CN102277569B - Plastic product preparation method and plastic product - Google Patents
Plastic product preparation method and plastic product Download PDFInfo
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- CN102277569B CN102277569B CN 201110239244 CN201110239244A CN102277569B CN 102277569 B CN102277569 B CN 102277569B CN 201110239244 CN201110239244 CN 201110239244 CN 201110239244 A CN201110239244 A CN 201110239244A CN 102277569 B CN102277569 B CN 102277569B
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Abstract
The invention provides a plastic product preparation method and a plastic product. The method comprises the following steps of: (1) forming a plastic substrate, wherein the plastic substrate contains a chemical plating accelerating agent, and the chemical plating accelerating agent is a perovskite structure compound having the general formula of ABO3, wherein A contains at least one of elements from No.9, No.10 and No.11 rows in the periodic table of elements and selectively contains one or more elements from IA and IIA families and lanthanide series; and B is one or more elements from IVB and VB families; (2) gasifying the surface of the plastic substrate through laser to expose the chemical plating accelerating agent; and (3) chemically plating copper or chemically plating nickel, continuing chemical plating and/or electroplating at least once to form a metal layer on the surface of the plastic substrate. The preparation method provided by the invention has simple technologies, low requirement for energy and low cost; in addition, the chemical plating accelerating agent is distributed over the plastic substrate, so that the binding force between the coating formed after chemical plating and the plastic matrix is extremely high.
Description
Related application
The application is that application number is 201010044447.0, the applying date is on January 15th, 2010, 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 the 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 first in the prior art to form metal core as the electroless plating catalytic active center on the plastic basis material surface, then carries out electroless plating.
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, then be reduced into metal simple-substance with Ultra-Violet Laser, as the catalyzer of electroless copper, then carry out again copper-plating technique.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, because of relatively poor with plastic substrate sticking power, so 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., then use Ultra-Violet Laser (wavelength is 248nm, 308nm, 355nm, 532nm) and infrared laser (wavelength is 1064nm and 10600nm) to activate, 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 the method, induce the electroless plating metal level after restoring metal simple-substance under the lasing, complex process, energy requirement is high and all higher to the requirement of equipment and process.
Summary of the invention
The metallization of plastic surface complex process, the energy requirement that exist in the prior art are high in order to solve in the present invention, the technical problem of coating and plastic basis material poor adhesive force.
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 for having general formula ABO
3Perovskite structure compound, wherein A contains at least a in the periodic table of elements the 9th, 10,11 column elements, the A selectivity contains one or more in IA, IIA family element, the lanthanon; B is one or more in IVB, the VB family element;
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 by great many of experiments, and the present invention adopts has general formula ABO
3Perovskite structure compound need not to restore metal simple-substance, can 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, technique is simple, and is low to energy requirement, with low cost; In addition, electroless plating promotor is distributed in the plastic substrate, so the 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 for having general formula ABO
3Perovskite structure compound, wherein A contains at least a in the periodic table of elements the 9th, 10,11 column elements, the A selectivity contains one or more in IA, IIA family element, the lanthanon; B is one or more in IVB, the VB family element;
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 speed of carrier surface deposition.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 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 easily causes the degraded of plastics in the plastics the inside.The contriver finds by great many of experiments, and the present invention adopts has general formula ABO
3Perovskite structure compound can be used as electroless plating promotor, can directly carry out on its surface electroless copper/nickel, simultaneously these materials are stored in the degraded that can not cause plastics in the plastics for a long time.
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 for having general formula ABO
3Perovskite structure compound, wherein A contains at least a in the periodic table of elements the 9th, 10,11 column elements, the A selectivity contains one or more in IA, IIA family element, the lanthanon; B is one or more in IVB, the VB family element.
The electroless plating promotor of adopting among the present invention, particle diameter are 20nm-100 μ m, are preferably 50nm-10 μ m, more preferably 200nm-4 μ m.
Electroless plating promotor of the present invention is for having general formula ABO
3Perovskite structure compound.Described perovskite structure compound is for well known to a person skilled in the art various compounds, and perovskite structure compound described in the present invention can directly adopt and be purchased product, and ball milling to required particle diameter gets final product.
The general formula of perovskite structure compound of the present invention is ABO
3, wherein A contains at least a in the periodic table of elements the 9th, 10,11 column elements, and the A selectivity contains one or more in IA, IIA family element, the lanthanon; B is one or more in IVB, the VB family element.For example, A contains at least a among Cu, Ni, Co, Rh, Pd, the Ag, also alternatively among the A contains among Na, Ca, La, the Ce one or more; B can be selected from least a among Ti, Zr, Nb, the V.Under the preferable case, described perovskite structure compound can be Ca
xCu
4-xTi
4O
12, Na
0.04Ca
0.98Cu
3Ti
4O
12, La
0.01Ca
0.99Cu
3Ti
4O
12, CuNiTi
2O
6, CuNbO
3, CuTaO
3Or CuZrO
3, 0≤x＜4 wherein.Among the present invention, described electroless plating promotor is preferably adopted CaCu
3Ti
4O
12, Na
0.04Ca
0.98Cu
3Ti
4O
12, La
0.01Ca
0.99Cu
3Ti
4O
12, CuTiO
3, CuNiTi
2O
6, CuNbO
3, CuTaO
3Or CuZrO
3, but be not limited to this.
Among the present invention, described perovskite structure compound also can prepare by oneself, and its preparation method is as well known to those skilled in the art.For example, described CaCu
3Ti
4O
12Can be prepared as follows: with high-purity CaCO
3, CuO, TiO
2Powder is raw material, mixes according to stoichiometric ratio, and ball milling 12h in distilled water, oven dry is sieved rear in 950 ℃ of lower pre-burning 2h; Ball milling adds binding agent polyvinyl alcohol (PVA) granulation after the oven dry again, is pressed into disc under the 100MPa pressure, in 1100 ℃ of lower sintering 6h, obtains electroless plating promotor required for the present invention at last.Similarly, described Na
0.04Ca
0.98Cu
3Ti
4O
12The preparation method can for: with Na
2CO
3, CaCO
3, CuO and TiO
2Mix by stoichiometric ratio, the ball milling pre-burning, the ball milling granulation, compacting sintering obtains; Described La
0.01Ca
0.99Cu
3Ti
4O
12The preparation method can for: with La
2O
3, CaCO
3, CuO and TiO
2Mix by stoichiometric ratio, the ball milling pre-burning, the ball milling granulation, compacting sintering obtains.
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 (LCP) be well known to a person skilled in the art a kind of that consisted of by the stiff molecule chain, existing liquid fluidity has again the polymer substance of crystallophy performance anisotropic states (being liquid crystal state) 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, first electroless plating promotor, thermoplasticity/thermosetting resin fluoropolymer resin are mixed, adopt Banbury mixer, single screw rod or the common plasticses such as twin screw extruder, the mixer machinery preparation plastics composite that is mixed, then pass through injection moulding, blowing, extrude or the hot pressing extrusion equipment, make the plastic substrate of various desired shapes.
Take the quality of plastic substrate as benchmark, 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.
Take the quality of plastic substrate as benchmark, 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 it is more even that plastic substrate is mixed to get.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, calcium 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, is conducive to 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 Cr etc. in the described mineral filler to environment and human body harmful's element.
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, so that the sticking power of the 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.The wavelength of described 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 so that the electroless plating promotor in the plastic substrate is come out, surface of plastic matrix forms on the microcosmic as 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 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 then electroless copper or chemical nickel plating are carried out in this electroless plating promotor surface.The chemical plating method that described method of carrying out electroless copper or chemical nickel plating is commonly used for those skilled in the art for example can contact the plastic substrate through laser gasification 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 copper coating or the nickel coating of the densification of interconnection formation one deck, thereby form fast the first layer coating in the laser radiation zone.
For decorative surface, practicality and the erosion resistance that improves coating, can also proceed on copper coating or nickel coating surface at least electroless plating and/or plating, obtain at last described metal level.
For example, carry out chemical nickel plating on electroless plating promotor surface, after plastic substrate laser gasification zone forms nickel coating, can also continue by the method for prior art routine to continue to form other metal plating at nickel coating.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 one time again, obtain complex metal layer, this complex metal layer outwards has a Ni-Cu-Ni structure from inner.More preferably in the situation, by dodging Gold plated Layer, the metal level that makes surface of plastic matrix outwards has a Ni-Cu-Ni-Au structure from inner on the complex metal layer 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 to continue to form other metal plating at copper coating.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 copper coating surface, the metal level of the surface of plastic matrix that obtains outwards has a Cu-Ni structure from inner.More preferably in the situation, by dodging Gold plated Layer, the metal level that makes surface of plastic matrix outwards has a Cu-Ni-Au structure from inner 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 adopts, 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 commonly use.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, " sufacing " in December, 2002 for example, the 31st volume 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, regulating pH with NaOH 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; It is 8-15 minute in the time of electroless plating promotor chemical nickel plating on surface.
The method of dodging Gold plated Layer at 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 speed of its metallochemistry deposition 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 directly in the purpose of selective metallization of plastic surface, and obtain plastics provided by the invention.
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 among the embodiment all be available commercially.
Embodiment 1
(1) with CaCu
3Ti
4O
12Put into high speed ball mill, ball milling 10 hours to powder median size is 700nm; With PPE/PPS resin alloy, CaCu
3Ti
4O
12, ca silicate fibre and antioxidant 1010, be after 100:10:30:0.2 adopts high mixer to mix, to be LED lamp circuit board carrier with twin screw extruder (Nanjing Rubber-Plastic Machinery Plant) extruding pelletization, injection moulding according to mass ratio.
(2) (the metallic circuit figure DPF-M12) is printed at LED lamp circuit board carrier in the Taide, and laser parameter is: wavelength 1064nm to adopt infrared laser, sweep velocity 1000mm/s, step-length 9 μ m, 30 μ s delay time, frequency 40KHz, power 3W fills spacing 50 μ m; After laser radiation is finished, this plastic carrier surface of ultrasonic cleaning.
(3) immerse in the chemical nickel-plating liquid 10 minutes, forming thickness is the nickel dam of 3 μ m; Immersed in the chemical bronze plating liquid 4 hours, forming thickness is the copper layer of 13 μ m; Immersed chemical nickel-plating liquid 10 minutes, forming thickness is the nickel dam of 3 μ m again; The gold layer of last flash 0.03 micron thick.Wherein, 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, regulating pH with NaOH is 5.2; Dodge 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 LED lamp circuit board carrier of the present embodiment.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare the plastics of the present embodiment, difference is:
In the step (1), with CuNiTi
2O
6Ball milling to median size is 800nm, drying; With PEEK resin, CuNiTi
2O
6, for after 100:20:30:0.2 mixes, extruding pelletization again injection moulding is the car engine electronic connector shell in mass ratio for glass fibre and antioxidant 168;
In the step (3), the order of electroless plating is: 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 13 μ m in 3 hours again, and chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes again, 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 the present embodiment.
Embodiment 3
Adopt the method identical with embodiment 1 to prepare the plastics of the present embodiment, difference is:
In the step (1), with CuNbO
3Ball milling to median size is 800nm, drying; With PES resin, CuNbO
3, for after 100:10:30:0.2:0.1 mixes, extruding pelletization again injection moulding is the electric power connector housing in mass ratio for potassium titanate crystal whisker, antioxidant 1010 and polyethylene wax;
In the step (3), electroless plating sequentially is: first electroless copper formed the thick copper layer of 5 μ m in 3 hours, and chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes again.
By above-mentioned steps, obtain the plastics as the electric power connector housing of the present embodiment.
Embodiment 4
Adopt the method identical with embodiment 1 to prepare the plastics of the present embodiment, difference is:
In the step (1), with CuTiO
3Ball milling to median size is 900nm, drying; With PC resin, CuTiO
3, antioxidant 1076 and polyethylene wax be in mass ratio for after 100:10:0.2:0.1 mixes, extruding pelletization, the shell of hollow blow molding road vehicle 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 10 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 road vehicle component of the present embodiment.
Embodiment 5
Adopt the method identical with embodiment 1 to prepare the plastics of the present embodiment, difference is:
In the step (1), with CuZrO
3Ball milling to median size is 900nm, drying; With PPO resin, CuZrO
3, ca silicate fibre, antioxidant 1076 and polyethylene wax mix for 100:10:10:0.2:0.1 adopts high mixer in mass ratio, then uses the twin screw extruder granulation, again by injection moulding, making solar cell outdoor connector shell;
In the step (3), the order of electroless plating is: 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 then chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes, the gold layer that last flash 0.03 μ m is thick.
By above-mentioned steps, obtain the plastics as solar cell outdoor connector shell of the present embodiment.
Embodiment 6
(1) with the Na of 2.2g
2CO
3, 98g CaCO
3, the CuO of 240g, the TiO of 330g
2Powder mixes, ball milling 12h in distilled water, and oven dry is sieved rear in 950 ℃ of pre-burning 2h; Ball milling 4h adds the PVA granulation after the oven dry again, is pressed into disc under the 100MPa pressure, 1100 ℃ of lower sintering 6h, and being milled to the powder median size through clipping the ball is 900nm, is Na with analysis means analysis product compositions such as XPS
0.04Ca
0.98Cu
3Ti
4O
12
(2) with PA6T resin, Na
0.04Ca
0.98Cu
3Ti
4O
12, for after 100:10:0.2:0.1 mixes, extruding pelletization by injection moulding, is made the electric power connector shell of motor car engine in mass ratio for antioxidant 1076 and polyethylene wax.
(3) adopt the method identical with step (2) among the embodiment 1 to print the metallic circuit figure at the electric power connector shell of motor car engine.
(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 metal layer of 15 μ m in 4 hours again, and then chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes, 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 the present embodiment.
Embodiment 7
(1) with the La of 3.3g
2O
3, 100g CaCO
3, the CuO of 240g, the TiO of 330g
2Powder mixes, ball milling 12h in distilled water, and oven dry is sieved rear in 950 ℃ of pre-burning 2h; Ball milling 4h adds the PVA granulation after the oven dry again, is pressed into disc under the 100MPa pressure, 1100 ℃ of lower sintering 6h, and being milled to the powder median size through clipping the ball is 1.0 μ m, is La with analysis means analysis product compositions such as XPS
0.01Ca
0.99Cu
3Ti
4O
12
In the step (2), with PPS resin, La
0.01Ca
0.99Cu
3Ti
4O
12, for after 100:10:0.2:0.1 mixes, extruding pelletization by injection moulding, is made the housing of electric power connector in mass ratio for antioxidant 1076 and polyethylene wax;
In the step (4), the electroless plating order: first electroless copper formed the thick copper layer of 12 μ m in 3 hours, and then chemical nickel plating formed the thick nickel dam of 3 μ m in 10 minutes.
By above-mentioned steps, obtain the plastics of the electric power connector housing of the 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 for having general formula ABO
3Perovskite structure compound, wherein A contains at least a in the periodic table of elements the 9th, 10,11 column elements, the A selectivity contains one or more in IA, IIA family element, the lanthanon; B is one or more in IVB, the VB family element;
2) laser gasification surface of plastic matrix exposes electroless plating promotor, and this electroless plating promotor need not to restore metal simple-substance;
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: the 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 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, described electroless plating promotor is CaCu
3Ti
4O
12, Na
0.04Ca
0.98Cu
3Ti
4O
12, La
0.01Ca
0.99Cu
3Ti
4O
12, CuTiO
3, CuNiTi
2O
6, CuNbO
3, CuTaO
3Or CuZrO
3
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, 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, take the quality of plastic substrate as benchmark, 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 or 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 method claimed in 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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| CN103756318A (en) * | 2013-11-28 | 2014-04-30 | 芜湖跃飞新型吸音材料股份有限公司 | Ageing-resistant modified polyphenylene sulfide material for automobile plastic parts |
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| CN1523138A (en) * | 2003-02-19 | 2004-08-25 | 宏达国际电子股份有限公司 | Process for making plastic surface by electroplating |
| WO2009141800A2 (en) * | 2008-05-23 | 2009-11-26 | Sabic Innovative Plastics Ip B.V. | High dielectric constant laser direct structuring materials |
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| CN1523138A (en) * | 2003-02-19 | 2004-08-25 | 宏达国际电子股份有限公司 | Process for making plastic surface by electroplating |
| WO2009141800A2 (en) * | 2008-05-23 | 2009-11-26 | Sabic Innovative Plastics Ip B.V. | High dielectric constant laser direct structuring materials |
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