11-27 2020-06-02 中国科学院沈阳自动化研究所 Laser cleaning assisted electroplating processing method
CN111205588A (en) * 2019-10-29 2020-05-29 浙江昊杨新能源科技有限公司 Concentrated sulfuric acid resistant lead-acid storage battery plastic shell

Citations (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN102071423A (en) 2011-05-25

Similar Documents

Publication Publication Date Title
CN102071423B (en) Preparation method of plastic product and plastic product
CN102071421B (en) Plastic product and preparation method thereof
CN102071424B (en) Plastic product and preparation method thereof
CN102071411B (en) Plastic product and preparation method thereof
EP2584065B1 (en) Surface metallizing method, method for preparing plastic article and plastic article made therefrom
CN101747650B (en) Plastic compound, application thereof and method of selective metallization of plastic surface
CN102206817A (en) Preparation method of plastic product
CN102409319B (en) Preparation method of plastic product and plastic product
CN102071412B (en) Plastic product and preparation method thereof
CN102492940B (en) Preparation method of plastic product and plastic product
CN102277569B (en) Plastic product preparation method and plastic product
CN102345123B (en) Method for producing plastic product and plastic product
CN102418091B (en) Plastic product and preparation method for same
CN102296292A (en) Preparation method of plastic product and plastic product
CN102337038A (en) Plastic composition, application thereof and selective plastic surface metalizing method
CN105647143A (en) Plastic composition and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant